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SYNTHESIS AND OPTICAL CONSTANTS OF SOME ACID AMIDES

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The Pennsylvania State College
The Graduate School
Department of Chemistry
Synthesis and Optical Constants
of Some Acid Amides
A Thesis
by
Charles Maresh
Submi t t e d in partial fulfillment
of the requirements
for the degree of
Doctor of Philosophy
February 1940
A ppro v e d :
Dept, of Chemistry
Head of the Dept.
~w
i
TABLE OF CONTENTS
page
Purpose of the Study...............................
.
Presentation of Material.............................
Part I
Introduction. . . . . . . . . . . . . . . . . . .
Historical. . . . . . . .
................ . . . .
A p p a r a t u s ..........................................
Experimental
Preparation of Aromatic Derivatives
Benzamide ........................
. . . . . .
O r t h o - ,M e t a - , and Para-Toluamides . . . . . .
1,4-Dimethyl Benzamide-2...........
2-Cyano 1,3-Dimethyl Benzene.
.
1 ,3-Diinethyl Benzamide-2. . . . . . . . . . .
1,3-Dimethyl Benzamide-4-. . . . . . . . . . .
o-Ethyl Benzamide . . . . . . . . . . . . . .
p-Ethyl Benzamide . . . . . . .
'p-Propyl Benzamide.
.............
pvisobutyl Benzamide. . . . . . . . . . . . .
p-Sec. Butyl Benzamide. . . . . . . . . . . .
p - N Butyl Benzamide . . . . . . . . . . . . .
The Aliphatic Amides
..........................
1
2
3
3
11
12
12
16
18
19
20
22
24
30
39
52
58
62
Part II
........... ............................
Introduction. . . . . . . . . . . . . . . . . . . .
63
Historical...................
63
Methods of Optical Analysis . . . . . . . . . . .
69
A p p a r a t u s ..........................................
83
Optical Data
Aromatic Compounds. . . . . . . . . . . . . . .
88
Aliphatic A m i d e s .................................... 106
Discussion of Results ...............................
Summary
113
............................................. 121
list
of
tables
Table
page
I
II
11A
III
Fractionation of 2-Cyano 1,4-Dimethyl'
Benzene. . .
16
Fractionation' of 4-Cyano 1,3-Dimethyl
Benzene. . .
•
Fractionation' of 4-Cyano 1,3-Dimethyl
Benzene. . .
Fractionation of o-Cyano Ethyl Benzene
20
21
. .
•
23
•
24
IV
ii
ii
p-Cyano Ethyl Benzene
. .
IVA
it
ii
p-Cyano Ethyl Benzene
. . •
V
ii
it
n-Propyl Bro m i d e .........
31
VI
ii
ti
Propyl B e n z e n e ...........
33
VIA
ii
u
ii
«
VIB
n
it
"
"
VII
11
ii
p-Nitropropyl Benzene
VIII
II
ii
p-Amino Propyl Benzene.
. •
37
IX
II
ii
p-Cyano Propyl. Benzene.
.
•
38
X
II
ti
Isobutyl Bromide.........
•
40
XI
II
it
Isobutyl Benzene.........
XIA
II
ii
ii
ti
4-4
XIB
II
ii
n
ti
45
XIC
X ID
XII
XIII
34
Residue . .
Fractional Distillation of. Isobutyl
Benzene R e s i d u e .................... ..
. .
34
•
36
46
. .
Fractionation of p-Nitroisobutyl Benzene
"
•
42
Material Balance o n 'Wurtz-Fittig (Isobutyl
Benzene) . . .
"
25
•
. .
p-Amino Isobutyl Benzene.
.
47
48
49
LIST OF TABLES (continued)
page
Table
XIV
Fractionation of o-Amino Isobutyl Benzene.
.
50
.
51
XV
♦1
"
p-Cyano Isobutyl Benzene.
XVI
tl
"
Sec.-Butyl Bromide.........
53
XVII
II
11
p-Nitro Sec.-Butyl Benzene.
54
XVIII
II
"
p-Amino Sec.-Butyl Benzene.
56
XIX
II
”
p-Cyano Sec.-Butyl Benzene.
56
XX
II
”
p-Nitrobutyl Benzene.
. . .
59
XXI
II
H
p-Amino N-Butyl Benzene . .
60
XXII
II
"
p-Cyano N-Butyl Benzene . .
61
Calibration for Melatope Distances . . . . .
73
XXIV
Ref ractive Indices from Oriented Sections.
.
78
XXV
Outline for Examination of Crystal Grains.
.
80
XXIII
XXVI
Immersion L i q u i d s .............................
86
XXVII
Calibration of Immersion Liquids ...........
87
XXVIII
Aromatic Amides...............................
88
XXIX
XXX
Aliphatic Amides
............................. 107
Melting Points of Amides
....................
114
LIST OF FIGURES
Figure
1
.
page
Calibration of Optical Systern'for‘2V '
Measurement.................
•.
74
2.
Benzamide......................................... 92
3.
o-Toluarnide....................................... 94
4.
m-Toluamide..................
95
5.
p-Toluamide.
97
6
.
7.
8
.
9.
..................
p - T o l u a m i d e . .....................................97
o-Ethyl Benzamide......................
99
p-Ethyl Benzamide...........
100
p-Propyl Benzamide ...........................
101
10.
p-N Butyl Benzamide............................. 102
11.
p-Iso butyl B e n z a m i d e ...........................103
12.
2-Cyano 1,3-Dimethyl Benzene
13.
1, 3-Di methyl B e n z a m i d e - 2 ...................... 106
14.
Aromatic Amides,
15.
Aromatic Amides, Birefringence
16.
Indices of Refraction,
17.
Aliphatic Amides,
18.
Indices of Refraction, Aliphatic Amides.
2V Values
................
..................
104
113
.............. 116
Aromatic Amides . . . 117
2V Values..................
118
. . 119
1
SYNTHESIS AND OPTICAL CONSTANTS
OF SOME ACID AMIDES
Purpose of the Study
Two homologous series of organic compounds were
obtained or synthesized and studied optically for the
purpose of (1 ) making available methods of rapid
identification of isomers,
(2 ) gathering of optical
data on these compounds, and
(3) making possible
correlations of the optical data with structure and
chemical constitution.
Amides are especially adapted to optical study due
to their crystalline nature.
Furthermore, they are
readily prepared as derivatives either from the corres­
ponding nitriles or acids.
Two series of homologous
amides were studied, namely, an aromatic series based
on benzamide, and an aliphatic series based on acetamide.
The aliphatic and aromatic' amides were related in
structure except that the aromatic amides had a ben­
zene ring inserted between the aliphatic chain and the
carboxyl group in which the -OH radical was substituted
by the -NHg group.
The effect of the benzene ring on
the optical properties was in this way studied.
In addition to the gathering of optical data the
study served another purpose, namely, to show the
2
application of petrographic methods to chemistry.
sides the petrographic microscope,
Be­
a one circle
goniometer and a Federow universal stage as modified
by Emmons were used.
Methods which heretofor were
primarily applied by petrographers were used in this
work.
In many cases the optical methods are the only
methods possible in the identification of isomers,
whereas in other cases they are much more simple.
This method affords another tool in identification
in addition to melting points, freezing points,
methods,
x-ray
etc..
Presentation of Material
Part I of this study deals primarily with the
organic synthesis of the compounds studied.
Part II
gives the optical study of the materials prepared in
Part I.
The technique used is given in much detail
inasmuch as such material is lacking in our chemical
literature.
3
PART I
Introduction
The aromatic amides were prepared using bromobenzene and the aliphatic halides as starting materials,
the alkyl benzenes being prepared by the VVurtz-Fittig
synthesis.
The alkyl benzenes were nitrated, reduced,
diazotized, and the corresponding nitriles prepared.
The nitriles were then hydrolyzed to the amides.
In
some cases the alkyl benzenes, amines, or nitriles were
available, so the preparations started at those points.
In one case, more drastic hydrolysis had to be resorted
to in the preparation of the amide from the nitrile.
In all other cases the hydrogen peroxide hydrolysis was
sufficient.
The aliphatic amides were readily available
except isovaleramide which was prepared from the acid,
chloride.
The derivatives and reagents used in this study
were obtained from the Eastman Kodak Company.
Hi storical
The hydrogen peroxide hydrolysis.
Radziszewski^-
was the first to prepare amides by the treatment of the
corresponding nitriles with an alkaline solution of
3% hydrogen peroxide.
In this way he prepared benzamide
from benzo'nitrile and capronamide from capronitri 1 e.
Much work has followed on this controlled hydrolysis
1 Radziszewski,
B r . , Ber.
18, 355 (1885)
4
by means of hydrogen peroxide.
nitrile, p-toluni.tri l e ,
propionitrile..
Deinert^ worked on benzo-
- and^-naphthonitriles , and
He was unable to effect the hydrolysis
of o-tolunitrile or of diacetoni.tri le.
Friedlander and
Weisberg 3 prepared 1,4-nitronaphthoic acid amide; Rupe
and Majewski
A , the piperonylic acid amide; Bogert *5,
the quinazolines; Kattwinkel and Wo Iffenstein®, the three
toluamides.
Keiser and McMaster^ obtained almost quantitative
yields of fumararnide from fumarnitrile.
Dubsky 8 used
a large excess of 3^ hydrogen peroxide solution in the
conversion of o-tolunitrile and
corresponding amides.
<x. - naphthoni tri le to the
McMaster and Langreck 9 used more
concentrated solutions of hydrogen peroxide and con­
2
Deinert, J. , J. prakt. Chem., (2) 52, 431 (1895)
3Fri edlander, P. and Weisberg, J . , Ber. 28, 1841 (1895)
4 Rupe,
H. and Majewski, Karl von, Ber. 33, 3403 (1900)
5 Bogert,
M.T. and Hand, W.F. , J. Am. Chem. Soc. 24,
1034 (1902)
^Kattwinkel, P. and Wo Iffenstein, R . , Ber. 37, 3224
(1904)
7
Keiser, E.H. and McMaster, L. , Am.Chem. J. _49, 81 (1913)
8
Dubsky, J.V. , J. prakt. Chem.,
(2) 93, 137 (1916)
9
McMaster, L. and Langreck, F . B . , J.Am.Chem.Soc. 39,
103 (1917)
5
verted m-nitrobenzonitrile,
-naphthonitrile, tere-
phthalnitrile, trichloroacetonitrile, and isobutylacetonitrile.
Although Oli veri-Mandala ^
5
stated that
in a slightly alkaline solution of hydrogen peroxide
the aliphatic nitriles are hydrolyzed all the way to
the ammonium salts, the work of McMaster and Noller-^
gave no evidence of the formation of ammonium salts and
showed the general applicability of this method.
used a 30^ hydrogen peroxide solution.
They
Of 20 nitriles
studied, 13 were readily converted into the corresponding
acid amides.
Malonitrile was decomposed by the action
of alkaline hydrogen peroxide, while in the case of the
four cyanhydrines studied a splitting into aldehyde and
hydrocyanic acid took place, followed by oxidation of
the aldehyde.
With regard to the effect of ortho substituted con­
stituents on a reacting group, Remsen and R e i d ^ showed
that a protecting effect is exerted on an amide group.
The order in which the various groups produce re­
tardation in the hydrolysis to the acid, in the order
1001iveri-Mandala, E . , C.A. 16, 2112 (1922); Gazz.
chim. ital. , 52, I, 101 TT922)
^■■*-McMaster, L. and Noller, C.R., Wash. Univ. Studies,
XIII, Scientific Series #1, 23 (1925)
IP
Remsen, I. and Reid, E.E., Amer.Chem.J. <21, 281 (1899)
6
of decreasing influence is as follows:
-NOg, -I, -NHg,
— CH^, — Cl, -OH, —OCgHg, —OCHg*
The derivatives of 2, 4,
6 -trimethyl
benzoic acid
like other diortho substituted acids are notably in­
active in reactions which are supposed to involve an
addition to the keto group13.
The acid is not converted
into its ester by means of hydrochloric acid and alcohol1 4 .
The ester 1 5 and amide
are difficult to saponify while
the chloride is remarkably stable toward water and the
alkalies.
Diortho substituted acid chlorides, in general,
react readily with ammonia 1 6 however, and the silver
salt of trimethyl benzoic acid gives almost a quanti­
tative yield of the ester with methyl iodide1?.
It is
assumed that these latter reactions do not involve any
additions to the keto group but take place by direct
substitution.
Wegscheider 1 3 suggested that the reason
1 3 Henry,
L . , Ber. 10, 2041 (1877); Wegscheider, R. ,
Monatsh. 16, 75 (1895); Pechmann, H.v., Ber. 31,
504 (18981“
1 4 Meyen'
V. , Ber. 27, 510 (1894)
1 5 M.eyer,
V. , Ber. 28, 188 (1895)
1 5 Sudborough,
J.J., Jackson, P . G . , and Lloyd, L.L.,
J.Che'm.Soc. .71, 229 (1897)
1 7 Meyer,
V. , Ber.
2 £,
1580 (1894)
7
why diortho substituted acids do not yield ethereal
salts on treatment with alcohol and hydrochloric acid
is to he sought for in the fact that the substituted
groups prevent the formation of an addition compound
of the acid with alcohol;
this addition compound
always being an intermediate product in the preparation
of these salts.
The explanation put forward by Meyer of such facts
as these is based on what is^ca.lled steric hindrance.
It was thought that the groups in the ortho position
prevented by their presence other molecules from coming
into contact with the groups between them, and as a
result reaction could not take place.
Recent work has
shown, however, that the diortho acids form esters
normally but that the rate of the reaction is very slow.
The group itself which is attached to a carbon
atom protected by substituents in the two ortho
positions is unusually reactive chemically and can be
readily replaced by other groups.
The bond which links
an atom with the carbon atom in the ring is readily
broken; on the other hand, any other atom united to
such an atom is firmly bound.
It can be expected
that if a small amount of energy is used in establighing one valency of the carbon an additional amount
8
remains available to the other three valencies.
It has
often been shown that when a substituent is introduced
into a compound the reactivity of the elements present
changes.
There is no doubt that the replacement effects
the energy relationship involved in the union of all the
elements in the molecule.
Other methods must be used in the preparation of
such amides as 1,3-dimethyl benzamide-2.
In such cases
drastic hydrolysis with concentrated sulphuric acid or
alcoholic potassium hydroxide gives the amide pre-
I
dominantly.
The Wurtz-Fittig reaction.
As pointed out by Fittig
and others -^-8 the following reactions should take place;
(1)
2CgH5Br -+- 2Na
— * C 2 H 5 .CgH 5 -+ 2NaBr
(2)
2C 6 H5Br +
(3)
C 6 H5Br 4- 2Na 4- CgHgBr
2Na — r
C 6 H 5 .C6 H5 +
The third reaction, however,
2NaBr
CgH 5 .C 2 H 5 +- 2NaBr
is the predominant one
in this case due to the ease with which sodium phenyl
forms in comparison with sodium ethyl.
On the other
hand, the ethyl bromide reacts much faster with sodium
phenyl than with the bromobenzene.
Schlubach and Goesl^ have summarized the V/urtz-
J o h . , Ber. 3, 779 (1870); Fittig, R . ,
Schaeffer, C . , and Konig, J . , Ann.Chem.Pharm.
149, 324 (1869)
1 8 Riess,
1 9 Schlubach,
H.H. and Goes,
E.C., Ber. 55, 2889 (1922)
9
Fittig reactions as follows;
(1)
RHlg 4- Na —
R” + NaHlg
2Na
(2)
2R~
— I— >
2NaR
-II—*
R.R.
- III-»
(3)
RNa 4- HlgR
IV~ *
— V— r
R_H -i- R+ h
R *R *
R_ h +
r+h
In aliphatic series from ethyl on,
and V take place predominantly.
only one gets mostly reactions
reactions III
In the case of methyl
IV and possibly II.
yields of saturated hydrocarbons are good.
The
With in­
creasing length of chain one gets II and IV in preference
to III.
In the aromatic
series,
sodium alkyls are very
readily formed according to reaction I.
Therefore,
the
aromatic halogen reacts not readily according to reaction
IV; aliphatic halogen,
A cree 2 0
very well.
has shown that the following reaction takes
place:
^ CgH 5 .CgH 5 4- NaBr (main reaction)
C4 H^Na 4- B r C ^ H / ^ 7
S k C o H A + C g H g 4- NaBr (secondary
reaction)
Sodium phenyl was prepared as follows:
H g ( C g H 5 )g -t- 2Na 2
^Acree,
HgNag-h
2 NaCgH 5
S.F. , Am.Chem. J. £19, 591
(1903)
10
Bachinann and Clarke 2 1 ran a Wurtz-Fittig on
chlorobenzene at the boiling temperature using sodium.
Diphenyl was obtained in a 20% yield.
They obtained
a high proportion of benzene, and the residue on
distillation with steam yielded a hydrocarbon corres­
ponding to o-diphenyl benzene.
Others not volatile
with steam were triphenylene and o, o-diphenyl biphenyl,
also a small amount of p-diphenyl benzene.
The
equations given were:
C 6 H 5 C1 -h 2Na
C 6 H 5Na -+- NaCl
CgHgNa -j- CgHgCl —^ CgHg .CgHg -+- NaCl
CgHgNa +■ CgHg.CgHg --r CgHg +- CgHg.CgH4Na
C g H g . C g ^ N a +- CgHg Cl
2C6H5
=
CgHg+CgH4^
06H4 ^
306H ^ =
CgHg .CgH 4 .CgHg •+• NaCl
CI6
6H 44
c 6h 4
c 6h £
+ ao6H5" =
EC6h 4^ + 2 C 6H 5
c 6 h 5 .c 6 h 4 .c 6 h 5
=
c 6 h 5 .c
6h 4 .c 6h 4.c 6h 5
Schrarnm2 2 prepared isobutyl benzene from isobutyl
bromide, bromobenzene, and sodium in the presence of
prz
much ether and strong cooling (yield 27%).
2 1 Bachmann,
John Riess
V/.E. and Clarke, H.T. , J. Am. Chem. Soc. 4 9 ,
2089 (1927)
2 2 Schramm,
2 3 Riess,
J. , Monatsh. _9, 616 (1888)
Joh., Ber.
3, 779 (1870)
11
stated that it is difficult to prepare because of the
ease with which the isobutyl radical breaks up into
isobutylene and hydrogen.
Only by strong cooling by
means of ice and salt as well as the gradual addition
of the sodium in rather diluted ether solution of
the bromides can even small quantities by obtained.
Wreden and Znatovicz2^ prepared it from bromobenzene, isobutyliodide, and sodium favorably in the
presence of benzene with a yield of 20<£.
Spath 2 5
reported the preparation from phenylmagnesiurn bromide
and isobutyl bromide at 100° for 30 hours.
Besides
benzene fractions boiling at 78-84°, isobutyl benzene
and diphenyl were obtained.
benzene was
The yield for the isobutyl
2 0 °£.
Apparatus
The following columns were used in the fraction­
ations :
Column //I was of the total condensing variable
take-off t}'pe with an electrically heated jacket.
It was packed with glass helices.
The packed section
was 0.9 x 40 cin. , packed with single turn glass
2i
%reden,
2 5 Spath,
J. and Znatovicz, B., Ber. _9, 1606 (1876)
E . , Monatsh. 34, 1988 (1913)
12
helices.
It contained 9.1 theoretical plates, hence
the H.E.T.P. = 4.40.
Column #2 was of the same type as above.
The
packed section was 1.5 x 64 c m . , packed with single
turn glass helices.
It contained 13.5 theoretical
plates, hence the H.E.T.P. = 4.74.
Column #5 was an indented strip column.
The
indented portion was 32 cm. long and contained an
electrically heated jacket.
from the bottom opening.
electrically heated.
heated independently.
The take-off was 35 cm.
The take-off arm was likewise
Both lag and arm could be
The inside diameter was 1.4 cm..
An electrically controlled pressure regulator in
conjunction with an ordinary U-shaped mercury mano­
meter was used in all distillations below atmospheric
pressure.
Experimental
Preparation of Derivatives
Benzamide.
This was a product obtained from
Dr. R.v. McGrew, having been prepared by Dr. W.J. Keith.
After repeated recrystallizations from water the
melting point was 126.6-127.6° C.
(Lit. = 128° C . ) . 7 9
Ortho-, meta-, and para-toluamides.
Ortho-,
meta-, and para-toluamides were prepared from Eastman
4
1
13
ortho-, m e t a - , and p a r a - t o l u n i t r i l e s , respectively,
by the method of C.R.
Noller2 ^ using 30^ hydrogen
peroxide for the hydrolysis.
The hydrolysis was performed in a 50 ml. roundbottomed flask fitted with a thermometer.
About 0.025
mole of each of the nitriles was used in each case.
To the nitriles were added 10.2 cc. of 30^ hydrogen
peroxide, 13.7 cc. of 95<£ alcohol,
NaOH.
and 1.0 cc. of
The temperature soon rose owing to the heat of
reaction.
heating;
The ortho-compound required no external
the temperature remained at about 35° C..
The reaction in the case of the meta-and para-compounds
caused the temperature to rise suddenly to 60° C. and
had to be cooled with tap water to prevent excessive
frothing, due to the evolution of oxygen.
and p a r a - c o m p o u n d s , after cooling,
and 48° c . , respectively.
The meta-
remained at 55°
External heating was then
applied to all three maintaining the temperature at
55° C . .
reaction.
After three hours the ortho-
showed no further
After four hours the meta- showed no re­
action while the para- was still reacting, being com­
plete after about four and one-half hours.
The
solutions were neutralized with 5% sulphuric acid and
2 6 Noller,
C.R. , Org. Syntheses 1_3, 94 (1933)
14
steam distilled from the reaction flask.
A micro
flame was maintained under the flask during the
distillation to keep the volume of the solution
down.
The unreacted
nitrile was carried into the
distillate by the steam.
After about 30 cc. of
distillate had been collected, the distillation was
stopped.
The para-compound crystals came down dur­
ing the distillation,
while the Qrtho- and meta­
compounds did not crystallize until after cooling.
In the case of the meta-compound an oil first
separated,
later crystallizing.
poured while hot into a
to about 20° c..
100
The solutions were
ml. beaker and cooled
The crystals were filtered,
up in a mortar with a little cold water,
ground
filtered
again and washed on the filter with additional cold
water.
After repeated recrystallizations from water
the melting points for the ortho-,
meta-, and para-
compounds were found to be 141.0-141.4°
and 159.1-160.0°
C'£f 93.2-94.0° C§p
respectively.
1,3-Dimethyl benzamide-2,
1,4-dimethyl benzamide-2,
1,3-dimethyl benzamide-4, and ortho- and para-ethyl
benzamides were prepared from the corresponding East­
man amines by diazotization using the method of Clark
and Read2 7 , followed by the hydrogen peroxide hydrolysis
2 7 Clark,
H..T. and Read,
69 (1925)
R.R. , Org. Syntheses _4,
of the nitriles formed.
The required amount of commercial 28£ hydrochlori
acid was added to the amine in a beaker with stirring,
enough cracked ice being added to bring the solution
to 0° C..
The beaker was surrounded by a salt-ice
ba t h to help keep the solution between 0-5° C..
A
sodium nitrite solution was added slowly to the suspen
sion of the hydrochloride.
The end point was given
by a permanent free nitrous acid test with starchiodide paper.
Freshly prepared starch-iodide paper
must be used, and a definite iodine color must be
obtained.
After the definite test had been obtained,
the solution was tested
again after a few minutes to
insure complete reaction.
The mixture was then
cautiously neutralized by adding sodium carbonate.
It was found
that in order to prevent the caking of
the sodium carbonate added,
it was best to grind up
the NagCOg.lOHgO to a thick paste in a mortar and
add the paste slowly.
paper,
was not very
The end point, using litmus
satisfactory;
however,
lack of
effervescence upon the addition of NagCOg.lOHgO is
a sufficient test for the end point.
Usually a slight
excess was added.
Cuprous cyanide
solution prepared according to
the directions in "Organic S y n t h e s e s "27 was then
placed in a salt-ice bath,
and the stirrer transferred
16
to it.
It was kept at 0-5° C. by the addition of ice,
and benzene was added
to prevent excess frothing
due to the evolution of nitrogen.
To this solution the
cold neutralized diazonium solution was added slowly
with vigorous
stirring.
After all the solution had
been added and the solution allowed to stand at o-5° C.
for some time,
the temperature was raised to 50° c. by
running live steam into
the solution.
c ontaining the nitrile was removed,
once
The benzene layer
and the water layer
extracted with benzene and fractionated.
Often a heavy brown precipitate was obtained upo n
neutralizing with sodium carbonate even when the starchiodide test showed that all of the amine had been con­
verted.
This was most likely the diazo amino compound.
2-C.yano 1,4-dimethyl b e n z e n e .
1,4-dimethyl benzene,
In the case of 2-amino
0 . 4 4 mole of the amine was used.
The results of the fractionation of the benzene extract
is given in Table I.
TABLE I
Fractionation of 2-Cyano
No.
Wt. of
Liquid
1
2
3
4
5
6
7
8
9
10
1.80
1.46
0.92
1.26
1.46
1.74
1.68
0.26
0.64
0.42
1,4-Dimethyl Benzene
Pres s u r e mm.
10
10
11
10
10
10
17
11
Temperature °C.
97.0
96.9
98.0
96.8
97.0
97.4
111.0
98.0
(I 40)
n 20°
D
1.5263
1.5263
1.5263
1.5266
1.5266
1.5266
1.5266
1.5274
1.5283
1.5 286
17
Fraction 1 seemed to be darker in color than the rest,
probably containing some amine.
The fractions got
lighter in color as the fractionation progressed.
Although the refractive index of No. 8 was higher
than the earlier fractions,
comparable.
its boiling point was
Fractions 1-8, inclusive, were taken as
the pure compound which gave a 33 1/3^ yield.
The
boiling point was 97-98° C. at 10 mm.28, n^° - 1.5266.
1,4-Pi methyl benzamide-2.
In the case of 2- cyano
1,4-dimethyl benzene, 0.038 mole (4.91 gms.) of the
nitrile was placed in a 50 ml. round-bottomed flask
with 0.15 cc. of 30b£ hydrogen peroxide, 20 cc. of
95$ alcohol, and 1.5 cc. of 6N N a O H . . Upon the
addition of NaOH, it turned dark brown but cleared
up after the addition of the hydrogen peroxide.
