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A comparison of the electron donor properties of 1,3- and 1,4-dioxane

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COMPARISON OP THE ELECTRON DONOR PROPERTIES
OF 1 , 3 - AND 1,4 -D I O X A N E
A T hesis
P resen ted
the F a c u lty
to
of th e D epartm ent o f C hem istry
The U n i v e r s i t y
of S o u th ern C a lif o rn ia
In P a r ti a l F u lfillm e n t
of
th e R equirem ents
for
th e D egree
M aster o f S c ie n c e
by
V i n c e n t P e r r y G uinn
Ju n e 1941
UMI Number: EP41536
All rights reserved
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TABLE OP CONTENTS
CHAPTER
I.
PAGE
DISCUSSION OP THE P R O B L E M .............................................................
Types and m echanism s
of v alen ce
E le c tro n d o n o r-acce p to r a d d itio n
The d i o x a n e s a s
compounds
as
P o ssib le a d d itio n
compounds o f b o r o n
an e l e c t r o n a c c e p to r
th e d io x an es
• • •
1
1
2
3
• • • • • • • •
3
PERTINENT INFORMATION PROM THE LITERATURE . . . .
6
1 .3 -D io x an e
and
• •
• • • • • • • •
Boron t r i f l u o r i d e
triflu o rid e
II.
e le c tr o n donors
• • • • • • • .
1
• • • • • • • • • • • • • • • • • •
P h y sical p ro p e rtie s
• • • • • • • • • • • • •
M ethods o f p r e p a r a t i o n
6
6
• • • . . • • • • • •
7
C hem ical p r o p e r t i e s
• • • • • • • • • • • • •
7
A dditio n
• • • • • • • • • • • • •
7
• • • • • • • • • • • • • • • • • •
8
1.4 -D io x an e
compounds
P h y sical p ro p e rtie s
• • • • • • • • • • • • •
M ethods o f p r e p a r a t i o n
8
• • • • • • • • • • •
9
C hem ical p r o p e r t i e s
• • • • • • • • • • • • •
9
A d d itio n
• • • » • • • • • • • ♦ •
10
• « • • • • • . • • • • • • •
20
compounds
Boron t r i f l u o r i d e
P h y sical p ro p e rtie s
M ethods o f p r e p a r a t i o n
..........................................
20
..........................
20
C hem ical p r o p e r t i e s
• • • • • • • • • • • • •
21
A d d i t i o n compounds
• • • • • • • • • • • • •
21
iii
CHAPTER
III.
PAGE
PREPARATION AND PURIFICATION OF REAGENTS . . . .
............................
1 .3 -D io x an e
.
• • • • • • • • • •
22
1 .4 -D io x an e
• • • • • • • • • • • . • • • • •
24
Boron t r i f l u o r i d e
C hloroform
• • • • . • • • • • • • • •
......................
28
. . . . . .
29
• • • • • . • • • • • • •
29
• • • • • • •
C arbon t e t r a c h l o r i d e
IV.
22
APPARATUS, PROCEDURES, DATA, GRAPHS,
CALCULATED VALUES
.................................................
P r e li m i n a r y w ork • • • • • • • • • • • • • • •
B oron t r i f l u o r i d e — 1 ,3 - d io x a n e a d d i t i o n
T he M e n z i e s - S m i t h a p p a r a t u s
• •
30
30
30
• • • • • • • •
33
H igh-vacuum work • • • • • • • • • • • • • • •
37
The v a p o r t e n s i o n s
A dditio n
of 1 ,3 -d io x an e
• • • • •
37
compounds o f 1 , 3 - d i o x a n e and
horon f lu o r id e
• • • • • • • • • • • • • •
42
A d d i t i o n compounds o f 1 , 4 - d i o x a n e and
boron f lu o r id e
V.
V I.
DISCUSSION
• • • • • • • • • • • • • •
48
.............................................................................................
58
S U M M A R Y .............................................•..........................................................
62
BIBLIOGRAPHY
.......................................................................................................
63
LIST OP TABLES
TABLE
I.
II.
III.
IV .
V.
PAGE
A d d i t i o n Compounds o f 1 , 4 - D i o x a n e
I n d i c a t e d A d d i t i o n C o m po unds
V I.
. . . . . . . .
in
Th e V a p o r T e n s i o n s
F orm ation of th e 1 :1
• • • • • • • • • • • . • •
Com plex o f
in
of
t h e H igh-vacuum
D i s s o c i a t i o n D ata
— 1 ,4 -D io x an e
X I.
of
43
th e 1 :1 Boron T r i f l u o r i d e
— 1 , 3 - D i o x a n e Com plex
X.
40
1 ,3 -D io x an e
W o r k ............................................................................................................
D i s s o c i a t i o n D ata
32
37
and Boron T r i f l u o r i d e
IX.
25
of 1 ,3-D ioxane by th e
H ig h - v a c u u m M ethod
V III.
23
of 1 ,3-D ioxane by th e
M e n z i e s - S m i t h M ethod
V II.
17
the P re lim in a ry
• • • • • ...........................................................
The V a p o r T e n s i o n s
11
Com plex o f 1 , 3 - D i o x a n e
and Boron T r i f l u o r i d e
Work
• • •
. . . . . . . . .
Th e V a p o r T e n s i o n s o f 1 , 4 - D i o x a n e
the 1 :1
• • • • • • •
of 1 ,4-D ioxane
P r e p a r a tio n of th e 1 ,3 -D io x an e
F orm ation of
•
44
th e 1 :1 Boron T r i f l u o r i d e
Complex . • • . • • • • • . . . •
49
D i s s o c i a t i o n D ata o f th e 2 :1 B oron T r i f l u o r i d e
- - 1 , 4 - D i o x a n e Com plex • • • • . • • • • • • • •
55
LIST OF FIGURES
FIGURE
1.
2.
PAGE
The V a p o r T e n s i o n s
of 1 ,4 -D io x an e
D ia g ra m o f t h e A p p a r a t u s Used i n
..................................
27
the
P r e l i m i n a r y Work o n t h e B o r o n T r i f l u o r i d e - 1.3-D ioxane A d d itio n
• • • • • • • • • • • • •
3.
D iagram of
th e M enzies-S m ith A p p aratu s
4.
D iagram of
t h e B u lb Used i n
• .
• •
31
•
34
th e H igh-vacuum
Work on V a p o r . T e n s i o n s a n d D i s s o c i a t i o n
P ressures
38
5.
The V a p o r T e n s i o n s
of 1 ,3 -D io x an e •
6.
The D i s s o c i a t i o n P r e s s u r e s
of
The E q u i l i b r i u m
C onstants
R eactio n of th e
1 .3 -D io x an e
8.
of
.
The D i s s o c i a t i o n P r e s s u r e s
C o n stan ts
R ea ctio n of th e
1 .4 -D io x an e
10,
.................................
of
of
• • • • •
th e 1 :1 Boron
• • • • • • •
50
th e D is s o c ia tio n
Com plex • • • • • • • • • . . . • •
T he D i s s o c i a t i o n P r e s s u r e s
T he E q u i l i b r i u m
47
1 :1 Boron T r i f l u o r i d e —
T rifIu o rid e --l,4 -D io x a n e
11.
45
1 :1 Boron T r i f l u o r i d e - -
Com plex .
The E q u i l i b r i u m
• • • • • • •
the D is s o c ia tio n
T r i f l u o r i d e — 1 , 4 - D i o x a n e Com plex
9.
41
th e 1 :1 Boron
T r i f l u o r i d e — 1 , 3 - D i o x a n e C om plex
7.
• • • • • • •
C o n stan ts
52
o f t h e 2 : 1 Boron
Com plex
of
• • • • • • •
54
the D is s o c ia tio n
R e a c tio n o f th e 2 :1 Boron T r i f l u o r i d e —
1 . 4 - D i o x a n e Com plex • • • • • • • • • • • • • •
57
CHAPTER I
DISCUSSION OP THE PROBLEM
The s t u d y o f t h e
rad icals
and io n s
to
forces
one a n o th e r
fu n d am en tal ch em ical s tu d y .
ty p es
of
th ese
w hich h in d a to m s, m o le c u le s ,
so -called
"valence"
resu lts
of an in v e s tig a tio n
v alen ce
in an e ffo rt
in te ra c tio n
d in ate
co v alen t.
to
m o lecules
th ese
In
rep resen ts
i n t o a few c a s e s
the
o f one ty p e o f
th e n a tu r e and e x te n t o f
are u su a lly
placed
in
electro v alen t,
The m e a n in g o f
classifie d
(2)
tw o i s o m e r s .
in to
c o v a le n t and
th ese
term s
is
and need n o t h e d i s c u s s e d
th ree
ty p es
of
o f t e n com bine b e c a u s e
t h r e e m ain
(3)
coor­
common k n o w ­
here.
com bining f o r c e s
In
ions and
of hydrogen b o ndin g,
d i n a t i o n number o r c r y s t a l l a t t i c e
II.
th esis
h u t much m ore
TYPES AND MECHANISMS OF VALENCE
l e d g e among c h e m i s t s
ad d itio n
T his
to d eterm in e
V alence f o r c e s
(1)
known o f t h e v a r i o u s
forces,
o f atom s d i f f e r e n t l y
I.
categ o ries:
a v e ry im p o rta n t and
Much i s
rem ains y e t to be d is c o v e re d .
th e
is
coor­
forces.
ELECTRON DONOR-ACCEPTOR ADDITION COMPOUNDS
the p re s e n t stu d y
pounds by a d d i t i o n s
su b jec t of I n te r e s t.
the fo rm atio n of m o lecu lar
in v o lv in g
co o rd in ate
c o v a l e n c e was t h e
C o o rd in ate co v alen ce
ing o f m o lecu les by th e s h a rin g
of p airs
com­
e n tails
the bond­
of electro n s
in
2
w hich one o f th e
two m o l e c u l e s
th e bonding p a i r .
cu le u s u a lly
of
In t h i s manner th e
com ple^-tes o r t e n d s
electro n s.
spoken of as
to
T he c o n n e c t i n g p a i r
of
e l e c t r o n a c c e p to r m ole­
com plete a v a le n c e o c t e t
of e le c tro n s
is
som etim es
th e d a tiv e bond.
A sim p le
exam ple of
pound b y c o o r d i n a t e
the fo rm a tio n of a m o le c u la r
co v alen t fo rces
ammonia a n d b o r o n t r i f l u o r i d e
1
boron f lu o r id e :
H
:F :
•»
to
is
th e
com­
com bination of
fo rm t h e m ono-am m inate of
H.'F*
.•
H*N: +
.. ••
B :F:
••
It
*
H
*F:
4*
THE DIOXANES AS ELECTRON DONORS
im m ediately su g g e sts
on t h e i r p a r t .
of
the m o le c u le s
th e lik e lih o o d
of 1 ,3 - and 1 ,4 -d io x a n e
of e le c tro n donor a c tiv ­
T h e tw o c o m p o u n d s a r e
h erew ith r e p r e ­
electro n -b o n d in g p ic tu re s :
*'o‘
H - •* .. H
H:C
C :H
HtC
o!
H** •• •. *
.C..
H H
**
H:F :
The s t r u c t u r e
se n te d by sim p le
H-*N:B*F:
*•
III.
ity
fu rn ish e s b o th e le c tro n s
'o ’
H .. •• •* .. H
H:C
C:H
1 ,3 -d io x an e
H:C
C.-H
H *' .• •. *' H
.0 .
P r e p a r e d b y S i r Humphrey D av y .
1 ,4 -d io x an e
3
S ince
each of th e
it
was
each m olecule
oxygen atom s p o s s e s s e s
concluded
ad d itio n
co n tain s
two o x y g e n a t o m s , a n d
four unshared
electro n s,
t h a t b o t h compounds m ig h t p o s s i b l y fo rm
compounds i n w h ic h t h e d i o x a n e s w ould a c t a s
tro n donors.
It
is
known t h a t
eth y l
elec­
e th e r a c t u a l l y does
b ind boron f l u o r i d e .
IV.
BORON TRIFLUORIDE AS AN ELECTRON ACCEPTOR
An e x p e r i m e n t a l s t u d y o f
th e d ioxanes re q u ire d
accep to r
compound.
the
th e s e le c tio n
e le c tro n donor ac tio n
of a su itab le
B o r o n f l u o r i d e w as
v ery pow erful tendency to a c c e p t a p a ir
com plete th e b o ro n o c t e t ) ,
fact
th at i t
V.
is
its
of
electro n
chosen because of i t s
of
electro n s
ease of fo rm atio n ,
(to
and
th e
a g as a t room t e m p e r a t u r e .
POSSIBLE ADDITION COMPOUNDS OF BORON TRIFLUORIDE
AND THE DIOXANES
B o th s p a t i a l and
to r u l e
cules
ele c tro n -d rift
out th e p o s s i b i l i t y
attach in g
d io x an es.
to
t h e same oxygen a to m i n
1 d io x a n e and 1 b o ro n f l u o r i d e
o n ly ones
rath er
sim p lified
lik ely
eith er
of
the
of 2 boron f lu o r id e
to
t o 1 d io x a n e w ould a p p e a r
to be d e te c te d ,
acco rd in g
to
to
th is
tre atm e n t.
The q u e s t i o n o f t h e r e l a t i v e
compound a n d t h e
tend
o f two e l e c t r o n a c c e p t o r m o l e ­
Hence, m o le c u la r r a t i o s
be th e
c o n sid e ratio n s
corresp o n d in g 2 :1
sta b ilitie s
compound,
if
of
the 1 :1
b o th e x is te d ,
4
is next
t o tie t r e a t e d
sim p le
electro n -d rift
to th e
q u estio n .
