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Synthesis of alkyl cyclopropyl ethers

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1940
CHEMISTRY LIBRARY
UNIVERSITY OP MARYLAND
UMI Number: DP70351
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UMI
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UMI DP70351
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Syathoai* and iToperti#* offrojsyl Cyeiopropyl Etlior..
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thmtiMJieio and Properties of n»®otgrlOyclo propyl Kthor .........
71
m m im ^ o a r op Mitim* orcLoppom it hsr ...
SWART
RBPHRIHCBS
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76
77
H o t of abbra^rlfttiona
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Literatur# Oitod ....
76
L13T OF TAELE8
Tablo II©•
I
II
III
IV
Title
Peg®
Average Yield® of Cyolopropyl SthOF#
2f
Physical Properties of Oyeleprepyl Kthor
29
l%or®ie®l Gcawtoat® Reported for Allyl Sithor®
$0
Caapetrisoxi of Paroohora mid foloeular K®fr®otivitlo® of
Oyolopropyl mid Allyl Ethers
V
71
V II
Physical C & m tm ta of $ *
Physio®! Constant* of ^
«Dlhrosiopropyl Allyl Kthor®
31
,'y^Dibrosapropyl .Allyl Kthor®
32
bolting Points of ^5 •imaopropioni® Aoid, Obtained from
Cyolopropyl Ethers
fill
30
32
Physical Constant© of SVopylon® Bihrotdd® Obtained from
IX
X
th® Cyolisotion of^3 ,/3 *-Dibro«oieopro|*yl AUsyi Etfe®re
Physio®! Constants of Bibronopropano®
Attempts to Proper® a ‘etallio Alhoxldo Dorivatlv® of
35
38
XI
dyntfcosl® of ^/3 *
89
XII
XXII
XX7
XV
MX
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Yields of^/3 $
*-3iehloro1eoor©pyI Pethyl Kthor
* -Btohlorolsopropyl letiiyl Ether
40
Yields of /3 */3 1-Oibrosioisopropyl Methyl Ether
42
lothylatioa in the Proamoa of* a Eolronfe
48
raotionaticm of y3 » ^3 9 M h ra m ie o fro p y X Kbhyl Ether
thamory of iicsa® Cycllaction Sxporfcnoat®
48
4?
Crud® Yields of Buthyl Cynlo propyl E th er from / 4 y 3 *"
Bibromol sopropyl -'"ethyl Ether
4®
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Itetorminfttloa of Carbon and ifyitrogoa in Kthyl Cyolopropyl
tthsr
65
'hyeieal Pro-wrt!©* o f ^ #
Dibmaopropyl Fthyl Bthor
DotNnrninfttlon o f Halogoa in $ # ^t>ibr©Biej»ropyl Bthyl Sthor
65
65
Bobormlaabloa of Ratlogon In tho :>«torlttl Kocovorod from
iithanol
66
Fhyeical Proportion of tho Broaiao Dorivatl^o of tho 0n»
from tho Preparation o f Btfcgrl Cyclopropyl Bthor
m
Dotomination o f Halogon in tho bromine Dorimtiiro o f tho
Goo from tho Preparation of Stfcgrl cyelopropyl Sthor
m
Physical »n4 Moleeular Proportieo of xi^Propyl Cyelopropyl
69
Ethor
Determination of Carbon and %drogen in a*-Propyl Cyclopropyl
Bthor
PhyoioiOL Propertios
69
(jl #
ftibrcmopropyl n*Propyl iither
C alibration o f yanmaotor Ho* %
70
70
Phj® ioal r-roportlo# of tho 3reninatod 3ao i¥o® tho
Preparation o f n-Propyl Oyelopropyl Ether
71
Physical and iloloeulsr iVopertloa of n~jutyl vyolopropyl
n
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63
Gyclisatlon
j3 $ J 5 - dibrosaQlsopropyl n~propyl ether and puri­
fication of the product.
1.07 mols ®fy(3 * J$ - dibroaoisoprepyl n-propyl ©ther m s converted to
a-propyl cyclopropy1 other under the same conditions used to prepare methyl
oyolepropyl ether. She crud© yield was 77 gms. This liquid was washed wi1&
viter three times and twice with calcium ehXorid© solution to remove allyl
alcohol, aoetonitrile and acetaaid®. 46 pi, was loft after this treatsout.
She material was dried over magnesium sulfato, filtered and fractionated with
a small 71grom column* the fraction which distilled between S9«98*C. weighed
22.5 gas. ( 28.6 par sent. yield) and was chiefly n-propyl eyelopropy1 ether.
After the uns&barabe* wore determined by a porbensoi© acid titration,
an oxeooa (16 gms.) of finely powdered moneperphtfcalle acid was added to the
liquid. The solid did not dissolve completely* hut the mixture began to warm
up a little and thus indicated that a reaction waa taking plane.
The material
was plated in the refrigerator and shaken from time to time. After standing
in the told ever night, the reaction mixture m s allowed to stand at room
temperature for 64 hours* It was then extracted with 10 per e©nt, sodium
hydroxide wahhed with water and calcium chloride solution and dried over
powdered sodium hydroxide, The liquid was filtered and fractionated,
0.1 oo. of the product was allowed to react with 2 cc. of pcrbeneoie
acid solution for two days and then titrated, 1 oo. required 6.70 co. tenthnormal sodium thlosulfate while the undiluted standard solution required 3.65
cc.
Therefore, there is still a little unsaturated material present.
i
69
fable XLt
Physical and Molecular Properties of n«*Propyl Cyolopropyl Ether
Distilling range
Pyenometer Ho. Si and liquid
Weight of liquid
Density
Eefraotire Index
Bubbles from capillary
Bubbles from larger tube
Surface tension
Paraohor (experimental)
Parachor (calculated)
Molecular refmobility (experimental)
Molecular refraetirity (calculated)
94«*96°C.