The reaction was very vigorous.
the steam distillation,
Near the end of
crystals of the amide came
down; the distillate came over cloudy.
About a 34^
yield was obtained melting at 183.5-184.5°29.
After
repeated recrystallizations from water, it melted
at 187.1-187.8°.
The crystals were not very soluble
in hot water and were very soluble in alcohol.
28Schmid, A. and Decker, H. , Ber. 3£, 938 (1906)
KP 7 3 0 223-226° C.
29&attermann, L. and Schmidt, G-. , Ann.Chem. 244,
54 (1888) m.p. 186° C.
18
2-Cyano 1, 5-dimethyl b e n z e n e .
In the preparation
of the nitrile from 2-amino 1,3-dimethyl benzene, 0.44
mole of the amine was used.
off in benzene,
the benzene
The nitrile was taken
solution poured into a
large evaporating dish, and the benzene allowed to
evaporate.
appeared.
Beautiful large mahogany colored crystals
An attempt was made to recrystallize from
petroleum ether.
After four recrystallizations it
still remained dark,
sorted to.
and a sublimation had to be re­
The nitrile was placed in a large
evaporating dish.
The porcelain stand from a dessicator
covered with a perforated piece of filter paper was
placed over this.
The evaporating dish was covered
with a large watch glass over which was placed a
cold damp cloth serving as a cover and condenser.
The crude nitrile was first heated until the sublimed
material started
porating dish.
to appear at- the spout of the eva­
The flame was then cut down and the
sublimation allowed to progress
for a few hours.
The product came out as white needles having a
melting point of 89-90°
3 0 >31.
The yield was about
20fo.
^Noyes,
W. A., Am. Chem. J. 20, 792
(1898) m.p.« 89°
^ S c h o l l , R. and Kacer, F. , Ber. _36, 327
m . p . = 90-91°
(1903)
1,3-Dimethyl b e n z a m i d e - 2 .
The hydrolysis of the
nitrile to the amide could not be accomplished by
means of 30^ hydrogen peroxide as might be expected.
Although Victor M e y e r 32 prepared the amide from
symetrical trimethyl cyano-benzene and stated that
it was possible to prepare the amide corresponding
to 2-cyano 1,3-dimethyl benzene by refluxing for
72 hours with a saturated alcoholic potassium hydroxide
soltuion,
he did not report the data on this particular
compound.
Berger and O l i v i e r 33 prepared the amide by
hydrolysis of the nitrile with concentrated
sulphuric
acid at 75-80° for five hours with a yield of 565o.
Melting point - 138.5-139.0°.
The method of Victor Meyer was repeated using
4.6 gms. of the nitrile and hydrolyzed for 80 hours
-with 120 cc. of saturated alcoholic KOH solution.
After the hydrolysis,
with sulphuric acid,
the solution was neutralized
more alcohol was added, and the
potassium sulphate filtered off.
added,
Water was then,
and the solution evaporated slowly on the
waterbath.
More water was added,
and the slow
32M e y e r , V., Ber. 29, 830
(1896)
3% e r g e r , G. and Olivier,
46, 600 (1927)
S.C.J. , Rec.
trav. chim.
20
evaporation repeated until
the
alcohol
disappeared.
was
then c o o l e d
filtered.
The
The
needles.
solution
amide
The y i e l d
came o u t
as very
had
completely
and
fine
was
about
55^.
recrystallizations from
water
and p e t r o l e u m
w i t h a l i t t l e benz e n e ,
at
137.1-138.1°.
before
the f i n a l
results:
Calc.:
the
amine
were
9.40^
and
C.
Found:
benzene.
compound.
at 16 ram.3 ^,
two-tenths
some of
w h i c h was a y i e l d of
the
material
In the p r e p a r a t i o n
one-half
1.530.
nitrile
melted
9.55^
mole of
2-6,
the
inclusive
The bo i l i n g point
=
grams of the
ether
gave the f o l l o w i n g
In T a b l e II f r a c t i o n s
t a k e n as the
repeated
from water
recrystallizations
1,3-dimethyl benzene,
was used.
108-109°
material
A Micro Dumas on
4-C.yano 1 , 3 - d i m e t h y l
of 4 - c y a n o
After
white
is
Twenty-seven
were o b t a i n e d
40?£.
T A B L E II
F r a c t i o n a t i o n of 4 - C y a n o
No.
1
2
3
4
5
6
7
8
W t . of
Liquid
2. 6
3. 3
3.7
4. 9
7.2
8.1
4. 8
2.0
Pressure
15
16
14.5
14
14
14
1,3-Dimethyl Benzene
mm.
T e m p e r a t u r e °C.
106.5
108.5
105.0
81. 5
86.0
89.0
(II
35)
nD
20°
1.5286
1.5298
1.5299
1.5301
1. 5 3 0 1
1.5304
1.5311
1 . 5317
34G r i g n a r d , V., B e l l e t , E . , and Courtot, CH.,
chim. (9) 4, 45 (1915) K p 15 - 1 1 0 - 1 1 2 °
Ann.
21
In a n o t h e r r u n 131
gms.
of
5 3 ^ w a s o b t a i n e d i n the d i a z o t i z a t i o n .
A y i e l d of
Boiling point
- 1 1 4 - 1 1 4 . 5 ° at 22 mm.
TABLE
F r a c t i o n a t i o n of
IVt. of
Liquid
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
6.74
4.24
4. 36
5.42
3. 36
4. 94
5.90
6.46
5.78
5.78
5.96
4.58
-2. 80
2.48
5.4
3. 3
IIA
1,3- D i m e t h y l
4-Cyano
Pressure
mm.
22
22
22
22
22
22.5
22
22
22
22
22
22
22
22
21
20
114.0
114.0
114.0
114.0
113.6
114.5
114.0
114.0
114.5
114.5
114 . 5 114.5
11 4 . 5
114.5
114.5
128.0
0 . 0 3 8 mole of
first
there was a
slow
about
ten m i n u t e s
the
to be
cooled
the w a t e r b a t h for
out at the
of
three
hours.
1.5295
1. 5 2 9 7
1.5297
1.5299
1.5299
1 .5300
1 .5300
1. 5 3 0 1
1.5305
1.5304
1.5304
1.5304
1.5304
1.5304
1.5306
1. 5 3 1 2
n i t r i l e was used.
temperature
externally.
came
the d i s t i l l a t e
the
(I 47)
In the p r e p a r a t i o n of
e v o l u t i o n of
t e m p e r a t u r e of
The a m i d e
Benzene
T e m p e r a t u r e °C.
1 ,3-Di m e t h y l b e n z a m i d e - 4
this a mide,
(Table IIA).
0
O
WQ
c
No.
ha d
the am i n e was taken,
oxygen;
rose
to
At
after
62° and
It was k e p t at 60° in
Some amide crystallized
the wa t e r b a t h .
down profusely
a f t e r about
had b e e n c o l l e c t e d ;
4.9 gms.
5 cc.
of
the
22
amide
were
of 50^.
water,
o b t a i n e d m e l t i n g at
176-178°
After repeated recrystillizations from
the m a t e r i a l melted
at 1 8 1 . 9 - 1 8 2 . 5°3 5 .
came down as n e e d l e s f r o m w a t e r and
almost
It was
,3 - d i m e t h y l benzene,
in the
Fractions
e a c h case,
obtained
it will be
noted
r e f r a c t i v e i n d e x curve
0.038
amides obtained
mole
were
for F r a c t i o n
A 48^ yield
being
soluble in
the second b a t c h of 4-cyano
and 12 were h y d r o l y z e d
6
It
not d e c o m p o s e d w i t h NaOH.
In the p r e p a r a t i o n of
occurs
alcohol,
i n s o l u b l e in cold water and very
alcohol.
1
for a y i e l d
(4.91
gms.)
identical.
6
.
a break
(see T a b l e IIA).
separately.
was taken.
In
The
A 38^ y i e l d was
M e l t i n g p o i n t - 177-179°.
was o b t a i n e d f r o m Fraction
p o i n t = 176-178°.
that
12.
Melting
The ami d e s were i d e n t i c a l
optica l ly.
o-Cyano
ethyl b e n z e n e .
p a r e d u s i n g 0 . 3 gms.
3 3 Ador,
This
compound was p r e ­
of o - e t h y l aniline.
A great
E. and Meier, F r . , Ber. T2, 1970 (1879)—
P r e p a r e d this amide from the a c i d
chlo r i d e
of xylic acid, and a m m o n i u m carbonate,
rn.p. = 1 7 9 - 1 8 1 ° C.; Gattermann, L. and Rossolymo, A., Ber. 23, 1196 ( 1 8 9 0 ) - - P r epared it
by c o n d u c t i n g t h r o u g h a w a r m m i x t u r e of m-xylol
and A I C I 3 , s i m u l t a n e o u s l y HCNO and HC1 fumes,
m.p. = 178-1 7 9 ° C . ; Grignard, V. , Bellet, E . ,
and Courtot, Ch., Ann.chim. (9) 4L, 46 (1915)-P r e p a r e d by h e a t i n g 2 , 4 - d i m e t h y l b e n z o n i t r i l e
w i t h 2 0 ^ a l c o h o l i c KOH.
deal of f o a m i n g took p l a c e u p o n the addi t i o n of the
diazo
c ompound to the c u p r o u s
the r e a c t i o n went
in T a b l e
smoothly.
cyanide.
Fractions
Otherwise,
2-6,
inclusive,
III were c o m b i n e d a n d re p r e s e n t e d the o-cyano
ethyl b e n z e n e with a b o i l i n g p o i n t of 117° C. at
36 m m . 3 6 , n^° = 1.5233.
This rep r e s e n t e d a 45<£ yield.
T A E L S III
F r a c t i o n a t i o n of o-Cyano
Wt. of
L iquid
No.
P r e s s u r e mm.
3
4
5
6
7
113.0
116.0
1 17.0
117.0
117.0
116.5
116.5
o - Ethyl benzamide.
amide,
0. 0 3 8 mole of
external
f a l l e n to
(II 40)
n2 0 °
ng
1.5145
1.5233
1.5233
1.5233
1.5233
1.5233
1.5243
In the p r e p a r a t i o n o f thi s
the
nitrile was hydrolyzed.
c o o l i n g was needed.
at 44° for about
had
T e m p e r a t u r e °C.
34
34
36
36
36
35
35
2.5
4.1
2.7
3.8
2.4
2.9
1.5
1
2
Ethyl Ben z e n e
The
30 minutes.
No
temperature remained
After the temperature
42°, an attempt was made
to place the
f l a s k in the w a t e r b a t h at 60°; but the r e a c t i o n b e ­
came
too violent.
seemed slow.
was p l a c e d
At 42° the
Af t e r a lit t l e over
in the bath.
A rapid
p l a c e but w i t h no foaming.
36
0iebe,
evolution of o x y g e n
G. , Ber.
29,
two hours the flask
evolution of oxygen took
It remained in the bath
2535
(1896) Kp = 212°
24
fo r
another
amide
1
came
hour.
d o w n but
,3 - d i m e t h y l
of t h e
melting
a 65<% y i e l d .
the
After
came
down
water
forming
in a l c o h o l ,
in
cold
the
nitrile,
six-tenths
152.5-153.5°.
It is
chloroform.
It
ethyl
1/5
benzene.
mole
of
the a m i n e
as
in
this
soluble
which
115°
2-4,
gave
C.
at
excess
inclusive,
a yield
21.5
of
mm.,
were
30^.
n§° =
TABLE
Fractionation
No .
W t . of
Liquid
of p - C y a n o
Pressure
1
2
3. 5
2. 3
20
20
3
4
2.8
2.2
21 .5
21.5
37
soluble
slightly
(p-ethyl
white hydrochloride
fractions
from hot
In t h e p r e p a r a t i o n
No
is
is
from
water.
wa s d i a z o t i z e d .
it
for
The
mass
readily
the
grams
was obtained
crystalline
some
c a s e of
recrystallizations
m e l t e d at
and
in t h e
and
146-147037
needles.
ether,
p-Cyano
at
Three
as a w h i t e
long
steam distillation
as m u c h as
repeated
material
amide
soluble
not
benzamide-4.
amide
w a ter,
D u r i n g the
mm.
The
of
was
acid.
taken
as
In
of
aniline)
fo'rmed
Table
the p u r e
amine
b o i l i n g p o i n t =■
1.525.
IV
Ethyl
Benzene
Temperature
114.0
114.0
115.0
115.0
(II 59)
°C.
ng°°
1.5224
1.5243
1.5247
1.5252
Giefce, G. , B e r . 2 9 , 2535 (1896) — P r e p a r e d
e t h y l b e n z o y l c h l o r i d e and c o n c e n t r a t e d
ammonia solution.
m.p. = 1 5 1 - 1 5 3 ° .
IV
from
25
Another
pared
by
the
b a t c h of p - c y a n o
ethyl b e n z e n e
d i a z o t i z a t i o n of
1/5
IVA f r a c t i o n s
2-9,
of
Boiling point
= 103.5-104.0°
ng° =
1. 5 2 4 ,
pre­
m o l e of t h e amin e .
In T a b l e
37^.
was
inclusive,
gave a y i e l d
at
13 mm.,
T>§° - 0 . 9 7 0 1 .
T AB L E IVA
Fractionation
No .
' Wf. of
Liquid
Pressure
0.9
0.7
2.5
1
2
3
4
5
6
8
0.7
9
0.2
mm.
p-Ethyl benzamide.
amide,
was
0.019
treated
cooling had
reaction
solution.
crystals
mole
with
the
and
the
point
of
the
melted.
No
to
155-161°.
°
the p r e p a r a t i o n
o f thi s
of p - c y a n o
temperature
65°
reaction
ethyl
benzene
External
cooling,
fell
to
throughout
took place
residue
repeated
the
50°
the
in the w a t e r b a t h ,
The p- e t h y l
After
20
D
1.4970
1.5156
1.5231
1.5242
1.5242
1.5244
1.5245
1.5248
1.5232
After once
steam distillation
n
31)
low
104.0
105.5.
104.0
103.5
104.0
Temp, f a l l i n g
it
tt
tt
it
solidification
When heated
(III
°C.
30^ h y d r o g e n peroxide.
an h o u r a n d .o n e - h a l f .
from
In
to b e a p p l i e d .
by
Benzene
Temperature
(25 g m s . )
subsided
accompanied
Ethyl
15
15
14
13
13
13
13
13
13
1.0
0.8
2.0
1.6
7
of p - C y a n o
after
the
about
benzamide obtained
had a m e l t i n g
recrystallization
26
the m e l t i n g p o i n t
point
rose
to
163*7-164.8°.
The m e l t i n g
listed
in
the
was p r e p a r e d
by
c o n d u c t i n g a m i x t u r e of H C N O a n d
through a gently
l i t e r a t u r e is 1 1 5 - 1 1 6 ° 3 8 .
heated
aluminum chloride.
Rossolymo,
at
they
115-116°.
According
obtained
Upon
acid
m e l t i n g at
gave
the f o l l o w i n g
C alc.:
m i x t u r e of
colorless plates
.0 °.
and
and
melting
they o b t a i n e d
A nitrogen
HC1
benzene
to G a t t e r m a n n
saponification
112
ethyl
It
the
determination
results:
9.49^
Found:
9.19?£
7 Q
A Kjeldahl
m e l t i n g at
was
nitrogen
was
163.7-164.8°.
the m a t e r i a l ,
Sodium hydroxide
(0.1N)
s t a n d a r d i z e d a g a i n s t B u r e a u of S t a n d a r d s '
potassium biphthalate40.
in p l a c e of
4-5 h o u r s
congo
g r a m of
lO^NaOH
before
the
next
ammonia
and
Gatterman,
(1890)
The
orange
was
required
9.49<£
Found:
treated
It had
ceased
to
be
heated
dilute
sulphuric
L.
Rossolymo,
K o l t h o f f , I.M. and
Inorg. A n a l y s i s ;
from
9.66*^
to the acid.
w i t h 25 cc.
c o m i n g off.
and
was used
samples
was h y d r o l y z e d
^ H a w k and B e r g e i m m ,
Pg. 8 1 4
40
Methyl
Calc.:
acid
solution.
then c o o l e d
88
red.
digestion.
The amide
One
run o n
The
acid
of
for 5 h o u r s
s o l u t i o n was
was added
A., Ber.
2 5 , 1195
Practical Physiological
Chetn.
(
S a n d e l l , E . B ., Text of Quant.
M a c m i l l a n , 1937; Pg. 524
27
which brought
f r o m w a ter
down
and
the acid.
5
gms.
the a c i d
the am i d e f r o m this acid,
refluxed for
thus
formed
In o r d e r to
the a m m o n i u m
conditions,
was
minutes wit h
20
cooled and poured
of a c o n c e n t r a t e d a m m o n i a
w a s h i n g w i t h water.
amide
of
was
c c • of t h i o n y l chlor i d e ,
15 cc.
by
of
recrystallized
g a v e a m e l t i n g p o i n t of 1 1 2 . 0 - 1 1 3 . 5 ° .
In the p r e p a r a t i o n of
0.3
It was
The
solution,
into
followed
m e l t i n g p o i n t of
the
162.9-164.4°.
c h e c k the p o s s i b i l i t y of
salt of
the a c i d u n d e r
to a n o t h e r 0 . 3 gms.
the f o r m a t i o n
the a b o v e
of acid
w h i c h was
dissolved
in w a t e r a c o n c e n t r a t e d
ammonia
was a d ded
and
concentrated
evaporation
the
solution gently
with occassional
ammonium hydroxide.
a d d i t i o n of
No p r e c i p i t a t e
solution
by
concentrated
came d o w n at any
time .
P r e p a r a t i o n of
the R e m a i n i n g A r o m a t i c A m i d e s
p-Propyl benzamide
prepared
from
isobutyl benzamide
the c o r r e s p o n d i n g a l i p h a t i c
and b r o m o b e n z e n e by
by
and
the n i t r a t i o n ,
the W u r t z - F i t t i g
reduct i o n ,
by
the diazotization.
the a l c o h o l s ;
in the
the
The b r o m i d e s
case of
alcohols
reaction followed
d i a z o t i z a t i o n , and
h y d r o g e n p e r o x i d e h y d r o l y s i s of
were
the
nit r i l e f o r m e d
were p r e p a r e d
propyl bromide,
from
by the
28
sodium b romide-sulphuric
case of isobutyl
. . 41
bromide
a c i d m e t h o d 4 1 and in the
bromide,
by u s i n g p h o s p h o r u s
tri-
•
p-n Butyl benzamide
was p r e p a r e d
b e n z e n e as a s t a r t i n g material.
was o b t a i n e d
f r o m Dr.
R.v.
from n-butyl
The butyl ben z e n e
McG-rew and had been p r e ­
pared by the W u r t z - F i t t i g method.
The b u t y l ben z e n e
was
and f o l l o w e d by
nitrated,
the u s u a l
reduced,
diazotized,
h y d r o g e n p e r o x i d e h y d r o l y s i s of
the c o r r e s ­
p o n d i n g nitrile.
Although attempts were
butyl
benzamide
b e n zene as
slow;
and
obtained using secondary
This
obtained from amorphous
phorus
4.P
^Olewine,
finally
b u t y l b e n z e n e as a s t a r t i n g
s e c o ndary
in the p r e p a r a t i o n
butyl b r o m i d e was
red p h o s p h o r u s and b r o m i n e 4 ^.
(about 5 rnoles) of a m o r p h o u s
suspended
4 1 0rganic
this a m i d e was
t r i b r o m i d e used
i s o b u t y l b r o m i d e and
To 159 gra ms
the W u r t z - F i t t i g re­
was an E a s t m a n product.
The p h o s p h o r u s
of
to p r e p a r e p-sec.
f r o m the a l i p h a t i c b r o m i d e and bromo-
s t a r t i n g mater i a l ,
a c t i o n was very
mater i a l.
made
in 850 cc. of
S y n t h e s e s 1 5 , 20
J . H . , Private
red p h o s ­
carbon t e t r a c h l o r i d e
(1933)
communication
29
(distilled
f r o m a p r e v i o u s p r e p a r a t i o n of p h o s p h o r u s
tribromide)
and
contained
with a water-cooled
dropping
funnel,
was added
fast
as to
the m i x t u r e
A f t e r all
was a l l o w e d
the b r o m i n e
to
the carbon
had b e e n added
stand o v e r
excess a m o r p h o u s
so
night.
It was
red p h o s p h o r u s
l i t e r C l a i s s e n f l a s k to w h i c h was a t t a c h e d
r e m o v a l of h y d r o g e n b r o m i d e fumes.
the C l a i s s e n f l a s k was w r a p p e d
tape and p l a c e d
tetrachloride
changed
s t i r r i n g only
li t e r f l a s k r e c e i v e r h a v i n g a side a r m to
facilitate
top of
and
(about 1 0 tnoles) of b r o m i n e
and w i t h v i g o r o u s
then distilled over
a three
gms.
air-stirrer,
c a u s e a slight r e f l u x i n g of
tetrachloride.
f r o m a one
condenser,
871
dropwise
in a 1.5 l i t e r fl a s k fitted
in an oil bath.
had b e e n
and p h o s p h o r u s
1 6 5 . 0 - 1 7 1 . 5 ° C.
c o n t ained
removed,
The
with asbestos
A f t e r all the ca r b o n
the r e c e i v e r was
tribromide boiling between
at 734 mm.
was collected.
The p r o d u c t
a small a m o u n t of p h o s p h o r u s p e n t a b r o m i d e .
The y i e l d was a b o u t 73i£.
Without
waterbath,
formed.
too
In one
of a m o r p h o u s
of
carbon
sl o w l y
good
s t i r r i n g and w i t h c o o l i n g w i t h a
m u c h so l i d p h o s p h o r u s
run w i t h o u t
red p h o s p h o r u s
tetrachloride,
added.
good
was
stirring,
s u s p ended
and 1231
The p e n t a b r o m i d e
p e n t a b r o m i d e was
gms.
159 gms.
in 500 cc.
of bro m i n e was
formed around
the
30
e dges and o n
the b r o m i n e
the
had
stirrer.
When
been added,
the
all but 4 8 1
entire
gms.
of
flask became
solid.
Propyl
the
bromide.
Propyl bromide
sodium bromide-sulphuric
liter r o u n d - b o t t o m e d
added
with
stirring
flask
1545
powdered
sodium bromide,
n-propyl
alcohol,
concentrated
acid
was a d d e d
two
method.
1350
cc.
of
(15 m o l e s )
721.0
gms.
In
a five
water
of
was
finely
(12 moles)
of
gms.
of
gradually
2000
by
The
last h a l f of
the
through a dropping
funnel after
the
connected
acid because
layers.
gms.
acid.
shaken occassionally
sulphuric
to
then
sulphuric
flask had b e e n
was
and
acid
was p r e p a r e d
The
of
material
with
a ref l u x .
during
mixture
the a d d i t i o n of
a tendency
was
The
finally
to
the
separate
refluxed
into
two
hours.
The f l a s k was
downward,
and
the p r o d u c t
m i x t u r e by d i r e c t
l a y e r was
with
finally
NagGOg
as
with a
in
500
completely
and d r i e d
over
of
cold
sodium
cc.
with a condenser
removed
distillation.
separated,
gms.
200
then fitted
washed
f r o m the r e a c t i o n
The
first
concentrated
carbonate
Hg O ) .
as p o s s i b l e
night over
water insoluble
with water and then
sulphuric
solution
The product
from
was
acid
and
(50 gms.
separated
the a q u e o u s
a small
tipped
quantity
solution
of
calcium
(
31
chloride
(1 5 - 2 5
the y i e l d
was
gms.).
50^
Taking fractions
5-9,
inclusive,
(Table V).
TABLE V
F r a c t i o n a t i o n of
W t . of
Liquid
No.
3
4
5
6
7
-
8
Pressure
3.0
4.0
9.0
9.0
604.0
41.0
25.0
34.0
28.0
1
2
9
n-Propyl Bromide
Propyl
a reflux
nearly
to
(7 m o l e s )
thickness,
In t h e
sodium sliced
and
just
369
and
(3 m o l e s )
gms.
gms.
flask
(10°
C.),
to w a r m u p by
f l a s k was p l a c e d
into
(3 m o l e s )
pieces
h o w e v e r , when
in the
mm.
161
gms.
in
to co v e r .
n-propyl bromide
was a d d e d
during a period
when cold
standing
of
1-2
et h e r
of b r o m o b e n z e n e
f rom the d r o p p i n g funnel
reaction occurred
a n d broinobenzene
with a dropping funnel,
enough anhydrous
A m i x t u r e of
471
ngO°
and a thermometer which reached
the bottom.
of
)
benzene was prepared
flask fitted
condenser,
66
1.4260
1.4291
1.4 306
1.4319
1.4336
1.4336
1.4336
1.4336
1.4336
66.0
67.5
68.5-69.0
69.0-69.4
69.5-70.5
70.5-70.9
70.9-71.2
71.2-72.0
72.0-72.2
the p r o p y l b r o m i d e p r e p a r e d a b o v e
in a t h r e e l i t e r
No
T e m p e r a t u r e °C.
722
722
722
722
722
722
722
722
722
Frop.yl b e n z e n e .
from
mm.
(II
s lowly
of 7 hours.
w a t e r was a r o u n d
the
the f l a s k was a l l o w e d
air the
temperature
went
32
up
to 40° and
to cool
rapid
to 1 5 - 2 0 °
reaction occurred.
no r e a c t i o n o c c u r r e d .
was kept at 4 0 ° by a d d i n g
m i x e d b r o m i d e s and
surrounding
it.
thermometer
registered
was p r o b a b l y
c o o l i n g w i t h ice w a t e r
and
the
w h i c h was
40°,
r e m o v e d and
for
two d a y s a f t e r
added
refluxed until
Due to
dissolve
the fact
the oil
the
and w e r e
in most p l a c e s
the
cooling bath
the l i q u i d
100 cc.
care b e i n g
control
and
of
stand
as
methyl
t a k e n that
al c o h o l
the
the m i x t u r e f i n a l l y
s o d i u m had b e e n
it was
had b e e n
m i x t u r e a l l o w e d to
About
the
the f l a s k
the b r o m i d e s
subsided,
While
difficult
de s t r o y e d .
to d e t e r m i n e
t a k e n w h e n a d d i n g water to
s o d i u m b r o m i d e for u s u a l l y p i e c e s of
in e v i d e n c e by t h e i r r e a c t i o n .
that
the g l o b u l e s of
l a y e r by
above
that
care was
s o d i u m were
just
all of
the f a c t
this p o i n t ,
temperature
w h i c h as m u c h of
r e a c t i o n was k e p t u n d e r
in the b a t h
in the m i d d l e of
the r e a c t i o n
to the r e s i d u e ,
the
s o d i u m soon b e c a m e
A f t e r all
p o s s i b l e was decanted.
temperature
s o l u t i o n turned blue.
r e a c t i o n had
was
was
the
the a c t u a l
15-20°.
a d d e d and t h e
The
s u f f i c i e n t a m o u n t of
P i e c e s of
c o a t e d d a r k blue,
t he
On attempting
the h y d r o g e n
the i n t e r f a c e of
finally
consumed
s o d i u m were
evolved,
the water
without
Due to
lifted
into
they a p p e a r e d
and oil
layer,
m u c h e v o l u t i o n of
energy.