1:1 a d d itio n
electro n s
If
on t h e o r e t i c a l g r o u n d s .
con cep tio n g iv es
eith er
of
th e d io x a n e s w ere to form a
tow ard t h e oxygen atom in v o lv e d
th ereb y b in d in g
the
m ore t i g h t l y
th e oxygen atom .
w ould d e c r e a s e
share
its
cu le.
th e
tendency of
th at
intended
th e 1:1
th ese
T his
o th er
occur,
oxygen atom
in c re a se d b in d in g
th e second
oxygen atom to
th esis
th e
led
to
the
c o m p le x s h o u ld b e m ore s t a b l e
com plex.
to mean t h a t
"ad d itio n
the
sho u ld
c o n sid e ratio n s
the
The w o r d ,
term s,
"stab le",
compound e x h i b i t s
ten d en cy to d i s s o c i a t e
In th is
of
a " d r i f t ” of
e l e c t r o n - p a i r w ith a second bo ro n f l u o r i d e m ole­
corresp o n d in g 2 :1
slig h t
electro n -p airs
In o th e r w ords,
clu sio n
a q u a l i t a t i v e answ er
compound w i t h b o r o n f l u o r i d e ,
to
A gain, a
in to
th e
"com plex",
compound" a n d " m o l e c u l a r
con­
than
is
th e
here
o nly a r e l a t i v e l y
o rig in a l
com ponents.
"com plex com pound",
compound" a r e u s e d
in te r­
ch angeably.
A sim ila r
treatm en t lead s
boron f lu o r i d e — 1 ,4 -d io x a n e
th an the
one to
expect th at
compounds s h o u ld b e m ore s t a b l e
corresponding 1 ,3 -d io x an e
t a n c e b e t w e e n t h e two o x y g en a to m s
com pounds,
sin ce
is
the
less
in
th e 1 ,3 - d io x a n e and s in c e
oxygen i s
tro n e g a tiv e
T h e s e tw o f a c t o r s
oxygen atom s
firm ly
in g
than carbon.
in 1 ,3 -d io x an e
t h a n do t h e
in a decreased
the
to hold
two o x y g e n a t o m s
tendency f o r
the d i s ­
case of
c o n s i d e r a b l y m ore e l e c ­
th eir
cause th e
two
e l e c t r o n s m ore
in 1 ,4 -d io x an e,
the 1 ,3 -d io x an e
resu lt­
to form
5
m o lecu lar
compounds o f t h e
sim p le
e le c tro n d o n o r-acce p to r
ty p e.
I t was
p erim e n ta lly
of th is
th e p u rp o se of
th e h ypotheses h e re d ev elo p ed .
th esis
tu r e background
is
ta k e n up w ith a d i s c u s s io n
o f th e p ro b lem ,
c a tio n of th e re a g e n ts ,
sio n s
the p re s e n t stu d y
the
to
te st
ex­
The r e m a i n d e r
of th e
lite ra ­
th e p r e p a r a t i o n and p u r i f i ­
e x p e rim e n ta l w ork,
d ra w n and a summary o f t h e r e s u l t s .
th e
conclu­
CHAPTER II
PERTINENT INFORMATION FROM THE LITERATURE
I.
1,3 -D I O X A N E (META DIOXANE)
P h y sical p r o p e r tie s .
liq u id
1 ,3 -D io x an e i s
a c o lo rle ss
w ith an a g re e a b le ,
a c e t a l - l i k e odor.
Its b o ilin g
o
2
o
p o i n t h a s b e e n r e p o r t e d a s 1 0 5 C. a t 7 5 5 mm.
a n d 1 0 6 C.
3
a t 7 6 0 mm.
L i k e w i s e , tw o d i f f e r e n t v a l u e s f o r t h e f r e e z ­
in g p o in t o f 1 ,3 - d io x a n e a r e in th e l i t e r a t u r e , nam ely,
0 4
o
5
- 4 5 C.
a n d - 4 2 C.
I t s s p e c i f i c g r a v i t y , a s com pared w i t h
o 6
o
?
w a t e r a t 4 C . , i s 1 . 0 3 9 8 7 a t 1 5 C.
a n d 1 . 0 3 4 2 2 a t 2 0 C.
It
is
m isc ib le w ith w ater,
alco h o l,
e t h e r and m ost o r g a n ic
liq u id s.
^ Hans T. C l a r k e , " R e l a t i o n b e t w e e n R e s i d u a l A f f i n i t y
and C hem ical C o n s t i t u t i o n .
I I I . Some H e t e r o c y c l i c C o m p o u n d s '* ,
J o u r n a l o f t h e C hem ical S o c i e t y , 1 0 1 :1 7 8 8 -1 8 0 9 .
(C hem ical
A b s tr a c ts , 7 :593 (1 9 1 3 )).
L o u is Henry and Aug. D ew ael, " O b s e r v a tio n s of th e
A c tio n o f A lc o h o ls on E s t e r s " , C hem isches Z e n t r a l b l a t t , 9 2 8 30 (1 9 0 2 ).
4
W ils o n B a k e r and F r e d e r i c k B. F i e l d , " C y c l i c E s t e r s
o f S u lf u r ic A cid.
I I . C o n s t i t u t i o n o f M eth y le n e and G ly o x a l
S u l f a t e s and th e R e a c tio n o f M ethylene S u l f a t e w ith T e r t i a r y
B a s e s ” , J o u r n a l o f th e C hem ical S o c i e t y , 8 6 -9 1 (1 9 3 2 ).
( C hem ical A b s t r a c t s , 2 6 : 2 1 6 7 ( 1 9 3 2 ) ) .
Henry and D ew ael,
® Loc.
7
Loc.
cit.
c it.
op. c i t .,
p.
928*
,
7
M ethods
of p rep aratio n .
Two m e t h o d s o f p r e p a r i n g
1 .3 -d io x an e a re
given in th e l i t e r a t u r e :
(1) a m ethod c o v 8
ered by a B r i t i s h p a te n t
in w h ich hexam ethylene te tra m in e
is
t r e a t e d w i t h v a r i o u s mono- o r d i - h y d r i c
presence of acid s
such as h y d ro c h lo ric
alco h o ls
or su lfu ric ,
in
th e
and
(2)
t h e m e th o d b y w h ic h 1 , 3 - d i o x a n e was f i r s t p r e p a r e d , b y H e n ry
9
and Dewael
in 1902, nam ely, th e c o n d e n s a tio n o f t r i m e t h y l ­
ene g l y c o l and trioxyw ethylene i n
p h o ric a c id
th e p resen ce of o rth o p h o s-
as a d e h y d ra tin g agent#
C hem ical p r o p e r t i e s .
L ittle
chem ical p r o p e r tie s
of 1 ,3 -d io x an e,
o rg an ic d e riv a tiv e s
of i t
is
its
1 ,4 -
a re d escrib ed
in
th e l i t e r a t u r e #
to d eco m p o sitio n th an
isom er#
A d d itio n
compounds #
O nly two a d d i t i o n
1 .3 -d io x a n e have been r e p o r te d ,
th e sim p le
th e
a l t h o u g h a number o f
1 . 3 - D i o x a n e i s much m ore s u s c e p t i b l e
is
known c o n c e r n i n g
and n e ith e r
e le c tro n d o n o r-acce p to r
ty p e.
compounds
of th ese
is
of
of
They a r e a w h ite
c r y s t a l l i n e m e r c u r i c h l o r i d e w hich s i n t e r s and decom poses a t
o
10
a b o u t 126 C .,
and a p a l e y e llo w , c r y s t a l l i n e p i c r a t e w h ich
® T. B i r c h a l l and S. C o f f e y , " M e th y le n e E t h e r s ” ,
( B r i t i s h P a t e n t 3 3 8 , 6 2 4 , A u g u s t 3 0 , 1 9 2 9 , t o I m p e r i a l Chem­
i c a l I n d u s tr ie s , L td .)#
( C hem ical A b s t r a c t s , 2 5 :2 4 3 7 ( 1 9 3 1 ) ) .
® H enry and D ew ael,
^
C lark e,
ojd.
0£
.
c i t . , pp.
c i t . , p.
928.
1788-1809.
m elts
in d istin c tly
ad d itio n
at
0 11
57 C.
S m all sam p les
of each of
th ese
compounds w e re p r e p a r e d b y t h e a u t h o r a s a c h e c k on
th e b e h a v io u r of th e 1 ,3 -d io x a n e p re p a re d .
II.
1 , 4 -D I O X A N E (PARA DIOXANE)
P h y sical p r o p e r tie s .
av ailab le
b o ilin g
on t h e
C o n s id e r a b ly m ore d a t a a r e
1 ,4 -d io x an e
th a n on i t s
sp ecific
the v a lu e ,
is
g rav ity
The b e s t f r e e z i n g
the fre e z in g
of 1 ,4 -d io x a n e ,
1.0 3 4 8 4 a t
o
1 5 C.
15
as
liq u id
o
w ork on t h e p h y s i c a l c o n s t a n t s
H
Loc.
Th e
com pared w i t h w a t e r a t
a n d 1 . 0 3 0 3 4 a t 2 0 C.
p o ssessin g a stro n g ,
p o in t d ata
p o in t.
m is c ib le w ith w a te r and m ost o rg a n ic l i q u i d s .
o rle ss
Th e
has been v a r io u s ly re p o rte d in
e
12
1 0 1 . 3 1 C* a t 7 6 0 m m . ,
appar­
e n tly b e in g th e m ost a c c u r a te .
o 13
0 14
g i v e 1 1 . 7 C.
a n d 1 1 . 8 C.
as
o
iso m er.
p o in t of 1 ,4 -d io x an e
the l i t e r a t u r e ,
4 C .,
1 ,3 -
p leasan t
16
It
odor.
of 1 ,4 -d io x an e
is
It
is
a
is
co l­
T he e a r l y
sum m arized,
c it.
^ K u r t H ess a n d Hermann F rah m , " P r e p a r a t i o n a n d P r o p ­
e r t i e s o f P u re D io x a n e " , B e r i c h t e d e r D e u ts c h e n C hem isehen
G e s e l l s c h a f t , 71B :2627-36 (1 9 3 8 ).
( C hem ical A b s t r a c t s , 33:
1663 ( 1 9 3 9 ) ) .
13
F . H. G e t m a n , " F r e e z i n g P o i n t s o f t h e S y s t e m p D io x a n e -T e rtia ry -B u ta n o l" , R e c u e il des tra v a u x ch im iques,
5 6:9 2 7 -3 0 (1 9 3 7 ).
( C hem ical A b s t r a c t s . 3 2 :2 0 1 2 ( 1 9 3 8 ) ) .
14 Hess and F rahm , £ £ .
15 C l a r k e ,
1® L o c .
0£
cit.
.
c it.,
c i t . , pp.
pp.
2626-36.
1788-1809.
9
and th e
o rig in a l referen ces
17
O r g a n is c h e n C hem ie.
n oted
M ethods o f p r e p a r a t i o n .
i n B e i l s t e i n f3 Handbuch d e r
1 ,4 -D io x an e i s
prepared
18
com m ercially by c a t a l y t i c d e h y d r a tio n of d ie t h y l e n e g l y c o l .
19
O th e r m ethods o f p r e p a r a t i o n
are:
(1) h e a tin g e th y le n e
brom ide w ith e th y le n e g l y c o l ,
w ith eth y len e
ch lo ro h y d rin ,
(2)
(3)
com bining e th y le n e
h e a t i n g BB’ - d i c h l o r o d i e t h y l
e t h e r w i t h sodium h y d r o x id e o r w i t h m e r c u r i c o x i d e ,
o x ide,
silv e r
ene g l y c o l ,
o xide o r c u p ric
oxide
o x id e,
plum bous
(4) d e h y d ra tin g
e .g . w ith pho sp h o ric a c id and
(5)
eth y l­
h eatin g
eth y l­
ene o x id e w i t h so d iu m h y d r o x i d e .
20
C hem ical p r o p e r t i e s .
1 ,4 -D io x an e i s
to x ic,
and
can
21
form e x p lo s iv e m ix tu re s w ith a i r .
v e n t f o r many s u b s t a n c e s ,
in clu d in g
It
is
an e x c e lle n t s o l­
cellu lo se a c e ta te ,
resin s,
^ B e i l s t e i n ’ s H an d b u ch d e r O r g a n i s c h e n Chem ie ( B e r l i n :
J u l i u s S p r i n g e r , 1934). 1 9 :3 ( 4 t h E d i t i o n , u p to 1 9 1 0 ) ;
19:609 ( 4 th E d i t i o n , 1 9 1 0 -1 9 1 9 ).
Henry D r e y fu s , " C y c lic E t h e r s " , (U n ite d S t a t e s
P a t e n t 2 , 0 7 2 , 1 0 1 , M arch 2 , 1 9 3 7 ) .
(C hem ical A b s t r a c t s ,
31:2613 ( 1 9 3 7 )).
C a r l e t o n E l l i s , The C h e m i s t r y o f P e t r o l e u m D e r i v a ­
t i v e s , V o l u m e _I (New Y o r k :
The C h e m i c a l C a t a l o g Company,
I n c . , 1934)'", p . 5 5 5 .
C.
L . M. B r o w n , " C o n s t i t u t i o n a n d T o x i c i t y o f t h e
G ly c o ls " , P h a rm a c e u tic a l J o u r n a l , 140:49 (1 9 3 8 ).
( C hem ical
A b s t r a c t s , 5 2 : 5 5 5 4 ( 1 9 3 8 ) T»
^
G. W. J o n e s , H. S e a m a n a n d R . E . K e n n e d y , " E x p l o s ­
iv e P r o p e r t i e s o f D io x a n - a ir M ix tu r e s ” , I n d u s t r i a l and E n g i­
n e e rin g C hem istry, 2 5:1283-6 (1 9 3 3 ).
(C hem ical A b s t r a c t s ,
28:325 (1 9 3 4 )).
10
22
gums,
fats
and o i l s .
decom poses
On h e a t i n g
e ssen tially
C4 H8 ° 2
o
to 459-534 C .,
23
1 ,4 -d io x an e
as fo llo w s:
2 CO + Hg + C2 H6 .
C om m ercial 1 , 4 - d i o x a n e c o n t a i n s s e v e r a l i m p u r i t i e s : a
24
25
p ero x id e,
a c e ta l, g ly co l a c e ta l,
a c e t i c a c id , and w a te r.
26
D ioxane o x id iz e s io d id e s to f r e e i o d i n e .