26,796
7.510
.790
1.3933
7.64
1.05
21.17
272.0
270.7
30.31
30.06
Table XLII
Determination ©f Carbon ami Hydrogen la n-Propyl Cyclopropy1 Ether
I
II
Sample and sample tube
Sample tub©
Sample
H^O and HgO tube
8g0 tab#
l%0
C0a and C0fi tube
CCfc tub©
CO,
for sent H
far cent C
67,970
53.121
4.649
4.347
-.845
5.192
15.079
2.272
12.807
11.98
72.08
19.867
16.341
4.526
9.219
4.347
4.872
27.083
15.079
11.974
12.04
72.19
Calculated for C^Lm Q|
L* 12.08|
Analysis Number
C, 71*94
Preparation and physical properties of (X » ^-dibromopropyl n-propyl
ether*
n-$ropyl eyelop ropy1 ether m e brominated In the same way that methyl
oyelopropyl ether was brominated.
m
1 M | # JUdXS
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71
Ihble XL'"V
Physical Properties ©f the Bromin&ted Gas from the Preparation
of n-Propyl Cyolopropyl Ether
Bolhing range
Pycnometer Mo.2 and. liquid
Liquid
Density
Ref motive index
140-142#C,
2.5197
.4809
1.919
1.5166
Thea© physioal constants whew that the liquid is propylene dibromide
and the gas must have been propylene.
Preparation of monoperphthalio acid.
275 gms. of 15 per oent. sodium hydroxide in a liter Erlenmeyer flask
■was cooled in an lee and salt bath.
115 pis. of 50 per oent. hydrogen per*
oxide similarly cooled was added all at once.
375 gms. of phthalio anhydride
powdered to pass 100 mesh was added as quickly as possible with vigorous
stirring.
After a admits or two the entire mixture was added all at once
to 250 co« of 20 per cent, sulfuric acid chilled to *10*C.
the solution
was passed through a fritted glass filter, and extracted onee with 500 oo,
of ether and then three times with 250 ee. of ether.
The ecmbined ether
extracts were shaken with three 250 oo. portions of 40 per cent, ammonium
sulfate and dried over 20 pis. of magnesium sulfate.
orated off in vacuum without the use of heat.
The ether was evap-
66 gms. of solid remained.
0.2 gm. of the solid added to an acidified potassium iodide solution required
13.2 ©c. of tenth-normal sodium thiesulfate for the titration of the iodine
liberated,
therefore, the material was about 60 per cent, monoperphthalic
acid and represents a yield of 45.5 per cent.
Synthesis ard Properties of n-Butyl Oyolopropy1 Ether.
123 pss. (0.45 mol) of^
- dlbroatoisopropyl n-bu%l ether was cyclized
to n-butyl cyolopropyl ether in the same way that methyl cyolopropyl etherw&s
made.
The produet was fractionated and the portion boiling up to 145*C. was
n
treated in the same way that n-propyl cyolopropyl ether was treated.
About
0.5 gn. of liquid distilling between 121-122.5*0. was obtained as the yield
{l per cent,).
fable XLIVI
Fhysioal and Molecular Properties of n-Butyl Cyolopropyl Ether
Distilling range
Pycnometer No.2 and liquid
Liquid
Density
Eefraotive index
Molecular refraetivity (eaqaerimental)
Molecular refraetivity (calculated)
121-122.5*0.
2.2580
.2001
.799
1.4045
34.99
34.68
fable X L V H
Determination of Carbon and Hydrogen in n-Butyl Cyolopropyl Ether
Analysis Number
Sample and sample tube
Sample tube
Sample
% 0 and
tube
BgO tube
%0
COa and CO* tube
CCU tube
per cent. H
per cent. C
Calculated
G , % 40s
E, 12.36*
1
11
20.264
17.767
2.507
18,994
16.254
2.760
50.844
44.058
6.786
12.32
73.87
27.923
24.569
3.364
2.310
— 1.399
3.709
12.978
5.886
f.098
12.37
73.98
C, 73.63
Reactions of butyl Qyoldp^af^l other.
0,2 gms. of butyl oyclobutyl ether was bromin&ted to 0(.# V^dibroaiopropyl butyl ether,
fhe quantity obtained was not sufficient to determine
the physical constants •
fhe product m i oxidised with 45 per cent, nitric
acid in the same way that (L, Y "dibromopropyl ether m s treated.
A reaction
was evidenced by the formation of gas and by the production of a brown color
In the water imiscible layer.
These signs were characteristic of all the
73
previous nitric acid oxidations of this type of compound.
It was not possible
to isolate the ^3-bromopropionic acid, although the odor could be detected.
Gaseous by-products fro® the cyclisation of
-dibraao isopropyl
butyl ether,
/ The gas obtained from the cyclisation reaction was treated the same
way that the gas from the propyl cyolopropyl synthesis was treated,
k small
amount o f water insoluble liquid was obtained with a specific gravity greater
than that of water,
fhe quantity was too small to characterise.
mt or
cyc&o
a, smum
Mm 0# Kmat## «5r*# o* J« oarr* &#&* f;ema and «*■*# Emam$ «f,k5
io m
m i x M m A Hi# pfetowNtftoiogy of aothgrl
otbor ahloh is «*forred
bo s® "Cyfrwo K f e r |S in bho ^ © w r e f o r m * #
2h» ro&otry
ewaclualoao
ar# tguoboA bolow*
I# &ao union of tho
of @ f ® l & p m p m m through m otbor
llda&g© wltfe l&m a&yS,
tiotbyl* vooalto i» tiso for**
oottaot of a wiatlX© li^ a M poatteooia^ mmttbftti® pr©j»*rbl«*
la ^ms.^ opoolao ©£ r a ta ls*
2 * €|pae®o ©ttaor to it- sera potoat a&ftotiiftt&o thaa othyl ethor#
olthoM^h i t i t aot a© f©b«fe a i <&lorafbra«
fciott pmti%mim oargioal aaMrfchoola la tho
m m m g m 0*3.0 par
©oat#
5$** #©§ig®stfiM*
of fcfaa dog
its anoobhotle issMoc as tsoatMi*^
©a Hi® *1©g Is I #S i# th a t of o tiy l othsr is
I t ahouSA
b e onghaolsod that th is A l f f m m m ® & r % $ m m h 4 y fr©» Hi©
sh©rt ia&uotleA ported of eyp re m other eooparad with that
o f othyl ottur*
5. la Hj# neuicey* eypmao ether pyodtt©©* si© liiw* daaog’s as
•hows by the hiwHm lfofghthaleta toot#
in tbo ro t* hisbo*
Sfetholo^leal ©tms^®s nr© ro t foaisl i» the H ra r or kidis#^©
■after repeated
mim ^mimm
4# 3t» e*rctt*e to x ic ity «p®» porfuairo, o f the frag* a heart 3g*
1® of the order of suited# of that of ethyl other#
fo seifcljr e li« & t 3jr w ere w ad##
prodroe
it* r o r o r o tr a b ie r a req u ir ed t »
m v c $ f a * X aaestfceei* in the kl#&d o f Hi# d©|!# th©
75
i v t n nym irdluR 4M m t
betneaa &mm%%*»
i&ingpr1# solution m& f£m% eoeatKiaiag oyprcieie ^Mmrm
§• 'Xho eifltmi’
t* rm im o f eoaeontiufcieae s>f eypreMi *i$ w t
ethyl rniMm ’s lth m^sgm &a£ & ir *g$*ar be> be about the « ta ii
ieut of eyp ram t*ihe? is 49 per eont*
The oll/g&ter
g im ^ f fftoe that o f ethyl #tfa#r*
Tt»# eG *»«tttf*tiea la a ir
r*$olre& be preitioe *a**bh«eSA i * ooowMU’ to tMo^tiilrdo
that C&*£ ethyl ether*
Gyfnsa© ether bolls 9*9* higgler Urns oaue ethyl ether*
7* Hi# hXoeg ftresotue rao&lzift hi^h «n9 the $ul*e f^o& ouster
doof
marginal mimWtmifo in the <leg *dth uyfsene ether*
i# The anther* wl#sli to m^iayiii® thet sooty of the sta4i#i
reported in this ooeissmioation are still In their !»*•
4ilpifei®f,
i£otV'.