The oil
layer was t h e n s e p a r a t e d
and a d d e d to the
33
original decanted
with water
solution*
and d r i e d o v e r
material was
The
t o t a l oil was w a s h e d
c a l c i u m chloride.
fractionated
t h r o u g h C o l u m n #2
fractions boiling from 154.0-154.9°
t a k e n to give 1 6 0 . 7
of
gms.
The
(Table VI);
at 7 1 6 . 5
of p r o p y l b e n z e n e
mm. w e r e
for a yie l d
54<.
T A B L E VI
F r a c t i o n a t i o n of
Wt. of
Liquid
No .
Pressure
24.0
20.9
12.4
1
2
3
4
5
8.8
6
8
9
10
11
154.0
154.5
154.5
154.5
154.7
154.9
154.9
154.9
154
Falling
ti
Another batch prepared
121
.6
gms.
of p r o p y l
Boiling point
n|j0
=
(II 70)
T e m p e r a t u r e °c.
mm.
714.5
716.5
716. 5
716.5
716.5
716.5
716.5
716.5
716.5
716.5
716.5
16.8
15. 3
14.0
19.8
9. 6
11.4
7.7
7
Propyl Benzene
benzene
n2 0 °
D
1.4914
1.4911
1.4916
1.4916
1.4916
1.4916
1.4916
1.4916
1.4916
1.4916
1.4914
(see T a b l e VIA)
gave
for a y i e l d of
41<.
was 1 5 4 . 0 - 1 5 5 . 9 ° at 7 3 8 mm..
1.4916.
A 500 cc. p o t was u s e d
The residues
f r o m the
fractionated
from a
two
100
runs were
cc.
remove more propyl benzene.
f r o m T a b l e VIB,
in the a b o v e
practically
flask
c o m b i n e d and
in an a t t e m p t
However,
a l l of
distillation.
as
can be
to
seen
the p r o p y l b e n z e n e
34
had
b e en
removed.
Fraction
f r a c t i o n cutter.
About
w h i c h must h a v e b e e n
4 turned
50 cc.
s o l i d in the
remained
in the p o t
mostly diphenyl.
*v T A B L E V I A
F r a c t i o n a t i o n of P r o p y l B e n z e n e
No.
1
2
3
4
5
6
7
8
9
VYt. of
Liquid
Pressure
19.8
11.4
16.7
12.4
9.4
12.5
23. 2
23. 3
12.7
mm.
738
738
738
738
738
738.5
738.5
738. 5
738.5
(III 1)
T e m p e r a t u r e °C.
1.4872
1.4859
1.4905
1.4912
1.4918
1.4916
1.4916
1.4916
1.4916
154.0
154.5
155.0-155.5
155.5-156.0
155.6
155.9
TABLE VIB
F r a c t i o n a t i o n of P r o p y l B e n z e n e R e s i d u e
No.
Wt • of
Liquid
3.5
8.4
6.3
4.2
1
2
3
4
Pressure
mm.
40
40
40
40
nitrated according
to
D.B.
162 gms.
a
To
(III
Propyl
2)
o
T e m p e r a t u r e °C.
1.4940
1.4889
1.5321
135
150
155
p-Nitroprop.y 1 b e n z e n e .
Mullin4 3 .
n^°
b e n z e n e was
the m e t h o d of R.R.
R e a d and
of p r o p y l b e n z e n e
Read, R.R. and Mull i n , D.B. , J . A m . C h e m . S o c . 50,
1 7 6 3 (1928)
M u l l i n , D.B., Thesis, The D i s i n f e c t a n t P o w e r of
P h e n o l s , U. of V e r m o n t , (1924)
35
dissolved
added
in 162 gms.
slowly
b e l o w 10°,
180 gms.
with
360
of
of
s t i r r i n g and k e e p i n g
c c . of
fuming
glacial acetic
acid h ad all b e e n ad d e d ,
stand
for
some time.
s t e a m b a t h to
hours,
After
the
was c o oled
water,
acid.
was
the t e m p e r a t u r e
acid
After
mixed
the
with
nitric
to
t h e n hea t e d o n the
n i t r o g e n were
evolv e d ,
l i q u i d was p r o ­
standing
hour.
acid
the m i x t u r e was a l l o w e d
It was
twelve
heating was
for a n o t h e r
nitric
60° w h e n o x i d e s of
and a h o m o g e n e o u s
duced.
glacial acetic
resumed
The
and p o u r e d
mixture
into
ice
whereupon a yellow oily
l i q u i d was
t h r o w n down.
mixture was
solid N a O H
The
made alkaline
(required
with
ca.
lbs.)
and
extracted
benzene.
The benzene
s o l u t i o n was dried
sulphate;
the b e n z e n e
d i s t i l l e d off
liquid w i t h a c h a r a c t e r i s t i c
distilled
inclus ive,
odor.
in vacuo u s i n g C o l u m n
(Table VII)
pound giving 85.9
gms.
were
#2.
taken as
with
w i t h so d i u m
leaving a yellow
The l i q u i d
Fractions
the p u r e
was
3-9,
com­
f o r a 39<£ yield.
B o i l i n g p o i n t = 1 2 2 - 1 2 4 ° / 1 3 mm.
n|° = 1 . 5 2 9
36
T A B L E VII
F r a c t i o n a t i o n of p - N i t r o p r o p y l
No .
vn. of
Li quid
Pressure
7.1
12.4
14. 3
10. 3
18.8
12.5
8 .3
4.7
19. 6
12. 5
6 .8
14.2
1
2
3
4
5
6
7
8
9
10
11
12
13
In o r d e r
the
nitro
acid
to
mm.
ca. 125
129.5
128.5-130.0
128.5
125.0
125.5
13
13
13
12.5
14.5
14
123.0
122-124
124.0-126.5
127.5
132-134
136
check
the p o s i t i o n of
was oxidized
three
down w i t h d i l u t e
at
(Lit.
232-235°
at 147.5°,
i d e n t i t y of
241°).
so t h e r e was
this p a r t i c u l a r
p — Amino p r o p y l b e n z e n e .
nitropropyl
benzene
were placed
in a two
and
fifty
in portions
The
acid
compound
and ma l t e d
acid
no q u e s t i o n ab o u t
nitro
group
The acid
o-nitrobenzoic
the
compound.
Sixty-six
90 gms. of
l i t e r f l a s k as
g r a m s of the
granulated
shown.
tin
Two h u n ­
g r a m s of c o n c e n t r a t e d HC1 was added
t h r o u g h the reflux.
was c o m p l e t e ,
s o l u t i o n was
and
n 2°
the n i t r o b e n z o i c
sulphuric
The
)
1 .5265
1.5276
1.5290
1 .5290
1.5290
1.5305
1 .5305
1.5291
1.5303
1.5 3 3 2
1.5 349
1.5360
1.5 365
h o u r s u n d e r a reflux.
was b r o u g h t
dred
to
6
the nitro
by m e a n s of p o t a s s i u m p e r m a n g a n a t e .
for
(III
T e m p e r a t u r e °C.
18
18
19
16
15
compound
was h e a t e d
melts
Benzene
150
gms.
added.
of
The
W h e n the r e d u c t i o n
N a O H as a c o n c e n t r a t e d
l i b e r a t e d am i n e
37
was
e x t r a c t e d w i t h b e n z e n e and
dried over sodium
sulphate
T a ble VIII
F r a c t i o n s 7 and
gives
8
were o n ly faintly
the f r a c t i o n a l distillation.
were more yellow;
fractions
2 and
3
t i n g e d yellow.
B o i l i n g pt. = 1 1 3 . 5 - 1 1 4 . 0 0 / 1 4 mm.
ng° » 1.546
T A B L E VIII
F r a c t i o n a t i o n of p - A m i n o Propyl Benzene
No.
1
2
3
4
5
6
7
8
Wt. of
Liquid
P r e s s u r e mm.
2.2
3.8
5.2
6.5
5.6
1.9
5.2
1.4
14
14
14
14
15
15
15
15
T e m p e rature °C.
Ill
114
113.5-114.0
110.5
-117
-137
ca. 137
p - Cyano pr o p y l b e n z e n e .
was added
to
(III 11)
ngO°
1.5454
1.5461
1.5462
1.5461
1.5465
1.5468
1.5 5 5 3
1.5609
O n e - t e n t h mole of the
amine
(13.5 gms.)
30 cc. of concentrated
HC1.
The i n s o luble h y d r o c h l o r i d e formed a hard mass,
and it was neces s a r y
to grind it up before the addition
of p o t a s s i u m nitrite.
Ten grams of p o t a s s i u m nitrite.
38
in a
little water
below
was
5°.
After
obtained,
was
added
a good
the
slowly
test
for
solution was
k e e p i n g the t e m p e r a t u r e
excess
nitrous
neutralized
acid
with sodium
carbonate paste.
This
1 3 gms.
After
s o l u t i o n was
C U £ ( C N )2
s t a n d i n g for
r a i s i n g the
tracted
a yield
of
of
to
dried,
The
and
of
s t e a m was
nitrile
water.
run
was
in
ex­
fractionated.
(T a b l e
IX)
weighed
8.5 gms.
605^.
=
9 8 . 5-100.5°/ll
mm.
ng° =
1.516
0.957
ix
F r a c t i o n a t i o n of p - C y a n o
Wt. of
Liquid
1
2
P r e s sure
0.2
1.8
2.0
3
4
5
6
2 .4
0.9
1.4
7
1.1
nitrile
w i t h 10 cc.
and 0.75
Propyl
benzamide .
(0.019
of
cc. of
mole)
Benzene
Temperature or
o.
mm.
33
98.5-100.0
11
11
11
11
11
11
11
p-Propyl
the
s o l u t i o n of
N a C N in 50 cc.
60°.
table
No .
to a
t i m e at 0-5°,
inclusive,
B o i l i n g pt.
D4 ° =
some
temperature
2-5,
slowly
15 gms.
w i t h benzene,
Fractions
for
and
added
100.0
99.0
100. 5
105
Two
was
and
N NaOH.
treated
After
n
20°
nD
1.5140
1.5159
1.5154
1.5160
1.5183
1.5208
seven- t e n t h s
305^ h y d r o g e n p e r o x i d e ,
6
(III 17)
g r a m s of
in the u s u a l
15 cc.
of
method
9 5 ^ a l c ohol,
s t e a m d i s t i l l a t i o n of
the
39
reaction product,
tained a slight
One
and
the
amount
nine-tenths
for a y i e l d
of
p-Propyl
alcohol;
not
benzamide
ether;
and
moreso
and
soluble
g r a m s of
q u i t e as
is
at
125.5-127.0°.
soluble' in cold a b s o l u t e
In the
ether;
slightly
soluble
somewhat
in hot.
the amide was o b t a i n e d
very
somewhat
which con­
w a s h e d w i t h wa t e r .
s o l u b l e in cold
ether;
in hot;
the am i d e
of o i l were
62?£, m e l t i n g
in c o l d p e t r o l e u m
petroleum
c r y s t a l s of
insoluble
soluble in hot
in c o l d b e n z e n e ,
i n s o l u b l e in cold water;
cold the
s o l u b i l i t i e s are
as f o l l o w s :
Absolute alcohol >
petroleum
ether
> benzene y water >
ether.
T h e b e s t -r e c r y s t a l l i z a t i o n m e d i u m is a m i x t u r e of
benzene
the
and p e t r o l e u m
crystals
f r o m w ater,
balsam
came
as
d o w n as
they
M e l t i n g pt.
came
a dropping
dry
small
liter
stirrer,
This
recrystalli­
zations )
8 . 5 9 c£
three-necked
a ther m o m e t e r ,
518 gms.
was
from Canada
crosses.
Theoretical:
was p l a c e d
alcohol.
50^ alcohol,
(After two
In a two
w i t h an a i r
funnel,
isobutyl
d o w n in
8.58^
Isobuty1 bromide.
From
l o n g streamers;
= 127.9-128.9°
Dumas:
flask fitted
(1-1).
n e e d l e s and l o n g thin pri s m s ;
n e e d l e s and
(xylene)
M i cro
ether
cooled
and
(7 moles) of
to -10° by
i m m e r s i n g the f l a s k in a n i c e - s a l t bath,
and
695 gms.
40
(2.56 moles)
of p h o s p h o r u s
t r i b r o m i d e p r e p a r e d as
mentioned previously
w a s added.
removed
continued until
room
stirring
temperature.
night.
moved,
The
and
The
It was
stirrer,
and
fraction
distillate
and
the mixt u r e r e a c h e d
was d i s t i l l e d
three
to
stand over
t h e r m o m e t e r were
t a k e n was f r o m 4 7 - 5 3 °
was washed
c o o l i n g b a t h was
then a l l o w e d
funnel,
the m a t e r i a l
The
re­
through Column
at
200 mm.*
The
times w i t h 50 cc. p o r t i o n s
of c o n c e n t r a t e d
s u l p h u r i c a c i d at
w i t h 25 gms.
anhydrous p o t a s s i u m carbonate until
of
odor of hydrogen bromide
column.
The p r o d u c t
weighed 524.4
T a b l e X).
Several
0
°;
it was t h e n s h a k e n
disappeared;
through the
#2.
and
then r e d i s t i l l e d
Boiling point - 40.0-43.5°
gms.
b a t c h e s of
for
this
the
a y i e l d of
at 1 3 5 m m . .
55^
(see
b r o m i d e w e r e pr e p a r e d .
TABLE X
No .
F r a c t i o n a t i o n of
Isobutyl Bromide
Wt. of
Liquid
mm.
12.3
1
2
15.4
15.5
31.1
441.0
Residue
6
7
8
Isobutyl
benzene.
p r e p a r e d by
propyl
benzene.
(mixture)
the
Two
mo l e s of
slowly
18)
20
in
°
nD
1.4296
1.4286
1.4310
1.4335
1. 4 3 4 4
1.4345
1.5350
b a t c h e s of i s o b u t y l
methods used
Three
were added
T e m p e r a t u r e °C.
28.5-42.0
40.0-40.5
40.5-41.5
42.0-42.5
42.5-43.5
43.2
43.5-44.0
135
135
135
135
135
135
1 35
11.2
1 0 .2
3
4
5
were
Pressure
(III
be n z e n e
the p r e p a r a t i o n of
e a c h of the b r o m i d e s
to 7 m o l e s of
sliced
sodium
41
under
ether.
ether had
B a t c h No.
2 became
to be added.
No.
and
required
No.
2 was a deeper' blue,
1 remained a b l u e green color
h o u r s for the a d d i t i o n
6
a t u r e 40-48°).
also r e q u i r e d
The bromides
that a slight r e f l u x of the
days,
(temperature
6
hours
were added at
and
e a c h was
ether 1took place.
was a d ded c a u t i o u s l y
the o i l l a y e r was
refluxed
8
separated,
through Column
2-6,
followed
1
inclusive.
i s o b u t y l benz e n e .
but
s u itable
e a c h of the
runs were c o m b i n e d
Water
and
and
#2.
ben z e n e
8-20,
A f t e r the
came o v e r r e p r e s e n t e d
by the biisobutyl
Fractions
two
w a s h e d w i t h w a t e r and dried
The two
had been t a k e n off,
by f r a c t i o n
Afte r
hours.
The f r a c t i o n a t i o n is g i v e n in Table XI.
ether
(te m p e r ­
to d i s s o l v e the so d i u m b r o m i d e
c a l c i u m chloride.
fractionated
for about
30-34°).
such a rate
250 c c . of m e t h y l a l c o h o l was added to
batches,
over
rather viol e n t and more
in f r a c t i o n s
inclusive,
represented
The m a t e r i a l was not r e f r a c t i o n a t e d
f r a c t i o n s were
taken for the p u r e isob u t y l
benzene.
A m a t e r i a l b a l a n c e on this p a r t i c u l a r experime n t
gave
the f o l l o w i n g result:
Started
3.2
1.2
-4.4
with
moles
6
6
moles b r o m o b e n z e n e
moles i s o b u t y l bromide
i s o b u t y l b r o m i d e went to f o r m the 1 . 6 mole
bi isobutyl
moles i s o b u t y l b r o m i d e went to f o r m the 1 . 2 mole
isobutyl be n z e n e
42
L e a v i n g 1.6 m o l e s
the
1.68
i s o b u t y l b r o m i d e 'which check e d
m o l e s of b e n z e n e o b t a i n e d .
T A B L E XI
F r a c t i o n a t i o n of I s o b u t y l
No .
Wt. of
Liquid
P r e s s u r e mm.
13 1 . 2
108.0
1
2
3
45
20.7
22.1
6
5.'2
7
8.8
8
8.3
9
6.0
7.3
7.5
7.7
4. 3
10
11
12
13
14
15
16
17
18
19
6.8
9.1
86.0
6.7
4.8
7.6
8.4
Residue
20
21
(III 27)
T e m p e r a t u r e °C.
724.5
724. 5
60
60
60
60
60
60
60
60
60
60
60
60 .
60
60
35
20.2
Benzene
75.0-79.6
87.5-103.0
35
39
39.0-40.0
40
40
-78
81
86
89
87.5-88.5
8 8 .5
8 9.5
89. 5
90.0
90 .0- 90 .5
82
93
116.5
20
20
20
120
n20°
D
1.4848
1 . 4 6 4 5 - 1 .4(
1.3970
1.3941
1.3931
1.3930
1. 4 2 0 9
1.5154
1.5282
1 .5070
1.4955
1.4948
1.4915
1.490 5
1.4890
1.4856
1. 4 8 4 0
1. 4 8 1 6
1.4910
1.5329
(diphenyl)
The f o r m a t i o n of b e n z e n e was not
entirely unexpected.
bromobenzene
shown
by
R e d u c t i o n of
t o o k p l a c e and as
later this was
accompanied
the f o r m a t i o n of isobutylene.
Unfortunately
the G i l m a n trap
c o n t e n t s of this e x p e r i m e n t had
b e e n destroyed.
F r a c t i o n 21 gave
vaj
solid diphenyl
coming
43
out at the top
stopcock.
While no specific
b e n z e n e in this
mention of the formation of
r e a c t i o n had
been found in the literature,
it might readily be expected from the results
As
shown on page
8
reported.
the main reaction is the
f o r m a t i o n of an alkyl benzene.
It might be expected
that the same w o u l d hold for isobutyl b r o m i d e and br o m o ­
benzene.
As can be seen from the data w h i c h follows,
u n d e r the c o n d i t i o n s present,
of
the main reaction consists
the r e d u c t i o n o f b r o m o b e n z e n e
(33 1/3^).
A second W u r t z - F i t t i g was run on isobutyl bromide
and b r omobenzene.
The tem p e r a t u r e was kept at 35-45° C.
d u r i n g the a d d i t i o n of
The gases evolved
of
the mixed bromides
du r i n g the time that
to the sodium.
the second half
the mixed b r o m i d e s had been added were collected and
amounted
to
16 liters.
A gas a n a l y s i s on
this run gave
the following a v e r ­
age values:
O r i g i n a l volume:
32
14
4
w i t h a y e l l o w flame,
A third
It had
6
cc. ether
cc. isobutylene
cc. o l e f i n (gas burns
blue around the edges.)
W u r t z - F i t t i g was run on isobutyl bromide
and b r omobenzene.
before,
98 cc.
The
sodium had been cut up the day
so the r e a c t i o n was not very
rapid in starting.
to be heated up in order to start.
h o u r s to run in the bromides.
All of
It took about
the gases were
44
caught in this run and amou n t e d
to 18 liters.
T A B L E XIA
F r a c t i o n a t i o n of
No .
W t . of
Liquid
1
2
6.8
6.6
3
4
5
5.7
7.6
43.3
21.5
6.4.
6
7
8
9
10
11
12
13
14
15
16
17
18
6.1
8.1
5.6
25.5
6.2
4.8
9.4
8.9
41.7
7.8
2.7
(Diphenyl
Isobutyl Benzene
P r e s s u r e mm.
729
729
729
729
729
729
729
729
729
729
729
40
40
40
40
40
40
40
c o m i n g over)
(III 44)
Temperature °C.
65-74
74.5-77.0
77.0-77.5
77 . 5 - 7 8 . 3
78.3-80.5
80.5-82.0
82
-85
85
-90
90
-98
98 -101
101
-107
30.0
30
- 40
40
- 69
69.0- 71.5
81.0
145
145
-152
ng°°
1.4362 i
1.4657 (
1.4768 (
1.4820
1.4840
1.4780
1.4636
1.4485
1.4274
1.4074
1.3965
1.4000
1.39501.5160
1.5392
1.4910
1.5045
1.5552
A gas a n a l y s i s on this run gave the following
a v e r a g e values:
O r i g i n a l volume:
The
second and
100
cc.
32 cc. ether
34 cc. isobutylene
4 cc. olefin
third W u r t z - F i t t i g reactions were
f r a c t i o n a t e d t h r o u g h C o l u m n #2 and are given in Tables
XIA and XIB,
respectively.
45
TABLE XIB
No .
F r a c t i o n a t i o n of
Isobutyl
Wt. of
Liquid
mm.
Pressure
T e m p e r a t u r e °C.
724
35 - 7 5
724
75 - 7 7
724
78.0
722
78-81
722
81-85
722
83-85
722
85-92
722
92-104
722
105.0
722
105.0
40
29.0
40
29 .O- 30 .O
40
75
40
77
40
78.5
40
79.0
40
79.0-79.5
40
79.5
40
79.5-118
8.0
40-25
118-132
(Di p he ny 1 comi ng o v e r )
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
The o c c u r r e n c e
several
account
of
reactions;
t he i s o b u t y l
for
the
postulated
by B a c h m a n n
of b e n z e n e
besides
o-diphenyl
10
(see
After
(1 ) by
benzene,
and
and
biphenyl.
The
ng°°
1.4226
1.4815
1.4880
1.4860
1.4670
1.4575
1.4382
1.4049
1.3950
1.3935
1.3935
1.4008
1. 51 30
1.4940
1.4895
1.4863
1.4848
1.4820
1.4760
1 .5306
for
the d i s p r o p o r t i o n a t i o n of
radical
but
( 2 ) by
the m e c h a n i s m
benzene,
would
which would
formed
C l a r k e 2 -*- f o r
diphenyl
45)
might be accounted
the p h e n y l
isobutylene
the
page
benzene
r a d i c a l and
f o r a l l of
o,
(III
18.1
7.5
7.3
54.9
8 .3
7.0
7.7
5.7
4.5
16.8
15.8
6.7
7.1
7 .4
6.4
12.5
14. 2
7.0
4. 3
1
2
by
Benzene
not
account
the f o r m a t i o n
t r i p h e n y l e n e , and
equations
are g i v e n o n
Historical).
the f r a c t i o n a t i o n
in the p r e s e n t
experiment,
the r e sidue was tra n s f e r r e d
the removal of diphenyl,
(Table XIC)
to Column #3.
Following
fract i o n s were o b t a i n e d
w h i c h correspond
to the products
mentioned
by B a c h m a n n and Clarke.
TABLE XIC
F racti o nal D i s t i l l a t i o n of Isobutyl B e n z e n e Residue
Wt. of
No. Liquid P r e s s u r e mm.
15.5
1
2
11.0
3
11.7
R e sidue
T e m p e r a t u r e °C.
18
18
16
134-139
-189
-215
As shown by S h o r i g i n 4 4 , the
the course of the reaction.
(III 49)
L a g °C.
134 - 1 4 5
-223
-259
solvent may
Pot °C.
179-196
-228
-277
effect
While B a c h m a n n and Clarke
w o r k e d at the b o i l i n g point of c h l o r o b e n z e n e , namely
132°,
the p r e s e n t
ether.
doubt,
work was done at the boiling point of
W h i l e the reac tions of Bachmann and Clarke,
take p l a c e
be m e n t i o n e d
that
at this lower temperature,
no b enzene was
no
it should
noted as a p r o d u c t in
the p r e p a r a t i o n of pr o p y l benzene by this reaction.
T h e p r e s e n c e of b e n z e n e is probably due,
isobutyl
radical.
to the
Table X I D gives the collective results
f or the three different
Wurt z - F i t t i g reactions in the
case of isobutyl benzene.
44
namely,
Shorigin, P., Ber.
43,
In Runs 1 and 2, three moles
1931
(1910)
47
each of b r o m o b e n z e n e a n d
to
seven
amounts
m o l e s of
isobutyl b r omide were
sodium.
I n Run
No.
added
3 double
the
were used.
TABLE XID
Material
Balance on
Product
Wurtz-Fittig
Run N o . 1
I sobutyl b e n z e n e
Bii s o b u t y 1
Benzene
Diphenyl
I s o b u t y l e ne
- -________
Run
0.5 mo1 e
0.45
1.0
0.1
benzene.
and
forty
To
dissolved
fuming nitric
The
in
acid
and
the
as o n l y
9-16,
inclusive,
with
solid
solid
10
cooling
water
fractions
240
9,
a few
10,
240
gms.
below
cuts
solid
glacial acetic
480 cc.
glacial
of
acetic
acid.
sta r t e d
Hot
the
to come
w a t e r was
run
by c o l d
solid.
Fractions
in a H C l - i c e b a t h but o n l y
11 y i e l d e d
freezing.
was
isobutyl
was r e p l a c e d
contained
No.
benzene
10°.
s y s t e m but
were cooled
and
of
(Table XII).
from fraction
even b e f o r e
mo 1 e
1.7
grams of
g r a m s of
the f r a c t i o n a t i o n
i n f r a c t i o n No.
through
3
given for p-propyl
w a s a d d e d a m i x t u r e of
t e m p e r a t u r e was kept
During
out
hundred
this
1.2
1.6
Isobutyl
methods
acid.