A d d itio n com pounds.
d itio n
A lth o u g h a l a r g e number o f a d ­
compounds o f 1 , 4 - d i o x a n e h a v e b e e n p r e p a r e d ,
two a r e
o f the
n am ely,
th e
w ould a p p e a r
only
c le a r - c u t e le c tro n d o n o r-acce p to r
com pounds,
th at
in
ty p e,
27
C^HgOg^SOg a n d C ^ H g O g ^ S O ^ .
It
the l a t t e r
th e dioxane m olecule a r e
sh arin g
case b o th
oxygen atom s
e le c tro n s w ith s u lfu r
of
tri­
oxide m o le c u le s.
2 2
E llis,
0£
. .c it.,
p.
555.
23
P h . G r o s s a n d H. S u e s a , " T h e r m a l D e c o m p o s i t i o n o f
D ioxane", M o n a tsh a fte , 68:2 0 7 -1 4 (1 9 3 6 ).
(C hem ical A b s t r a c t s ,
3 0:7989 ( 1 9 3 6 ) ) .
^
E r n s t E ig e n b e r g e r , " O c c u rre n c e o f P e r o x id e i n Crude
D io x a n e " , J o u r n a l f u r p r a k t i s c h e C hem ie, 1 3 0 :7 5 - 8 (1 9 3 1 ).
( C hem ical A b s t r a c t s , 2 5 :3 3 1 5 (1 9 3 1 ))•
^
Hess and F rahm ,
ojs.
c i t . , pp.
2627-36.
A braham S a i f e r a n d James H u g h e s , " D io x a n e a s a
R e a g e n t f o r t h e D e t e c t i o n a n d D e t e r m i n a t i o n o f S m a l l Amounts
of Io d id e .
I ts A p p lic a tio n to th e D e te c tio n of Io d id e in
Io d iz e d S a l t " , J o u rn a l o f B io lo g ic a l C h em istry , 118:241-5
(1937).
( C hem ical A b s t r a c t s , 31:3 9 5 3 '( 1 9 3 7 ) ) .
^
C. M. S u t e r , P . B . E v a n s a n d J a m e s M. K i e f e r ,
" D i o x a n e S u l f o t r i o x i d e , a New S u l f a t i n g a n d S u l f o n a t i n g
A g e n t" , J o u r n a l of th e A m erican C hem ical S o c i e t y , 6 0 :5 3 8 -4 0
(1938).
( C hem ical A b s t r a c t s , 3 2 :3 4 0 5 ( 1 9 3 8 ) ) .
©
11
T ab le I l i s t s
every m o lecu lar
w hich th e w r i t e r has b e e n a b le
literatu re,
w ith th e
o rig in a l reference
Handbuch i s
in
referred
compound o f 1 , 4 - d i o x a n e
to d is c o v e r m ention of in
C hem ical A b s t r a c t s
each c a se .
to
in stead
the
r e f e r e n c e and th e
In c e rta in
cases B eilstein * s
of C hem ical A b s t r a c t s .
TABLE I
ADDITION COMPOUNDS OP 1 , 4 -D IO X A N E
F orm ula
C hem ical A b s t r a c t s
reference
O rig in a l re fe re n c e
D«SO,
32:3405
(1938)
D*2S03
2D*InBr-:
32:3405
32:2913
(1938)
(1938)
D*(C0C1)2
32:2130
(1938)
D 'H gC lg
( S e e B e i l s t e i n 1s
Handbuch, 19:3)"'
J o u r n a l o f th e A m eri­
can C hem ical S o c i e t y ,
6 0 :5 3 8 -4 0 (1938)
Loc. c i t .
J o u r n a l of th e A m erican C hem ical S o c i e t y ,
6 0 :3 0 6 -8 (1938)
B e r ic h te d e r D eutschen
C hem ischen G e s e l l s c h a f t , 71B :32-4 (1938)
A t t i d e l l a R ea le Accadem ia d e l L i n c e i ( R end i e o n t i ) , ('5) ', 1 6 1 : 8 9
See a l s o :
Journal of
th e A m erican C hem ical
S o c ie ty , 60 :23 0 8 -1 1
“( 1 9 3 8 )
See a l s o :
Journal fu r
p r a k t i s c h e C hem ie,
1 4 9 :30-54 (1937)
J o u r n a l o f th e A m erican C hem ical S o c i e t y ,
6 0 :2 3 0 8 -1 1 (1938)
Loc. c i t .
(B oth a r ­
ticles )
P harm azeutiache Z entr a l h a l l e f u r D euts chl a n d , 7 7 :5 9 1 -3 (1936)
33:69
(1939)
31:6615
(1937)
D • HgB rg
33:69
D*HgIg
31:6615 (1937)
3 3 :6 9 (1939)
3 1 :2 1 2 (1937)
2D * H g C lg
(1939)
12
TABLE I (Continued)
3 1:212
31:212
3 1:212
31:212
31:1815
(1937)
(1937)
(1937)
(1937)
(1937)
31:1815
31:1815
31:1815
31:1815
31:4321
(1937)
(1937)
(1937)
(1937)
(1937)
31:4321
31:4321
31:4321
31:4321
31:4321
31:6615
(1937)
(1937)
(1937)
(1937)
(1937)
(1937)
35:1717
(1941)
D*CdCl2
31:6615
(1937)
D * C d B r2
31:6615
(1937)
D»CdI2
31:6615
(1937)
D*C o C12
31:6615
(1937)
2D*ZnClg
31:6615
(1937)
2D*ZnBr2
31:6615
(1937)
2D*ZnI2
31:6615
(1937)
2D .C oB r2
31:6615
(1937)
2D *H gB r?
2D*HgIo
2D*Hg(CN).
D-HCIO^H^O
12D *N i(C104 )2
1 2 D*C o ( C 1 0 J ) 2
12D «M n(C 104 ) 2
12D*Cu(C10a )2
D *L iC l
D *LiB r
2 D * L iI
3D»lTaI
D*KI
2D*NH4 I
D«CaCI2
«6H2 0
«6H2 0
« 6 Ho 0
»6H20
Loc. c i t .
Loc. c i t .
Loc. c i t .
Loc. c i t .
Na t u u r w e t e n s c h a p p e l i .1k
T i.id s c h r if t, 1 9:12-5
(1937)
Loc. c i t .
Loc. c i t .
Loc. c i t .
Loc. c i t .
Journal fu r p ra k tisc h e
C hem ie. 1 4 8 :8 1 -7 (1937)
Loc. c i t .
Lo c . c i t .
Loc. c i t .
Loc. c i t .
L oc. c i t .^
Journal f u r p ra k tisc h e
Chem ie. 1 4 9 :3 0 - 5 4
(19371
T ran sactio n s
S e e a l s o : __ ________________
o f t h e K e n tu c k y Academy
of S cien ce, 7 :85-9
119381
J
Journal fu r p rak tisch e
C hem ie. 1 4 9 :3 0 -5 4
(1937)
See a l s o :
Jo u rn a l of
th e A m erican C hem ical
S o c i e t y , 6 2 :3 5 2 2 (1940)
Loc. c i t .
(B oth a r t i c le s)
Loc. c i t .
(B oth a r t i c le s)
Loc. c i t .
( B oth a r t i c le s)
Loc * c i t .
( B oth a r t i c le s)
Loc • c i t .
(B oth a r t i c le s)
Loc. c i t .
(B oth a r t i c les)
Loc. c i t .
( B oth a r t i c le s)
13
TABLE I (Continued)
2D *N iI2
31:6615
(1937)
L oc * c i t .
(B oth a r t i c "1 /\
Xuo
L oc * c i t .
(B oth a r t i c JLOO )
Journal fu r p ra k tisc h e
C hem ie, 1 4 9 :3 0 - 5 4
(1937)
See a l s o :
T ran sactio n s
o f t h e K e n tu c k y Academy
of S cien ce, 7:85-9
11938)
L oc * c i t .
(B oth a r t i c le s)
Loc. c i t .
(B oth a r t i c le s)
Loc. c i t .
(B oth a r t i e le s)
Journal fu r p ra k tisc h e
Chem ie, 1 4 9 :3 0 - 5 4
(1937)
Loc. c i t .
Loc. e x t.
Loc • c i t .
Loc. c i t .
Loc. c i t .
Loc. c i t .
Loc* c i t .
Loc* c i t .
Loc. c i t .
Loc. c i t .
Loc. c i t .
Loc. c i t .
Loc. c i t .
Loc. c i t .
Loc. c i t .
Loc. c i t .
Loc. c i t .
Loc. c i t .
Loc. c i t .
See a l s o :
Journal of
P h y sic a l C hem istry, 38:
1 5 3 - 60 (1 9 3 4 )
J o u r n a l of th e A m erican
P harm aceu tical A sso cia­
t i o n , 2 3 :5 4 1 -3 (1934)
Q Q
2D*CoI0
31:6615
(1937)
2D«CaBiv
31:6615
(1937)
35:1717
(1941)
31:6615
3 5 :1717
31:6615
35:1717
31:6615
35:1717
31:6615
(1937)
(1941)
(1937)
(1941)
(1937)
(1941)
(1937)
D*Cu C12
D*CuBr2
D*SnBr2
D*MnCl2
2D*SrBr2
2D*M gCl2
2D*MgBr2
2D*MgI2
2D*Hg(CN)2
2D*MnBr2
2D*MnI2
2D .P eC l2
2D*FeBr2
2D *FeI2
2D *N iC l2
2D*NiBrp
D*Hg(CN)2
4D*C o I 2
D *SnCl2
31:6615
31:6615
31:6615
31:6615
31:6615
31:6615
31:6615
31:6615
31:6615
31:6615
31:6615
31:6615
31:6615
31:6615
31:6615
31:6615
31:6615
31:6615
31:66X 5
28:2599
(1937)
(1937)
(1937)
(1937)
(1937)
(1937)
(1937)
(1937)
(1937)
(1937)
(1937)
(1937)
(1937)
(1937)
(1937)
(1937)
(1937)
(1937)
(1937)
(1934)
3D *2A sC lg
29:2539
(1935)
2D*CaI2
2D *SrI0
2D* Bair
D * H g(C N S )g
14
TABLE I (Continued)
27:5053
(1933)
*c h i 3
26:3481
(1932)
D*CoI2
d *c 4 h n i 4
D «2SbCl5
2D «SnCl4
26:3481
26:3481
26:3481
26:3481
25:2691
(1932)
(1932)
(1932)
(1932)
(1931)
D*BF3 *2H20
d
2D*SnBr4
2D‘ S n I 4
D»Brf
2 5:2691 (1931)
25:2 6 9 1 (1931)
( S e e B e i l a t e i n 1a
H andbuch, 1 9 :5 )
B e i l a t e i n , 19:3
B eilatein ,
19:3
B eilatein ,
19:3
B e i l a t e i n , 19:3
B eils te in ,
25:2691
D-Ig
19:3
(1931)
(See B e i l s t e i n |a
H andbuch, 19:5)"
B eilatein ,
25:26 91
19:3
(1931)
B e r ic h te d e r D eutachen
C hem ischen G e s e l l s c h a f t ,
6 6 6 :4 1 1 -4 ,,(1 9 3 3 )
Journal fu r p rak tisch e
C hem ie, 1 3 3 :2 8 4 -8 (1932)
Loc. c i t .
Loc. c i t .
Loc. c i t .
Loc. c i t .
Journal fu r p ra k tisc h e
C hem ie, 1 2 9 :2 6 8 -7 2
(1931)
Loc. c i t .
Loc. c i t .
A nnalea d e ch im ie e t de
p h y s iq u e , ( 3 ) , 69:321
See a l s o :
L i e b i g 1s
A n n a le n d e r Chem ie,
122:354
See a l s o :
Journal der
R u ssischen P h y s ik a lis c h chem ischen G e s e l l s c h a f t ,
38:747
See a l s o :
C hem isches
Z e n t r a l b l a t t , (1907 I ) :
16
See a l s o :
A tti d ella
R
e
a
l
e
______ A c c a d e m i a d e i
L in cei (R e n d ic o n ti),
( 5 ) , 16 1 :8 8
See a l s o :
G azzetta
C him ica I t a l i a n a ,
37 1 :1 0 7
See a l s o :
Journal fu r
p r a k t i s c h e Chem ie,
1 2 9 :2 7 3 -7 (1931)
A t t i d e l l a R eale Accad­
emia d e i L i n c e i ( R e n d i c o n t i ) , (5 )', 1 6 1 :8 8
See a l s o :
Journal der
R u ssischen P h y s ik a lis c h chem ischen G e s e l l s c h a f t ,
38 :747
See a l s o :
Journal fu r
p r a k t i s c h e C hem ie, 129:
2 7 3 - 7 ( 1 9 3 1 ’)
15
TABLE I (Continued)
D -IC 1
D *lB r
D*Au C13
2 5 {2691 ( 1 9 3 1 )
2 5 {2691 ( 1 9 3 1 )
27 :653 ( 1 9 3 3 )
D *PtC l,
D * L iC l * H g O
2D *2LiB r.H gO
2D *L iI*2H 20
2D -U aI.2H g0
D*C uC lg.2H g0
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
27
25
D*MnCl2 *2HgO
D *CoClg.2H 20
D *N iC lg.2H 20
D *C aC lg.H 20
3D*ZnClg*2H20
D«ZnBrg*2HgO
2D *2Z nIg.E20
D « A uC l3 . H g 0
D * P tC l4 .2H20
2D «SnCl4 .2Hg0
3D*4HN03
653 ( 1 9 3 3 )
653 ( 1 9 3 3 )
653 ( 1 9 3 3 )
653 (1 9 3 3 )
653 ( 1 9 3 3 )
653 ( 1 9 3 3 )
653 (1 9 3 3 )
653 ( 1 9 3 3 )
653 ( 1 9 3 3 )
653 (1 9 3 3 )
653 ( 1 9 3 3 )
653 (1 9 3 3 )
653 ( 1 9 3 3 )
653 ( 1 9 3 3 )
653 (1 9 3 3 )
653 ( 1 9 3 3 )
75 (1931)
D*ZnClg
D*2CdClg
3D*CoIo
D «C ol2.2H 2 0
D 'C o Ig ^ H g O
D »N iC l2
D- N i B r g
D« S r B r g
35:1717
(1941)
2 D * C u C l2
2 D * C uB rg
D » C g H 5 * S b C lg
35:1717
35:1717
34:2327
(1941)
(1941)
(1940)
D*3((NH3 ) 3 CrC lgO
CHgCHpOCrClo
( nh3 ) S )
34:2330
(1940)
Loc. c i t .