assbsnalre ism etijp tieB ft «*# In prco'ee**
Bil® first *gqut»ciR&t&*gi of the
ether* in w
of eyprone
ofinio% mrxmte Its eerefUl cuvi juaioi&l
-trial in a&n by skilled rnmmUurhlete*
"fills eos$eta»& M s boon a»od etseeeeeft&ly la three mxrslmt eaestheslee
on tmmimm
76
SMIARY
1. An attempt to make bisoyclopropyl ©thor was unsuccessful.
, p> '-aichloroisopropyl methyl other and
2. The
propyl
^
WibroniQ iso-
methyl,ethyl, n-propyl and n-butyi ethers were prepared by
alkylation of the corresponding dlhaloisopropanol with the proper dialkyl sulfate.
3. Cyclisation of these ^ $ f t 1-dihaloisopropyl ethers in aoetamide with
sine in the presence of sodium iodide and sodium carbonate resulted in
the formation of methyl, ethyl, n-propyl and n-butyl cyolopropyl ethers.
4. Many of the physical properties of these cyolopropyl ethers have been
determined.
5. All of these cyolopropyl ©there can be brominated to the corresponding
O U Y -dibromopropy1 alkyl ether any one of which can be oxidised to
-broaopropioni© acid.
6. fhe structure attributed to the cyolopropyl ethers has been proved by
physical and chemical evidence.
7. Propylene is a by-product la all of the cyclisation reactions described
in Conclusion 3.
8. f t $ f t ’-dlbromoisopropyl bromoethyl ether has been synthesised from
f t • f t ^ikromoisoproppaol# trioxymethylen© and dry hydrogen bromide.
9. The anesthetic action of methyl cyolopropyl ether has been studied by
J.G. Krants, Jr. et al.***.
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23* Xxigold, 0*K«
123* 1206( l m ) ,
Ibid* 121, 2@78*36 (1§22)*
84* Llpp am! Padborg,
85* Xngald, 0*9#
Ibid*
>&r. 1816 (1921).
J. Chm . boo, lit, 306-329 (1921).
28* In-gold, \*.K„ . .bubo ami J.F, Thorp©, ibid* 121 1177*68 (1 0 2 1 ’*
&? * ' B m lm *
Wsueh© «ur Taratollimg */oa GyolopropAaol imd Oyaloprop&mm*
l>EKtt©r*s dissart-stloa* Teohaisabsa Hooheeliul® su Oaehsn* I3SX*
29* Damjaaov. JavaMl of lanara! ’‘hamisfcry*
•::*A* 84, 888 (1940).
ft* Lipp, ?*, J# iki$Mkr®rmr ted £©©1m, n»
80* Standing*** a«d R®©b«r*
H** *d,H*
840-00 (1939)
Ana* 490* 1-25 (1^12}#
dolwtie© fhicila© iota 4, 8 (1921)*
31* fiamjanov, H* tmd U ;* Oojarontea*
^llstin d® I’ aaadatia das
m im w m do 1 1uiasa d«g Bspublicpj©* d©Ti«tiqu©©.3o<iisl 1st©* •
91*s&© das soi«m©«* n*th©mttiqttti at naturallas, 1323,(7 ).
683-86..
6.4. 24* 1048 (1980).
82. '.©roshkovski, b*H.
JS, 1965 (19X4)*
»?* bus®, rhya. Cham. 46, ST-128 (1914)
33. HohX©r, *9* and Harlin * H.F.
(18301*
84. .'usiav&on*
55* 0®?tjteSv*
9. prakt. Than.
.?. 4m* Chsva. Sac*
c.i*
02, 1174-81,
2 43, 396 (1891).
J*Hass. Miy*. cbsou 34, SIS (1902)
$6* Bruylant,ted A* btassens, -bill tla
Halgiqn© 1921, 702-18.
font. 1902,1» 1277.
da I ’aeadami© royal© d©
3?* Freund, A* ;-#©iuits«h«ft» fur Chssd© 3, 626 (1882). «?• prakt. Cfe©si.
2 j!§, 868 (1882).
38* Vlolkow end Xfenselititkixt, «!. dung* Fby#* Ch«m. 32, 128 (1900)* Coat*
m m s XI, 4 3 .
39. rhmtnrson, d. prt&t. ghea.
2
Sf, 300 (1857).