R u n No.
O. 33
the
were
Benzene)
0.1
n i t r a t e d a c c o r d i n g to
benzene
No . 2
0.44 mole
0.44
0.9
p-Nitroisobuty1 benzene.
Two
(Isobutyl
solid.
All
were
10 w h i c h c o n t a i n e d
Fraction
No.
11 w a s
seeded
th e
com-
48
pl-etely solid;
removed
fraction
and w a s h e d
Melting point =
9,
the
least.
with petroleum
124-1 2 7 ° .
It
is
The solid was
ether three times.
most
likely a dinitro
compound.
TABLE XII
F r a c t i o n a t i o n of p - N i t r o i s o b u t y 1 B e n z e n e
No .
Wt. of
Liquid
1
2
11.2
Pressure
9.0
6
7
8
9
10
11
12
13
14
15
16
two
9.5
9.5
9.5
9.0
9.5
9.5
9.0
9.0
9.0
9.0
109.0
109.5
123
125 .0
125.0
125.0
125.5
formed
were o x i d i z e d
about
2
°
taken as'representative
d u r i n g the
nitration.
The
of
two
with potassium permanganate.
F r a c t i o n 13 r e q u i r e d a b o u t
quired
20
nD
54)
1.5302
1.5526
1. 4 7 9 5
1.5123
1.5230
1.5 2 3 0
1.5238
1.5241
1.5260
1.5280
1.5324
1 .5300
1.5290
1.5294
1.5294
1.5294
110.0
110.0
110.0
7 and 1 3 were
compounds
fractions
30-50
48
115
1 26
18
18
Fractions
the
T e m p e r a t u r e °C.
20
20
7.7
9. 3
7.1
6.5
16.8
30 . 6
15.4
16. 3
14.7
16.4
25. 4
28.7
23.0
6.7
3
4
5
mm.
(III
two
hours,
while
No.
7 re­
^ hours.
Melting points for
the
two acids;
Fraction 7 = 140-143°
F r a c t i o n 13 =
Fractions
4-8,
(Lit. - ortho = 144°
meta - 140°)
210-230° (Lit. - p a r a - 241°)
inclusive,
were t a k e n as the o r t h o
49
compound,
and f r a c t i o n s
12-16,
inclusive,
as the p a r a
c ompound.
Densities on Fractions
F r a c t i o n 7 = 1.095
”
13 = 1.061
p-Amino
p l a c e d 71.6
granulated
added
gms.
slowly.
The a m i n e
of
tin and
c r y s t a l s of
ated.
isobutyl
7 and 13:
b.pt.
b.pt.
benzene.
the nitro
250 gms.
A f t e r the
H O - l l l o / 9 . 5 mm.
125-125., 5°/9 mm.
In a o n e liter fl a s k was
compound,
of
l i b e rated,
a n d 90 gms. of
c o n c e n t r a t e d HC1 was
r e a c t i o n was c o m p l e t e d and cooled,
the a m i n e h y d r o c h l o r i d e
was
20
nn
= 1 .5238
ng° = 1.5294
a p p e a r e d throughout.
extracted,
dried,
and f r a c t i o n ­
The f r a c t i o n a t i o n is g i v e n in Ta b l e XIII.
Fractions
2-6,
for a y i e l d of
inclusive,
gave
33.4 gms.
of the amine
56°b.
B o i l i n g pt.
= 102-1040/7
mm.
n^° = 1.5322
D§0 r 0 . 9 3 8
T A B L E XIII
F r a c t i o n a t i o n of p - A m i n o
No .
1
2
3
4
5
6
7
Wt. of
Liquid
9.5
6.9
6 .9
7.9
6.5
5.2
1.4
o-Amino
Pressure
mm.
of the c o r r e s p o n d i n g
(III
T e m p e r a t u r e °C.
n20°
D
103.0
103.0
103.0
7
7
7
7
7
7
7
isobutyl
Isobutyl B e n z e n e
-104.0
104.5
105.0
benzene.
nitro
62)
1.5343
1.5 330
1.5322
1.5 322
1.5322
1.5338
1.5439
T h e reduction of
49.5 gms.
c o m p o u n d was carried out w i t h
50
70 gms.
HC1.
of g r a n u l a t e d t i n and
The a m i n e
fractionated
(Table XIV)
49£.
was l i b e r a t e d ,
through Column
gave 20.1
B o i l i n g pt.
d|° = 0 . 9 4 6
200 gms.
(Fr.
=
gms.
extracted,
//I.
of
of
c onc e n t r a t e d
dried,
Fractions
the a m i n e
97.5-98.0°/7
mm.
1- 3
and
, inclusive,
for a yi eld of
n§° =* 1 . 5 3 4 8
#2)
TABLE XIV
F r a c t i o n a t i o n of o - A m i n o
No .
1
2
3
4
5
Wt. of
Liquid
Pressure
7.5
7.6
5.0
2.9
11.7
I s o b u t y l B enz e n e
mm.
Temperature
7
7
7
7
7
of the am i n e was a d d e d
all went
s o l u t i o n was
into
cooled
E i g h t e e n gr ams of
so d i u m
5°.
O n e - f i f t h mole
stirring.
0- 5°
wa t e r was a d d e d slowly,
rise above
1.5329
1.5348
1. 534 9
1.5667
1.5685
Water was added
Ice was added,
to
and the
by a salt-ice bath.
nit rit e in a small amount of
so that the temperature
A little m ore
had to be added.
n e u t r a l i z a t i o n w i t h s o d i u m c a r b o n a t e paste,
was a d d e d
(29.8
slowly to 59 cc. of c o n c e n ­
solution.
to
the c y a n i d e
63)
ng°°
-121
t r a t e d HC1 w i t h v i g o r o u s
until
°c.
-97 •
97.5
98.0
107.5
p-C.yano i s o b u t y l b e n z e n e .
gms.)
(III
solution
(23 gms.
NaCN).
did not
Af ter
the solution
C u 2 (CN ) 2
in 90 c c . of water and
28 gms.
After
standing
for some time at 0-5°,
the t e m p e r a t u r e was r aised to 50°
51
by ru n n i n g st eam into
the
solution.
Th e benzene layer
(benzene hav ing been ad ded to p r e v e n t
removed,
and the water
The two be nz e n e
Fractions
2-5,
frothing)
was
layer o n c e extracted w i t h benzene.
e xtracts were combine d and fractionated.
inclusive,
(Table XV) gave 1 0.8 gms. of
the nitrile for a y i e l d of 34^.
B o i l i n g pt.
= 1 0 5 - 106 °/6 mm.
n^° - 1.5124
D?° - 0 .93 9
T A B L E XV
F r a c t i o n a t i o n of p- Cya no
Wt • of
Li quid
No .
1
2
1.7
2.7
3
4
5
2.2
2.1
6
0.7
P r e s s u r e mrn.
I s o b u t y l Benzene
(III
Tem p e r a t u r e °C
n2 0 °
D
ca.
6
6
6
6
3.8
p-Isobutyl
benzamide.
of the nit ril e was treated w i t h
peroxide,
20 cc. of 9 5 ^ alcohol,
The r eac tio n
had to be cooled
45 min ute s the a m i d e
temperature
(0.019 moles)
cc. of 30^ hydrogen
and 0. 75 cc. of
several times.
having fallen to 42°.
6N
NaOH.
After
started to c rys tal liz e out,
w a t e r b a t h at 50-60°.
hours.
10
)
1.4859
1.5135
1.5125
1.5124
1.5134
1.5150
62
105.0
106.0
106.0
106*0
Three grams
68
the
It was pl ace d in a
The rea ction was complete in three
U p o n n e u t r a l i z a t i o n w i t h d ilu te sulphuric acid,
the amide p r e c i p i t a t e d
completely.
The amide was not
steam d i s t i l l e d but was f i l t e r e d off and washed with
52
water.
It is ver y
i n s o l u b l e in water, and as a result
was r e c r y s t a l l i z e d f r o m p e t r o l e u m ether and benzene
(2:1).
It is
s lig htl y
i n s o l u b l e in cold,
soluble in hot petroleum' ether,
and more soluble in benzene.
M e l t i n g pt.
= 15 1 . 0 - 1 5 1 . 4 ° (2 re cry sta l l i z a t i o n s
f rom p e t r o l e u m ether-benzene
Micro Dumas:
7.30%
The ore tic al
7.91^
Sec.-butyl b r o m i d e .
2
:1 )
This bromide was pr epa red in
the same way as the isobutyl
bromide
(page
39
).
Upon
a l l o w i n g to come to r o o m t e m p e r a t u r e w i t h stirring after
the a d d i t i o n of
the ,pho sphorus tribromide,
of f u m i n g took; place.
t hrough C o l u m n #2,
taken.
T he crude
quite a bit
bromide was fractionated
the f r a c t i o n 46-53°
Th e d i s t i l l a t e was washed first
at 200 mm.
w i t h sulphuric
acid and then w i t h a n h y dr ous p o t a s s i u m carbonate.
was then f r a c t i o n a t e d again
ing 88 .5- 89 .5° at 725 mm.,
(Table XVI).
being
It
collec tin g the po r t i o n boil­
fr act i o n s 4-7,
Th e p roduct we i g h e d 466 gms.
inclusive,
for a yield
of 49£.
In a not her
at 726.5 mm.
run 564 gms. of
bromide bo i l i n g 88.5-89.5°
was c o l l e c t e d for a y iel d of 59^.
53
T A B L E XVI
F r a c t i o n a t i o n of
No .
W t . of
Liquid
3
4
5
6
7
8
9
Sec.
of
Pressure
14. 5
8 .2
6.6
14. 3
19. 2
10. 4
422.0
40. 3
25. 8
1
2
secondary
reaction
after
mm.
of
took place
A
some
the
initial
addition,
on ly
very
slowly,
even
case
the
ether
In b o t h c a s e s
was
the
mixture
n2 0 °
D
1.4250
1.430 2
1.4312
1.4325
1.4336
1.4335
1.4350
1.4355
1.4360
of
time.
t he
and
moles
were
anhydrous
reaction
the
each
added
ether.
Twenty-four
with external
removed
th r e e
bromobenzene
sodium under
for
21)
89.5
89.5
90.0
bromide and
sliced
(III
77.0-84.5
87 .5
87.0
88.5
88.5
benzene.
butyl
Bromide
T e m p e r a t u r e °C.
72 5
725
72 5
725
725
72 5
7 25
723.5
723.5
Butyl
to 7 m o l e s
Sec.-Butyl
No-
hours
was p r o c e e d i n g
heating.
In o n e
heating continued.
s o d i u m p u f f e d up,
became
v e r y blue,
<
and d e t e r i o r a t e d .
ether
h ad b e e n
some time.
the
to
grams
no
case
the
of t he
solvent
concluded
reaction was
p-Nitro
sixty
removed,
It w a s
in p r e f e r e n c e
and
In t h e
was
evident
that d i p h e n y l
formation
of
was
sec.-butyl
after
formed
ben zene,
abandoned.
sec.-butyl benz e n e .
of
b a t c h w h e r e th e
Eastman
sec.-butyl
Three
hundred and -
benzene
was
nitrated
us ing the usual
using Column
it a p p e a r s
method.
#2 is given in Ta ble XVII.
that b o t h the ortho
pounds were formed.
10-16,
The f r a c t i o n a l d i s t i l l a t i o n
inclusiv e,
the m e l t i n g p o i n t s
for
melted at ca.
i n c l us ive ,
to be all
the acids,
The
Fractions
3- 8
"
10-16
8
22 .4
25. 3
7.9
32.3
28. 2
27.7
32. 8
32.4
9
10.0
1
2
3
4
5'
6
7
10
11
12
13
14
15
16
17
24.4
24.7
15 .9
28.9
30.7
30.0
26.1
2.5
nit rob enz oic
for a y i e l d
Pressure
110
9
9
9
9
8
-123.5
8
8
8
-129
129
130
14
1 2 0 - 1 2 1 ° / 9 mm.
1 3 1 - 1 3 3 ° / 9 mm.
T e m p e r a t u r e °C.
10
10
of 72£.
Sec.-Butyl Benzene
24
8
It thus a p p e a r e d
Boi l i n g po int
26
9
acid f r o m fractions
^4°
mm.
acid
120.0
121.0
120
131.0-133.0
133.0
-141
-144
(III 43)
0
Wt. of
Liqui d
taking
o
Ofcl
c
No.
The
1.5214
1.0617
1.5300
1.0621
TABLE XVII
F r a c t i o n a t i o n of p - N i t r o
In
and it was dif fic ult
me l t e d at 237-241°.
nD°
and
f r a c t i o n s 3-8,
nitrobenzoic
the p a r a va r i e t y
com­
inclusive,
r esp ect ive ly.
the m e l t i n g point.
235°.
nitro
The o x i d a t i o n was
d a r k e n e d q u i t e a bit,
to d e t e r m i n e
10-16,
3-8,
w ere ox idi zed .
3 hours,
inclusive,
and p a r a
Fractions
complete in 5^ and
Here again
1.4990
1.4990
1.5224
1. 5 2 1 0
1 .5210
1. 5 2 0 2 (
1 .5226 (
1.5225
1.5246
1.5280
1 .52 90
1.5297
1.5 301
1. 5 3 0 7
1.5310
1 .5326
1.5363
55
p-Amino
inclusive,
were
and
reduced
In a two
nitro
same
compound
set-up
of
two
and
propyl
reduced.
added
and
added
the
1-5,
R e a d 4 ^.
the
tin.
The
i n the p r e p a r a t i o n
Five
hundred
a p p e a r e d to
through
take p l a c e
O n c o o l i n g it
evidently
gave
not
s o l i d u p o n c o o l i n g and
Three hundred
w i t h c o o l i n g and
and
of
in p o r t i o n s
it w a s
were
R.R.
amine
was
were
of
stirring
extracted
was f r a c t i o n a t e d
inclusive,
grams
through
t a k e n as
the
(Table XVIII).
D^° = 0 . 9 3 9 8
p — Cyano
the a m i n e
37.
reaction
material
ffl; f r a c t i o n s
amine
on p a g e
of
gms.
granulated
had .been u s e d
10-16
was
The
143.2
3-8 fractions.
the amine,
B o i l i n g pt.
(Fr.
-
1 2 1 - 1 22P/19
(29.8 gms.)
solid
potassium nitrite
mm.
ng° =
1.5348
#2)
sec.— butyl
t r a t e d H C 1 ; no
plete
as
of
3-8,
(see T a b l e X V I I )
directions
with subsequently.
with benzene.
pure
gms.
HC1 were
Fractions
liberate
Column
the
as o r i g i n a l l y ,
worked
Both fractions
were placed
little
t he
sodium hydroxide
to
to
benzene
Very
c a s e of
benzene.
inclusive,
180
concentrated
layers
we re
flask
was used
the r e f l u x .
in t h e
10-16,
according
liter
of p - a m i n o
cc.
sec.-butyl
benzene.
was
added
O n e - f i f t h m o l e of
to
wa s o b t a i n e d .
in w a t e r
59 c c . of
About
18 gms.
solution was added
d i a z o t i zatio n, k e e p i n g
the
concen­
temperature
to
of
com­
below
5°•
56
TABLE XVIII
F r a c t i o natio n o f
No.
Wt • of
Liquid
1
2
8 .3
23.1
3
4
5
Pressure
8
9
10
The
carbonate paste,
reaction
nitriles.
were
In
taken as
y i eld
of
w as
to
the
completed
as
in the
cyanide
1.5347
1.5347
1.5349
1.5359
1.5354
1.5364
1.5373
1.5370
1.5375
1.5455
XIX fractions
sodium
so lut i o n ,
c a s e of
2-5,
55)
n2
D0°
neutralized witb
added
the
°c.
-127
-129
-131
127
-133
-138
5°)
Table
(III
121.8-123.5
1 23. 0
123.5
19
(below
Benzene
Temperature
20
20
20
20
20
solution
the
mm
19
19
8.2
7
Sec.-Butyl
.20
6.7
13. 8
6.5
6.9
7.5
ca. 8
7.7
6
and
the o th er
i ncl us i v e ,
n i t r i l e , w e i g h i n g IO gms.
for
a
32^.
Bo i l i n g
h420
d
p - A m i no
pt.
=
113-113.50/7
mm.
ng° =
1
.5 1 5 7
- 0. 9 4 3
TABLE XIX
F r a c t i o natio n of p - C y a n o
No •
1
2
3
4
5
6
Wt. of
Liquid
2.6
2.4
2. 9
2.2
2.5
0.9
Pressure
7
7
7
7
7
7
mm
Sec.-Butyl Benzene
(III
T e m p e r a t u r e °G.
r%o
-I ll
113.0
113.0
113.0
113.5
6 6
1.5070
1 .5131
1.5147
1.5162
1. 5 1 6 5
1.5210
)
57
p-Sec.-butyl
grams
benzamide.
(0.019 m o l e )
of
nitrile
of h y d r o g e n p e r o x i d e ,
20
0.75 cc.
The
of
6
N NaOH.
only o n c e
in o r d e r to
A f t e r on e
hour
out.
W h e n the
it w as p l a c e d
a c t i o n was
only upon
reaction
i n a hot
complete
in
was
treated
the
still
seven-tenths
w i t h 10 cc.
95# alcohol,
reaction
had
to
be
cooled
d id
not
crystallize
b e l o w 40°,
w a t e r b a t h at 50 -60°.
3|- hours.
60°.
The
The a m i d e
re­
came down
c ooling.
The s o l u t i o n w h i l e
still
nitrile.
intercrystallized
filter paper
volatilized
Upon
off,
hot
remove
the
nitrile.
amide
2. 4 gms.
was o b t a i n e d
M e l t i n g pt.
It was p l a c e d on a
T he n i t r i l e
was
which remained
fo r a y i e l d
was
A total
of 72#.
(4 r e c r y s t a l l i z a t i o n s
f r o m w ate r)
"
« = 1 2 6 . 9 - 1 2 9 . 9 ° (4 r e c r y s t a 11i z a t i o n s
f r o m p e t r o l e u m ether)
Micro Dumas:
7.99#
Theoretical:
7 . 9 1 # (on
product before recrystallization)
It a p p e a r s
butyl
group
different
=
the
the n i t r i l e b e c a m e
amide.
hot pl a t e .
a nd
t he
w as p o u r e d o f f f r o m
cooling,
w i t h the
o n t he
not
c o m b i n e d w i t h the a m i d e o b t a i n e d o r i g i n a l l y .
of
and
temperature below
temperature fell
Steam distillation did
remaining
and
c c . of
keep
the a m i d e
Two
116.7-117.7°
that
might
the o p t i c a l a c t i v i t y
have
something
melting points.
f r o m w a t e r and p e t r o l e u m
melting points.
the
sec.-
to do w i t h t h e s e
Alternate
et h e r
of
gave
two
recrystallization
the
respective
58
p-Nitrobut.yl b e n z e n e .
using
of
the
m e t h o d o f R.R.
fuming nitric
acid
was a d d e d
butyl
benzene
acid
in
slowly
benzene
Read43.
A m i x t u r e of
180
of
gms.
gl a c i a l
gms.
upon
of
heating
to 50°.
required
about
1 kg.
of
out w i t h g o o d
stirring using
solid
NaOH,
Ice had to
have
while
top
benzene
Column
As can be
made to
the
distillation
at
they
for
XX,
33mm..
gms.
t a k e n as
to
explode
the
nitro
acid.
The
the amine
to
was
was
fell
first
f r o m the
necessitating
Fractions
3-12,
be nzene.
50^.
n§° =
group
in the c a s e o f t he p - n i t r o p r o p y l
with potassium permanganate
the b e a k e r
amine
the p - n i t r o b u t y l
= 1 3 1 . 5 ° / l 0 mm.
T h e p o s i t i o n of
even a
the f r a c t i o n a t i o n .
the drops
g a v e a y i e l d of
B o i l i n g pt.
nitrobenzoic
the
at t h e l o w e r p r e s s u r e .
were
was carried
and
an a t t e m p t
As
appeared
It
s o l u t i o n tu r n e d a red
s o l u t i o n of
seen from Table
condenser,
The 119.9
water
#1 was u s e d
distill
inclusive,
The
n-
large a vo lume.
in a s a l t - i c e b a t h to p r e v e n t
from volatilizing.
ye l l o w .
too
of
neutral­
for
be a d d e d a l o n g w i t h the NaOH,
was i m m e r s e d
co lor
required
360 cc.
acid.
The
NaOH..
nitrated
acetic
glacial acetic
ization which
5N s o l u t i o n w o u l d
was
to a m i x t u r e o f 1 8 0 gms.
and 180
became homogeneous
n-Butyl
benzene
the
a c i d g ave
was
1.5245
c h e c k e d as
by o x i d a t i o n
corresponding
the
melting point
of
233.0-234•5°
was u n d o u b t e d l y
(Lit.
241®).
formed
but t his c o m p o u n d w as
here
M o r e of the o r t h o
as
variety
seen f r o m T a b l e XX,
not w o r k e d up.
TABLE XX
F r a c t i o n a t i p n of p - N i t r o b u t y l B e n z e n e
wr; oT"
Liquid
No.
Pressure
2.5
1
2
6.6
3
4
5
7.2
8.7
7. 4
6
11.1
7
9. 3
15.1
15.9
15.9
14.8
1 4 .5
14.8
16 .7
12. 4
11.4
8.7
8
9
10
11
12
13
14
15
16
17
43.-Ami
tenths
mm.
9
9
9
9
9
9
9
9
9
n-butyl
grams
of
difficult
to
The'amine
was
the
benzene •
nitro
usual
where
compound
s t a r t but o n c e
liberated
It w as
removal
was
The
was
six-
The r e a c t i o n was
s t a r t e d went v i o l e n t l y .
benzene
N a O H and
was r e m o v e d
sodium sulphate
then transferred
of b e n z e n e
and
red u c e d ac­
with concentrated
drying over anhydrous
#3.
1.4834
1.5182
1. 5231
1.5243
1.5220
1.5243
1.5245
1 .5241
1.5255
1.5255
1.5247
1.5252
1. 5 2 8 5
1.5290
1. 5 2 9 9
1 .52 30
1 .5231
Seventy-one
directions.
extracted w i t h benzene.
Column
ngo°
151
.156.5
131.5
124
123.5
126.5
131.5
127.5
128.5
128.5
130
-134.5
-135.5
-136
-137
137
11
11
10
10
10
10
c o r d i n g to the
after
T e m p e r a t u r e °C .
33
36
no
(II 71)
using
to C o l u m n
c o m p l e t e d by
#1
reducing
%
the p r e s s u r e
to
(lag 80- 100 °)
14 mrn. and h e a t i n g the pot
for
fractionation.
After
standing
were a l m o s t
hours.
This
to 1 00- 1 1 0 °
gave a s m o o t h
The f r a c t i o n a t i o n is given
t h r e e days,
colorless,
while
F r a c t i o n s 1-6,
inclusive,
f o r a y i e l d of
55^.
B o i l i n g pt.
fractions
3-6,
in Table XXI.
inclus ive ,
the o t h e r s were deep pink.
gave
32.6 gms. of
= 1 2 1 - 1 2 3 ° / 1 3.5 mm.
the amine
n§° - 1 . 5 3 7 3
T A B L E XXI
F r a c t i o n a t i o n of p - A m i n o
No.
Wt. of
Liquid
3.4
5.0
4.7
5.2
7.9
7.2
4.9
1
2
3
4
5
6
7
t r ate d H C 1 .
temperature
treated
n g°o
1.5372
1. 5375
1.5373
1.5372
1.5375
1.5375
1.5466
w i t h 59 cc. of
the
concen­
grams of p o t a s s i u m n i t r i t e in
5°.
T his
stand
by r u n n i n g
The f r a c t i o n a t i o n
sl owl y k e e p i n g the
s o l u t i o n was a d d e d
A f t e r all
a l l o w e d to
to 50°
(III 4)
O n e - f i f t h mole of
s o l u t i o n was a d d e d
below
s o lu t i o n was
was
Eighteen
solution.
solution.
120
121
-123
1 22. 5
-126
-127
-149
n-Butyl b e n z e n e .
a concentrated
then h e a t e d
T e m p e r a t u r e °C.
14
14
( 29. 8 gms.)
c y ani de
mm.
13
13
13.5
13.5
p-C.yano
amine
Pressure
n -B u t y l B e n z e n e
had b e e n added,
for one
live
to the
the
hour at 0-5°,
st e a m t h r o u g h the
is g i v e n in T a b l e XXII.
61
This is a r e f r a c t i o n a t i o n ;
gave
5. 4 gms.
fractions
for a 1 7 ^ yi e l d of
B o i l i n g pt.
the p u r e
= 1 2 3 - 1 2 3 . 5 ° / 1 6 mm.
D?° « 0 . 9 4 8
4
inclusive,
compound.
n§° = 1.5139
T A B L E XXII
F r a c t i o n a t i o n of p - C y a n o
Pressure
n -B u t y l B e n z e n e
mm.
(III 4)
o
O
Wt. of
Liquid
No.
5-8,
T e m p e r a t u r e °C.
1
I
1. 3
2. 2
1.5
2.5
1.4
1.2
1.2
1.1
1
2
3
4
5
6
7
8
16 .5
16
16
16
15
15
15
15
p-Butyl
of the
of
85
123
-1 2 3 . 5
123. 5
122
- 124.5
125.5
benzarnide.
ni tri le
Two and
(0.019 mole)
30^ h y d r o g e n pe rox i d e ,
0.75 cc.
of
6 N NaOH.
steam d i s t i l l e d
proved
since
successful
of o t h e r bu t y l
lost.
15 cc. of 9 5 ^ alcohol,
was o b t a i n e d
steam d i s t i l l a t i o n had not
b enzamides.
nitrile in the case
The globule of
mechanically.
eight-tenths
It contained
some
some amide was undoubtedly
grams of
the crude amide
for a y i e l d of 54^.
M e l t i n g pt.