Loc. c i t .
Z e its c h rift fu r anorg a n i s c h e und a l l s e m e i n e
C hem ie, 2 0 8 :
(1932)
Loc. c i t .
Loc. c i t .
Loc. c i t .
Loc. c i t .
Loc. c i t .
Loc. c i t .
Loc. c i t .
Loc. c i t .
Loc. c i t .
Loc. c i t .
Loc. c i t .
Loc. c i t .
Loc. c i t .
Hoe". c i t .
Loc. c i t .
Loc . c i t .
R e c u e il des tra v a u x
ch im iquea, 4 9:1040-4
(1930)
J o u r n a l o f th e A m erican
C hem ical S o c i e t y , 62:
T1940)
Loc . c i t »
Loc. c i t .
Loc. c i t .
Loc. c i t .
Loc. c i t .
Loc. c i t .
T ran sactio n s of th e
K e n tu c k y Academy o f
S c i e n c e , 7 :8 5 - 9 (1938)
Loc. c i t .
Loc. c i t .
Journal fu r p ra k tisc h e
C h em ie, 154 8 3 - 1 5 6
(1939)
Journal fu r p ra k tisc h e
C hem ie, 1 5 4 :2 8 5 -3 0 8
(1940)
16
TABLE I (Continued)
D*NH2 «((NH3)3CrBr2
OCHo CHp 0CrBr2
34:2330
D * B r2 * H B r
(See B e i l a t e i n ^
H a n d b u c h , 19:3")
B e i l s t e i n , 19:3
D*H2 S 04
D^CgHgOyNg
2D *o-phenylened iarsin e te tr a ­
ch lo rid e
N otes:
(1940)
B eilatein ,
19:3
B eilatein ,
19:3
B eilatein ,
19:3
B e i l s t e i n , 19:3
3 3 :5 3 7 7 (1939)
Loc.
c it.
A nnalea d e ch im ie e t de
p h y s iq u e , ( 3 ) , 69:321
See a l s o :
L i e b i g 13
A n n a le n d e r C hem ie,
122:354
See a l s o :
H elv etica
C him ica A c ta , 7 :9 9 3
"(1924)
A t t i d e l l a R ea le A ccadem ia d e i L i n c e i ( R e n d i c o n t i T 7 ~ ( 5 ) , 16 1 : 8 8
See a l s o :
Journal der
R ussiachen P h y s ik a lis c h chem ischen G e s e l l s c h a f t ,
38 :747
Loc. c i t .
J o u r n a l o f th e C hem ical
S o c i e t y , 610-5 (1939)
In th is ta b le , D re p re s e n ts 1 ,4 -d io x a n e .
A ll re fe r e n c e s to B e i l s t e i n in th is ta b le r e f e r to
s e r i e s w hich c o v ers th e l i t e r a t u r e up to 1910.
O ther p o s s i b l e a d d i t i o n
been in d ic a te d ,
T ab le I I .
o rig in al
compounds w hose e x i s t e n c e h as
but not d e fin ite ly
A gain,
the
proved,
t h e C hem ical A b s t r a c t s
are
liste d
in
r e f e r e n c e and th e
jo u rn a l re fe re n c e a re b o th g iv en .
17
TABLE II
INDICATED ADDITION COMPOUNDS OF 1,4 -D I O X A N E
In d ic ated
compound
Compounds o f D a n d
v ario u s a lip h a tic
and a r o m a tic a l c o ­
h o ls, in v olvin g
hydrogen bonds.
A deuterium -bonded
deu teriu m o x id eD com plex.
A zobenzene-D and
a z ob e n z e n e - t r i n i tro p h e n o l-D
com plexes.
A d e u te riu m m ethyl
a l c o h o l - D com plex
in v o lv in g d e u te r­
ium b o n d s .
A w a te r -D com plex
form ed b y h y d ro ­
gen bonds.
C hem ical A b s t r a c t s
reference
O rig in a l re fe re n c e
32:6115
(1938)
32:5674
(1938)
32:5683
(1938)
32:4877
(1938)
32:7319
(1938)
T ran sactio n s of
Faraday S o c ie ty ,
72 8 -4 2 (1938)
See a l s o :
Journal of
th e C hem ical S o c i e t y ,
4 6 0 -4 (1938)
See a l s o :
R ecueil des
tra v a u x chim iques, 56:
1025-33 (1937)
J o u rn a l of th e A m erican
C hem ical S o c i e t y , 60:
605-12(1938)
B e r ic h te d e r D eutschen
C hem ischen G e s e l l s c h a f t ,
7 I B :1 4 1 5 -2 1 (1938)
33:2396
(1939)
J o u r n a l o f C hem ical
P h y s i c s , 7 :9 3 - 9 (1939)
33:4521
(1939)
B u l l e t i n des acadam ie
des s c ie n c e , 373-82
1 1 9 3 8 1 ---------See a l s o :
Journal of
th e A m erican C hem ical
S o c ie ty , 55:4832-7
(1933)
B u l l e t i n des acadam ie
des s c ie n c e , 373-82
119381
J o u r n a l of th e A m erican
C hem ical S o c i e t y , 61:
1 1 5 2 -6 (19391
J o u r n a l o f th e C hem ical
S o c i e t y , 1 4 3 2 -5 (1935)
Journa1 of P h y sic a l
C hem istry, 38:1 5 3 -6 0
T T o f lT
28:945
A m ethyl a lc o h o l-D
com plex i n v o l v i n g
hydrogen bo n d s.
A d i o x a n a t e o f mag­
nesium d im e th y l.
A trich lo ro acetic
a c id - D com plex.
A hydrogen c h lo r id e-D com plex.
(1934)
33:4521
(1939)
33:6263
(1939)
30:1285
(1936)
28:2599
(1934)
TABLE II (Continued)
P r a k t i k a Akad A t h e n o n ,
1 3 :4 2 -4 (1938)
( S u m m a r i z e d , i n Chemisch es Z e n tr a lb la tt,
1 1 9 3 8 I I ) :1 3 9 4 -5 )
Jo u rn a l of G eneral
C h em istry (T J.S .S .R .),
1 0 :1 2 0 2 T l9 4 0 F
A cyl c h l o r i d e - and
benzyl c h lo rid e D com plexes.
An a r s e n i c t r i - -------------- --------------------------c h l o r i d e - D com­
p le x , m eltin g a t
6 6 - 8 C.
(May b e
t h e 3D»2AsCl-z com­
plex re p o rte d in
T ab le I ) .
A q u in o l- D com plex
24:4772 (1930)
m e ltin g a t 93-100
°C
D . C H C l g , D. 2CHC13 ,
3 0 :4 7 3 6 (1936)
D*CC14 a n d D«2CC14
( r e p o r t e d on t h e
b asis of p o la riz a ­
t io n d a ta on ly —
not iso lated ).
N ote:
In
th is
S ince
tab le,
th e
t r i o x i d e — 1 ,4 - d i o x a n e com plexes
28
Evans and K i e f e r
a re a p p a r e n tly of the
th e boron f lu o r id e — 1 ,4 -d io x an e
p r e p a r a t i o n was a t t e m p t e d
t h e i r work i s
1 ,4 -d io x an e,
two s u l f u r
prepared by S u te r,
same t y p e a s
D rep resen ts
J o u r n a l o f t h e A m erican
C hem ical S o c i e t y , 52:
3 2 0 4 -6 (1930]
J o u r n a l o f th e C hem ical
S o c i e t y , 1720-3 (1935)
in th is
w ork,
com plexes whose
some d i s c u s s i o n
of
ap p ro p riate.
They r e p o r t
th a t su lfu r
trio x id e
d i o x a n e a t room t e m p e r a t u r e p r o d u c e s
28 S u te r ,
Evans and K ie f e r ,
0£
d ire c tly
ch arrin g ,
.
added to 1 ,4 -
but
c i t , , pp,
t h a t when
538-40,
19
th e
su lfu r
trio x id e
is
carbon t e t r a c h lo r id e
pounds
sep arate
of dioxane
in
ethy len e
in
m o n o su lfo trio x id e
produces
c h l o r i d e was
ice box.
is
tetra ch lo rid e
cru sts.
ch illed
If
and s t i r r e d
excess
it
mech­
f ro m 60
unchanged f o r
in
su lfu r
The a d d i t i o n
the d i s u l f o t r i o x id e
produces
in to
th e d io x an e is
form ed, w hereas
com­
The s o l u t i o n
could b e p re s e rv e d
th e d is u lf o tr io x id e .
to a su sp en sio n of
or
the a d d itio n
t r i o x i d e was d i s t i l l e d
The s o l u t i o n
the
of th e d io x an e in
ch lo rid e ,
out in w hite f la k e s
c e n t oleum .
s e v e ra l days
to a s o lu tio n
or eth y len e
a n i c a lly w h ile s u lf u r
per
added
excess,
th e
trio x id e
of 1 ,4 -d io x an e
compound i n
carbon
h e a t and th e m o n o s u lfo trio x id e
com plex.
Under anhydrous
c o n d i t i o n s b o t h compounds a r e s t a b l e a t room
O
t e m p e r a t u r e , b u t u p o n h e a t i n g t o 75 C. i n c a r b o n t e t r a c h l o r i d e ,
d eco m p o sitio n ensues w ith
u cts.
B o th compounds r e a c t w i t h w a t e r i n s t a n t l y
fu ric
th at
the
th e fo rm atio n of w a te r-s o lu b le
acid
and r e g e n e r a te d io x a n e .
from th e
ev id en ce of s u lf a tin g
com pounds,
no d i f f e r e n c e
A lthough th e a u th o rs
report
n o t giv e any a n a ly tic a l d ata
U n fo rtu n ately ,
It
is
It
is
im p o rta n t to n o te
the r a t i o s
o f 1 :1 and 2 : 1 ,
su p p o rt of th e se
in tere st
su lfu r
t r i o x i d e — th io x an e a d d itio n
pared,
and
th e m ethods
th at
of
could be d e te c te d .
no d i s s o c i a t i o n p r e s s u r e d a ta
of c o n sid e ra b le
to g iv e s u l ­
and s u l f o n a t i n g a c t i o n
in re a c tiv ity
in
prod­
are
th e
t h e y do
co m p o sitio n s.
g iv en .
corresp o n d in g
compounds h a v e b e e n p r e 29
of p r e p a r a tio n p a te n te d .
T hioxane
29 P a u l N aw iasky and G e rh a rd E . S p r e n g e r ( t o G e n e r a l
A n i l i n e a n d F i l m C o r p o r a t i o n ) , " T h i o x a n e S u l f u r T r i o x i d e Ad­
d i t i o n Compounds", U n ite d S t a t e s P a t e n t 2 , 2 1 9 ,7 4 8 , O c to b e r
29, 1940.
( C h e m ic a l A b s t r a c t s , 3 5 :1 0 6 7 (1941)).
20
is
a s u lf u r an alo g u e of 1 ,4 -d io x a n e ,
having
th e fo rm u la,
C.HoOS.
1 ,4 -T h io x a n e a l s o form s o x o n iu m -ty p e
4
p
30
a m e r c u r l c h l o r i d e w h i c h m e l t s a t 1 7 1 C*
com pounds,
e.g*
The o t h e r a n a l o g u e o f 1 , 4 - d i o x a n e , 1 , 4 - d i t h i a n e , f o rm s
31
s e v e r a l o x o n iu m -ty p e a d d i t i o n com pounds,
e . g . C4 H8 S g * H g l 2 >
3C4HgSg»4AgN0;5, C4H 8Sg»2AuCl2, C4H 8Sg.HgClg, ^HgSg^HgBrg,
2C 4 H8 S2 . 3 H g C l g a n d C4 H8 S g . P t C l 4 .
It
sho uld be n o ted
th a t th e boron f lu o r i d e — 1 ,4 -d io x an e
32
com plex r e p o r t e d b y M eerw ein
(s e e T ab le I ) a l s o c o n ta in s
w ater.
The p r e s e n c e
changes
th e ty p e o f bond in g c o n s id e r a b ly from th e
volved
tem pted
in
in
of w ater
th e anhydrous
in
th e m o lecule v e ry l i k e l y
type in ­
c o m p l e x e s w h o s e p r e p a r a t i o n was a t ­
th e p r e s e n t w ork.
III.
BORON TRIFLUORIDE
P h y sical p r o p e rtie s .
g a s a t room te m p e r a t u r e *
o 33
- 9 9 . 9 C.
M ethods
Boron t r i f l u o r i d e
O
I t m e lts a t -128 C .,
of p re p a ra tio n .
Boron f l u o r i d e
m ost c o n v e n ie n tly by th e r e a c t i o n
3^ B e i l s t e i n ,
31 I b i d . , 1 9 :3
op.
c it.,
(series
is
a co lo rle ss
and b o l l s
is
at
prepared
o f am m onium f l u o b o r a t e ,
19:609
up to
(1910-1919 s e r i e s ) .
1910).
32 Hans M e e r w e in , " B o r o n F l u o r i d e C o m p le x e s a n d t h e
Use o f B oron F l u o r i d e f o r S y n t h e s e s .
P r e l i m i n a r y Communica­
t i o n " , B e r i c h t e d e r D e u ts c h e n C h em isch en G e s e l l s c h a f t , 66B:
411-4 (1 9 3 3 ).
( C hem ical A b s t r a c t s . 2 7 :5 0 5 3 (1 9 3 3 )) .
3 3 E . P o h l a n d a n d W. H a r l o s , " N o n - m e t a l l i c H a l o g e n Com­
pounds.