40. H«#fea, Arohiv. cler i^srsasst©. 245, 518 ^1907).
41 * £©Utt*ky and Sutt,
M r . 40, 3049 (1907*4 •
42* Ohablay*Coopt©* r©ndu*
da l?A©adasai® d©« Sol©maos* 141, 94 (1906)*
4$.
and &©hl©aing*r*
44* 9«r .a&itsdU
Far# 41, 2430 (X9-.S)#
4# Fuss* fhye* £hasu
47, 1793. (1916) Cent* 19X6 11# 313*
43# HEaaa, 9*9*# 7,7* ie.;©#* o#?.,
zm& l>#*** duMm&kamp*
and Fa^laiMirliig ch©?ilatry, w28*
1178-1181
(1936)*
weHtt-W
46* A^ohnar# 0# and /•* ftappoiifliaek*
47* 7@rk.las* 7**9#
43* 0uta«lt,
Industrial
Asm* 284* 2X2-26 (1896 )*
7* ohaw, S m * 47# 307 (1886)*
Ana* j§6# 171-201 (XS90)#
t*
49* arugrlant# K«©u«Xl d©«
(1909**
trmrmm ohim iquo* dm hsgra-i*s* 28# 180-28S
SO* K iahnar, •**, 9 . Kusa* -''hys. Cham* 44* 166-180 (1912)
(1912)*
"
e l* 9©'hX®r, 9.9* tiasl ;.■*?’* purling.
32* 9©@sl«y and Thorpe#
o*A*
g^ 1431*
8* Am* Otam* so©# 62* 424-32 (1930}*
J* Ohm# Boo, 1X7* 59 Clfil).
S3* dole©# Aader*on, X*cfeaii# Anderson «md Faith*
S3, 2791 (Xf3X)*
8* Am* Ahum* Boo#
54# U**©, J* Am* Chaa# BOO* 68, 2927 (1033)* 56^ 7X6 (1934)*
Sl.ltejmioT,
8. Fftasa* >tiya. Chen* ^
8 6 * P«s»|J«»7 i m d
97*
Hfidwut, %
9# D o j a r e n k o .
828-48 (1911)* Cent* 1911, IX, 1681#
For. 4 0 , 4 9 6 1 - 8 8
( 1 9 0 7 )| 4 1 , 4 3 - 4 6 ( 1 9 0 8 ) *
,^r* £1# 988 (1918)*
68* .f^lfrioh* ?*# Opeldel and 9* fooldte. Far* £0# 789 (1923)*
89#
Far tholotf. .Ana* Ghisa.
60*
Oeitel*
61. 9#@lig*
82.
yhys.
9*$r«d£t* Oh«ti#
2
41,
278
(1864)*
96# 418 (1897)*
6 * % S4, 3466 (1891)*
tauter* d«>.hreeberich4a dber die Kerteohritte dor oheal* 1876, 346.
63* Aogtoh#!dor and Haaraltkar*
84# .rSerthelot tm4 huea**
13X7, 477 *
$8#
8
i*rthelot#
Ann#
Chi m *
doaataheite £&r Chemi©
34, 1061 (1913).
dahreeberiohte liber di© kertaohritte dor ohcntie
phys*
8
41, 297
(1864)*
81
88 , yuuttoaniwr,
0?*
oboul,
2
• *oc, Chim*
Anik# ^upplcfttaat I
SO# 212 (IS08),
282* 284 (1861),
:Sbfi#r t r i m n * r g Am, 189, 170# 176 (1371)*
*'arkownl&ow, tot. 305, 3117
(1881 )*
d i l l , A .J. and O .J7T l*eh*r, 4* ia* dtost, S o o .^ 4 , 2682-913 (1022),
O o m m t, *J.d. «nd o .H * Quayla.
6 3 , O s m a n pofemts
o rg an !® S yn th es® * I I #
1 9 7 5 0 8 , 19730 9
C a n t* 1 9 0 8 ,
3 3 -3 6 ( 1 9 2 7 ) .
I# 1 6 £ 5 .
09. CalaM# Asa* U » # 73 (1802).
* Olauo, tat. 108, 42 (1873)
70.
Ana, shim. pliys,
6
22, 436 (1981)*
pat#**. 288341*
71. Oerimn patent*# 272537, 277901.
72. (Jarman pnX m t 265108.
73.
"Salt.
t|# 789 (1918).
74. -iVI. vatant# 44613*
C .A .
38# 2914 (1089),
7 6 . :*« r$ h o l# ti and b u s * * , A im . ohim# p h y t .
K*bo:il.
Ibid,
3
5
4 0 . 518 ( 1 8 0 6 ) ,
00# 32 (I860).
76.
76. darth. dan. 124, 349 (1682),
*'7. Cotta.
Ami, 174, 96 (1874). daf, Ann. 336# 224 (1904).
78. Asehaa.
Aar, H , 2800
Umpiaaxu
Ann, ©Mm* phy*.
25,
1S20 ( 1 6 9 0 ) ,
7 TT# 258 (1897),
79,
79* 8 m m , 9.,
80, c«rr®,
ym m m4
ftabooafc# Organl® 3yntb**»* VDf, 42 (1934)♦
.-h ill. See, ©him. 4
£ , 880 (1910).
81. Lusitpiani# %
6»li<rtino ©hi*ieo48rm«urMit loo. 78, 667-9 (1940;,
Clam, tot. 16b, 14, (1873).
~“
92* Robot*!. toi. Supplement I, 226, 227 (1801),
L. Sltaotau*. bull. *©e, ©him. 4 41, 624-33 (1927).
85. Kling,
Cempta* rendu* 4® l^eadaetie da* Salomes
e in. 5 SI, 14 (1004).
137, 796 (1903)
b u ll, soo,
@4. -as« and 51nk. dor, 4£ 2003 (1016)
tfi*ys&tt# 9,j, and C,dT"?ur^i«, J* Cham, oc . 127, 2758-46 (1926),
Hibbert , H, md ftfcolaa# V.U. J, m
, O
hara. 00©. SI, 1945 (1929),
82
88# Blanchard, L.
Bull# soc. ohim.
4
41, 824 (1927)#
86. Ibid. ^59, 119-21 (1925).
87# Allan, 8.7# and H.R, Han*®,
88. Blanchard, L#
J. Am. Chem. Soc. 59, 540-2 (1937)#
Bull,soc. chlm.445, 1194-1204 (1951)#
89# Sattler, L# M, Altamara and S. FToner.
90. Paal.
J . Am. Chem# Soc# 57,353 (1935)#
3@r.21 2917-73 (1888).