Micro
and
r e a c t i o n p r o d u c t was not
i n t e r c r y s t a l l i z e d and
One a n d
sev e n - t e n t h s grams
were treated w i t h 10 c c .
in removing the
nitrile was r e m o v e d
amide
The
1.4905
1.5089
1.5131
1.5139
1.5140
1.5149
1.5161
1.5164
Dumas:
= 121.1-121.8°
7 .89 ^
(3 r e c r y s t a l l i z a t i o n s
f r o m water)
Theoretical:
7.9 1^
62
The A l i p h a t i c A m i d e s
The a l i p h a t i c
amides
were o b t a i n e d as such
from the E a s t m a n K o d a k Com p a n y ,
except i s o v a l e r a m i d e .
Acetamide was r e e r y s t a l l i z e d f r o m 9 5 < alcohol
at 80.6-81.6° C ? 9 .
used as o b t a i n e d
P r o p i o n a m i d e an d but.yramide were
m e l t i n g at 77.5-78. 5°
113.6-11 4.6 ° C ? 1 r e s p e c t i v e l y .
recrystallized
Isovale ram ide
C ? ° and
n - V a l e r a m i d e was
fr om f u s i o n mel t i n g at 1 0 0 . 3 - 1 0 1 . 6 ° C ? 2 .
was p r e p a r e d
from Eastman isovaleryl
chloride by a d d i n g to c o n c e n t r a t e d a m m o n i a
strongly c o o l e d by a s a l t - i c e bath.
o b tained was
ammonia
was hed o n c e w i t h cold
drying it m e l t e d at 1 2 2 - 1 2 5 . 5 °
C..
solution,
The p r o d u c t
concentrated
s o l u t i o n in w h i c h it wa s quite
by s u b l i m a t i o n
melting
soluble.
On
After purification
it m e l t e d at 125.4- 126 .4° C . 93.
63
PART
II
Introduction
The amides
(e xce pt
discussed.in Part
1,4-ditnethyl b e n z a m i d e - 2 and
b e n z a m i d e - 4 ) were
microscope
and
the u n i v e r s a l
constants
b e h a v i o r of
substances
the
refraction were
Th e o p t i c a x i a l
th e
melatope
se r v e d
as a
of
method
for
used,
well
of p l a t y
material
oriented properly
The m o r e
well
the c r y s t a l
wer e
to
as
determined.
the
determining
stage,
indices
r a n g e of
determine
get
method.
and
The universal
of
stage
re-
the i n d e x o i l s
i n d i c e s of
which ordinarily
to
Indices
immersion
the u n i v e r s a l
of
im­
d e t e r m i n e d by m e a n s of
refraction.
w h i c h were out
as
as
we re
distances,
fraction
as
1,3-dimethyl
stage.
d e t e r m i n e d by
angles
f r o m the i n d i c e s
this w o r k
s t u d i e d w i t h the p e t r o g r a p h i c
portant optical
of
I of
refraction
could
the p a r t i c u l a r
not be
i n d e x of
re­
fraction.
Hi s t o r i c a l
The
scope by
r e c o g n i t i o n of
its
properties
a substance
characteristic
geometrical
has l o n g b e e n known.
Wormley4 ^ published
45 Wormley,
under
a t r e a t i s e on
As
and o p t i c a l
early
the
the m i c r o ­
as
1867,
microchemistry
T.G-. , Mi cro chemi st ry of P o i s o n s , N e w Y o r k ,
(1867)
of poisons.
B o r i c k y 46 was
chemical t e s t s
to minera ls.
to a rapid d e v e l o p m e n t of
until the end of
those who
the first to apply microH i s work gave impetus
m i c r o c h e m i s t r y w h i c h la s t e d
the century.
D u r i n g th is pe r i o d
mad e the most v a l u a b l e c o n t r i b u t i o n s were
associated with petrography
and mineral ogy .
them was Streng,
McMahon,
Renard,
Huysse,
Haushofer,
Among
K lem ent and
and Be hrens.
The w o r k of B e h r e n s 47 marked the gre atest
v elo pme nt of
m i c r o c h e m i s t r y up to the
He i m p r o v e d and
editions of
last
decade.
e x p a n d e d the wor k of Boricky.
his w o r k have app ea r e d ,
de­
Several
a nd the latest in
1921 by K l e y 4 ® is the f o r e m o s t aut hority o n the sub­
ject in Europe.
century
D u r i n g the first qu a r t e r of this
there was
du rin g the
last
a definite
decade
there
lag in interest;
has b e e n a r e a w a k e n i n g
of i n t e r e s t in m i c r o c h e m i s t r y .
work has b e e n
Wh ile
however,
In mineralogy
done in the f i e l d of o p a q u e
the e x a m i n a t i o n of o p a q u e
most
minerals.
minerals by means
4 6B oricky, E . , E l e m e n t e einer me uen chemischm i k r o s k o p i s c h e n M ine r a l - und Ges tei ns analyse:
Ar chiv. d. naturwiss.
L a n d e s d u r c h f o r s c h , von
Bohmen, Band III, Prag, 1877
4 7 Behrens, H. , A Ma n u a l of Microchernical Analysis,
Lo ndon, 1894
4 ®Behrens, H. and Kley, P.D.C., M i k r o c h e m i s c h e
An al y s e , 4th e d . , Leipzig, 1921
65
of
the
m e t h o d s of
developed
mo de o f
since
attack,
minerals under
perfection,
the
microchemical
the
mineral).
the
i d e n t i f y i n g ore
the
technique
of
microscope
methods
Thus,
there
lines
(the
McKinstry
still
are
wa3
etc.
of
In
1931
Short^9 published
determination
and
by
D r e y e r 5 -1- on
tests.
other paper
appeared
4 9 Sho rt,
mutual
H.
and R o b e r t s
and
by
methods
metal
l i n e of
H . J . , Am.
Dreyer,
In r e c e n t
this
and by F r a s e r
w i t h the
elements.
work,
An­
by
the o p t i c a l
Bull.
21_, 613
8 2 5 , (1931)
(1936)
R.M. , A m . M i n e r a l
Mineral.
a nd B e r m a n ,
(1934)
t e s t s in
in m i c r o c h e m i c a l
F r a s e r 5 ^ deals
B e r m a n 53 lists
and
and
S t a p l e s 50 on m i n e r a l
interference
the
complete
minerals.
L.W. , A m . M i n e r a l .
5 3 L a r s e n , E.S.
Bull. 848,
the
microchemical
M . N . , U . S . G e o l . Survey
5 1 F r a s e r , H.J.
94 9 (1937)
approach
surface of
a very
the p r e c i o u s
mor e i n
50Staples,
5 ^Fraser,
along
microchemical
of
L a r s e n and
of
the ore
A n o t h e r p a p e r by
microchemistry
E.S.
of
have
the d e v e lopment
contributions.
description
years papers
short o f
check
and Putnam,
helpful
field
required
this
to
the
made
limited
falls
metallographic
Selchow
the
rapidly
first applied
etching,
satisfactory
has been
William Campbell
and o t h e r
results.
requires
metallographers
22,
22,
(1937)
H. , U . S . G e o 1 . S u r v e y
'66
properties
of
minerals.
o p t i c a l d a t a on
It
should
be
n ote d
as i n t r o d u c e d
the
term
artificial
that
to a v o i d
in w h i c h
The present
microchemistry
was
by
chemistry
the p e t r o g r a p h e r
chemical
mineralogist
microscopy
that
even
as
of A r t i f i c i a l
In
pu p i l ,
this
is
the
a
sequel
in t his
his
fi rst
the
che mis ts.
m o s t of
and
today
rise ofIn
the w o r k
the m i n e r a l o g i s t .
b e e n so
Winchell
compounds
"Microscopic
dominated
is
w h i c h is
Characters
Minerals".
country
E m i l e M.
foremost
He o r g a n i z e d t h e
by c h e m i s t s .
to
new m i c r o -
not used.
has
g a t h e r i n g o p t i c a l d a t a on o r g a n i c
to a p p e a r
to
i n t r o d u c e d by C h a m o t
is p r e d o m i n a t e d
by
the
is i d e n t i c a l
m o v e m e n t unlilce the
has b e e n d o n e
m i n e r als .
’’m i c r o c h e m i s t r y "
above
microscope
inorganic
by
term
c o n f u s i o n w i t h many
the
gathered
inorganic
microscopy"
the b r a n c h of
The f i e l d of
the
by W o r m l e y u s e d
"chemical
in o r d e r
methods
the
W i n c h e l l 54 has
His
Chamot,
exponent
fi r s t
of c h e m i c a l m i c r o s c o p y .
existing information
t e x t b o o k 55 is
Behrens'
in a f o r m u s a b l e
the f o r e m o s t a u t h o r i t y
f i e l d today.
5 4 W i n c h e l l , A . N . , M i c r o s c o p i c C h a r a c t e r s of A r t i ­
f i c i a l M i n e r a l s , J o h n W i l e y & Sons, Inc.,
N e w Y o r k , 1931
55 C h a m o t , E.M. a n d Mason, C . W . , H a n d b o o k of C h e m i c a l
Microscopy, Wiley
& S o n s , N e w York, 1931
Unfortunately,
under
the d e v e l o p m e n t of
new
microchemistry
lines d i f f e r e n t
under
the d i r e c t i o n of
than
the c h e m i s t s
has b e e n a l o n g
had b e e n in t he case
the m i n e r a l o g i s t s .
1'he m i n e r a l o g i s t s were
a c q u a i n t e d w i t h the p o l a r i z i n g
m i c r o s c o p e and
study of c r y s t a 1 1 o g r a p h y , a nd as a r e s u l t
precipitates
were used
the c h e m i s t s ,
as
in the
mig ht be
the
ch e m i s t
exp ect ed,
m i c r o s c o p e a nd
has l e a r n e d
m ore p r o m i n e n t .
instead
how
to us e
Stuart's
From
Under
t h e r e was a d e ­
and
Recently,
c o l o r re­
however,
d i s c a r d i n g the p o l a r i z i n g
other instruments
are b e i n g a p p l i e d
c h e m is try .
of
crystalline
identifications.
parture from crystalline precipitates,
actions became
the
them,
mo re and
the m i n e r a l o g i s t
and p e t r o g r a p h i c
more to
this p o i n t of
w o r k 56 is p r o b a b l y
of
m ethods
the p r o b l e m s of
v iew H a r t s h o r n e and
superior
to
that of
Chamo t a n d M a s o n .
F r y 57 has d o n e w o r k in the i d e n t i f i c a t i o n of
soil
constituents
by m e a n s of o p t i c a l
W h e r r y 56 has d e t e r m i n e d
methods.
the o p t i c a l p r o p e r t i e s of
5 6 H a r t s h o r n e , N.H. and Stuart, A., C r y s t a l s and the
P o l a r i z i n g M i c r o s c o p e , Ed ward A rnold & C o . ,
L o n d o n , 19 34
57 F r y , W . H . , U . S .D e p t . A g r . B u l l . 5 4 4 , 1
(1933)
58Wherry, E . T ., J . W a s h i n g t o n Aca d.S ci. 18, 302
(1928)
W h e r r y , E.T. and Y a n o v s k y , E ., J .A m .C h e m .S o c .
40, 1 0 6 3 (1918)
68
many alkaloids
B r y a n t 59 a n d
a s well
as a
num ber of
carbohydrates.
his c o - w o r k e r s
have d o n e
m u c h w ork w i t h
c e r t a i n al co h o l ,
aldehyde,
and a c i d d e r i v a t i v e s
a d d i t i o n to m a n y o t h e r o r g a n i c
and
H a r t s h o r n e 60 w o r k e d o u t
some a r o m a t i c
graphic
c omp oun ds.
in
^avies
m e t h o d s of i d e n t i f y i n g
n i t r o - c o m p o u n d s by' o p t i c a l
crystallo-
methods.
A number of
experimenters
cr ystal b e h a v i o r of
and h y d r o c a r b o n
Other
have
s t u d i e d the
low m e l t i n g hydro c a r b o n s 5 ***»5 ^ »5 5
viiaxes^i®^.
w o r k e r s 5 ® have determined indices of
f r a c t i o n more
accurately
by
re­
the m et h o d of m i n i m u m
5 9 B r y a n t , W . M . D . , J.Ara.Chem.Soc. 54, 3 7 5 8 (1932);
55, 3201 (1933); 60, 1 3 9 4 (1938); 60, 274 8
T T 9 3 8 ) ; 60, 2 8 1 4 T T 9 3 8 )
60D a v i e s , E.S. a n d H a r t s h o r n e ,
1 830 P a r t 2 (1934)
H.H. , J. Chern. So c . ,
® l L e s l i e , R.T., J . R e s e a r c h N a t l . B u r .S t a n d a r d s 15 ,
41 (1935) R.P. 8 0 8
5 ^Leslie, R.T., J . R e s e a r c h N a t l . B u r .S t a n d a r d s
761 (1936) R.P. 943
17,
® ^ L e s l i e , R.T. a n d H e u e r , W . W . , J . R e s e a r c h Natl.
B u r . S t a n d a r d s 18, 639 (1937) R.P. 1000
^ F e r r i s , S. IV. , Cowles, H.C., and Henderson,
I n d .E n g .C h e m . , I n d .E d ., 2 3 , 681 (1931)
5 5 Graves,
L.IvI. ,
G-.D. , I n d . En g.Chem. , Ind.Ed., _23, 7 6 2
66Hendri cks a nd
Jefferson,
J.Opt.Soc.Am.
23,
299
(1931)
(1933)
69
d e v i a t i o n w i t h a p r i s m and
flat
su rface w i t h the p u r p o s e in mind of c o r r e l a t i n g
s t r u c t u r e w i t h i n d i c e s of
The u n i v e r s a l
to purely
involved
stage
refraction..
had bee n very
chemical problems.
F e d e r o w was
m u c h too
l en gth y
It has
stage of
c o m p l i c a t e d for r out ine work and
g r a p h i c a l pr o c e d u r e s .
E m m o n s 6 7 , the
of r o t a t i o n p e r m i t t i n g
crystal.
little a p p l i e d
The o r i g i n a l
and c u m b e r s o m e
As m o d i f i e d by R.C.
T.A.
total r e f l e c t i o n f r o m a
stage has three axes,
easier o r i e n t a t i o n of a p a r t i c u l a r
been a p p l i e d
to
the study of f e l s p a r s 6 8 .
D o d g e r s has w o r k e d out B e r e k ' s 7 0 m eth od for
m e a s u r i n g the o p t i c
using the m o d i f i e d
measurement
a x i a l angle of a biaxial crystal
stage of E m m o n s when the direct
is i m p o s sib le.
Methods
of O p t i c a l .Analysis
I n d e x of R e f r a c t i o n .
determined
by
The r e f r a c t i v e indices were
the met hod of a x i a l
i llumination.
87Emmons,
R.C.,
A m . M i ner al.
1 4 , 441
(1929)
68Emmons,
R . C . , Am.Mi ner al.
1 9 , 237
(1934)
6 9 Dodge,
70
T.A. , A m . M i n e r a l .
Berek, M. , Ne ue s Jahrb.
B e i l a g e Band, 19 23
1_9, 62
f.
The
(1934)
Min., Geol.,
und Pal.,
70
c o m p a r i s o n liquids w h i c h are d isc u s s e d later were c a r e ­
fully
and
s t a n d a r d i z e d by
in the case of
constant
means of an Abbe r e f r a c t o m e t e r ,
the h i g h e r l i q u i d s by means of a
t e m p e r a t u r e h o l l o w p r i s m m o u n t e d on a goniometer.
The test
or higher,
is best
made w i t h a m a g n i f i c a t i o n of 80x
w i t h the d i a p h r a g m p a r t l y
condenser lowered.
Some
difficulty
too h i g h m a g n i f i c a t i o n s .
travels
into
the tube of
is e x p e r i e n c e d at
The B e c k e line or wh ite halo
the m e d i u m of
higher index upon r ai s i n g
the m i c r o s c o p e f r o m the p o i n t of focus.
The p h e n o m e n o n d ep e n d s u p o n
light
c los ed and the
in cid e n t
at more
the total r e f l e c t i o n of
t h a n the critical an gle when
p a s s i n g f r o m a s u b s t a n c e of gr eater to a substance of
lesser index.
In p r e l i m i n a r y o b s e r v a t i o n s white light was used.
W i t h the r e f i n e m e n t s of
ag ainst the crystal,
the d i s p e r s i o n of
results
the oil
can be o b t a i n e d
tot
0.003.
The f o l l o w i n g p h e n o m e n a are o b s e r v e d u s i n g white light:
or a n g e
\
dark b l u e
green
I n d e x of oil = Ind ex of
crystal
red brown
t b l u i s h white
I n dex of oil
In dex of crystal
71
y e l l o w or y e l l o w w h i t e
bright blue green
Index of oil <
The f i n a l
results w e r e wo r k e d out for m o n o c h r o m a t i c
light w h i c h ins ured r e s u l t s to
lamp was u s e d
Index of crystal
as a source of
0.003.
A mercury vapor
m o n o c h r o m a t i c light.
The
green line of the m e r c u r y arc was i sol ate d by C o r n i n g
filters.
light,
W h e n the
end p o i n t
is reached
the B e c k e line d i s a p p e a r s
li quids w h i c h are d i s c u s s e d
for m o n o c h r o m a t i c
entirely.
later were
s t a n d a r d i z e d at
25° f o r b o t h the g r e e n l i n e of the mercury
the sodium line,
preliminary
source of
white
The c a l i b r a t i o n of
t e r m i n e d by
angles and
axial
being u s e d for the
a Ge n e r a l Ele ctr ic
is g i v e n in Tab le XXVII,
Optic
spe c t r u m and
light i n d e x d e t e r min ati ons .
s o d i u m light,
lamp was used.
l i quids
the' s o d i u m v a l u e s
The i m m e r s i o n
angles.
three general
the in dic es of
As a
sodium vajoor
the imm er s i o n
p a g e 87.
Optic axial an g l e s were de ­
methods.
The optic axial
r e f r a c t i o n are r elated
in the
f o l l o w i n g manner:
c o s sV = y 2 Q?2 ~ t*-2)
for a neg ati ve crystal.
p 2 Qr2 c o s 2V = oc 2 (JT2 - S 2 )
for a p o s i t i v e crystal.
- cc 2)
A lpha,
beta,
and gamma r efe r to the three i ndices
of
refraction,
to
oc
and y
{3 - <*. y
<
X
determine
y
"/St
- {3
formulas
angle.
the
by w h i c h
ployed
crossed
is
an
the f i g u r e
while
in
distance
The
of
and
45°
apart
the
figure.
a uniaxial
two
angles,
the
as
as
an oil
immersion
The
enters
is
or
what
90° p o s i t i o n
figure,
appear
whose
axial
angle.
As a
th e p o i n t s
second method
an o c u l a r
light
minerals.
micro­
against
In o r d e r
to
measurement
of
acute
optic
axial
the
obtuse optic
axial
angles,
smaller
suitable
micrometer
high
all
em­
with
appears
th e
monochromatic
system of
with a
lens
represent
axial
of
first
interference
the optic
sections
axial
light
the optic
melatopes
above
light
melatopes
of
the
the
there
ax e s .
thin
well
that
In
if ft - oc
were determined.
Bertrand
out,
if
and
optic
angles
optic
for
in
afforded
two
angles
aperature.
t he
V
convergent
and
ocular
like
of
of
make p o s s i b l e
along
the
calibrated
standardized
used
nicols
is a m e a s u r e
of d e t e r m i n i n g
was
and
position
centers
convention,
the acute
so o r i e n t e d
bisectrix
appears
immergence
meter
is
relation of ^
negative;
axial
interference
the
is
The
is p o s i t i v e .
optic
crossed
nicols
called
crystal
•
By
relationships
crystal
with
n^
sign.
one-half
the
th e a c u t e
, and
the
crystal
above
When a
along
the
represents
The
method
, w^
n^
numerical
condenser
ocular
was
aperature
was
of hi-gh n u m e r i c a l
calibrated
for
each o p t i c a l
system.
for the 4 mm.
used
with an
and
Table
the
XXIII
1 . 8 mm.
8x o c u l a r
(tube
gi ves
oil
the c a l i b r a t i o n
immersion objectives
l e n g t h 170
mm.).
TABLE XXIII
Calibration for Melatope
Distances
8x o c u l a r
X = 5461A
Th in
Ni t r e
Cerrusite
A r a g o nite
Diopside
Cyani te
Di s t h e n e
Andalusite
O l i v i ne
Section
2V
2V
2V
2V
2V
2V
2V
2V
=
=
=
=
=
=
7°
8°
18°
59°
82°
82°
85°
88°
1 . 8 mm.
Obj.
4 ram. Ob j .
ca. 1.0
c a • 2.0
3. 9
11.2
16.0
16.0
16.5
17.0
Di v .
2 .3 Di v .
4.6
8.6
27
ca.
8x o c u l a r
A - 5893a
Nitre
Cerrusite
Ar a g o nite
Diopside
Cyanite
Di st h e n e
A n d a l u s ite
Ol ivi ne
Th e
The
so
7o
=
8°
=
= iaP
- 59
= 82°
= 82°
= 850
= 88°
values are
thin
that
2V
2V
2V
2V
2V
2V
2V
2V
sections
axial
17.0
given
in g r a p h i c a l
f o r m in F i g u r e 1.
w e r e of
sufficiently
low dispersion
angles.
the a b s c i s s a , a n d
2.2 Di v.
4. 8
8. 6
c a . 27
c a . 1. 0 Di v.
2.0
3. 8
11.5
16.1
16.1
th e w a v e l e n g t h m a d e very
the o p t i c
4 mrn. Ob j .
1 . 8 m m . Obj .
Thin Section
the
The
little
divisions
2V v a l u e s
difference
in
were p l o t t e d
as
as the o r d i n a t e .
foo
j
:
Figure 1
|.
Calibration of Optical System for 2V Measurement
70
1.8 mm
4 mm., 8x
fz
Divisions
75
It will
be noted
that a mu ch g r e a t e r error was en­
c o u n te red
in the us e of
jective.
An
the 1. 8 mm.
i mme rsi on o b ­
error of one d i v i s i o n in the m eas ure men t
of the m e l a t o p e d i s t a n c e
spectively,
oil
ca use d an err or of 5° and 2°,
in the case of the 1.8 mm.
o bjectives.
In talcing m e a s u rem ent s,
v a l u e s were
t a k e n and averaged.
mum e r r o r s in the 2V v a l u e s
in the case of
and 4 mm.
at least
ten
In this way the m axi ­
were 2° and
the 1.8 mm. oil
1°, r e s p ect ive ly,
i mme rsi on and
4 mm.
objectives.
The m o d i f i e d u n i v e r s a l
u s ed as a third
op tic
axial
st age were u s e d
stage of R.C.
E m m o n s 67
was
m e t h o d for the d e t e r m i n a t i o n of the
angles.
for
a
B a u s c h and L o m b m icr os c o p e and
this work as will be m ent i o n e d
later.
If the cry sta l
obtuse bisectrices
m i c r o sco pe,
other
one
noting
difference
index of
ob t u s e
is so o r i e n t e d
are p a r a l l e l
in i n d e x of
a n g l e was large,
In cas e
graphical
to the axis of the
t aking into a cco unt
to the
the
the h e m i s p h e r e s and the
the c r y s t a l u n d e r
d o w n by u s i n g
that the acute or
can rotate f r o m o ne opt ic axis
the angle and
c ons ide rat ion .
When the
the angle of rot ation was cut
the h i g h i nde x hemispheres.
the
cr y s t a l was not
m e t h o d as w o r k e d out
The f o l l o w i n g p r o c e d u r e
re­
so o rie nte d
the Berek
by D o d g e 69 was used.
was u s e d for the determination.
76
of 2V in biaxial
c r y s t a l s u s i n g the curves of B e r e k as
m o d i f i e d by Dodge:
1.
2.
3.
O r i e n t crystal so as two pl a n e s are vertical
an d the third p l a n e horizontal.
On o u t e r v e r t i c a l axis rotate 45° either
c l o c k w i s e or c o u n t e r clockwise.
Note
d i r e c t i o n of rotation.
(reference
position,
).
On o u t e r E.W. rotate e ither N o r t h or S o u t h
5 4 . 7 ° ( c o r r e c t e d ,^ ).
4.
On m i c r o s c o p e stage rotate to e x t i n c t i o n
c o u n t e r c l o c k w i s e d i r e c t i o n ( <£) ).
5.
From Berek's
a.
b.
c.
in
curves d e t e r m i n e
The p o s i t i o n of the optic p l a n e in the
r e f e r e n c e p osi tion.
The a p p r o x i m a t e val ue of 2V.
The curves of D o d g e for a more acc ura te
d e t e r m i n a t i o n of 2V.
6.
R e t u r n to
sign of
r e f e r e n c e p o s i t i o n and
crystal.
7.
Make B x a o r o p t i c p l a n e N - S.
determine
(Note:
If 0 . P. and B x a or BX q are vertical,
r o t a t e 45° on O.V. f r o m O.P. and measure
2V direct.
Cor rec t r e a d i n g s for d if f e r e n c e s
of index b e t w e e n h e m i s p h e r e s and crystal.)
In all other p o s i t i o n s of O.P.
follows:
p r o c e e d as
1.
Se l e c t c o r r e c t
2.
M a k e c or r e c t rot ati on
r o t a t i o n X.
3.
Make r o t a t i o n <j> in o p p o s i t e d i r e c t i o n f r o m
4.
B e f o r e l o o k i n g up rot a t i o n X, .correct for
he mis phe re.
Th ese r o t a t i o n s when looked
up on p r o p e r chart, give 2V w i t h a maxi­
mu m accuracy.
f
curve of Dodge.
(p and
T
corresponding
•
77
X = Rotation
either
N or
S o n o u t e r E.W.
(j) - R o t a t i o n o n m i c r o s c o p e
stage.
Extinction
ang le.
(f> = R o t a t i o n o n O.V.
A
32 mm.
to p e r m i t
objective
the
microscope
m o u n t i n g of
stage.
ference figures
It
are
mea n s of
All
points
chart
were
fitted
ium,
and
and
three
be
be
but one
Stage
that
deals
on a
no
the
inter­
entirely
with
2V v a l u e s
sets of
steriographic
Protractor),
difference
crystal under
methods
s t a g e on
sta ge.
for
noted
noted
be p l o t t e d
low refractive
determinations
d e t e r m i n a t i o n of
(Universal
w i t h three
It w i l l
the
must
corrected
hemispheres
was
the
the u n i v e r s a l
movements
projection
should
in
in the
the u n i v e r s a l
visible,
extinction positions
by
was used
and
in i n d e x of
all
the
investigation.