I I I . S a t u r a t i o n P r e s s u r e s o f B oron T r i f l u o r i d e " ,
Z e i t s c h r i f t f u r a n o r g a n i s c h e und a l l g e m e i n e C hem ie, 2 0 7 : 2 4 2 - 5
(1932).
(“C h e m i c a l A b s t r a c t s , 2 6 : 5 4 7 0 ( 1 9 3 2 ) 7 T ^
21
34
b o ric
o x id e and c o n c e n tra te d
6NH4 BP4
4-
B oron f l u o r i d e
form ing f lu o b o r i c a c id
n o t a t t a c k m ercury n o r e tc h g la s s
under anhydrous
co n d itio n s).
g re a se , b u t n o t neoprene,
e le c tr o n a c c e p to r pow er,
is
q u ite re a c tiv e
and b o r i c a c i d .
(b u t does
I t attack s
apiezon g re a se
A d d itio n compounds.
i n w hich i t
acid :
B2 0 3 + 6H gS 04 ---- >» 8BF3 4- 6NH4 HS04 -I- 3 1 ^ 0 .
C hem ical p r o p e r t i e s .
tow ard w a t e r ,
su lfu ric
I t does
etch g lass
if not
r u b b e r and s to p c o c k
or p icein
Boron t r i f l u o r i d e
cem ent.
ex h ib its
stro n g
f o rm in g n um erous m o l e c u l a r compounds
as an e l e c t r o n - p a i r a c c e p to r .
A few e x 35
a m p l e s a r e t h e c o m p o u n d , PH3 «BF3
and th e b o ro n f l u o r i d e —
36
hexam ethylene te tr a m in e com plexes.
L arg ely because of i t s
tendency
behaves
to form m o le c u la r com plexes, b o ro n f l u o r i d e
ployed v e ry
e x te n siv e ly as an in d u s tr ia l
cataly st for
is
em­
o rg an ic
reactio n s•
^
(New Y o r k :
H a r o l d S im m ons B o o t h , I n o r g a n i c S y n t h e s e s , V o l u m e I
M c G ra w -H ill Book Company, I n c . , 1 9 3 9 ) .
pp. 21-4.
E gon W ib e rg and U l r i c h Heubaum, "T he A c t i o n o f P h o s p h in e on B oron F l u o r i d e ( 2 . W ith R e f e r e n c e t o t h e Q u e s tio n o f
t h e E x i s t e n c e o f B o ro n H a l i d e A d d i t i o n Compounds o f A nom olous
C o m p o s itio n )" , Z e i t s c h r i f t f u r a n o r g a n is c h e und a llg e m e in e
C hem ie, 2 2 5 : 2 7 0 - 2 ( 1 9 3 5 ) .
( C hem ical A b s t r a c t s , 3 0 :2 5 1 3 ( 1 9 3 6 ) ) .
C alifo rn ia
M a r t i n , M.A. t h e s i s ,
L ib r a r ie s , 1940.
The U n i v e r s i t y
o f S outhern
CHAPTER III
PREPARATION AND PURIFICATION OF REAGENTS
I.
S ince 1 ,3 -d io x a n e
had to be s y n th e s iz e d
a r a t i o n was
is
n o t co m m ercially a v a i l a b l e ,
in
th e la b o r a to ry .
37
t h a t o f H enry and D ew ael:
C3 H6 ( 0 H ) 2 -t- HCHO
The d e t a i l s
38
C lark e,
1 , 3 -D I O X A N E
H3 P 0 4
■~
g1 0 0 C,
of th e s y n th e s is
C4 H8 0 g
a re w ell
Due t o a l a c k o f s u f f i c i e n t l y
p rep aratio n s
ent stu d y .
of the
1 ,3 - d io x a n e had
T rim eth y len e g ly c o l,
The m e th o d
(1 ,3 -)
sta te d
larg e
+■ HgO
it
of prep-
.
b y Hans T.
equipm ent t h r e e
t o b e made f o r
the p re s ­
t r i o x y m e t h y l e n e and 85 p e r
c e n t p h o s p h o r i c a c i d w e r e h e a t e d i n a P y r e x bomb t u b e i n a
O
f u r n a c e , a t 100 C ., f o r one o r m ore d a y s .
The m i x t u r e was
then co o led ,
rendered
h y d ro x id e s o lu t i o n ,
w ith in
th e 90-110°C ,
siu m h y d r o x i d e ,
fa in tly
a l k a l i n e w i t h 6 n o rm a l sodium
and d i s t i l l e d .
The f r a c t i o n b o i l i n g
r a n g e was s a t u r a t e d
and th e
sep arated
liq u id
w ith s o lid
d rie d
p o tas­
by r e f lu x in g
3 7 L o u is H enry and Aug, D ew ael,
11O b s e r v a t i o n s o f t h e
A c t i o n o f A l c o h o ls on E s t e r s ” , C h em isch es Z e n t r a l b l a t t ,
928-30 (1 9 0 2 ),
3 ® Hans T, C l a r k e ,
" R e la tio n betw een R e s id u a l A f f i n i t y
and C hem ical C o n s t i t u t i o n ,
I I I . Some H e t e r o c y c l i c Com­
p o u n d s” , J o u r n a l o f th e C hem ical S o c i e t y , 1 0 1 :1 7 8 8 -1 8 0 9 ,
( C hem ical A b s t r a c t s , 7 :5 9 3 (1913)T»
23
w ith s o lid
d rie d
p otassium
liq u id
h y d ro x id e f o r
w as t h e n d i s t i l l e d
sodium i n h o t - a i r - d r i e d
oughly d r i e d ,
m o istu re.
are
The d e t a i l s
sum m arized
i n T ab le
of the
th ree
hours.
Th e
tw ice over f r e s h l y - c u t m e ta llic
ap p aratu s,
g lass-sto p p ered
two t o
and
co llected
dark b o ttle
th ree
in
sep arate
in a th o r­
th e a b sen ce of
p rep aratio n s
III.
TABLE I I I
PREPARATION OP THE 1,3 -D I O X A N E
W eight
of t r i m ethyl ene
g ly co l
W eight
of tr ioxym eth y len e
W eight
T im e I n
o f 85
bomb
p e r c e n t tube
phosphor­
ic acid
T heoret - A ctual
ical
y ield
y ield
Per cent
y ield
gram s
gram s
gram s
hours
gram s
per cent
1 7 .5
3 5 .5
3 0 .0
24
48
66
35
69
58
30
59
50
15
30
25
gram s
13
39
->30
37
56
52
■*This s a m p l e w a s p l a c e d i n a d r i e d a m p o u l e , s e a l e d a n d g i v e n
t o D r . C h a r l e s ;S. C o p e l a n d , o f T h e U n i v e r s i t y o f S o u t h e r n
C a lif o r n ia , f o r u se in a stu d y of th e d i e l e c t r i c c o n s ta n t
a n d d i p o l e moment o f 1 , 3 - d i o x a n e , n e i t h e r o f w h i c h h a s b e e n
r e p o rte d in the l i t e r a t u r e .
The t r i m e t h y l e n e g l y c o l u s e d was
p a n y ’’ P r a c t i c a l "
grade,
red istilled
u n til
The t r i o x y m e t h y l e n e
( polyoxym ethylene
w as
grade,
th e " P ra c tic a l"
and
the
t h e E a s t m a n K o d a k Com­
alm o st c o lo r le s s .
or parafo rm ald eh y d e)
85 p e r
cen t o rth o p h o sp h o ric
24
a c i d was
of "C .P ."
q u ality
(B ak er’s A n aly zed ).
The p u r i f i e d
1 , 3 - d i o x a n e b o i l e d a t 1 0 4 - 5 ° C . a t 7 5 8 - 6 0 nun. a n d f r o z e a t
o
a b o u t - 4 0 C.
I t was c o l o r l e s s w i t h a p u n g e n t o d o r l i k e a c e t a l .
For use
p u rifie d 1 ,3 39
d i o x a n e was d r i e d o v e r a n h y d r o u s c a l c i u m s u l f a t e
and th e n
O
f r a c t i o n a l l y d i s t i l l e d u n d e r h ig h -v a c u u m , r e f l u x i n g a t 21 C .,
o
t h e r e f l u x i n g j a c k e t b e i n g h e l d a t 0 C. a n d t h e r e c e i v i n g
O
t u b e a t - 3 C.
A ll th r e e f r a c t i o n s w ere k e p t f o r u s e , s in c e
th e ir vapor
in
th e high-vacuum w ork,
ten sio n s
w ere p r a c t i c a l l y
II.
th is
id e n tic a l.
1,4 -D I O X A N E
C o m m e rc ia l 1 , 4 - d i o x a n e was a l l o w e d
drous
calcium
cut m etallic
c h lo rid e fo r
sodium f o r
h o t-a ir-d rie d
ap p aratu s,
th oroughly d r ie d ,
and b o ile d
liq u id
at
tus
th u s
hours,
reflu x ed
and f i n a l l y
the d i s t i l l a t e
b ein g
over anhy­
over fre s h ly -
d istille d
co llected
in
in a
g lass-sto p p ered
100-2°C . a t
w ith a stro n g ,
In o rder
dioxane
th ree
stan d
d ark b o t t l e in the absence
O
T h e f i n a l p r o d u c t m e l t e d a t 1 2 C. ( a p p r o x i m a t e ­
of m o istu re.
ly)
tw elve h o u rs,
to
but not d isp leasin g
to be d o u b ly s u re o f
o b ta in e d and to
co n stru cted ,
7 5 8 - 6 0 mm.
the vapor
I t was a c o l o r l e s s
odor.
the p u r it y
of th e 1 ,4 -
check th e M en zies-S m ith a p p a r a ­
ten sio n s
s ta n c e w ere d e te rm in e d a t a s e r i e s
o f a sam ple o f th e s u b ­
of tem p eratu res
by th e
W. A . Hammond a n d J a m e s R . W i t h r o w , " S o l u b l e A n h y ­
d r i t e as a D e s ic c a tin g A gent", J o u rn a l o f I n d u s t r i a l and E n g i­
n e e rin g C hem istry, 2 5 :6 5 3 -9 (1 9 3 3 ).
("Chem ical A b s t r a c t s ,
27:3562 (1 9 3 3 )).
25
40
M e n z ie s - S m ith m ethod*
The v a l u e s
T a b l e IV a l o n g w i t h v a l u e s
l o g l O ^ C 1™1*) ”
8*0588
o b tain ed a re
calcu lated
- 1933*8/T ,
listed
in
from th e fo rm u la ,
g iv e n by H ovorka,
S chaefer
41
and D reisb ach *
TABLE IV
THE VAPOR TENSIONS OF 1 , 4 -D I O X A N E
E xperim ental v alu es
o
•
o
T em p eratu re Vapor te n s io n
2 1 .7
2 3 .6
2 6 .4
2 8 .1
3 0 .1
3 1 .7
4 9 .4
5 2 .1
5 5 .1
57 .7
62 .9
66.7
7 2 .4
7 6 .8
8 1.2
8 5.3
8 9 .0
mm.
27
31
35
40
44
48
112
127
146
163
197
231
287335
394
452
510
C alcu lated
v alues
T em p eratu re Vapor te n s i o n
*c.
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
mm.
2 2 .2
2 8 .8
3 7 .1
4 7 .4
6 0 .5
7 6 .0
9 5 .1
118.
146.
178.
218.
264.
318.
382.
455.
539.
637.
4 0 A l e x a n d e r S m i t h a n d A l a n W, C. M e n z i e s , " S t u d i e s i n
Vapor P r e s s u r e :
I I . A S im p le D ynam ic M e th o d , A p p l i c a b l e t o
B oth S o lid s and L iq u id s , f o r D e te rm in in g V apor P r e s s u r e s , and
A lso B o ilin g P o in ts a t S tan d ard P r e s s u r e s " , J o u rn a l of th e
A m erican C hem ical S o c i e t y , 3 2 :9 0 7 -1 4 ( 1 9 1 0 ).
( C hem ical
A b s t r a c t s , 4:2595 (1 9 1 0 )).
F r a n k H o v o rk a , R a lp h A. S c h a e f e r an d D a le D r e i s b a c h ,
"The S ystem D io x an e and W a te r" , J o u r n a l o f th e A m erican C hem ical
S o c ie ty , 58:2264-7 (1 9 3 6 ).
( C hem ical A b s t r a c t s , 3 1 :9 3 5 ( 1 9 3 7 ) ) .
26
In F ig u re 1 th ese
exp erim en tal d ata
are
p lo tted
along
w ith
t h e v a l u e s com puted fro m t h e H o v o rk a, S c h a e f e r , D r e i s b a c h
42
fo rm u la.
I t is a p p a re n t th a t the check is f a i r l y c lo s e , th e
fact
th at
th e
less
th an th e
ex p erim en tal v alu es a re
com puted ones a t
b e in g due to a s l i g h t
lig h t liq u id
eratu res
th e low er te m p e ra tu re s
so lu b ility
probably
of th e dioxane vapor in
the
on a
th e su rro u n d in g l i q u i d .
Temp­
ts
c a l i b r a t e d 110 C. t h e r m o m e t e r a n d s t e m
c o r r e c t i o n s made a c c o r d i n g
to
the fo rm u la,
co rrectio n
t - t 1)
p ro b ab ly a c c u ra te
l i s t e d i n T a b l e IV a r e c o r r e c t e d
O
t o ± 0 . 2 C.
P r e s s u r e s w ere re a d o n ly
th e n e a re s t m illim e te r
on a m e r c u r y m a n o m e te r e q u ip p e d w i t h
and a r e
to
slig h tly
p e tro la tu m used as
w ere re a d
0 .0 0 0 1 5 4 .
c o n siste n tly
The t e m p e r a t u r e s
an attach ed
cu rate
m eter s t i c k .
The r e a d i n g s a r e
p ro b ab ly on ly a c ­
t o i 1 mm.
The v a l u e s
com puted fro m t h e p r e v i o u s l y m e n tio n e d
for-
43
m ula
check c lo s e ly w ith th o se
l o g 2_QP(mm.) sa 7 . 8 6 4 2
44
H ib b ert.