91# Suter, 0. !. and H#L* Oerhart
Organic Syntheses IIX, 27, 29 (1939).
92. Filipcrw, 0. J# Russ. Ihys. Chem. 46, 1199-1201 (1914)
93. Ruigh, V Z # L # Industrial and Engineering
JJ* 250 (1939).
Cent. 1916,1, 1057.
Chemistry. Analytical Edition
94. Henry, Ber# £, 455 (1872).
95. Irvine, McDonald and Sontar•
J. Chem. Soc. 107, 349 (1919).
96. Berthelot and Lucas,
Ann. ohim.
97. Cahours and Hofmann,
Ann, 102, 290 (1867).
98. Bruhl#
phys.
3 48, 292 (1858).
Ann. 200, 178 (1880).
99. Tollens and Heninger.
Ann. 156 (1870).
100. Kirmann, A. and M. (foudard and f. Chahidsodek,
2143-52 (1938).
101. Abderhalden and Sichwald,
102. Marknownikow.
103* Suarts.
Bull, soc, chim.
Ber• 49, 2098 (1916).
Zeit. 1865, 554.
Bull. soc. ehim.
104. Jacobs and Heidelberger.
425, 103 (1919).
J,
Am. Soc. Chem.
39,
1465(1917).
105. Simpson, J# Amer, Chen. Soc. 40, 675 (1918).
106* Kendall and HoKensie.
107. Rojahn, C.A.
Organic Syntheses III, 25 (1923).
Ber. 54B, 3115-8 (1921).
5
2,
83
108. Lederer. J. prakt. Cham.
2
42, 384 (1890).
109. Yolhard. A m * 242, 163 (1887).
Romberg. A m . iToT 238 (1909).
110. Reboul • Ana. ohim. phye.
6
14, 467(1878),
111. Llnneman. A m , 161, 42 (1872).
Zander, Ann.. 214~TT5, (1888).
Kdtlbaum. ZelST 86, 686-646.
Bodgnaa, Handbook of Chemistry and Physics, 23rd Kdn. pg. 766(1939).
112. Zander. Ann. 213, 178 (i860).
Freund. MonetsEejfte ffir Chemie 2, 639 (1881).
Gustavs on. J. pxakt. Chem, 2, SjL 506 fl399)
Bbdgman. Handbook of Chemistry and Physios, 23rd Ida. p. 768 (1939).
Friedel and Ladenberg. Zeit. 1868, 48.
Reboul. A m . ohim. phye. 3 i f 465, 479 (1878).
113. Heilbroa, I.M, Dictionary of Organic Compounds
Press. Vol. II, p. 16 (1936).
114. Meemveia and Schmidt.
Ann.
R.7, Oxford University
444, 236 (1925).
115. Ruhoff, J.R., R.F., Burnett, E,B. Reid, W.H. Carothers
Organi® Syntheses X¥» 36 (1935),
118. Tiffeneau, R. Adams and P.B. Kendall,
117. Sugden, S.Parachor and ¥alenoy.
(1930).
andrf.L. MeEwen,
Organic Synthes#*
¥1X1. 30 (1928).
London. Geo. Routledge and Sons
Ltd.
118. Hodgman, Handbook of Chemistry and Physics, 18th Eda, p. 731. Ohio,
Cleveland, Chem, Rubber Pub, Co. 1933.
119.
Ibid,
1041,
120. International Critical tables Yol. III. page 29, N.T.MoGror.Hill, 1928.
121. Gilman, H,
Organic Chemistry, Yol. II, p. 1739,
122. Cohen, J.B, Organic Chemistry for Advanced Students,
pp. 19*»2Q
5thEdn. Yol. II
123. Roth. H. Quantitative Organic Mioroanalysis of Frits Prsgl 3rd Ida.
Trans, by E.B. Daw. Fhila. Pa, Blakistom'a Son and Co. (1937).
124. Bohme. Manuscript subm tted for publication in Organic Syntheses.
Ber. J70, 379 (1937).
Bayer and Yilliger. Ber, 34, 763 (1901).
Eigenberger. J. patfrfc. Chem. 2 130, 78 (1932).
125. Krantz, J.C. Jr., C.J. Carr, S.E. Forman and W.E. Evans, Jr. Anesthesia X
The Anesthetic Action of Cyolopropyl Methyl Ether, to be published.
v
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[ j I I 4 H (1 4 z i j
U N IV E R S IT Y O F M A R Y L A N D
S C H O O L O F MEDICINE
D
epartment
of
P
h a r m a c o l o g y
R esearch Laboratory
29 S. GREENE STREET
eessler
BALTIMORE. M A R Y L A N D
October 14, 1940
Dr, Nathan L,
Department of
University of
College Park,
Drake,
Chemistry,
Maryland,
Md,
Dear Dr, Drake,
I am mailing you "Alkyl Cyolopropyl Ethers” for your revision.
There are a few differences between this paper and my thesis.
The constants for n-butyl cyolopropyl ether were determined on a sample made
since my thesis was completed. Also, Mumford and Philips parachor values, as
reproduced in Gilmanfs Organic Chemistry, pg, 1733, were used to calculate
the parachors since these values are more recent than Sd-gden^ values.
Yours truly,
Sylvan E. Forman
Alkyl Cyolopropyl Ethers*
Nathan
2
L, Drake and Sylvan E, Forman
Contribution from the Departments of Chemistry and Pharmacology,
School of Medicine, University of Maryland
Cyolopropyl alcohol has never been synthesized despite many attempts to
do so*
It -was therefore of interest to see whether or not ethers of cyclo-
propyl alcohol could be made*
Also, since diethyl ether and cyclopropane
are both good anesthetics, it was of interest to determine whether or not
a combination of the ether and cyclopropane structure in the same molecule
would result in a valuable anesthetic*
Consequently,the methyl, ethyl, n-
propyl and n-butyl ethers of cyclopropanol were prepared and -the pharmacology
3
of methyl cyolopropyl ether has been studied.