The
hemispheres
high,
f or
stage
med­
indices.
that
agreed
the
2V v a l u e s
in m o s t
cases
obtained
by
to w i t h i n 1°.
A f o u r t h m e t h o d w h i c h w a s u s e d for e s t i m a t i o n s
only,
being
tioned,
is b a s e d u p o n
melatopes.
for
the
not a s a c c u r a t e
In t h e
the
case
45° p o s i t i o n
are
curvature
depending on
the
figures
where
represented
the
those p r e v i o u s l y
c u r v a t u r e of
w i l l be
2V v a l u e s
by
as
by
2V =
90°
lines
page
of
line.
more or
This
80.
isogyres
or
the m e l a t o p e
a straight
v alu e.
in T a b l e XXV,
the
men­
is
Smaller
less
represented
78
Birefringence.
between
the
of
the
sam e
is
g i v e n by
crossed
optic
extreme
the
plane.
of
when
can
the
Furthermore,
is
an
means
crystal
the
indicate
indicate
Optical
lation
If
is p o s i t i v e ;
th e
in
The
three
a n d jQ v i b r a t e
OC
crystal
the
and
is
acute
n u m b e r of
birefringence
between
normal
Levy
to
provided
rings
rings or
of
that
the
the
l i n e s of
a high birefringence
equal
while
few
if
or
As mentioned previously,
negative d e p e n d i n g on
indices
in the
they
makes
of
refraction
the
clear
crystal
the
each other.
the
in th e o b t u s e
Likewise,
if ^
is
Indices
and
Optical
bisectrix
Acute b i s e c t r i x
Sign
Sections
Indices
<=c, (3
—
crystal
bisectrix,
vibrate
negative,
abov e.
from Oriented
y./3
a
the r e ­
to
acute bisectrix,
vibrate
negative.
F i gur e
Acute
the
in a n i n t e r f e r e n c e
TABLE XXIV
Refractive
the
chart,
the b i r e f r i n g e n c e
n u m b e r of
bisectrix,
following
crystals
is known.
character.
the
For
color o b t a i n e d
emerges
difference
a low birefringence.
is p o s i t i v e
of
the
the
by d e t e r m i n e d
i n d i c a t i o n of
retardation
of
the M i c h a e l
readily
A large
crystal
of
is
refractions.
indication
th e l i g h t
substance.
rings
an
interference
By
birefringence
figure
i n d i c e s of
thickness
nicols
thickness
The birefringence
Shown
etc..
79
TABLE XXIV
Figure
Optical
Obtuse
bisectrix
Obtuse
bisectrix
Optic
(continued)
Sign
Indices
+
Vifi
<x,/9
—
normal
+
or -
<*, r
*
Single
optic
axis
The optical
means
of
-h o r -
character
accessories
or g y p s u m plate,
is u s u a l l y
s u c h as
and
the
the
quartz
o b t a i n e d u s i n g the
accessories
ative
given
crystals
Reactions
been
of
are
the
American
be
Ceramic
of
fraction
ca n
oriented
t hat o n e
figures
deals
reactions
column headed
T a b l e XXV,
neg­
"Optical
w h i c h has
the
"Bulletin
.
Before
the
an i n d e x of
crystal
mus t
the p r o p e r
ray.
as a
guide
in
be
re ­
so
Inter­
selecting
crystals.
bisectrix
centered
interference
figure
depending on whether
is p o s i t i v e
positions
r e p r e s e n t oc a n d ^
or
negative,
or ^
vibrates perpendicular
7 1 Buclc,
Am.
The
by
selenite
wi t h p o s i t i v e or
in
with
character
always
wed ge.
t he
crystal.
were used
an a c u t e
been properly
mica plate,
Society
determined,
correctly oriented
When
determined
w i t h t he p e r m i s s i o n of
Orientation
ference
in
with Accessories"
reproduced
Shown
to
the
and ¥
has
the o p t i c a l
extinction
.
the l i n e
The ^3 ray
joining
K.E., Outline for Examining Crystals,
C e r a m . Soc. 16, 61 (1937)
the
Bul l.
80
TABLE XXV
O U T L IN E
FOR
E X A M IN A T IO N
OF
C R Y S T A L
GRAINS
OPTICAL REACT
ION IN PARALLEL
LIGHT AND
CROSSEO NICOLS
OPTICAL REACTIONS IN CONVERGENT
LIGHT WITH CROSStDH IC OLS ANDBER
TRAM LENS OR WITH CROSSED NICOLS
AND OEP1CCE OUT.
-INTERfCRENCC FIGURE A d a rk cross is r » « lr n t cen1m *d in
Held. or neatly so .is stage is levolved
the cross does net te>olve.
.t V
Se ction a ppears is o lio p ic ; o rd in a ry ray.
Tor po sitive m inerals.
us. o n ly can be d e te rm in e d ; u r n broad
G ypsum
Mica
Q u a rt/
Y ellow
(Cross disappears)
Side an d gives f u ll v alu e in any d ire c to n
ill*
i5iS
y D o ts
%8
If
S'S
z
D
The center c l th e cross is o ff th e c en­
ter o l th e H ek). but as c ro s s c e n te r rotates
aro u n d held th e e » te r> stn -o f th e a rm s of
th e cross pass across the Held.
M tn v frrv J Ii
G ypsum
L in e Iro m th e cen te r ot in te rle ren ce
fig u re cross to c e n te r o l Held is protect
io n o l op tic a n s a n d v ibratio n d irectio n
o l c , b u t inder. o l c is not tru e u n lit optic o l a n s is lifte d com p le te ly broadsid e,
t o vibrates 9 0 * to C a n d is a lm a rt a hu e
value.
Mrca
«
(B :
'©;r
O ptic a iis is h o rizo ntal (b ro a d sid e !;
on ly a flash fig u re is evident, it is m a n d
ou t in 10s to 15® stage re v o lu tio n ; two
very in d is tin c t hyperbolas fla s h in to d e a r
field in op po site q u a d ra n ts and em erge
from adjacent quadrants.
SIS
—
I^
C o lo r How
F o r positive m in e ra ls
Yellow
N ote
A ll of above rea ction s w ith acce ssor­
ies ap ply to e ith e r of ad jace nt q u ad ran ts
w he n the crystal is negative.
Lin e separa ting en te rin g a n d e tre rg
in g hyperbolas (convergent lig h li is dire c­
tio n o f op tic a n s and v ibratio n d ire c tio n
o f c ; e is broadside a n d at 9 0 ’u r s b ro ad­
sid e ; to d e te rm in e * m c h is faster ray is
che ck on sign o f m in e ra l as dete rm ine d
b y accessories__________________________
OPTICAL REACT
ION IN PARALLEL
LIGHT AND
CROSSED NICOLS
Is
I*
I*
5§ff
O nfy one lin e o r b ru s h is evident, vt
revolves opposite to stage, center o f io ta
b o n d bru sh is em ergence o f opt cat a n s ;
b ru s h is straig ht at 90® p o sition and c u rv ­
ed a t 4 5 * position, c u rv a tu re is ind icatio n
o f op tic ang'e s ite
F or positive m in e ra ls
Rla.ca
tl p e rfectly c entered and a n gle rs sm all.
. th e fig u re is
If op tic an gle is neat 9 0 " . accessories
are useless.
V ib ra tio n d .re c to n o f th e optic n o irn ji
Y rs ta ng en t to th e Curve at 4 5 posit
io n . it is broadside, hence fu ll > a iu t for
If em ergence ot optic 4 '-s is pe rfect­
ly centered, th e e a uiva 'e nt c ! fi ca n t e
m easured tn jr-,- d ire ct'cn
I l f I
-J
<
Blue
X
<
III
fc&£
©
sa
!2
9 0 " Position
©
AS* Position
(
W ith condensor rem oved,
i l l b ire fn n g e n c e jn o t to o h ig h !
Gypsum
C enter tin e th ro u g h hyperbolas at - S ’
is v ib ra to n d irectio n of B « , ibroaas.cTel
Positive B«.v » X i « l
N egative B « j « Z f r f
T angent to hyperbolas at 4 5 ' is v it'f j
hon d irectio n o f cpt>: norm al yT ^T rbrojdside)
If op tic a n gle is large hyperbolas are
seen e*cept possibly d i 4 5 " p o sition , stage
ro ta tion Ihype rb ola s en te rin g to hyper,
bofas e m e rg ing ) is greater th an 3 5 ’’ for
lower ind ices and greater th an 3 0 " lor
h ig he r indices.
H a ry hyperbolas seen e»cept at 4 5 l .
stage ro ta tio n (hyp erbo las en te rin g lu
hyperbolas e m u p /n g i is less th a n 3 5 lr
a n d m o re th a n 15 lo i tow in d ite s and
le ts th a n 3 0 ‘ for hvgti in d ic ts
A flash fig u re only, is f •.id i r t « 1 0 ''- l5 u
ro ta tio n i, tw o b i ta silt-. itid is lin c t hyper­
bolas flash in a r d err ergu fro m adjacent
quadrants
A IL o fa b o v^ reactions w ith accessor
■es apply t o eith er of ad jace nt q u ad ran ts
w he n |f.e c rysta l is negative
L in d sep ara ting en te rin g a n d e m c g
m g hyperbolas - v ibratio n d ire ctio n of
B ...
Positive B«, - Z (/•»
N egative B «, - X It* l
X and Z (b ro a d s id e !. a t rig h t j r y V .
81
p o i n t s of
eme rge nce of
direction perpendicular
pending upon whether
negative,
the two o p t i c axes.
ray i s oc or y'
to the
the c rystal
r e s p e cti vel y,
in the
The
de-
is p o s i t i v e or
ca se of an acute b i­
se c t r i x figure.
B e t a or
provided
the i n t e r m e d i a t e i n d e x can be measured
the p l a n e of the .optic axes is p a r a l l e l
the axis of
the m icroscope.
i s o g y r e s or melatopes,
found.
to the axis of
b y the normal
F r o m the movemen t of the
the p o s i t i o n of
When the p l a n e of
to
is readily
the o p t i c axes i s . p a r a l l e l
the microscope,
to the p l a n e
the dir ect ion
represe nte d
is the d i r e c t i o n of the in t e r ­
m e dia te index.
F u r t h erm ore ,
through a properly
as seen f r o m T abl e XXIV,
centered
all
di rec tio ns
single opt ic axis r e p r e s e n t
the i n t e r m e d i a t e index.
The ob t u s e b i s e c t r i x fi g u r e u s i n g an oil i m m e r s i o n
o b j e c t i v e was also used for' s e l e c t i n g correctly or ien ted
sections.
F u r t h e r r e a c t i o n s w h i c h were used in the
o r i e n t a t i o n of a c r y s t a l are g i v e n
A thin C a n a d a b a l s a m
in Table XXV.
so lut i o n was use d in the
p r e p a r a t i o n of mounts in the d e t e r m i n a t i o n of 2V values.
The h i g h vi sco sit y p e r m i t t e d the grains
into any d e s i r e d positio n.
i n d i c e s of refraction,
In
cru s h e d
to be rolled
the d e t e r m i n a t i o n of
glass or tripoli po w d e r
82
was a d d e d to the
crystal
gr a i n s
to help in the o r i e n t ­
ation.
Universal
stage in i n d e x d e t e r m i n a t i o n s .
case of b e n z a m i d e ,
li quids on hand.
of
was b e y o n d
stage,
the
c rystal was
h i g h e s t i n d e x o il o r any oil whose
gr eat er
th an
that of n p
on the o u t e r E.W.
was o r i e n t e d
The
g
the
a r o t a t i o n of
the oil and
90° wou ld
was o b t a i n e d f r o m graphs
by means
index is
sufficiently
sufficient
rotation
The crystal
were ver ti c a l and
the
ray was next p l a c e d in
set-up for
stage was r o t a t e d to the
end p o i n t by the o u t e r
i n d e x of
the index
im me r s e d in the
Wit h the u s u a l opt ica l
index determinations,
the
n y
g reatest accuracy.
so that two p l a n e s
position.
B e e k e lin e
to a llow
for the
third plane h orizontal.
the N.S.
the limit of
In the d e t e r m i n a t i o n of
the u n i v e r s a l
In the
E.W.
at w h i c h point
the crystal were'equal.
give
the
included
ray,
the
Since
value
in the p a p e r of
R.'C. E m m o n s 6? on p a g e 458.
This me thod of d e t e r m i n i n g u l t i m a t e indices of
r e f r a c t i o n by r o t a t i n g only p a r t way to the end po i n t s
was also u s e d
in the case of platy
materia ls
such as
the a l i p h a t i c ami des w h i c h could not be oriented,
th at
the p r o p e r
ray v i b r a t e d
in the section.
Recrystallization from Canada b a l s a m .
c r y s t a l s were not
so
Many of the
su ita ble as suc h for op tic al
study.
S3
By r e c r y s t a l l i z a t i o n fr om thin C a n a d a b a l s a m
o b t a i n e d f r o m E.P.
Dolbey & Company,
c o n t a i n i n g xy lene)
the g r o w t h of many
suppres sed m a k i n g it much simpler
system of
c r y s t a l s is also
The m a t e r i a l
microscope
balsam.
Pa.,
faces were
The gr o w t h of
facilitated
in this medium.
to be r e c r y s t a l l i z e d was placed on a
slide covered
w i t h a dro p of
the Canada
A large c o v e r glass was t h e n pl a c e d on the
m ate rial.
The mount
was p l a c e d
h e a t e d o ven kep t at 50-60° C.
in an electrically
for about 12 hours a fte r
w h i c h the p r e p a r a t i o n was a l l o w e d
g r ad u a l l y
that
Philadelphia,
to det ect the crystal
the p a r t i c u l a r substance.
well f o r m e d
(a p r o d u c t
lowering
to cool
the te mpe rat ure .
the C a n a d a b a l s a m - x y l e n e
slowly by
Care was taken
s o l u t i o n was saturated
w i t h the s u b s t a n c e u n d e r c o n s i d e r a t i o n b efo re p l a c i n g
in
the oven.
A f t e r rem ova l from the oven,
r o ll ed
into any d e s i r e d p o s i t i o n
the crystals were
by slight p res s u r e o n
the c o v e r glass.
Apparatus
Microscope.
A S pen c e r No. 35 p e t r o g r a p h i c m i c r o ­
scope was. u s e d in all of
i n v o l v i n g the uni versal
the work e xce p t i n g that
stage.
T he instrument was
fi t t e d w i t h an A m i c i - B e r t r a n d lens,
prisms
were
of
the Ahr ens
type.
and the nicol
A Spencer Sx o c u l a r
84
was u s e d
(oil
w i t h the
immersion)
numerical
an
junction
aperature
A
wide
1.40.
with
the
The
usual
1 . 8 mm.
immersion
was used
had
along
a
with
having a numerical
condenser used
objectives
had
ocular
micrometer
was used
stage.
universal
A Bausch
stage
in c o n ­
a numerical
three pairs
the
of
work.
for
measuring
Optical
1.649,
Co.72.
in
t he
by
objective
was p r o v i d e d
the f o l l o w i n g
with
indices
and 1.516.
This
Websky
32 mm.
instrument
Model
slit
was
II,
w as
made
used
a
by
for
single
the
the
w o r k w i t h the hollow prism.
Monochromatic
furnished
with
goniometer,
The
.
a
instrument
1.559,
goniometer.
reflecting
Fuess
The
modified
fitted on a Bausch
microscope.
hemispheres
refraction:
and L o m b
was used,
in
used
signal
and
other
was
R.
an d
condenser
LC p e t r o g r a p h i c
circle
The oil
1.25
and L o m b
of
4 mm.,
distances.
Universal
Federow
8 mm.,
1 .0.
removable
melatope
of
angle
of
of
mm.,
objectives.
aperature
aplanatic
aperature
16
an
mercury
vapor
Corning
filters.
light.
85
watt
lamp,
Type
The
Monochromatic
high
intensity
H - 3,
green
light
was
Westinghouse
along with suitable
line
( X
- 5461%)
7 2 D i e O p t i s c h e n I n s t r u m e n t e d e r F i r m a R.
C. L e i s s , L e i p z i g , 1 8 9 9 , Pg. 1 1 9
was
Fuess,
iso­
85
lated by
and
the use
512 w h i c h
sodium line
of C o r n i n g
ga ve
( A
=
a transmission
sodium vapor
liminary
exami nation was
lamp
of
lamp.
for
X
=
the
Th e l i q u i d
from
5461$
Th e l i q u i d s
constant
measuring
=
were
up
The
made
1.668
were
on
index
measured
The
value 0.006
Company'74 was
slides
cement.
The
^^Glass Color Filters,
Ne w Y o r k
is b a s e d u p o n
The hollow p r i s m
of b r a s s
were
M.J. , Am.
to w h i c h s u i t a b l e
c e m e n t e d by
slides
used for
Corning Glass
Mineral.
a
m ethod of
.18,
325
means
th e
Works,
'74T h e E m m o n s D o u b l e V a r i a t i o n A p p a r a t u s ,
L o m b , R o c h e s t e r , N.Y., Pg. 4
"75B u e r g e r ,
added
m e a n s of
This
of l i q u i d s
61°
made
with
the Abbe'refractometer.
of
was
the v a l u e s
determinations.
w e r e c a l i b r a t e d by
refractive
"Duco"
Only
h o l l o w prism"75.
microscope
calibrated
the final
wit h an angle
Dupont
were
used
minimum deviation.
of
type.
25°.
about
The
f o r the p r e ­
5893$ at
for
1
a ribbon filament
liquids
of
of
.
430,
from a General
by
the p r i n c i p l e
sections
4
refractorneter.
1.668
temperature
th e
1
351,
light
the B a u s c h and L o m b
readings
above
White
spotlight
to
Lomb Abbe
as o b t a i n e d
all
line
indices
a B a u s c h and
to
X
5461$ and
the g r e e n
of
supplied
Immersion liqu i d s .
fo r
Nos.
5 8 9 3 a ) w as o b t a i n e d
Electric
incandescent
filters
sides
Corning,
Bausch &
(1933)
86
of
the p r i s m
by t he
brass
were
method
carefully
s u g g e s t e d by L a r s e n
p r i s m w as
by w h i c h it w a s
f i t t e d on
fastened
to
platform.
temperature
by a w a t e r b a t h ,
water being
measured
the p r i s m .
It was
used
as
following
shown
and B e r m a n
the
goniometer
T h e p r i s m w as
the
53
.
sides
Th e
kept
in p l a c e
at
of
constant
t e m p e r a t u r e of
just b e f o r e
kept
for p a r a l l e l
the b o t t o m w i t h a steel p i n
the c r y s t a l
The
examined
the
e n t e r i n g and .on l e a v i n g
w i t h i n *£ 1°.
s e r i e s of
immersion liquids
wa s
in T a b l e XXVI.
TABLE XXVI
> =
5 4 6 1 % at
250
Range
1.419
1.450
1.500
1.646
1.756
Constituents
-
1.450
1.500
1.646
1.756
1.793
n-nonane - kerosene
k e r o s e n e - n- b u t y l p h t h a l a t e
n - b u t y l p h t h a l a t e - h a l l o w a x oil
h a l l o w a x oil - m e t h y l e n e iodide
m e t h y l e n e iodide-*- s u l p h u r
In m a k i n g u p
the
n -
v 2 n2
V 1 nl
V1
volumes
of
+-
intermediate
waS u s e d
li qu i d s ,
where
the f o r m u l a
vi
and
Vo a re
the
v2
liquids
whose
indices
are
n-j_ an d
n^,
respect­
^
ively7 6 .
Table XXVII
index liquids.
7 6 Johannsen,
2n d Ed.,
gives
the
Th e s o l v e n t
A.,
Pg.
c a l i b r a t i o n of
a c t i o n was
the i n d i v i d u a l
very
s lig ht
except
M a n u a l of F e t r o g r a p h i c Me th o d s ,
255, M c G r a w Hill, N e w Y ork , 1 9 1 8
•;
in the
error
This
u p of
cas e
might
one
a
of
2-cyano
1,3-dimethyl
have occurred
compound,
s e r i e s of
due
however,
aqueous
benzene
to t h e
did
not
87
where
solvent
warrant
some
a cti on.
the
making
li qu i d s .
TABLE XXVII
C a l i b r a t i o n of
Immersion Liquids
No .
Wa ve L e n g t h
5893a
5461A
No .
Wave L e n g t h
5893A
5461A
200
201
202
100
101
102
103
1
2
3
4
5
6
7
8
9
10
11
1.410
1.418
1.428
1. 441
1.455
1.465
1.476
1. 490
1.508
1.518
1.527
1. 537
1.546
1.556
1.566
1.576
1.586
1.595
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
1.609
1.615
1.619
1. 634
1.642
1.652
1.662
1. 672
1. 682
1.694
1.707
1.716
1.725
1.734
1 .735
1.742
1.761
1.779
were
1.419
1.428
1.438
1.450
1 .464
1. 47 5
1.485
1.500
1.517
1.528
1.538
1.547
1.557
1 .567
1 .577
1.587
1.597
1. 607
Melting point
apparatus.
given
I of
in P a r t
II,
in P a r t
thereby,
p e n d e n t p o r t i o n of
The
capillary
this
small
electric
tube,
rotary
Although melting points
study,
m a k i n g P a r t II
melting point
usual
this
1 .621
1.626
1. 631
1. 646
1.65 3
1.663
1.674
1. 684
1. 694
1.706
1.719
1.728
1 .737
1 .747
1.748
1.756
1.776
1.793
they
an
are
repeated
e nti r e l y
inde­
work.
apparatus
c o n s i s t e d of
sulphuric acid ba t h
stirre r.
A 360°
the
type,
with a
t h e r m o m e t e r was
88
calibrated
against Anschutz,
B u r e a u of St and a r d s '
thermometers.
Optical Data
Aromatic
compounds.
were e n c o u n t e r e d
made
to d e t e r m i n e
XX V I I I
are
gi ven
birefringence,
op tic al
the r e f r a c t i v e
orientation,
is g i v e n by
three
res ear ch,
their o p t i c a l
sign,
aromatic amides
the
in this
A l t h o u g h m e t a s t a b l e f orm s
crystal
indices
The
system,
was
In T a b l e
(n^
, n^
an gle
(2V),
and h a b i t for
The a c c u r a c y
the a g r e e m e n t of
w i t h an a c c u r a c y
constants.
acute optic axial
st udi ed.
met h o d s .
no a tt e m p t
of
the
, n
the
2V va l u e s
the v a l u e s o b t a i n e d by
i n d i c e s of
of ±. 0 . 0 0 3 e xce pt
refraction
are gi ven
w her e indicated.
TAELE XXVIII
Aromatic Amides
A = 5461A
Benzamide
n<x
n^
n#
Biref.
Sign
2V
Opt. Ori ent .
Crystal System
Habit-
1.541
1.666
1.830
0.289
Pos.
6 7 0 a b ,88oc
P.O.S. II to (010)
Mono clinic
Prismatic plates
from HgO
o-Ethyl
B enz amide
1.547
1.592
1.693
0.146
Pos.
7 1 o a C ,73ob
P.O.S. // to (010)
Mono clinic
R e c t a n g u l a r cryst als
f r o m Hg O elong. to jQ
89
TABLE XXVIII
Hoc
n3
n r
Biref .
Sign
2V
Opt. Orient.
Cr y s t a l S y s t e m
Habit
(continued)
p-Ethyl. B e n z a m i d e
o-Toluamide
1 .505
1.638
1.726
1. 470
1.715
1.761
0.291
Neg.
4 4 o a ,42oC
0.221
Neg.
7 2 O a b >7 3 0
C
P.O.S. // to (0 1 0 )
Mo no c l i n i c •
T a b u l a r f r o m Hg O
elong. to
m-Toluamide
1. 4 6 8
1.737
nr
1.752
Bi ref .
0.284
Neg.
Sign
23° c ,20° a
2V '
Opt. Orient.
P.O.S. // to (0 1
Crystal System Monoclinic
P r i s m s f r o m HgO
Habit
p-Propyl
Tricli ni c?
T a b l e t s f r o m HgO
p-Toluamide
0
)
1.510
1.708
1.734
0. 224
Neg.
35 o a ,3 8 obt36°c
b m Z = BXq
Monoclinic
Sq uar e pl a t e s
f r o m HgO
Benzamide
2- C y a n o 1,3Di m e t h y l Be nzene
1.526
1. 6 7 4
1.689
nr
Bi ref .
0.163
Si gn
Neg.
3 3 0 ac f3 g o b
2V
Op t . Ori en t .
b = Y ,X A c= c a . 40°
Crystal System Monoclinic
Ha b i t
R e c t a n g u l a r cryst.
f r o m HgO; p r i s m s
from xylene-Canada
balsam
1.454
1.737
1 .7.48
0. 294
Neg.
gooac
a = X , b = Y ,c=Z
Orthorhombic?
Long rectangular
crystals from
Hg O
n«
90
TABLE XXVIII
(continued)
1 , 3 - Dimethyl
Benzamide-2
p-n-Butyl
Benzamide
1.565
1.547
1.591
1.577
nf
1. 673
1.700
Biref .
0.108
0.153
Sign
Po S .
Po s .
5l o a b c
2V
5 5 o a ,56obc
Opt. Orient.
P.O.S. / to (010) P.O.S. // to (010)
c A X- c a . 8°
c/]X= 40°
Cr ys t a l S y s t e m Mo no cli ni c
Mo noclini c
Habit
L o n g r e c t a n g u l a r P r i s m a t i c needles
p l a t e s fro m HgO
f r o m HgO
n*c
p-Isobutyl
Benzamide
p-sec. Butyl
Benzami de
1. 464
1.49 ± .01
1.605
1.596
1 .724
1.72 ± .01
nr
Bi ref .
0 .260
0. 23
Sign
Neg.
Neg.
7 9 “ a b , 7 8 oc
2V
8E?a ,86° c
Opt. Orient.
P.O.S. 1/ to (010)
C r y s t a l S y s t e m Mo n o c 1 i n i c
Mo noc lin ic
Habi t
M i c a - l i k e p l a t e s Needles and long
f r o m 50^ a l e .;
r e c t a ngu lar plates
Prisms from
fr om H P0 elongated
to p
xylene-Canaaa
balsam; r e c ­
t a ng u l a r plates
f r o m HgO
“ indices
Melatooes
“U n i v e r s a l S tase
t
Benzamide.