For use in
- 1 8 6 6 .7 /T ,
com puted fro m t h e
g iv e n b y G a lla u g h e r and
t h e h ig h -v a c u u m work t h e p u r i f i e d
d i o x a n e was f r a c t i o n a l l y d i s t i l l e d
^
form ula,
koc.
c it.
43 L o c .
c it.
1 ,4 -
u n d e r high-vacuum .
The
44 A. F . G a l l a u g h e r an d H. H i b b e r t , " R e a c t i o n s R e l a t i n g
to C arb o h y d rates and P o ly s a c c h a r id e s .
LV. V a p o r P r e s s u r e s o f
th e P o ly e th y le n e G lycols and T h e ir D e r iv a tiv e s " , J o u rn a l o f
th e A m erican C hem ical S o c i e t y , 5 9 :2 5 1 4 -2 1 ( 1 9 3 7 ).
(C hem ical
A b s t r a c t s , 3 2 :9 1 4 (193877^
Vapor T en sio n
(m m .)
1000
900
800
700
500
390
200
100
80
F I g u y a LI____
__
The
so
_
ii
f a p a r Ttenalono
C a l c n l £ t e 4 va^Lue
30
a.s
3.3
3.7
d i o x a n e was r e f l u x e d
from a b a t h a t 30 C ., th e r e f l u x i n g
o
O
j a c k e t b e i n g h e l d a t 1 5 C . , a n d t h e r e c e i v i n g t u b e a t 0 C.
The f i r s t
fractio n
showed a n e a r l y a c c e p t a b l e v a p o r t e n s i o n
o
o f 3 5 . 5 mm. a t 2 3 . 3 C . , b u t w a s d i s c a r d e d t o b e d o u b l y s u r e
of p u rity .
The m i d d l e f r a c t i o n
3 4 . 0 mm. a t 2 3 . 3
was r e j e c t e d
o
C .,
showed a v a p o r t e n s i o n
an d was k e p t f o r u s e .
w ith o u t even checking
III.
its
used
In
o x id e and
th e r e a c tio n
co n cen trated
acid .
su lfu ric
th e
system .
to
acid .
"R eag en t"
o x id e w ere u s e d ,
o f a b o u t 2 0 mm.
th e a p p a ra tu s
d rie d ap p aratu s,
b ein g used
on p a g e 21 o f
th is
b o ric
q u ality
and "C .P ."
T he m i x t u r e w a s w a r m e d w i t h a n o p e n f l a m e
under a p ressu re
tu b e betw een
ten sio n .
o f am m o n iu m f l u o b o r a t e ,
a m m o n iu m f l u o b o r a t e a n d b o r i c
su lfu ric
vapor
t h e p r e l i m i n a r y w ork
was p r e p a r e d b y t h e r e a c t i o n d i s c u s s e d
nam ely,
The e n d f r a c t i o n
BORON TRIFLUORIDE
The b o r o n t r i f l u o r i d e
th esis,
of
th e f i r s t
and
(w ater a s p i r a t o r w ith d ry in g
th e a s p ir a t o r )
p o rtio n
in
of boron f lu o r id e
sweep o u t t h e s m a ll am ount of a i r
T he b o r o n f l u o r i d e w a s p a s s e d
jack eted
co n d en ser and
m o istu re
in
the
flu o b o ric acid .
th en a d r y - i c e
evolved g a s ,
h o t-a ir-
and a l s o
evolved
rem ain in g in
through a w a te r-
jack et
to
tra p
any s u lf u r ic
any
acid
or
29
The b o r o n
p rep ared by th e
U n iv ersity
lite r
t r i f l u o r i d e u s e d i n t h e h i g h - v a c u u m w o r k was
45
same m ethod
b y D r . A n t o n B. B u r g , a t The
of S o u th ern C a lif o r n ia ,
c a p a c ity b ulb a tta c h e d
of a m ercu ry -flo ated ,
The c h l o r o f o r m u s e d
c h lo rid e fo r
m etallic
sodium f o r
in
I t was d r i e d
in
over anhydrous
th en over f r e s h ly - c u t
CARBON TETRACHLORIDE
w as a c o m m e r c i a l g r a d e
as
used
in
of hig h p u r ity ,
th e p r e l i m i n a r y w ork
and was d r i e d
c h l o r i d e and f r e s h l y - c u t m e t a l l i c
th e p u r i f i c a t i o n
B ooth, £ £ .
com­
one h o u r b e f o r e u se*
The c a r b o n t e t r a c h l o r i d e
calcium
valve*
t h e p r e l i m i n a r y w o r k was a
two h o u r s a n d
V.
anhydrous
b y means
CHLOROFORM
of hig h p u r it y .
calciu m
in a one-
th e vacuum a p p a r a t u s
g ro u nd -g lass
IV.
m e rc ia l grade
to
a n d w as s t o r e d
of th e
c i t *, p.
ch lo ro fo rm
21.
over
sodium
(d e s c rib e d above)*
CHAPTER IV
APPARATUS, PROCEDURES, DATA, GRAPHS, CALCULATED VALUES
I.
PRELIMINARY WORK
Boron t r i f l u o r i d e - - 1 , 5 -d io x a n e a d d i t i o n .
used
in
the p re lim in a ry stu d y is
was d r i e d
in a
hydrous
from th e
tube packed w ith a n ­
c a lc iu m c h l o r id e and a s c a r i t e ) .
d id n o t r e a c t w ith
or chloroform ,
e ith er
c h l o r o f o r m and 10 c c .
p o in t),
of boron f lu o r id e
gas
in
carbon te tr a c h lo r id e
through th e
d io x an e s o lu t i o n ,
boron f lu o r id e n o t
order
in to a
carbon te tr a c h lo r id e
to o b ta in a s o lv e n t w ith a
in w hich th e d io x an e d i s s o l v e d .
in
1 : 1 a d d i t i o n was a d d e d ,
slo w ly
in
th a t boron f lu o r id e
a s a m p le o f 1 , 3 - d i o x a n e was p i p e t t e d
o f 35 c c .
low f r e e z i n g
check re v e a le d
or d isso lv e
( t h e m i x t u r e was u s e d
it
excess
An a m o u n t
o f t h e volum e n e e d e d f o r a
in se v e ra l
sm a ll am ounts,
ch lo ro fo rm -carb o n
th e s o lu tio n bein g
by b ubbling
te tra c h lo rid e -1 ,3-
cooled
to
-40°C .
Any
t a k e n u p b y t h e 1 , 3 - d i o x a n e was a b s o r b e d
i n a w eighed a b s o r p t i o n
tu b e f i l l e d
w ith p e lle ts
of potassium
h y d ro x id e.
T he d a t a
in
It
evacuated by a w a te r a s p i r a t o r
system by a d ry in g
A fte r a p relim in ary
m ix tu re
in F ig u re 2.
c u r r e n t o f warm a i r a n d t h e n s t r o n g l y h e a t e d
w ith an open flam e w h ile b e in g
(sep arated
illu strated
The a p p a r a t u s
T a b l e V.
from th e
two s e p a r a t e
ex p erim en ts a r e
shown
ASPIRATOR
u
DRf ICE
KQH
A
M
a r it e
ETMERjORt ICE
ASPjRAfTOR
ft
«<
FI6URE Z
d ia ^ f w
04
o f t h e a p p a r a t u s u s e d in t h e p r e l im in a r y w ork
THE b o r o n TMFUJORIDE — 1,3-D lO M N E ADDITION
32
TABLE V
FORMATION OF THE' 1 : 1 COMPLEX OF 1,3 -D I O X A N E AND BORON
TRIFLUORIDE IN THE PRELIMINARY WORK
W eight
T o tal
of 1 ,3 - w eight
d i o x a n e o f BFg
used
M oles
M oles
Y feight W eig h t
o f BF 3
of 1 ,3 o f BFg
o f BFg
n o t a b ­ a b s o rb ­ a b s o rb ­ d ioxane
ed
used
sorbed
ed
gram s
gram s
gram s
gram s
m oles
m oles
0 .8 8
0 .8 2 6
1 .5 6 3
0 .2 0 7
0*375
0 .6 1 9
1 .1 8 8
0.00910
0*0175
0 .0 1 0 0
0 .0 2 0 0
1 .7 6
The p r i n c i p a l
m easurem ent of
errors
t h e volum es
involved
in
Per cent
d ev ia­
tio n
f r o m 1 :1
M ole
c o m b i n ­in g
ra tio
per
0 .9 1 0
0 .8 7 5
cent
8 .9 6
1 2 .5
t h e m ethod w ere t h e
of boron f lu o r id e
and
th e la c k
of
i n t i m a t e m ixing o f
the boron f l u o r i d e w ith
th e d io x a n e when t h e
f o r m e r was b u b b l e d
th ro u g h th e
the l a t t e r .
th e e r r o r
in
2
per
involved
cen t,
an o th er,
and s in c e
th e p r in c ip a l
one m e n tio n e d .
so lu tio n
of
S ince
e a c h volum e m e a s u r e m e n t was o n l y a b o u t
th e
errors
source of
larg ely
error
T h is w ould a c c o u n t f o r
tended
seems
the
to
c a n c e l one
to be th e second
slig h tly
l o w com­
b in in g ra tio s *
The a d d i t i o n
compound a p p a r e n t l y c r y s t a l l i z e d f r o m t h e
o
m i x t u r e a s w h i t e n e e d l e s ' a t - 4 0 C.
An a t t e m p t t o f i l t e r o u t
the
cry stals
by r a p id
in advance, because
su c tio n f i l t r a t i o n
of th e
fa ile d ,
a s was f e a r e d
im m ediate d e c o m p o s itio n o f th e
p lex by atm ospheric m o istu re .
com­
55
A nother a tte m p t
to
e v a p o r a te away th e
carbon t e tr a c h lo r id e
a t 25°C.
ra to r fa ile d
the
because
alm o st n o n - v o la tile
t o 5 0 #C. u s i n g
com plex decom posed
liq u id
c h lo ro fo rm and
before a l l
of
th e w ater a s p i ­
to a brow n,
th e
v isco u s,
s o lv e n t had ev ap -
o r a t ed •
The s m a l l p o r t i o n
fu lly
sep arated
in dry a i r
ab le,
as
how ever,
of
from t h e
long,
th at
the
c o m p le x w h i c h was s u c c e s s ­
s o l u t i o n rem ained f o r
w h ite,
th ese
n eed le-lik e
cry stals
s e v e r a l hours
cry stals.
con tain ed
It
is
prob­
some c h l o r o f o r m
of s o lv a tio n .
I t was a t
cessity
th is
p o in t
th at
th e ad v an tag e and n e a r n e ­
o f a high-vacuum a p p ro a c h to
t h e p r o b le m was d e f i n i t e l y
reco g n ized •
The M e n z i e s - S m i t h a p p a r a t u s .
it
was a s s u m e d t h a t
rela tio n sh ip s
th e d is s o c ia tio n
At th e
sta rt
pressure,
of any of th e proposed a d d itio n
of
t h e work
tem p eratu re
compounds
could
46
be stu d ied
c o n v e n i e n t l y b y means
A diagram o f t h e
pose is
apparatus
shown i n F i g u r e 5 .
o f t h e M e n z ie s - S m ith m ethod*
co n stru cted
For d e t a i l s
of
tech n iq u e
involved
in
th e m a n ip u la tio n of
reader
referred
to
th e o r ig in a l a r t i c l e
is
th e
for
th is
pur­
ex p erim en tal
th e a p p a ra tu s
the
b y M enzies and
4 6 A l e x a n d e r S m i t h a n d A l a n W. C. M e n z i e s , " S t u d i e s i n
Vapor P re s s u re s
I I * A S im p le Dynam ic M e th o d , A p p l i c a b l e t o
B oth S o lid s and L iq u id s , f o r D ete rm in in g V apor P r e s s u r e s , and
A lso B o ilin g P o in ts a t S tan d ard P r e s s u r e s " , J o u rn a l o f th e
A m erican C hem ical S o c i e t y , 5 2 :9 0 7 -1 4 ( 1 9 1 0 ).
fC hem ical
A b s t r a c t s , 4 :2595 (1 9 1 0 )J .
to
snivavddv miws-saizNaw awi jo wvaovw
e
3 fc r i9 U
47
S m ith.
B efore a tte m p tin g
of
th e 1 ,3 -d io x an e or
ad d itio n
th e
to d eterm in e th e vapor
th e d is s o c ia tio n p re s s u re
compounds p r e p a r e d ,
efficacy
it
of th e a p p a ra tu s,
tech n iq u e by d eterm in in g
ten sio n
curves
was deemed a d v i s a b l e
curve
of any
to
check
t h e m ethod a n d t h e a u t h o r ’s
the vapor
ten sio n
curve
of 1 ,4 -
d io x a n e and
com paring th e d a t a w i t h th o s e r e p o r t e d i n th e
48,4 9
literatu re.
The r e s u l t s , a l r e a d y d i s c u s s e d o n p a g e 2 5 ,
are
listed
lated
in
v alu es,
T a b l e IV a n d p l o t t e d ,
in F ig u re 1.
to g e th e r w ith
The r e s u l t s
When t h e a t t e m p t w a s m a d e t o
curve
of th e 1 ,3 -d io x an e,
w hich i s
t u r e a n d w h ic h was n e c e s s a r y f o r
are
o b tain
sa tisfa c to ry .
th e vapor te n sio n
n o t giv en
th e
th e calcu ­
in
th e l i t e r a ­
in te rp re ta tio n
d is s o c ia tio n p ressu re d ata
ob tain ed
com plexes,
c u r v e w a s o b t a i n e d w h e n lo g -j^ P
a stra ig h t lin e
was p l o t t e d
accu rate,
th at
a g ain st l/T ,
stu d y
em ploying
th e p ressu res
47
Loc.
in
but a la te r,
th e stu d y of
of any
the
and d e f i n i t e l y m ore
th e high-vacuum sy stem re v e a le d
o b ta in e d by th e M en zies-S m ith te c h n iq u e
c it.