The method of synthesis and the proof of the structure of these compounds
are represented by the following series of reactions:
CHgX
'
CHOH
CEgX
J
CHOR
Reso<fc
CflaX
CHS\
J CHOR
CH/
^CHsBrCH^CHo]
CH3CONHg, Zn
CifeX
Brs
NaI^
C%BrCHaCHOR
*
°
a
HN03
ifeO
----- } CHgBrCHgCOOH
•
Although all of the ^ ^
'-dihaloisopropyl alkyl ethers which were used
in this research had been prepared previously,attempts were made to devise
better methods of preparation.
been prepared fromj3 ,
,^/3 1-dichloroisopropyl methyl ether had
1-dichloroisopropanol by treatment with methyl iodide
and
^
and silver oxide4,by heating the former with methyl p-toluenesulfonate0 at 150°C.
A
The material used in the experiments described in this paper was prepared from
3 ,
’-dichloroisopropanol by heating it at 125 °C for 3*5 hours with an ex­
cess of dimethyl sulfate,
A general method for the preparation of ethers of
/3 ,ji -dibromoisopropanol form allyl bromide, mercuric acetate and an alcohol
and subsequent treatment of the resulting product with bromine and aqueous po6
tassium bromide had already been described.
However, we chose to prepare the
methyl, ethyl, n-propyl and n-butyl ethers from A ,^ -aibromoisopropanol and the
corresponding dialkyl sulfates.
t
h
a
t
The methyl ether was prepared in the same way
’-dichloroisopropyl methyl ether was made, except that a lower tem­
perature and a longer heating period were required.
The ethyl, n-propyl and n-
butyl ethers were prepared in xylene solution at the boiling temperature in
the presence of calcium carbonate.
Only the halogenated isopropyl methyl ethers were obtained in pure condition.
It was not possible to apply chemical methods of purification to the others, nor
was it possible to successfully fractionate by distillation the mixtures which
resulted after the removal of the xylene.
The use of these impure mixtures in
the preparation of the cyolopropyl ethers caused the yields of the cyclization
-experiments experiments to appear lower than they really were*
Pure^/3 ,^/3> '-dibromoisopropyl n-butyl ether was prepared according to
the following equations:
CHaBr
i
CHOH
I
CHgBr
+ (HCHO)
+
HBr
GHgBr
>
----» CHOCHsBr
I
CHgBr
n-C3H7MgBr
---------- *
CHoBr
i
CHOC.Ho-n
|
CHgBr
An excess of trio3?ymethylene was suspended in ^/3 #//3 idibromoisopropanol and dry
hydrogen bromide was led in until the solid disappeared,
The^/3 ,^/3 -dibromoiso­
propyl bromomethyl ether was purified by fractional distillation and reacted with
n-propyl magnesium bromide in ether solution to o b t a i n ,/2> ’dibromoisopropyl nbutyl ether.
A Ai
This procedure is an adaptation of the method used to prepare
e th y l 7
3
,
A i
-dichloroisopropyl^ether, wherein a suspension of trioxymethylene in / tf'* *
dichloroisopropanol was treated with dry hydrogen chloride, and the chloromethyl
ether which results was treated with a methyl magnesium halide,
Cyclization of
’-dihaloisopropyl alkyl ethers to alkyl cyolopropyl ethers
was accomplished by an adaptation of a method described for the preparation of
cyclopropane from trimethylene dichloride8 . Sodium iodide, sodium carbonate and
an excess of zinc dust were stirred in molten acetamide maintained at 140°,
The
halogenated ether was slowly added, and the product was allowed to distill off
through a short fractionating column,
Unsaturates were removed from the products
by means of perbenzoic acid in toluene solution or by solid monoperphthalic acid.
Table I gives the yields of cyolopropyl ethers obtained and the results of micro
combustion analyses for carbon and hydrogen.
Table I
Yields and Combustion Analyses of Cyolopropyl Alkyl Ethers
Alkyl
Group
Per oent.
Yield
a
CHa
22
c4h8o
66 ,63
11.18
b
CHS
80
c4h8g
66 .63
11.18
66.39, 66 .62
11.07, 11.08
CsA
64
G5H10O
69.72
11.70
69.42, 69.29
11.70, 11.64
n-C3H7
c
n-C4He
d
n—C4Hq
22
CeHiaO
71.94
12.08
11.98, 12,04
1
G7H140
73.63
12.36
72.08, 72.19
*
73.87, 73.98
70
c7h14o
73.63
12.36
a.
b.
c.
d.
Empirical
Formula
c
Calc,
H
From
*diohloroisopropyl methyl
From /b9 ft* f-dibromoisopropyl methyl
Impure starting material prepared by
Pure starting material prepared from
Found
C
-
-
H
-
-
-
12.32, 12.37
-
-
m*
ether
ether
dibutyl sulfate method
propyl magnesium bromide
The distilling range under atmospheric pressure, density in vacuo, refractive
index and surface tension in dynes/cm,
detwrniiiimd of each of the cyolopropyl
were determined,
ethers^ The surface tension was determined by the well known bubble method , The
physical constants are listed in Table II,
Table II
Ether
Distilling
j Range
10
Oi
Physical Constants of Cyolopropyl Ethers
„ 26
n 0
y l t 25°C
Methyl
43.5- 44
0.786
1.3749
19.92
Ethyl
67
- 69
0.780
1.3830
20.34
n-Propyl
94
- 96
0.790
1.3933
21.17
122
-124
0.807
1.4026
22.76
n-Butyl
The molecular refraetivity and the parachor of each compound were calculated
from physical constants and from atomic and structural values.
The experimental
in
values were always better agreement with the values calculated for cyolopropyl
ethers than for the isomeric allyl ethers.
Table III contains the atomic and
structural values used in the calculations and Table IV contains the paraahors
and molecular refraotivities.
Table III
Atomic and Structural Refractivities and Parachors
Refractivities
X 0 ^X
*
Parachors
C
2.418
9.2
H
1.100
15.4
0
1.643
20.0
.71
12.5
3 membered ring
Double bond
1.60
12
19.0
Table TV
Molecular Refraotivities and Parachors of Cyolopropyl and Allyl Ethers
Alkyl
Group
Molecular Refraotivities
Allyl
Cyolopropyl
Expt.
Expt.
Calc.
Calc.
Parachors
Cyolopropyl
Allyl
Calc.
Expt.
Calc.
Expt.