Benzamide
L i e b i g 177 as p l a t e s
needles
benzene,
and
was p rep a r e d
needles.
were o b t a i n e d f r o m hot
x ylene,
and tol uen e by
7 7 Wo h l e r a n d L i e b i g ,
by Wohler and
The tri clinic
metastable
solutions of water,
rapid cooling.
J. , A n n . C h e m . P h a r m .
The
j3, 2 68
(1832)
91
stable
monoclinic
plates
zation
and
cooling.
form
is
slower
transformed
fication.
A.H.R.
crystallization
of
of
has
been worked
clinic
many
The
vibration
of
The
triclinic
the
stable
out
v,
and
According
as
are
evident
axes
is
From
the
as
it.
at
R.
Ann.
1 6 6 , 184
8 ^-Mohr, E. a n d G o l d s c h m i d t ,
6 7 8 (1907)
ra te
128 ° C . ’*’9 .
and
are
et h e r
axes.
the
parallel
The
main
to
(110),
dispersion
8 6 , 177
G . , Ber.
mono­
solution
the optic
O n e of
form
Gol d-
2 H - 1 0 2 ° 10»
79Schiff,
Tassinari,
r a t e of
a melting
Mohr
an
by
modi­
the
G r o t h 8 ^ the b i s e c t r i x f o r m s
an d
metastable
monoclinic
(010).
(red);
the
crystals
A . H . R . , Z .p h y s i k .Chem.
C.,
melts
by
7 8 Muller,
aoKlein,
out
well
is a p p r o x i m a t e l y
to
of
f o r m h as
the
3 8 ’.
crystalli­
monoclinic
stable
90°
1 0 0 ° 15'
to
all
form
the
to K l e i n
the o p t i c
2H =
forms
by K l e i n 80 and
crystals
directions
of
the other p e r p e n d i c u l a r
<
long
stable
two
According
twinned
time
the
p r i s m a t i c , ft =
plane
and
the
crystallography
s c h m i d t 8 ^.
r
for
115° while
The
into
In
by
Muller^*8 has w o r k e d
transformation.
point
resulted
10,
is
(blue).
an a n g l e
(1914)
17 85
(1877)
(1873)
V. , Z . K r y s t .Mi neral.
8 2 G r o t h , P ., C h e m i s c h e K r y s t a l l o g r a p h i e , IV,
W. E n g e l m a n n , L e i p z i g , 1917
523,
42,
92
of
40°
with the
through
(lOO).
elongated
to
c axis.
An optic
From the
melt
the
b or
CL01) , (102),
and
parallel
(100)
to
c axes
it f o r m s
(100)
(OOl) w h i c h due
have
a x i s is a p p a r e n t
to
t h e f o r m of
thin plates
w i t h t he
edges
(110),
twin form a t i o n
s imp le
rhombic
crystals.
i
Figure 2
B e n z a m i d e (HgO)
240x
The
sample u s e d
f r o m w a t e r by
solvent
ment
M
o
h
r
for
slow
8 3
fo u n d
83Mohr,
cool i n g and
several
contained
very
that
for o p t i c a l
days.
The
little
of
the
was
left
crystals
the
triclinic
E . , J.prakt.Chem.
st u d y
70,
was' r e c r y s t a l l i z e d
to d i g e s t
after
metastable
this
in the
treat­
form.
form w h i c h was o b t a i n e d
310
(1904)
93
from a
solution in a vacuum desicator
form
transformed
room
temperature.
The
two
f o r m s of
t i n g u i s h e d by
a 2V of
2V of
44°,
their
simple
to
the
centered
measured
page
by
82.
n
but
modification
immediately
triclinic
monoclinic
at
dis-
form had
form had
m e a n s of
indices
2V v a l u e
refraction
was
stage
as
88°.
a
of
the o t h e r
interference
w as
metastable
from
as o u t l i n e d
was 1.830.
manner.
the t h r e e
indices
A Canada balsam
than
the
g r a i n s a 2V
was p r a c t i c a l l y
str aig ht
val ues .
and
optically positive.
melatope distances.
stage
in the usual
87°.
(0.289)
colors
form other
and
the i n d e x l i q u i d s
so o b t a i n e d
r o l l i n g of
isogyre
Th e b i r e f r i n g e n c e
crystal
index
n^
The value obtained from several
value
t he
of
showed
w h i c h made it
to o b t a i n
the u n i v e r s a l
readings was
T he
figures
difficult
calculated
ga ve w i t h s u i t a b l e
which confirmed
axis
were f o u n d
mo unt
87°.
2) w h i c h p r e d o m i n a t e d
the l i m i t
Th e a v e r a g e
remaining
universal
by
The
stable
optic
being above
The
of
sta ble
benzamide were
(see F i g u r e
measure
ny .
The
the
in the dry
87°.
beautifully
on
into
2V val ues .
whereas
The plates
was
slowly
even
was very
h i g h as
noted
i n t e r f e r e n c e bands.
No w o r k was done on
the d e t e r m i n a t i o n of
The
the
2V f r o m
94
o-Toluamide.
any of
the
No w o r k h a d
remaining aromatic
recrystallization
found
to
literature
The
substance
values
most
good
was
li kel y
44°.
c l e a v a g e a n d off
repeated
was
with various
extinction.
distances
F r o m wa t e r ,
After
f r o m 1 3 8 - 1 4 7 ° 8 »8 »9 »8 6 >® 4 .
triclinic.
melatope
this or on
melting point
as c o m p a r e d
sh o w e d o b l i q u e
o b t a i n e d f r o m the
objective
the
which ranged
crystals
w as
am ides.
f r o m wat er,
be 1 4 1 . 0 - 1 4 1 . 4 °
been done on
The
using
The
2V v a l u e
the
1.8 mm.
tablets exhibiting
c e n t e r e d B x 0 f i g u r e s were
obtained.
4
Figure 3
o - T o l u a m i d e (HgO)
2 4 0x
m-Toluamide.
8 4 Weith,
After
V7. , Ber.
sev e r a l
6,
420
recrystallizations
(1873)
from
95
wa t e r ,
the
melting point
compared with
and
97°
as
the v a l u e
given
F r o m water,
prisms
of
43°.
9 3-9 4°
the a m i d e
4)
crystals
to
be
93.2-94.0°
o b t a i n e d by
and
as
Scherpenzeel®^
Wolffenstein6 .
crystallized
out
as
monoclinic
w h i c h showed an extinction angle
37° , the m a x i m u m
The
found
by K a t t w i n k e l
(see F i g u r e
about
was
were
extinction
angle
elongated parallel
b e i n g about
to the
c axis.
Figure 4
m- To 1 ua mi d e (HgO )
240x
The optic
Best
results
fusing
and
axis
for
carefully
allowing
figure obtained
the o p t i c a l
study
a l i t t l e of t h e
to cool
without
8 ^ S c h e r p e n z e e l , M.L.
van.,
w as
not c ent ere d.
was o b t a i n e d by
a m i d e on a micro
a cover
glass.
Rec.trav.chim.
flame
The
20,
162
(1901)
96
material
was
t h e n c r u s h e d and
mixed
with
some p o w d e r e d
glass.
2V v a l u e s o b t a i n e d
using
the 4 mm.
three
indices
of
f r o m the
objective
of
distances
gave a n a v e r a g e of
refraction gave
20°.
a calculated
The
2V value
23° .
p-Toluamide.
water
After
the m e l t i n g p o i n t
Values
i n the
cording
tained
wa s f o u n d
literature
as
monoclinic
vary
from
recrystallization
to be
microscope
sli de
showing
about
159.1-160.0°.
1 5 1 - 1 5 9 ° 9 »8 6 .
substance
5 mm.
Ac­
is o b ­
in l e n g t h f r o m
monoclinic
crystals
due
to
good
uniaxial
square
cleava ge.
Careful
tub e
g a v e large
elongated parallel
to Y
(see F i g u r e
center
interference
was e a s i l y
f igu re.
The
good acute b i s e c t r i x figures,
s lig ht
o n the
in a test
g ave a b i a x i a l
b e i n g off
crystallized
rectangular
from water
crystals
The
from water
(see F i g u r e 5) as m o n o c l i n i c
very
recrystallization
centered
needles
from
alcohol.
Th e p - t o l u a m i d e
plates
repeated
to Mclvlaster and L a n g r e c k 9 the
absolute
was
melatope
figure
which
m i s t a k e n f o r an un­
crushed material yielded
ho we v e r .
The d i s p e r s i o n
(v "7 r).
8 6 F i s c h l i , H. , Ber. 12, 615 (1679); G-attermann, L.
an d Schrnidt, G-. , Ann. 24-4, 51 (1838); Hol le m a n ,
A.L. , R e c . trav. chi m. .6, 79 (
); Re mse n, I.
a n d Rei d, E.E. , Am.Chern.J. 21, 290 (1899)
6).
97
*
*
•-■
*
.**-V^„ w>
I
__
F i gure 5
p - T o l u a m i d e (H20)
240x
Figure 6
p-Toluamide
25 x
(HgO)
98
The
2V of
three
ind ice s of
36° as c o m p a r e d
distances
and
o~Ethyl
to
r e f r a c t i o n gave
35° o b t a i n e d f r o m m e l a t o p e
38° o b t a i n e d
benzamide.
152.5-153.5°.
f r o m the u n i v e r s a l
This am i d e
crystallized from water
a calculated
was
stage.
likewise
re­
g i v i n g a f i n a l m e l t i n g p o i n t of
G i e b e 37 r e p o r t e d a m e l t i n g p o i n t of
151-153°.
The c r y s t a l s
extinction
and
xylene-Canada
were
b o t h in cli ned
elongated parallel
balsam,
and p a r a l l e l
to^
.
From
m o n o c l i n i c p r i s m s we re o b t a i n e d
A m e t a s t a b l e f o r m was o b t a i n e d f r o m the
(Figure 7).
me lt of
showed
this m a t e r i a l
the
stable
The
section
The
metastable
w h i c h was
m o d i f i c a t i o n on
became opaque
form gave
r apidly
immersion
and
c o n v e r t e d into
in the i n d e x oils.
u n u s a b l e for o p t i c a l
a beautifully
study.
c e n t e r e d acute
b i s e c t r i x figure.
F r o m the
value
three
indices of
fo r 2 V was 71°.
as o b t a i n e d
Th is c o m p a r e d
(1.8 mm.)
universal
stage.
objective
The d i s p e r s i o n was
character positive.
(0.146).
slight
the c a l c u l a t e d
favorably
from melatope distances using
immersion
low
refraction
w i t h 71°
the oil
and 73° o b t a i n e d by the
(v T' r),
and the o p t i c a l
The b i r e f r i n g e n c e was c o m p a r a t i v e l y
F i gur e 7
o - E t h y l Benzarnide
( x y l e n e - C a n a d a b alsam)
lOO x
p-Ethyl
benzarnide.
This amide was
three
times f r o m an a l c o h o l - w a t e r
final
m e l t i n g p o i n t of
solution giving a
163.7-164.8°.
w i t h the l i t e r a t u r e va lue
r e c r y sta lli zed
The
d isc rep anc y
has already b e e n d i s c u s s e d
(page 25).
The
plates
c r y s t a l s from w a t e r o c c u r r e d as monoclinic
(Figure 8) e l o n g a t e d p ara l l e l
to
exhibiting
g o o d B x 0 f i g u r e s and p a r a l l e l
extinction.
readily
to give the B x a figure.
Op t i c
turned over,
however,
axi s f i g u r e s were also
They were
readily obtained.
100
Yi
Y
/=K
\=^
Figure 8
p - E t h y l Benzarnide
The
t h r e e i n d i c e s of
2V of
73°.
using
the 1 . 8 mm.
w a s 7 2°.
r e f r a c t i o n gave a c a l c u l a t e d
The 2V v a l u e o b t a i n e d
objective
T h e c u r v a t u r e of
from melatope
and the u n i v e r s a l
the
is ogy r e s
distances
stage
i n d i c a t e d a 2V
of a b o u t 70°.
Th e d i s p e r s i o n wa s
character
greater
n ega tiv e.
sl igh t
(r y v)
Th e b i r e f r i n g e n c e
t h a n that of o - e t h y l
2V v a l u e s ,
the o p t i c a l
(0.221)
was
benzarnide had
the
benzarnide.
Although both o-and p-ethyl
same
and the optical
character permitted
differentiation.
p-Propyl
f r o m water
Th e
t hat o nly
benzarnide.
Repeated
gave a m e l t i n g p o i n t of
crystal plates obtained
n a
was
everywhere
recrystallizations
127.9- 128 .9° .
f r o m w ate r wer e
ori ented.
such
The c l e a v a g e was
101
very p r o m i n e n t ,
axes.
parallel
From Canada
(Figure
9)
to
balsam,
the p l a n e of the optic
beautiful
elongated parallel
The t h r e e
2V va l u e of
value
(1.8 mm.
value
of
to the c axis were obtained.
i n d i c e s of r e f r a c t i o n
33°.
T his a g r e e d
objective)
of
monoclinic prisms
gave a c a l c u l a t e d
f a v o r a b l y w i t h the m ela top e
33° a n d the u n i v e r s a l
stage
32°.
Figure 9
p-Fropyl Eenzamide
( x y l e n e - C a n a d a balsam)
80x
Th e d i s p e r s i o n of the o p t i c axes was not
Th e c r y s t a l s
were b i a x i a l
p-n-Butyl
from water
benzarnide.
negative.
Three
recrystallizations
gave a m e l t i n g p o i n t of
xylene-Canada
balsam,
noticeable.
1 21. 1 - 1 2 1 . 8 ° .
monoclinic prisms
From
(Figure 10)
102
elongated parallel
water,
the
t he
optic
to
prominent
axes
the
c axis
face
w i t h an
were
fo rmed.
was p a r a l l e l
extinction
to
angle
From
the p l a n e of
of
40°.
F i g u r e 10
p - n - B u t y l Benzarnide
(xylene-Canada balsam)
50x
The
three
indices
compared
of
2 V of
56°
as
ive)
for
the u n i v e r s a l
refraction gave
w i t h 5 6 ° and
stage
and
55°
a calculated
C l.8 mm.
melatope
object­
distances,
r espectively.
p-Isobutyl
from petroleum
benzarnide.
ether,
From petroleum
needles;
and
the
After
several
substance
melted
e t h e r - b e n z e n e , it
f r o m a 50?£ a l c o h o l
r ecr ys t a l l i z a t i o n s '
at
came out
solution,
151.0-151.4°.
as
as f l a t
thin
mi ca-
103
like plates.
F r o m water,
parallel
to
angle
about
from
of
the
clinic
axis
the p l a n e of
two
37°
and
ends w e r e
prisms
(Figure
small
plates representing
the o p t i c
ax es
with v-shaped
formed.
11)
w i t h an
cavities
sections
extinction
running
in
Fro m Canada balsam mono­
elongated parallel
to
the c
were obtained.
rtfHMSMffcM
F i g u r e 11
p-Isobutyl Eenzamide
(xylene-Canada balsam)
1 60x
F r o m th e
value
of
melatope
stage,
7 8 ° as
(page
of
compared
distances
refraction
w a s o b t a i n e d a 2V
to
78° obtained from
(1.8 mm.
7 9 ° and
objective)
and
the u n i v e r s a l
respectively.
p-Sec.
points
indices
butyl
from water
57),
the
benzarnide.
I n a s m u c h as
and p e t r o l e u m
material
ether
recrystallized
were
the
melting
different
from water
four
104
times
was
studied optically,
being
sma l l e r .
monoclinic
needles
interference
optic
axis
n^
wa s
The
its
crystals
melting point
were
in the f o r m of
elongated parallel
figure usually
range
to ft .
o b t a i n e d was
small
The
that of
the
section.
was determined
experienced
with
value
calculated
with
85° o b t a i n e d
easily
the o t h e r
from
the
from
e n o u g h but
two i ndi ces .
indices
the
some d i f f i c u l t y
was
melatope
86°
T he
2V
as c o m p a r e d
distances
(1 . 8
mm.
o b j e c t i v e ).
2-Gyano
by
sublimation
ether,
the
w i t h the
literature
prismatic
solvent
a
ai r
and
obtained
they
melted
characteristic
as l a r g e
(see F i g u r e
f r o m the
became
rapidly
heavy
2-Cyano
After purification
at 90-91°,
values0 0 » .
c ame o u t
crystals
benzene.
recrystallization from petroleum
substance
the c r y s t a l s
to
1,5-dimethyl
corresponding
Before
sublimation
mahogany
colored
12)
the b e n z e n e
from
diazotization.
eroded.
The
n i t r i l e odor.
i
I
I
F i g u r e 12
1,3-Dimethyl Benzene
On e x p o s u r e
crystals
had
105
So me
difficulty was
t e r m i n a t i o n due
s o m e of
higher
to
the
encountered
s o l u b i l i t y of
the i n d e x oils.
than that of
p e r s i o n was
crystals
any
substance
As
biaxial
negative;
this
an d no
classified
su b s t a n c e ,
20
the
melatope
c were o b t a i n e d .
melted
138.5-1390
So me
8 °.
formed monoclinic
were
could
be
Fo r this r e a s o n it
the
in dices of
refraction
After recrystallization
at 137-138°
needle-lilce p l a t e s
needles
gi v i n g p e r ­
to
gave a m a x i m u m ext inc t i o n
crystals modified
balsam,
well
with pinacoids
and
(see F i g u r e 13).
Th e d i s p e r s i o n was
character positive.
and
elongated parallel
From xylene-Canada
formed
as compared
o b t a i n e d by B e r g e r
c e n t e r e d B x a f i g u r e s and
pyramids
was.
the 4 mm. o b j e c t i v e .
benzarai d e - 2 .
F r o m water,
a n g l e of a b o u t
The
i d e n t i c a l w i t h the value o b t a i n e d f r o m
the a m i d e
w i t h the v a l u e of
fectly
from
distances u s ing
1,5-Dimethyl
Olivier^.
the
"orthorhombic?” .
° w h i c h was
f r o m water,
was
The d i s ­
however,
e x t i n c t i o n an gle
The 2V v alu e o b t a i n e d
was
(0.294)
pseudo-hexagonal.
n o t i c e d a f t e r a t h o r o u g h search.
was
studied.
in
n o t e d f r o m F i g u r e 12,
m i g h t be m o n o c l i n i c ,
c h a r a c t e r of
the. ni t r i l e
The b i r e f r i n g e n c e
negligible.
optical
in the i n d e x de­
The
small
(v > r) a nd the o p t i c a l
b i r e f r i n g e n c e was r e l a t i v e l y
smal1 .
The
2V v a l u e
calculated
f r o m the indices,
namely
106
61°,
corresponded
ex a c t l y
b o t h f r o m the u n i v e r s a l
(1 . 8
mm.
w i t h the
stage
2V values o b t a i n e d
and m ela t o p e d i s t a n c e s
objective).
\
~
~
.
“
Figure 13
1 , 3 - D i m e t h y l Benzarnide-2
( x y l e n e - C a n a d a b al s a m )
50x
Aliphatic
G-eneral.
its h o m o l o g s
According
do es
not
The
has
crystallography
to
(IOO)),
complete
cl eavage.
a C K 3 - group
(the c r y s t a l s b eing platy,
but only
The
thoroughly.
the a d d i t i o n of
the a axis
parallel
8 7 Ka hrs ,
of a c e t a m i d e and
been w o r k e d out q u i t e
to E. K a h r s 8 7
effect
Am ide s
the b-c p l a n e w h i c h shows
addition accordingly
E. , Z . K r y s t .M i n e r a l . 40,
475
takes
(1905)
107
place
in a d e f i n i t e p l a n e w h i c h in the c r y s t a l l i n e
state
is the p l a n e
the
molecule.
parallel
of
to
The
(1
the o p t i c
w i t h the d e n s e s t a r r a n g e m e n t of
00
c r y s t a l s have
complete
) w h i c h is p e r p e n d i c u l a r
cleavage
to the p l a n e
axes.
In T a b l e X X I X is g i v e n the d a t a for the a l i p h a t i c
amides.
The i n d i c e s of
accuracy
of ±
0.003
of
the
of
their a c c u r a c y .
r e f r a c t i o n are
except where
2V v a l u e s by
given w i t h a n
noted.
the d i f f e r e n t
me tho ds
The a g r e e m e n t
is an in dic ati
.
TABLE XXIX
Aliphatic Amides
A = 5461A
Hot
n /3
nr
Bi r e f .
Si gn
2V
Opt. Orient.
Crystal System
Ha b i t
Ac eta mi de
Propionamide
1.461
1. 4 4 5 d (1. 44 ± . 0 1 e )
1.461
1.530
0.085
Pos.
5 2 ° a ,53°b
a=X,b=Y,c=Z
Orthorhombic '
Mica-like plates
(nf
)
C.
1.507 (n^ )
0.046
Neg.
0°
c = X
Hexagonal
Short prismatic
needles
Butyramide
n-Valeramide
1 . 4 6 5 d (1 . 4 6 4 ± .0 0 5 e )
1.482
1
.530
nr
0
.
065
Biref .
Po s .
Si gn
61o a ,63° b
2V '
a-X,
b-Y , c - Z
Opt. Ori e n t .
C r y s t a l S y s t e m Ortho r h o m b i c
Ha bit
Mica-like plates
n<*
n*P
1 . 4 6 6 d ( 1 . 4 7 ± ,01e )
1. 488
1.5 30
0.064
Pos.
75oa, 74°b
P.O.S. II to (010)
Mono clinic
Mica-like plates
108
TABLE XXIX (continued)
Isovaleramide
1.458d (1.45 ± .01e )
1 . 466
1. 498
0 . 040
Po s.
5 7°b •
P.O. S. Il to (010)
Mo noclinic ?
M i c a - l i k e p lates
nf
Bi r e f .
Sign
2V '
Opt. Orient.
Crystal System
Habit
d Calc. f r o m 2V
eUn i v e r s a l Stage
aMelatopes
^ U n i v e r s a l Sta ge
Acetamide.
Bodewig8 8
c r y s t a l l o g r a p h y of the
Acetamide
shows
negative,
and
these
no
at
cleavage,
trigonal.
colorless
The two
and 1.461
optical ly
K a h r s ,87 wor k confirms
low.
The
n^
.
benzene
of course,
8 9 Hofrnann,
(0.046)
was
was 0°.
A c c o r d i n g to E. K a h r s 8 7 , pr opionis o r t h o r h o m b i c bipyramidal.
it is o b t a i n e d in thin plates
8 8 Bodewig,
me lti ng
r e f r a c t i o n were 1.507 for n ^
The b i r e f r i n g e n c e
2V value,
m e l t i n g at 79°
needles,
It was hygroscopic.
i n d i c e s of
for
r e c r y s t a l l i z e d from 95 ^ alcohol
short th ick p r i s m a t i c
Fropionamide.
a m ide
E.
is isotropic,
results.
8 0 . 6 - 8 1 . 6 ° C . d ^.
very
the
stable m o d i f i c a t i o n of acetamide.
An E a s t m a n p r o d u c t
g a ve
likewise w o r k e d out
elongated par all el
., Z .Kry s t .Mi n e r a l . 5_, 554
A.W. , Ber.
14,
2729
From
(1881)
(1881) m.p.
= 82-83°
109
to
the
(less
c axis
than
parallel
th e
ver y
flexible
They
show
acetamide).
to
optic
w h i c h are
the front p i n a c o i d
axes
is
the
is p e r p e n d i c u l a r
crystals,
namely
The p r o d u c t
(1
00
v ery
T h e p l a n e of
(OlO).
obtained
from
Eastman was found
considered
s u c h for o p t i c a l
The
crystals
figures.
The
amide
crystal
study.
was found
set up o n
to
the
axis
of
of
10 d i v i s i o n s ,
edge
of
stage
by u s i n g B e r e k ' s
too
tating
large
to be
oriented position
rotation
The
smaller
two
determined
method
measured
axis
to
to a s i n g l e
which
(see p a g e
i n d i c e s of
f r o m the
^ M e l d r u m , A.N.
1 6 0 7 (1910)
gave
were platy
a melatope
th e 1 . 8 mm.
hemispheres
suitable
as
giving
A
acute bisectrix parallel
objective
2V v a l u e o b t a i n e d
from one optic
the h i g h e s t
w i t h the
using
The
the
to
to be b i a x i a l p o s i t i v e .
the m i c r o s c o p e
value
wa s
52°.
f a c e of
).
was
Bx0
The obtuse
to t h e p r o m i n e n t
rnelt at 7 7 . 5 - 7 8 . 5 ° ^ ° and
good
hygroscopic
good cleavage
(1O0).
side p i n a c o i d
bisectrix
and
was
f r o m the
53°.
optic
made
for a 2V
universal
The o b t u s e
in the u s u a l
another
distance
way by
angle
ro­
or f r o m an
axis,
even u s i n g
the
a n g l e of
n^
and n^.
75).
refraction,
obtuse bisectrix
figure.
and Turner , W.E.S.,
m . p . = 80°
, were
Due
J.Chem.Soc.
to
97,
110
, the p l a t y
n a t u r e of
the p r o p e r
m e ans
a
of
lower
value
crystals
orientation,
the
universal
index
suitable
the
value
graphs
the
not p e r m i t
v a l u e w as o b t a i n e d by
sta ge by r o t a t i n g f r o m
and
i n t e r p o l a t i n g by
f r o m the
so o b t a i n e d
w h i c h did
w o r k of E.
was 1.44 ±
.01.
n^
to
m e a n s of
Emmons6 7 .
The n ^
The
calculated
f r o m the u n i v e r s a l
2V v a l u e s was 1.449 w h i c h c h e c k e d
n^c
of
1
f o u n d by
.44 ±
means
of b u t y r a m i d e
the
to
(100)
to
axe s is
(0
115°.
plane.
1 0
the
are very
similar
They are flexible
They h a v e
i n a s m u c h as
lM eyer,
ben­
complete
and f l a t t e n e d
cleavage
The o b t u s e b i s e c t r i x
The p l a n e
in
parallel
is p e r p e n ­
of
the optic
s t u d i e d was o b t a i n e d f r o m Eas tma n,
The plates
The platy
measure
From
).
study.
figures.
crystalline form
to p r o p i o n a m i d e ,
at 1 1 3 . 6 - 1 1 4 . S91 and w a s u s e d as
optical
9
g ive s
the f r o n t p i n a c o i d .