A . F . G a l l a u g h e r a n d H . H i b b e r t , ’’R e a c t i o n s R e l a t i n g
to C a rb o h y d ra te s and P o ly s a c c h a r id e s .
LV. V a p o r P r e s s u r e s o f
th e P o ly e th y le n e G ly c o ls and T h e ir D e r i v a t i v e s ” , J o u rn a l o f
th e A m erican C hem ical S o c i e t y , 5 9 :2 5 1 4 -2 1 ( 1 9 3 7 ).
{c f i e m i c a l
A b s t r a c t s , 3 2 :9 1 4 (19387T;
49 F r a n k H o v o r k a , R a l p h A. S c h a e f e r a n d D a l e D r e i s b a c h ,
’’T h e S y s t e m D i o x a n e a n d W a t e r " , J o u r n a l o f t h e A m e r i c a n
C h em ical S o c i e t y , 5 8 :2 2 6 4 (1936)T
( C hem ical A b s t r a c t s ,
3 1 T 9 3 5 Tl937TTi»
36
w ere c o n s i s t e n t l y and m ark ed ly to o h ig h a t
eratu res.
No p l a u s i b l e
ex p lan atio n
of
th e low er
th is
tem p­
d ev iatio n
could
be reco g n ized .
Q u alitativ ely ,
parent s o lu b ility
p etro latu m ,
a p relim in ary
of e ith er
of th e d io x an es
lay er a f te r
th e liq u id
it
from th e
was s h a k e n v i g o r ­
the p e tro la tu m .
A lth o u g h a n o th e r f a i r l y
t h e 1 , 3 - d i o x a n e was
after
in
e i t h e r d io x an e im m ediately s e p a r a tin g
p e tro la tu m as a d i s t i n c t
o u sly w ith
c h e c k had shown no a p ­
in so lu b le,
sev eral attem p ts,
abandon th e use
of
it
p ro b ab ly
liq u id ,
for
i n w hich
could have been found
was c o n s i d e r e d m o re e f f i c i e n t
th e M e n z ie s-S m ith m ethod and u s e
high-vacuum a p p a r a tu s
Even though
n o n -v o la tile
the
th e w ork.
th ese d ata
for
1 ,3 -d io x an e,
o b ta in e d by
th e M e n zies-S m ith m ethod, a r e u n d o u b te d ly 'i n a c c u r a t e ,
are here lis te d
d io x an e,
in
to
T ab le V I.
As i n
th e d a ta
for
th ey
th e 1 ,4 -
te m p e ra tu re s l i s t e d in the t a b l e a re c o rre c te d
O
and a r e a c c u r a t e t o t 0 .2 C ., and t h e p r e s s u r e r e a d in g s w ere
made t o
the
the n e a re s t m illim e te r.
P art
p a re d w i t h t h e m ore a c c u r a t e d a t a ,
high-vacuum a p p a r a tu s ,
i n F i g u r e 5*
of
th ese d ata
are
o b tain ed by u se of
com­
the
37
TABLE V I
THE VAPOR TENSIONS OF 1,3 -D I O X A N E BY THE
MENZIES-SMITH METHOD
T em perature
Vapor
ten sio n
(l/T )1 0 3
°C .
mm.
l/°A .
2 6 .7
2 9 .6
3 1 .3
4 9 .4
5 1.2
52 .8
5 5 .1
57.2
59 .2
6 1 .0
63.3
6 5 .0
67.2
6 9 .4
7 1 .3
38
43
47
3 .3 3 6
3.3 0 4
3 .285
3 .1 0 1
3 .0 8 4
3 .0 6 8
3.047
3.0 2 8
3 .009
2 .9 9 3
2.973
2.958
2 .9 3 9
2 .9 2 0
2.904
111
122
131
143
157
170
182
198
216
232
249
271
The v a p o r
°c.
mm.
l/°A .
7 3 .3
7 5 .2 .
77 .4
7 9 .5
81 .3
83.3
8 5 .4
8 7 .6
8 9.2
9 1 .4
9 2 .2
93 .2
94 .2
9 5 .1
293
313
338
363
386
406
434
461
488
517
526
539
552
560
2 .8 8 7
2.8 7 1
2 .8 5 3
2.8 3 6
2.822
2.8 0 6
2 .7 8 9
2.7 7 2
2 .7 6 0
2 .7 4 3
2 .7 3 8
2 .7 3 0
2 .723
2 .716
HIGH-VACUUM WORK
ten sio n s
of 1 ,3 -d io x an e.
attach ed a c c e sso rie s,
The b u l b
(l/T )1 0 3
II.
c u r v e o f 1 , 3 - d i o x a n e was d e t e r m i n e d
Its
Vapor
ten sio n
T em perature
is
in
The v a p o r t e n s i o n
th e b u lb shown, w ith
In F ig u re 4.
co n stru cted
so
th at
th e m ercury le v e l
b e d r a w n d o w n b e l o w t h e p o i n t m a r k e d !IAH i n F i g u r e 4 ,
order
th a t sub stan ces
of th e bulb p ro p e r.
can be
condensed in to
in
or d is tille d
When t h e m e r c u r y r e s e r v o i r
is
can
out
connected
38
m
m
m
r m
P iau R E
m
4*
DlftQRAM OF THE BULB « S t O
^ H ) S H - V « U W WORK
ON VftPORTEHSIOWS
DISSOCIATION PRESSURES
mo
39
w ith
the atm osphere by tu rn in g
"B ", and th e g ro u n d -g la s s
fo rc e d up in to
th e bulb
th r e e - w a y s to p c o c k m arked
HC” l i f t e d ,
t h e m anom eter s p a c e a s
in creases.
creasin g ,
rod
th e
If
the p re s s u re w ith in
th e p re ssu re w ith in
th e m ercury le v e ls
connected
to
The p r e s s u r e
T he l e f t - h a n d
th e m ain p a r t of
in
sid e
10
—5
is
is
de­
sto p ­
connected w ith
th e
o f t h e m anom eter i s
th e high-vacuum a p p a r a t u s .
t h e m a i n a p p a r a t u s was c o n s t a n t l y
b y a McLeod g a u g e a n d w a s k e p t w i t h i n
and
th e b ulb
may b e l o w e r e d b y t u r n i n g
c o c k ,rB” s o t h a t t h e m e r c u r y r e s e r v o i r
w ater a s p ir a t o r .
m e r c u r y may b e
checked
the l i m i t s ,
10
ram.
mm.
A larg e
sam ple of
th e p u r if ie d
1 , 3 - d i o x a n e was c o n Q
densed
vapor
in to
th e b u lb by a d r y - i c e - e t h e r b a th
t e n s i o n r e a d i n g s made b y means
accu rate
t o £ 0 . 0 5 m m ., a t v a r i o u s
in g b a th a
tw o -lite r beaker,
and m ercury r e s e r v o i r ,
enough w a te r
th e
to
enclosed b u lb ,
and
of a cath eto m eter,
tem p eratu res.
For a h e a t­
w hich su rro u n d e d b o th
was u s e d .
come a t l e a s t
(-8 0 C .)
th e b ulb
The b e a k e r was f i l l e d
tw o i n c h e s
above th e
warmed w i t h a g a s b u r n e r ,
and
w ith
to p of
th e w ater
stirre d
w ith a s t i r r i n g rod by hand.
T em peratures w ere h e ld
O
c o n s t a n t w i t h i n 0 . 1 C, f o r f r o m t w o t o f i v e m i n u t e s f o r e a c h
r e a d i n g , and w e re r e a d t o t h e n e a r e s t 0 . 1 ° C . on a c a l i b r a t e d
o
2 0 0 C. t h e r m o m e t e r .
The t e m p e r a t u r e r e a d i n g s w e r e c o r r e c t e d
o
f o r e x p o s e d s t e m a n d a r e p r o b a b l y a c c u r a t e t o ± 0 . 1 C. f o r
te m p e ra tu re s up to a b o u t 75°C. and
100°C.
to ± 0 .2 °C .
from 75°C.
to
40
The d a t a a r e
giv en in
curve g iv en in F ig u re
ten sio n s
m ethod
5*
of 1 ,3 -d io x a n e ,
(see p ag e,37,
T ab le V II and
The p r e v i o u s
d ata
th e log-j^P ,
l/T
on t h e v a p o r
d e te rm in e d by th e M enzies-S m ith
T ab le V I),
are also
p lo tted
in F ig u re
5*
TABLE V I I
THE VAPOR TENSIONS OF 1 , 3 -D I O X A N E BY THE HIGH-VACUUM METHOD
Vapor t e n s i o n
T em perature
(l/T )1 0 5
E xpT tl . C a lc .
°c.
mm.
3 7 .9
4 0 .2
4 2 .8
4 4 .9
4 7 .7
5 0 .3
5 2 .8
5 5 .0
5 8 .0
6 2 .0
4 4 .1
5 0 .9
58.3
P is
S ince
p lo tted
the f iv e
6 6 .1
accord w ith th e
versus
d ata
at
8 8 .2
8 8 .1
9 8 .6
110 .5
125 .4
151.2
9 9 .1
109 .6
1 2 6.2
151 .0
ic a l
of
l/T ,
o nly
p resen ted
in
l/° A .
3 .2 1 5
3.1 9 2
3 .1 6 6
3.1 4 5
3.1 1 7
3 .0 9 2
3.0 6 8
3 .0 4 8
3.0 2 0
2.9 8 4
on a s t r a i g h t l i n e when
but reveal a slig h t
the h ig h e s t
the vapor te n sio n
eq u atio n s
fa ll
tem p eratu res
o b serv ed and l i t e r a t u r e
p o in t of 1 ,3 -d io x an e,
tatio n
-----------------------------
7 5 .8
The d a t a d o n o t q u i t e
lo g
mm.
v alu es
th e s e f i v e w ere used
eq u atio n .
th is
(N ote:
convexness.
a r e m ost in
for
in
th e b o ilin g
th e
compu­
a l l m athem at­
t h e s i s w ere c a lc u la te d
from
Vapor T en sio n
41
(mm*)
7500
600
SOQ
400
300
200
100
80
60
50
P lg im q
E
'
_______
TJ-ie Vapoi*- Tene-£-<»*&
o f l,3-j«DiPJcan!i
C) “
0
■-
H ig ji^ r a c tttn i P a tte n
= P r o1 fttjina
<3a turn
So
IQ
2.9
3.0
3.1
3.4
3.5
42
t h e d a t a b y t h e m ethod
of l e a s t
These f i v e d a t a g iv e
8.652 - 2 1 6 9 /T .
of
1 , 3- d
Prom t h i s
io x a n e is
p e r m ole, a r a t h e r
is
to
h igh v alu e
the
for
and a
1:1
of 1 ,3 -d io x a n e and boron f l u o r i d e .
2:1
and
(2)
in an attem p t
compound r e v e a l e d
is
ev id en tly
two
so l­
of boron f lu o r id e
th a t boron f lu o r id e
ev id en tly d is ­
th e 1 ,3 - d io x a n e m o le c u le on s ta n d in g w i t h th e l a t t e r
v o la tile ,
v o latile
v isco u s
in
w ith
to
the
fo rm atio n o f an alm o st non­
brow n l i q u i d ,
p ro d u cts.
boron f lu o r id e
form
o th er non­
of 1 ,3 -d io x a n e by
th e brow n l i q u i d
had b e e n p r e v i o u s l y
th e p r e l i m i n a r y w ork ( s e e page 3 3 ) .
of
th ese
two c o m p l i c a t i o n s ,
w ere worked w i t h a t
first
1 .4 3 :1 and 1 . 8 8 : 1 .
However,
h a n d le d m ore r a p i d l y
th e 1:1 r a t i o .
th is
and p o s s i b l e
The d e c o m p o s i t i o n
As a r e s u l t
from
ad d itio n
o b tain ed by th e a c tio n
sev eral hours,
n oted
per degree
T routon c o n s ta n t f o r
(1 ) th a t boron f lu o r id e
liq u id
on 1 , 3 - d i o x a n e ,
ru p ts
(th e
p e r m ole.
2 3 .7 ).
im p o rtan t f a c t s :
in
th e norm al b o i l i n g p o in t
o
t o b e 1 0 2 .7 C. and t h e l a t e n t
h ig h -v a c u u m w ork done by th e a u t h o r
form b o t h a
ub le
eq u atio n
th en 2 6 .4 g ra m -c a lo rie s
A d d i t i o n compounds
The f i r s t
l o g 1 0 P ( in m . ) =•
to be 9920*40 g ra m -c a lo rie s
The T r o u t o n c o n s t a n t i s
1 ,4 -d io x an e
th e r e la tio n s h ip ,
calcu lated
heat of v ap o rizatio n
squares).
th ree
produced d a ta
These d a ta
p o in t on,
gave a p p a re n t
a ll
are
sam ples w hich
com bining r a t i o s
of
o t h e r sam p les w hich w ere
w hich d e f i n i t e l y
listed
in
volum es r e p o r t e d
e sta b lish
T ab le V I I I . ' (N ote:
are
understood
to be
43
gaseous
volum es a t
sta n d a rd
te m p e ra tu re and p r e s s u r e ) ,
TABLE V I I I
FORMATION OF THE 1 : 1
COMPLEX OF 1 , 3 - D I O X A N E AND
BORON TRIFLUORIDE IN THE HIGH-VACUUM WORK
E x p e rim e n t number
1
O r i g i n a l volum e o f
bf3
11.8
cc.
2 .0 7
cc.
3 5 .8
cc.
O r i g i n a l volum e of
1 ,3 -d io x an e
3 . 67cc *
3 .6 1
cc.
1 4 .1
cc.
V o l u m e o f BF 3 a b ­
sorbed
4 . 02 c c ,
2 .0 7
cc •
1 4 .9
cc.
Volum e o f 1 , 3 dio x an e absorbed
3 .6 7 cc.
1 .7 6
cc.
1 4 .1
cc.