Methyl
20.83
21.00
21.72
22 .05
192.5
194.0
199.0
200.4
Ethyl
25.44
25.77
26.33
26 .60
232.5
234.7
239 .0
-
n-Propyl
30.06
30.31
30.95
-
272 .5
272.0
279 .0
-
n-Butyl
34.68
34.49
35.57
-
312.5
309 .0
319.0
-
The experimental molecular refraetivity of ethyl allyl ether was calculated
from physical constants obtained from the literature
pared from allyl iodide and sodium methoxide
14
X<3
• Allyl methyl ether pre-
had the following physical constants
b. 43-45°C, D^50.757 gms./cc. in vacuo, / (at 25°C.) 19.46 dynes/cm., n^51.3799.
Combustion analyses indicated that the sample was not completely pure, but the
physical data obtained is probably not far from the correct values and is valuable
for comparison with the data obtained from methyl cyolopropyl ether.
The cyclopropyl ethere were reacted with bromine in chloroform, solution
to obtain the G f c i , dibromopropyl alkyl ethers*
Table V gives the constants
obtained for these compounds.
Table V
Physical Constants of At, ^Dibromopropyl Alkyl Ethers
Ether
Boiling range
25
25
D
n^
1.790
1.5060
Methyl
68
Ethyl
75.5-77.5°/9.5
1.666
1.4939
n-Propyl
96
1.594
1.4898
- 70°/9
- 98°/l8.5
These compounds were oxidized wi(th nitric acid to
/3 -bromopr op ionic
acid.
One sample of this acid obtained from methyl cyclopropyl ether was identified by
its melting point and by combustion analyses for carbon and hydrogen. The
by mixed melting points with
other samples were identified by their melting points and^the analyzed sample.
n-Butyl cyclopropyl ether reacted with bromine to yield a product which
reacted with nitric acid.
Although the odor of/3-bromopropionic acid was much
in evidence, it was not possible to isolate the crystalline material.
This is
not surprising, because, in the case of the other ethers, this derivative was
isolated and purified only with difficulty.
All other properties of the n-
butyl ether were consistent with -those of a cyclopropyl ether.
The following melting points were obtained from the literature15 for
-bromopropionic acid; 60-61°C., 62°C., 62.5°C. and 62-63°C.
dl C& -bromopropionic acid16 melts at 25°G.
The isomeric
The melting points and the mixed
melting points of the compound obtained are given in Table VI*
Table VI
Melting Points of y(3-Bromopropionic Acid from Cyclopropyl Ethers
M .P .
Mixed M.P.
Methyl ( from 3r)
60.5 - 61.5
(analyzed sample)
Methyl ( from Cl)
59.0 - 60.0
60.0 - 61.5
Ethyl
58 .0 - 59.0
59.0 - 61.0
n-Propyl
56.0 - 57.0
57.5 - 59.5
Ether
Thus, it can be seen that the cyclopropyl ethers differ from the isomeric
allyl ethers.
The parachors and molecular refractivities are different. Cyclo­
propyl ethers react only very slowly with perbenzoic acid, while allyl methyl
ether reacts quantitatively in about 24 hours.
with cyclopropyl ethers than with allyl ethers.
Bromine reacts a little less readily
The bromination product of allyl
methyl ether does not react with fuming nitric acid even when heated in a bath at
100°C.
The bromination products from the cyclopropyl ethers are oxidized by nitric
acid to
-bromopropionic acid which cannot result from the bromination and sub­
sequent oxidation of an allyl ether.
Experimental
$,/3 1-Dibromoisopropyl 3romomethyl Ether. 9 mols of formaldehyde in the form of
trioxymethylene was suspended in 3 mols of /$,
an ice water bath.
solid •warn dissolved.
’-dibromoisopropanol and cooled in
755 gms. of dry hydrogen bromide was led in, whereupon, all the
The upper layer of the reaction mixture was removed and the
lower layer was fractionated by distillation.
The fraction which distilled between
129-135°C./l2 mm. weighed 775 gms. (83 per cent.).
is very hygroscopic.
The product fumes in air and
Determination of halogen by means of a Parr bomb indicated
that this sample was not pure.
Anal.
Calcd. for C4H7Br3Q:
75.39, 75.40.
-7-
Br, 77.12. Found • Br,
3 ,/3
1-Diehloroisopropyl Methyl Ether. 5 mols of ^3 ,
*-dichloroisopropanol
and 18 mols of dimethyl sulfate were heated at 125° for 3.5 hours.
The mixture
was cooled, poured into water, and neutralised by the addition of solid sodium
bicarbonate.
The lower layer was shaken with 50 per cent, sodium hydroxide to
convert the unreacted alcohol to the lower boiling, more easily separated
epichlorohydrin.
Dimethyl sulfate was removed by shaking with cone. ammonia*
The liquid was then washed with water and dried over magnesium sulfate.
It
was distilled under diminished pressure to remove tarry products and then
fractionated under atmospheric pressure.
The fraction which distilled between
159-131 *5°C* weighed 660 gms. ( 31%).
* A >-Dibromoisopropyl Methyl Ether. 2.5 mols of /^3,^/3'-dibromoisopropanol
and 3 mols of dimethyl sulfate were heated for 12 hours on a boiling water bath.
The purification procedure was the same as described for the chlorine analog.
The product distilled from calcium carbonate between 46-49°C./l.5 mm.
The
yields varied from 11 to 40 per cent, and were usually about 30 per cent.
aj^ 1-Dibromoisopropyl Ethyl Ether. 3 mols of 3
1-dibromoisopropanol,
3.6 mols of diethyl sulfate, 6 mols of calcium oarbonate and 2100 cc. of xylene
were mechanically stirred and fractionated for 15 hours to remove water formed
during the reaction.
The liquid was filtered and fractionated from 100 gms* of
fresh calcium carbonate.
The xylene was removed, but it was not possible to
further purify the product which distilled 69*5-78°C./8ram. and weighed 329 gms.
(44 per cent.).
3
,
1-Dibromoisopropyl n-Propyl Ether. This compound was prepared in the
same manner as the ethyl ether.
The impure product from a 3 mol batch distilled
between 84-88°C./9mm. and weighed 258 gms. (33 per cent.).
•was removed by extraction with 10 per cent* sodium hydroxide.
Sodium and potassium
metals reacted with the cyclopropyl ethers and could not be used as drying agents.
The purification was completed by a fractional distillation.