The pr o d u c t
melted
n ame ly
as o r t h o r h o m b i c b i p y r a m i d a l .
the f r o n t p i n a c o i d .
dicular
to
E. K a h r s ^ 7
crystals
m e l t i n g at
the
stage,
.01.
Butyramide.
zene
the u n i v e r s a l
the
all
character
2V v a l u e s by
the o b t u s e
s u c h fo r
gave o b t u s e b i s e c t r i x
a g a i n m a d e it d i f f i c u l t
me ans of m e l a t o p e
angle
H. , M o n a t s h .
the
was
27_, 43
too
distances
large.
(1906)
m.p.
Further,
=
115-116°C.
4
Ill
the l o w e s t
universal
i n d e x a g a i n had to be m e a s u r e d u s i n g the
stage.
Th e a v e r a g e
distances,
ac ute
some
angle,
2V v a l u e o b t a i n e d
f r o m the o b t u s e a n d some f r o m the
was
the u n i v e r s a l
61°.
The a v e r a g e v alu e o b t a i n e d
st a g e was 63°.
c u l a t e d f r o m the u n i v e r s a l
The o p t i c a l
found
by me ans
of
E.
as 1 1 4 - 1 1 6 ° C..
the
( ft = 92°
lo west ind ex c a l ­
Kahrs87
stage was 1 . 4 6 4 ± . 0 0 5 .
li ste d
F r o m alcohol
f lex ible,
as
the me lti ng
s o l u t i o n he o b t a i n e d
m o n o c l i n i c plates.
S').
The c r y s t a l s
have
good
cleavage,
A bisectrix position
to the
(o btu se)
is l o c a t e d on this f r o n t pinacoid,
slightly
to w a r d
the
front p i n a c o i d .
(101).
The p l a n e of
s u c h it was
not
melted
s u i t a b l e for
c r y s t a l l i z a t i o n f r o m fu sion ,
giving
leaning
the optic axis
s y m m e t r y plane.
The Eastman product
As
He
c r y s t a l l i n e f o r m as m o n o c l i n i c p r i s m a t i c
parallel
is
from
s tage value was 1.465.
the u n i v e r s a l
it as r a t h e r thic'x,
gave
The
c h a r a c t e r was positive.
n-Valeramide.
point
f r o m the m e l a t o p e
at 1 0 0 . 3 - 1 0 1 . 6 ° C.^^.
study;
but a fte r
flat pl a t e s
the o b t u s e b i s e c t r i x f i g u r e s
slightly off
The c r y s t a l s were b i a x i a l posit ive .
9 % o bertson,
P.W. , J . C h e m. Soc .
appeared
The
1 1 5 , 1220
center.
2V value
(1919) m.p.
= 106°
112
obtained from melatope distances
w a s ab out 75°,
(1 . 8
mm. objecti ve)
w hil e the best 2V value f r o m the universal
stage was 74°.
The l o w e s t
i n d e x of r e f r a c t i o n as cal cul a t e d fr om
the 2V value of 74° was
by the u n i v e r s a l
probably
to
(1
00
while
stage was 1.47 ±
I s o v a 1 e r a mi d e~.
flexible plates
1.466,
According
.01.
to E. K a h r s ® ^ , the thin
w h i c h he o bta i n e d f r o m alcohol were
mon ocl ini c.
They have
most
good c lea vag e parallel
).
The c r y s t a l s
w hic h were obtained
c h l o r i d e and c o n c e n t r a t e d a mmonia
tion by s u b l i m a t i o n
Like
figures.
the o t h e r s of this
The
series,
gave values
lowest
1.458,
the BX q
figure was
from the u n i v er sal
method was 57°.
so mew hat
the cry stals were
gave good ob t u s e bis ec t r i x
2V value ob tai n e d
stage by the d ire ct
The
solution after p u r i f i c a ­
It was u n c e r t a i n whether
off center.
from iso-valeryl
melted at 1 2 5 . 4 - 1 2 6 . 4 ° ^ .
b i a x i a l p o s i t i v e p l a t e s and
57° was
the ind ex ob ta i n e d
The Bereic method
greater. -
i n d e x c a l c u l a t e d from the 2V value of
while the value ob tained f rom the universal
stage was 1.45 -jc. .01.
^Aschan,
0
. , Ber.
51 , 2348
(1898)
m.p.
*
1 2 6 -1 2 8 °
113
D I S C U S S I O N OF R E S U L T S
The amides
with
for
the
the
case
studied
are
melting points.
new amides
th e
a nd
listed
in T a b l e -XXX a l o n g
Nitrogen
values
for p - e t h y l
melting point
wa s
a re
given
benzarnide in w h i c h
reported
incorrectly
in the
li t e r a t u r e .
In Figure
amides
noted
plotted
14 are
against
a fluctuation
aliphatic
acid
carbon
lower
atoms
than
carbon
the
atoms
the
2V v a l u e s
carbon
amides.
i n the
homolog
the
compounds
vary
in a r e g u l a r
content.
The
the a r o m a t i c
Here
aliphatic
the
substances
are
chain
containing
it a p p e a r s
the
manner.
iip
-4
Figure
14
the
all
number
has a 2V v a l u e
eve n n u m b e r of
pre c e d e or follow
that
is
of
T he o n e w i t h the o d d
which immediately
From
of
w h i c h is c h a r a c t e r i s t i c
melting points.
para-substituted
of
g i v e n the
it.
even and odds
TABLE XXX
Melting Points of Amides
Amide
Medium
126.6-127.6
141.0-141.4
93.2- 94.2
159.1-160.0
152.5-153.5
163.7-164.8
89 - 90
137.1-138.1
127.9-128.9
121.1-121.8
151.0-151.4
116.7-117.7
126.9-129.9
80.6- 81.6
77.5- 78.5
113.6-114,6
100.3-101.6
125.4-126.4
128 79
141. 0-141. 526
93 - 94 85
158 -159 86
151 -153 37
38
115 -116
31
90 - 91
138. 5-139. q 3 3
Water
Obt.
1theory
9.62
9.49
8.58
7.89
Pet. ether-Eenzene 7.80
7.99
Water
Pet. ether
89
- 83
95^ ale.
80 90
-116 91
Fusion
106 92
-128 93
Subl.
8.59
7.91
7.91
7.91
ti
ii
ii
ti
t-.
<0
.
o
<r.
Acetamide
propionamide
Butyramide
n-Valeramide
Isovaleramide
Literature °C.
1— I
Benzarnide
o-Toluamide
m-Toluamide
p-Toluamide
o-Ethyl benzarnide
p-Ethyl benzarnide
(2-Cyano 1,3-dimethyl benzene)
1,3-Dimethyl benzarnide-2
p-Propyl benzarnide
p-Butyl benzarnide
p-Isobutyl benzarnide
p-sec. Butyl benzarnide
Obtained °C.
Subl.
Water
ii
i?
82
115
126
114
115
In each, ca se
(melatopes,
It
is
noticed
crystal
given
i n d i c e s of
t h e first
refraction).
m e m b e r o f this
the
next
three,
and p - p r o p y l benzarnide,
case of p - n but yl
benzarnide,
the
positive.
A l t h o u g h o-
and p-ethyl
the
sam e 2V v alu es,
due
to
they
the d i f f e r e n c e
benzarnide
an d
benzarnide,
In the
is a g a i n
2V v a l u e s are
is p o s i t i v e ;
p-ethyl
negative.
stage,
that
benzarnide,
p-toluamide,
are
three
universal
also
series,
the
benzamides
can be
easily
in o p t i c a l
is p o s i t i v e ,
have p r a c t i c a l l y
distinguished
character.
wh ile p - e t h y l
o-Ethyl
benzarnide
is
negati v e .
When
aromatic
the b i r e f r i n g e n c e of
amides
in F i g u r e
15,
a d d i t i o n of
s m all
in
a step-like
every o t h e r
difference
l e n g t h of
in the
The
the
substance
against
the
spectively
carbon
chain
carbon
change
the
The
a t o m c a u s e s only
carbon
16
content
c h a r a c t e r app eared.
a
W i t h an i n c r e a s e
t h e r e was a d e c r e a s e
w h i c h is what
t o o k o n an a l i p h a t i c
bottom curves
the ca r b o n
birefringence.
chain became
In F i g u r e
against
in the
birefringence
aliphatic
and
was p l o t t e d
the p a r a - s u b s t i t u t e d
w oul d
be expected.
character
as
the
more prominent.
refractive
c ontent.
i n d i c e s are p l o t t e d
It is n o t e d
which represent
gradually,
wh ile
n^
it
an d
that
n^
the top
, re­
is n p w h i c h
116
fluctuates
f r o m one c a r b o n to
tiie next g i v i n g rise
the c h a n g e
in the
In the case of benzarnide
it
2V values.
is in the p o s i t i v e
three
amides
returns
area;
it is in the
to the p o s i t i v e
in the case of the
n e g a t i v e area;
area
Figure
15
next
and f i n a l l y
in the case of p - n
benzarnide.
to
b utyl
117
.1—
?n
U&H3
]?]•
nii
tut
Hit
F i g u r e 16
In F i g u r e
17 are pl ott ed
a l i p h a t i c ami des a gai nst
encircled
stage.
the 2V values of the
the carbon content.
v alu es were o b t a i n e d
from the u n i v e r s a l
The o the r v a l u e s were f rom m ela top e distances.
While acetamide
is u n i a x i a l n ega t i v e and trigonal,
the
r e m a i n d e r are b i a x i a l positive.
and
b u t y r a m i d e are o r t h o r h o m b i c .
clinic.
The
orthorhombic
possible
that
fall
Propionamide
V a l e r a m i d e is mono-
m e t a sta ble f orm of ac eta mid e
cr ystals w h i c h seem.to
c r y s t a l l o g r a p h y of
would
The
the
fit
into
the rest of the series.
2V
values of
gives
the
It is
this m e t a s t a b l e
form
in line w ith the remaind er of the series.
118
jc,
Figure
In F i g u r e
the
aliphatic
tent.
It
is
1 8 are
amides
noted
perimental
error
refraction
change
w o r k of
Kahrs87
S.
17
given
the
plotted
t hat
while
n y
the
against
is
the C H 3 —
group
does
b-c p l a n e
which
shows
states
not
lower
complete
within
indices
This
agrees
that
the
effect
indices
the c a r b o n
constant
two
gradually.
who
refractive
con­
ex­
of
w i t h the
addition
of
the a a x i s b u t o n l y
cleavage.
of
the
119
- 0 -4 -.. _ I
!
Ur-
Figure
According
worked
an d
out
the
alcohols
possibilities
in
space,
zigzag
to
three
for
namely
and
(3)
the
to
there
the f r e e
are
atoms
(2 ) a s p i r a l ,
structure.
alcohols,
(2 ) s eem s
compounds,
saturated
acids
three
the c a r b o n
an alternate
in a l i p h a t i c
have
the a l i p h a t i c
structure,
saturated
who
4 *9 5
fatty
an d
a cid s.
*■
It
the
94
(1 ) a z i g z a g
to
of
d i s p o s i t i o n of
counterpart
corresponds
.
to
no
Shearer9
measurements,
the
structure,
to h a v e
and
dimensions
by x - r a y
(1 ) c o r r e s p o n d s
(3)
Muller
18
appears
aliphatic
M u l 1 e r , A.
(1923)
that
and
and
structures
aromatic
Shearer,
(1)
and
amides,
(3) w o u l d a p p l y
respectively.
G. , J . C h e m . S o c .
123,
----
3156
9 5 S e e D a v e y , V/.p. , S t u d y o f C r y s t a l S t r u c t u r e and
It s A p p l i c a t i o n , M e G r a w H i l l , New Y o r k , 192J4
120
The aromatic para-substituted
odd
number
manner.
of
carbon atoms
Possibly
the a l t e r n a t e
each vary
the b e n z e n e
structure.
a m i d e s w i t h the
e v e n and
in a r e g u l a r
r i n g is t he
cause of
121
SUMMARY
1.
A homologous
series
of a r o m a t i c a c i d
b a s e d o n benzarnide wa s p r e p a r e d .
have
was
not
been reported
reported
2.
amides
based
indices,
system,
as well
in
The
w a s w o r k e d ou t for
w h i c h were
the a r o m a t i c
s e r i e s of a m i d e s
Eastman products.
a p p l i c a b i l i t y of p e t r o g r a p h i c
Some
t e r m s of
another
optical character,
as f o r a h o m o l o g o u s
i n c l u d i n g the u s e of
4.
l i t e r a t u r e and
i n c l u d i n g the p r i n c i p l e
2V v alues,
etc.
on acetamide
3.
these
incorrectly.
T he o p t i c a l d a t a
refractive
crystal
in the
F o u r of
amides
the u n i v e r s a l
attempt was
structure
m ade
to
and chemical
methods
stage was
shown.
e x p l a i n the
d ata
constitution.
ACKNOWLEDGMENT
I want
to thank Dr.
M.L.
W i l l a r d u n d e r whose
d i r e c t i o n this wor k was carried out for her su g g e s t i o n
of the problem,
Mr.
E.F.
guidance,
Williams
and helpful
advice.
for the use of the u n i v e r s a l
as w e l l as
timely aid d u r i n g
its use.
is due Dr.
C.D.
i n s t r u c t i o n on the
J e f f r i e s for
R.J.
P f i s t e r for
w i t h C o r n i n g fil t e r s
light used
f o r his
Du mas
stage
A c k n o w led gme nt
p r i n c i p l e s u n d e r l y i n g the u s e of the u niv ers al
Mr.
Also
stage,
the use of a mercury vapor
for the
source of monochr oma tic
in this inv est iga tio n,
t e c h n i c a l aid in the
d e t e r m i n a t i o n s of
lamp
and Dr.
G.H.
Fleming
synthesis and Micro
some of the compounds.
VITA
C h a r l e s M ar e s h
Bo rn D e c e m b e r 4th,
Attended
grammar
1 9 1 3 in Cleveland,
and h i g h school
in Cleveland.
M a t r i c u l a t e d at W e s t e r n R e s e r v e University,
Ohio,
Sept.
1931;
B.A.,
Ohio.
June 1935.
Cleveland,
Sch o l a r in
C h e m i s t r y at The Gra d u a t e School of W estern Reserve
Un i v e r s i t y ,
1938.
1 935 -19 36.
M.S.
S c h o l a r in Chemistry,
in P hys ica l Chemistry,
1936-1939,
at The
P e n n s y l v a n i a S t a t e College,
State College,
vania.
The P e n n s y l v a n i a State
College,
Ph.D.
Feb.
in Chemistry,
1940.
Pennsyl­
BIBLIOGRAPHY
1.
R a d z i s z e w s k i , Br. , Ber.
2.
Deinert,
J. , J . p r a k t .Chem. ,
3.
F r i e d l a n d e r , P.
(1895)
4.
Rupe,
5.
B o g s r t , M.T. and
1 0 3 4 (1902)
6
.
7.
8
.
9.
18_, 355
H.
and
(1885)
(2)
Weisberg,
B2,
J. , Ber.
a n d M a j e w s k i , K a r l von,
Kattwinkel,
(1904)
p.
K e i s e r , E.H.
(1913)
and
and
Duhsky , J.V.,
Hand ,
W.F.,
Ber.
(1895)
28,
5 5 , 3403
R . , Ber.
M c M a s t e r , L. a nd L a n g r e c k ,
1 0 3 (1917)
(1900)
37, 3 2 2 4
L. , Am. Chem. J.
J . p r a k t .C h e m . ,
1841
J . A m . C h e m . S o c . 24,
Wolffenstein,
McMaster,
431
(2)
F.B.,
92>, 137
_49, 81,
(1916)
J.Am.Chem.Soc.
10.
O l i v e r i - M a n d a l a , E . , C.A. 16, 2 1 1 2
chim. ita l. 52., I, 1 0 1 (1 $ 2 2 )
11.
M c M a s t e r , L. and N o l l e r , C.R. , W a s h . U n i v .S t u d i e s ,
XI I I , S c i e n t i f i c S e r i e s #1, 23 (1925)
12.
Rerasen,
13.
Henry,
14.
W e g s c h e i d e r , R . , Monatsh.
15.
Pechraann, H . v . ,
16.
M e y e r , -V. ,
Ber. 2 7 ,
510
(1894)
17.
Meyer,
Ber. 2 8 ,
188
(1895)
18.
S u d b o r o u g h , J.J., J a c k s o n , P.G. , and L l o y d ,
J . C h e m . S o c . 71_, 2 2 9 (1897)
19.
Meyer,
I.
L. ,
V.,
V.,
and
Reid,
Ber. 1C),
Ber.
Ber.
27,
E.E.,
(1922);
59,
Am.Chem.J.
21 ,
Gazz.
281
(1899)
2041 (1877)
1 6 , 75
5 1 , 504
1580
(1895)
(1898)
(1894)
L.L. ,
20
.
Rie ss ,
Joh. , Ber. j3, 7 7 9
(1870)
21. Fittig,
R. , S c h a e f f e r , C., and
C h e m . p h a r m . 1 4 9 , 324 (1869)
22
.
Schlubach,
H.H.
and
Goes,
K oni g,
E.C.,
Ber.
J. , Ann.
5J5, 2 8 8 9
(1922)
23.
Ac ree ,
24.
B a c h m a n n , V7.E. and C l a r k e ,
2 0 8 9 (1927)
25 .
Schramm,
26.
Wreden,
27.
Spath,
28.
Noller,
29.
C l a r k , H.T .
69 ( 1925)
a nd Read,
30.
Schmid,
and D ec k e r ,
31.
Gattermann,
(1888)
32.
No y e s ,
33.
Scholl,
34.
Me y e r ,
35.
B e r g e r , G.
and O l i v i e r ,
600 (1927)
36.
G r i g n a r d , V., B e l l e t , E . , a n d
chim. (9) 4, 45 (1915)
Courtot,
Ch.,
37.
Ador,
1 2 , 1970
(1879)
38.
Gattermann,
(1890)
A.,
2j3, 1195
39.
Giebe,
40.
Haw k and Bergeimm,
Pg. 8 1 4
S.F.,
A m . C h e m . J. _29, 591
J. , M o n a t s h .
J.
and
A.
9_, 616
34,
Crg.
L.and
and
V . ,Ber.
E.
and
J. Am. C hem . S o c . 49,
(1888)
1988
R.R.,
29,
Meier,
G . , Ber.
Org.
(1933)
Syntheses
2 0 , 7 92
244,
51,
(1898)
5 6 , 327
(1903)
(1896)
S. C . J . , R e c .t r a v . chijn.
F r . , Ber.
an d R o s s o l y m o ,
2 9 , 2535
4,
(1906)
G . , Ann.Chem.
F . , Ber.
830
(1876)
(1913)
H . , Ber. 5 9 , 9 3 8
Schmidt,
Kac er,
L.
9_, 1 6 0 6
S y n t h e s e s JL3, 9 4
V7.A. , Am. Chem. J.
R.
H.T.,
Z n a t o v i c z , B. , Ber.
E . , Monatsh.
C.R.,
(1903)
Ber.
46,
Ann.
(1896)
Practical
Physiological
Chem.,
41.
K o l t h o f f , I.M. and
Inorg. Analysis;
42.
Organic
43.
Re ad, R.R. and Mullin,
1 7 6 3 (1928)
44.
Mu llin, D . B . , T hesis, The D i s i n f e c t a n t P o w e r of
Ph eno ls, U. of Vermont, (1924)
45.
Sh ori gin ,
46.
Wormley, T.G. , M i c r o c h e m i s t r y
New York, (1867)
47.
Boricky , E . , E l e m e n t e einer me uen chemisch. mikros k o p i s c h e n M i n e r a l - und G e s t e i n s analyse: Archiv.
d. naturwiss.
L a n d e s d u r c h f o r s c h , von Bohmen,
Band III, Prag, 1877
48.
Be hre ns, H . , A M a n u a l of
Lo ndon, 1894
49.
B e h r e n s , H. and Kley, P .D . C . , Mikro che mi sche
A n alyse, 4t h e d . , L e i p z i g , 1921
50.
Short,
51 .
Staples,
52.
F r ase r, H. J. an d Dreyer,
949 (1937)
53.
Fr ase r,
54.
L a r s e n , E.S. a n d Berman,
8 4 8 , (1934)
55.
W i n c h e l l , A.N., M i c r o s c o p i c C h a r a c t e r s of Ar tif ici al
M i n e r a l s , Joh n Wiley & Sons, Inc., New York, 1931
56.
Chamot, E.M. and Mason, C . VV. , H a n d b o o k of C h e m i c a l
M i c r o s c o p y , Wiley He Sons, New York, 1 9 3 1
57.
H a r t s hor ne, NiH. and Stuart, A., C r y s t a l s and the
P o l a r i z i n g M i c r o s c o p e , Edward Arnold Sc Co.,
L o nd on, 1 934
Sandell, E.B. , Text of Quant.
Mac mil lan , 1937; Pg. 524
S y n t h e s e s JL3, 20
P.,
M.N.,
Ber.
43,
(1933)
D . B . , J . A m . C h e m . S o c . 50,
1931
of Foisons,
Microchemical
U . S . G e o 1.S u r v e y Bull.
L.W. , Am. Mineral.
H.J.,
(1910)
Am.
23^, 613
Analysis,
8 2 5 , (1931)
(1936)
R.M. , Am.Mi ner al.
Min eral.
22,
22,
(1937)
H . , U. S .Geo 1 .Survey Bull.
58.
•Fry,
W.H. , U .S .D e p t .A g r .B u l l . 5 4 4 , 1
(1933)
59.
Wh erry,
60.
Wherry, E.T. and Yanovsky,
1063 (1918)
61.
Bryant, W.M.D., J. Am.Chem. Soc . 54
3758 (1932);
5 5 , 3201 (1933); 60, 1 3 9 4 (1938); 60, 2748 (1938)
60, 2814 (1938)
62.
Davies, E.S. and Hartshorne,
1830, Part 2, (1934)
63.
Le s l i e , R . T . ,'J . R e s e a r c h N a t 1.B u r .S t a n d a r d s 15,
41 (1935) R.P. 808
64.
L e s l i e , R.T., J . R e s e a r c h N a t l . B u r .S t a n d a r d s
761 (.1936) R.P. 943
65.
Le sli e, R . T . , a n d Heuer, W . W . , J. R e s e a r c h Natl.
B u r . S t a n d a r d s 18, 639 (1937) R.P. 1000
66
.
E.T. , J. Wa s h i n g t o n
Ferris, S.W. , Cowles,
I n d .E n g . C h e m . , Ind.
Acad.Sci.
18,
302
(1928)
E . , J . A m . C h e m . S o c . 40
--
H . H . , J.Chem.Soc.,
H.C., and Henderson,
Ed., 23, 681 (1931)
17,
L.M.,
67.
Gr aves, G. D. , Ind .E n g .C h e m . , Ind.Ed.,
(1931)
68 .
H e n d r i c k s and Jefferson,
(1933)
69.
Emmons,
R.C.,
Am.Mineral.
1 4 , 441
(1929)
70.
Emmons,
R.C.,
Am.Mineral.
19_, 237
(1934)
71 .
Dodge,
72.
Berek, M. , Neues Jahrb.
B e i l a g e Eand, 1923
73.
Buck, K.E., O ut l i n e for E x a m i n i n g Crystals,
A m . C e r a m . S o c . 1j5, 61 (1937)
74.
Die O p t i s c h e n I n s t r u m e n t s der Firrna R. Fuess,
C. Leiss, Leipzig, 1899, pg. 119
75.
Glass C o l o r Filters,
Nev? Y o r k
T.A.,
Am. Mineral.
J . O p t .S o c .Am.
1_9, 62
f.
Min.,
2_3, 762
2 5 , 299
(1934)
Geol., und Pal.,
C o r n i n g Glass Works,
Bull.
Corning,
76.
Th e Eramons Double V a r i a t i o n Apparatus,
Lomb, R och est er, N . Y . , Pg. 4
77.
Buerger,
78.
Johannseh, A.,
2nd Ed. , Pg.
79.
W o h l e r and Liebig,
80.
Muller,
A.H.R.,
81.
Schiff,
R.
82.
Klein,
83.
Mohr, E. and Goldschmidt,
678 (1907)
84.
Groth, P., C h e m i s c h e Kry s t a l l o g r a p h i e ,
W. Engelmann, Lei pzi g, (1917)
85.
Mohr,
86
.
87.
88
.
M.J. , Am.Mineral.
J. , -Ann.Chem. pharm. ^3, 268
Z.physik. Chem. j36, 177
Ann.
w . , Ber.
S c h e r pen zee l,
(190i)
Fischli,
G . , Ber.
1 6 6 , 184
E . , J.prakt. Che m.
Weith,
(1933)
Manual of P e t r o g r a p h i c Methods,
255, McGraw Hill, New York, 1 918
and Tassinari,
C.,
18., 325
Bausch &
6,
420
M.L.
(1914)
1 0 , 1785
(1877)
(1873)
V.,
7£,
Z . K r y s t .M i n e r a l . 4 2 ,
310
IV,
525,
(1904)
(1873)
van., R e c .t r a v .chirn. 2D,
H. , Ber. JL2, 615
89.
Hollema n,
90.
Kahrs,
91.
Bodewig,
92.
Hofmann,
93.
Me Id rum, A.M.
1607 (1910)
94.
Meyer,
95.
Robertson,
96.
Aschan,
97.
Muller, A. and Shearer,
(1923)
(1832)
162
(1879)
A.L. , R e c . trav. chirn.
6.,- 79
E . , Z . K r y s t .M i n e r a l . 40,
475
(
)
(1905)
., Z .Kry s t .M i n e r a l . 5_, 554.(1881)
A . W . , Ber.
and
2729
Turner,
H. , Monatsh.
0.,
14,
2 7 , 43
W.E.S.,
31,
2348
J.Chem.Soc.
97,
(1906)
P . W . , J.Chem.Soc.
Ber.
(1881)
1 1 5 , 1220
(1919)
(1898)
G . , J.Chem.Soc.
123,
3156
98.
Da v e y , W.P. , S t u d y of C r y s t a l S t r u c t u r e a n d
A p p l i c a t i o n , M c G r a w Hill, New Y o r k , 1 9 0 4
Its
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