Tests for Impurities in Cyclopropyl Ethers. Perbenzoic acid in toluene solution was
used to determine the unsaturates present in cyclopropyl ethers.
However, the per­
benzoic acid reacted very slowly with the methyl ether over the course of many days.
Persumably the same slow reaction occurs with the other cyclopropyl ethers.
Halogens were detected by means of a modified Beilstein test17.
Peroxides were detected by shaking a small portion of the ether with a neutral
solution of aqueous, potassium iodide.
Absence of a yellow color within half an hour
indicated absence of peroxides.
-Dibromopropyl Alkyl Ethers.
5 gms. of each alkyl cyclopropyl ether was dis­
solved in 50 cc. of chloroform and immersed in an ice water bath.
Slightly less than
an equivalent amount of bromine in 50 cc. of cold chloroform was added slowly.
The
chloroform was evaporated and the residue was fractionated under diminished pressure.
Anal, of methyl ether: Calcd. for C4H6Br20 ; Br, 68.91. Found: Br, 68.51, 6Q.47.
Anal, of ethyl ether: Calcd. for CQH10BrsO: Br, 64.96. Found; Br, 63.67, 63.98.
P -Bromopropionic Acid. 2 gms.
of (X, Y -dibromopropyl
alkyl ether was reacted with
7 cc. of 45 per cent, nitric acid in a test tube immersed in tap water.
The tube
was shaken from time to time and allowed to react for 2G hours. The aqueous portion
was extracted 5 times with diethyl ether and the ether was extracted with dilute
sodium hydroxide, taking care against a rise in temperature.
The solution was made
acid to methyl orange with sulfuric acid and was extracted with ether as before.
The ether was evaporated and the residue was extracted with hot petroleum ether.
The /3-bromopropionic acid was recrystallized from this solvent until further re­
crystallization did not change the melting point.
The product obtained from methyl cyclopropyl ether which was prepared from
-10-
?
3j^/3'-dibromoisopropyl methyl ether was analyzed.
23.55;
H, 3.29.
Found; C, 23.58, 23.57;
Physical Properties.
Anal,
Calcd, for C3H5BrOs ; C,
H, 3.35, 3.34.
All density, refractive index and surface tension measurements
were made under thermostatic control at 25°C.
pyknometer and were corrected for air bouyancy.
Density measurements were made by a
hefractive index measurements were
made with an Abbe/ refractometer. Surface tension measurments were determined by the
well known bubble method9 .
The vapor pressure of methyl cyclopropyl ether at 26°C. was found to be 414 mm.
An excess of this ether was introduced into a gas burette containing a measured
volume of air.
The vapor pressure was calculated from trie increase in volume.
Allyl Methyl Ether. This compound was prepared from allyl iodide and sodium methoxide1*.
Anal,
Calcd. for C4HeO;
C, 66.63;
H, 11.18.
Found; C, 67.40,67.30;
H, 11,22, 11,31.
Summary
I.
*-dichloroisopropyl methyl ether,.3 ,y/3 '-dibromoisopropyl methyl,ethyl,
n-propyl and n-butyl ethers were prepared by alkylation of the corresponding dihaloisopropanol with the proper dialkyl sulfate.
2*
^9
f-dibromoisopropyl bromomethyl ether was prepared from
'-dibromo-
isopropanol, trioxymethylene and hydrogen bromide.
3. /4,^/3 1-dibromoisopropyl n-butyl ether was prepared froin/3 ,^3 '-dibromoisopropyl
bromomethyl ether and propyl magnesium bromide*
4. Cyclopropyl methyl, ethyl, n-propyl and n-butyl ethers were prepared by cyclization of
^dihaloisopropyl alkyl ethers in acetamide with zinc in the presence
of sodium iodide and sodium carbonate at 14C°C.
The distilling range, density,
refscactive index and surface tension of each cyclopropyl ether was determined.
11-
Footnotes
1, Abstract presented before the Organic Division at the 100th meeting
of the American Chemical Society, Detroit, Michigan, September 12, 1940,
2, Abstracted from the thesis submitted by Sylvan E, Forman to the Faculty
of the Draduate School of t.„e University of Maryland in partial fulfill­
ment of the requirements for the degree of Doctor of Philosophy, June,1940,
3, Krantz, Carr, Forman and Evans; J, Pharmacol, and Exp, Therap, 6D, 207-220
(1940), Black, Shannon and Krantz; Anesthesiology, in press,
4, Hess and Fink, Ber, 48, 2003 (191b), Simpson and Purvis, J, Chem,S6c,
127 2735-45 (1925),
Hibbert and Whelan, J, Am, Chem, Soc, bl 1943 (1929),
5, Blanchard, Bull, soc,
chim, 4 41, 824 (1927),
6 , Sattler, Altamara and
Prener, J, Am, Chem, Soc, J57 333 (1935),
7, Blanchard, Bull, soc,
chim, 4 45, 1194-1204 (1931),
8 , Haas, McBee, Hands and
Gluesenkamp, Ind, Emg, Chem,
9 , Su^fjen, Parachor and Valency,
Boutledge
28_
1178-1181(1936),
and Sons, Ltd, 1930,
10, Gillian. Organic Chemistry, Vol, II. p, 1739,
11, Cohen, Organic Chemistry for Advanced Students, 5th Edn. Vol, II, pp 19-28,
12, Mumford and Philips, J, Chem, Soc. 2112 (1929). Gilman, Organic Chemistry,
p, 1733. John Wiiey and Sons, Inc, New York, 1938,
13, Bruhl, Ann, 200,178 t(l880) ♦
14, Irvine, MacDonald and Soutar:^ J, Chem, Soc, 107, 349 (1915),
15, Jacobs and Heidelberger, J. Am. Chem. Soc. 39, 1465 (1917), Simpson, J,
Am. Chem, Soc._40, 675 (1918). Lederer, J, Prakt, Chem. 2 42, 384 (1890).
Kendall and McKenzie, Org, Synth. Ill, 25 (1923). Roj&hn, Ber. 54B 3115
(1921).
16, Volhard, Ann, 242, 163
(1887).
Romberg. Ann, 370, 238 (1909).
17, Ruigh, Ind. Eng, Chem.
Anal. Ed, IX, 250 (1939),
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