M ole c o m b i n i n g
ra tio
1
. 10:1
1 .1 8
•
o
H
P ercen tag e d e v ia ­
t i o n fro m 1:1
S in ce
to
3
2
even la rg e
p ro d u ce a com bining r a t i o
th e
ex isten ce
com plex i s
co n d itio n s
2:1
em ployed i n
lim its
th is
6 .0
%
of boron flu o r id e
g reater
deco m p o sin g ), w i t h i n
of any
18.
excesses
1 .0 6 :1
:1
of
th an
1:1
com bining r a t i o s
g iv en in
T ab le V p ro d u c e s
an average r a t i o
faile d
( e x c e p t on
exp erim en tal e r r o r ,
d isp ro v ed ,
w ork.
%
at
A veraging
T ab le V I II and
th e
of 1 .0 2 :1 ,
le a st for
th e
th e
th e
t h r e e m ole
two g i v e n i n
44
The s a m p le i n w h ic h 2 . 0 7
so rb ed 1 .7 6
o b tain
cc.
o b tain ed a re
tio n pressure
th e low er p o r ti o n
hand,
th e
of
th e
in
curve of
th e
T a b l e IX a n d
in F ig u re
6.
by th e 1:1
of
irrev ersib le
d eco m p o sitio n of
th e d is s o c ia ­
On t h e
of
th e
th e com plex.
to
th e
second a l t e r n a ­
1 , 3 -D I O X A N E COMPLEX
.
o
o
3 6 .5
5 0 .4
6 0 .0
7 0 .5
8 0 .6
8 3 .0
5.2
6.4
8 .4
1 2.0
1 8 .0
1 9 .8
The
in b o th th e p re lim in a ry
DISSOCIATION DATA OF THE 1 : 1 BORON TRIFLUORIDE—
mm.
of
curve
TABLE IX
T o tal
d isso c ia tio n
pressure
of
o th er
tiv e.
T em perature
to
com plex.
the r e le a s e
th e upper p o rtio n
th e h ig h -v acu u m w ork le n d s w e ig h t
1:1
The c u r v a t u r e
com plex.
com plex o b s e rv e d
ab­
in an e ffo rt
c u r v e may i n d i c a t e
d isso lv ed
d eco m p o sitio n of th e
and
listed
s te e p e r slo p e
may i n d i c a t e
pressure
curve p lo tte d
boron f lu o r id e
of boron flu o rid e
o f 1 , 3 - d i o x a n e was s t u d i e d
th e d is s o c ia tio n
The d a t a
cc.
(l/T )1 0 3
l/°A .
3 .2 3 0
3 .0 9 1
3 .002
2 .9 1 0
2 .8 2 7
2 .8 0 8
Ka t m
.x l° 5
a tm .^
1.2
1 .8
3 .0
6.23
1 4 .0
1 7 .0
D isso ciatio n P ressure
(rtcie)
100
do
so
4Q
zo
rP h .© : D i s s o c i a t i o n
tP n essu r ss
©f tiib l s l Bb"On T.cifiuo:<:-i^O'
1. 5-'D:iokano Cottolose _
3.0
3.Z
3.3
3.4
46
The d i s s o c i a t i o n p r e s s u r e m e a s u r e m e n t s w e r e t a k e n w i t h
th e bulb
illu strated
165*6 c c . m inus 0 .7
th e
in F ig u re 4.
tim es
The v o lu m e o f t h e b u l b
th e d is ta n c e
in
cen tim eters
to p o f t h e r i g h t - h a n d m e r c u ry colum n t o
" A 11 i n
th e d iagram .
S .T .P .
(2 .0 7
was u s e d
S ince a t o t a l
cc. boron f lu o r id e
to form th e a d d i t i o n
th at
if
(see
T able IX ),
of 3 .8 3
plu s
1 .7 6
th e
cc,
cc.
is
from
p o i n t m arked
of gas a t
1 ,3 -d io x an e)
com pound, a c o m p u t a t i o n shows
th e
com plex w ere c o m p l e t e l y v a p o r i z e d and c o m p le te ly
O
d i s s o c i a t e d a t 8 3 .0 C ., th e o b serv ed p r e s s u r e sh o u ld be 2 3 .2
o
mm.
T h e p r e s s u r e a c t u a l l y o b s e r v e d a t 8 3 * 0 C. w a s 1 9 * 8 mm.
are v alid ,
en tire ly
a d ev iatio n
o f 15 p e r
i t w ould a p p e a r t h a t
d isso ciated
in
the
cen t.
If
com plex i s
th e vapor s t a t e .
th ese d ata
at
l e a s t alm o st
U n fo rtu n ately ,
a
lack of
tim e p r e v e n te d th e d a t a from b e in g e x te n d e d upw ards
o
t o a b o u t 10 0 C. ( d e c o m p o s i t i o n o c c u r r e d s o o n a f t e r t h e 8 3 . 0
C. r e a d i n g was
F ig u re
to p ,
6
tak en ).
If
m ig h t h av e shown a
th ereb y d e f i n it e l y
of th e vapor.
L ik ew ise,
to
as
o b ta in d ata
th e
is
certain ,
sharp d e c re a se
it
th e
in
th e
curve
slo p e a t
in
th e
com plete d i s s o c i a t i o n
w ould h a v e b e e n h i g h l y v a l u a b l e
t e m p e r a t u r e was d e c r e a s i n g ,
i n v o l v e d was r e a l l y
so a s
to
a rev ersib le
or m erely an i r r e v e r s i b l e d eco m p o sitio n .
The v a l i d i t y
6
had b e e n d o n e ,
e sta b lish in g
t e l l w h eth er th e r e a c t i o n
d isso c ia tio n
th is
of n e ith e r p o rtio n
and e i t h e r
of th e
one g iv e s a v a lu e
a t w hich th e d i s s o c i a t i o n p r e s s u r e
eq uals
for
curve in F ig u re
th e
tem p eratu re
3 8 0 mm. h i g h e r
th an
M
( l/T
5-r #
00
ci
)* ■
o.
48
th a t for
the
th a t n e ith e r
rev ersib le
1 ,4 -d io x an e an alo g u e.
of
th ese
p o rtio n s
d isso ciatio n
of
of
Hence,
th e
it
seems
lik ely
curve re p re s e n ts
th e
the 1 ,3 -d io x a n e — boron f lu o r id e
com plex.
A d d i t i o n compounds o f 1 , 4 - d i o x a n e and b o r o n f l u o r i d e .
The f i r s t
h ig h -v acu u m w ork a tte m p te d w i t h th e a d d i t i o n
excess boron f lu o r id e
2:1
to 1 ,4 -d io x a n e re v e a le d
com plex fo rm ed s lo w ly fro m a
th at
com plex,
1:1
of
e ith er a
or else
th e
1 , 4 - d i o x a n e was b e i n g d e c o m p o s e d b y t h e b o r o n f l u o r i d e .
The
fact
t h a t no e v id e n c e
and
th at
t h e p r o d u c t was w h i t e ,
caused
a
1:1
th e
and a
of d eco m p o sitio n
was m a d e , u s i n g
to
to be d is c a rd e d .
form th e 1 :1
excess d iox ane.
w ere condensed w ith 4 .5 3
i n F i g u r e 4 b y means
th e m ix tu re
cc.
com plex i n
1 .4 7
E v id en tly b o th
th e p u re form
in
th e bu lb
shown
w ith liq u id
a ir.
h ad b e e n warmed t o room t e m p e r a t u r e a n d
a ir
several
The e x c e s s
sin ce
im m ed iately a t
so lid ified
ure
to
t h a n 1 mm.
cc.
of 1 ,4 -d io x an e used ,
boron f lu o r i d e .
su b lim ed
of boron f lu o r id e
of 1 ,4 -d io x an e
d u cib le p re ssu re s.
less
cc.
o f a Dewar f l a s k f i l l e d
re-condensed w ith liq u id
it
and r e a d i l y
com plex w ere b e in g fo rm e d .
An a t t e m p t
A fter
cry stallin e,
second h y p o th e sis
2:1
could be d e te c te d
T his
tim es,
v a p o r was
o
0 C .,
it
ev id en tly
1 ,4 -d io x an e,
d ecreasin g
th e p r e s s ­
C o m p u ta tio n showed t h a t
o n ly 1 .5 6
g iv es
cc.
a v alu e
com bining r a t i o
of boron f lu o r id e
of o nly 5 .8 per
c e n t from
th e
to
showed r e p r o ­
of th e 4 .5 3
had r e a c t e d w i t h t h e
o f 0 .9 4 2 :1 f o r
t h e m ole
1 ,4 -d io x an e,
a d ev iatio n
th eo retic a l
1 :1 r a t i o .
49
The d i s s o c i a t i o n p r e s s u r e d a t a
are
listed
in
T ab le X and a r e p l o t t e d
of
th e 1:1
in F ig u re
com plex
8,
TABLE X
DISSOCIATION DATA OF THE 1 : 1 BORON TRIFLUORIDE—
1 , 4 -D I O X A N E COMPLEX
T em perature
°c.
56 .7
65 .7
7 1 .0
7 8 .6
92 .0
8 1 .6
7 5 .5
Exp* t l .
C alc.
mm.
mm.
l/°A .
5.2
8.3
1 1 .3
1 4 .9
1 7 .7
16.2
1 3 .8
5.2
8.4
3 .0 3 2
2 .9 5 2
2.906
2 .843
2 .739
2 .819
2 .869
11.1
mm mm
— .
—
1 3 .9
The com p lex e x i s t e d
cry stals
(l/T )1 0 3
T o tal
d isso ciatio n
pressure
w hich m e lte d
in
th e form
to tal
of boron f lu o r id e
v a p o r i z a t i o n and
C alc.
atm .^
a tm .^
1 .2
1 .2
3 .0
5 .5 3
3 .1
5 .3 1
~
—
—
•MM
—
—
8.2 8
8 .2 4
of w h ite ,
n eed le-lik e
estim ated *
of 3*03 cc.
plu s
re tic a l d isso ciatio n
Expft l .
a t a p p ro x im a te ly 5 0 °C ., a lth o u g h th e
m e l t i n g p o i n t was o n l y r o u g h l y
S ince a
^atm . xlO 5
1 .5 6
o f v a p o r was u s e d
(1 .4 7
cc,
cc.
of 1 ,4 -d io x a n e ), th e th e o O
p r e s s u r e a t 9 2 .0 C ., assum ing com p lete
com plete d i s s o c i a t i o n
1 8 . 7 ram.
The p r e s s u r e
o f t h e com plex i s
o
o b s e r v e d a t 9 2 . 0 C . w a s 1 7 . 7 mm. ( s e e
T ab le X ),
a d iffe re n c e
of o n ly 5 .3
per
cen t.
It
is
p o ssib le,
109
90
do
51
how ever,
th at
the d is s o c ia tio n
sin ce a t
th e p o i n t w here
(P = 1 4 . 4 m m .,
d isso ciatio n
ic a l,
the
is
pressure
to be
tem p eratu re
0 .0 0 2 7 2 5 /°A .) th e d is s o c ia tio n
break in
th e o re tic a l.
the
c o m p le x was
tu re
curve
d isso ciated .
so n ear
atic
H ow ever,
sin ce
th ey
ex p erim en tal e r ro r
th e low er p o r tio n
represent
the
of
th e
ure
th is
>■ l ^ - C ^ H g O g
-
5146/T
as
180°C.
could
**
th a t
th e sh arp
th e p o i n t a t w hich th e
and
th a t above th is
e a s ily be
in F ig u re
of
th e curve
lo g ^ P
tem pera­
8
are
caused by a system ­
is
hence
co n sid ered
to
com plex and g a s e o u s
the
calcu lated
in F ig u re
(mm*) =*
8 .666
8
may b e r e p r e ­
- 2622/T .
Ac­
com plex h a s a d i s s o c i a t i o n p r e s s ­
AH f o r
(Q ) +■ BF 3 ( q ) ,
(see F ig u re 9 ),
A F g g s e 9u a l s
l/T
th e a p p a re n t d is s o c ia tio n s
curve
eq u atio n ,
o f 7 6 0 mm. a t
p e r m ole,
th eo ret­
and 1 ,4 - d io x a n e .
sen te d by th e e q u a tio n ,
to
appear
o r by v a n d e r W aals f o r c e s ,
The l o w e r p o r t i o n
co rd in g
thus
e q u ilib r iu m betw een l i q u i d
boron f lu o r id e
th e
th e
com plex g r a d u a l l y becam e m ore c o m p l e t e l y
per cen t,
100
cen t of
(P = 1 8 . 2 m m .,
d enotes
8
com pletely v a p o riz e d ,
th e v ap o rized
shows
8
p r e s s u r e h a s become 9 6 .7 p e r
I t w ould
in F ig u re
cen t,
in F ig u re
calcu latio n
o n ly 8 0 .5 p e r
per
100
sharp b re a k occurs
l / T = 0 .0 0 2 8 6 8 /°A .) a
w hereas a t a h ig h e r
cent of th e
not actu ally
from th e
the r e a c tio n ,
is
4 - C 4 HQ0 g * B F 3
2 3 >500±500 g r a m - c a l o r i e s
eq u atio n ,
w here K ^ . =
9000i200 g r a m - c a lo r ie s
l ,
l°S io ^atm
pc4H802 x PBF 3
p e r m ole.
=
•
(
loo
90
70
CLQ
50
4Q
|® P e _ 9
!Uie
C o n stan ts a
t>£i ia a c i a t i c m B e a c a t i o n a
th s'
1 .;B oron| ^±flu<j>ricl
3-p^rl>i-OXane Comp' e x
th e
2.80
2.90
3.00
3.05
3.10
53
In an e f f o r t
2:1
com plex,
was
tre ated
th e
to p r e p a r e a sam ple
sam ple
ju s t d iscu ssed
° C . , m aking th e
on ly 1 .8 1
com bining r a t i o
volum e o f b o ro n f l u o r i d e ad d ed
was 1 . 4 7
cc.
by on ly 4 .5
plu s
per
1 .8 1
c c .,
w hich r e a d i l y
in
th e
cc.
to
com plex
6.9 9
cc.
of
was a b s o r b e d a t
th e 1 ,5 6
cc.
sin ce
cc.
th e
-80
to tal
of 1 ,4 -d io x a n e
T his r a t i o
d iffers
th e o r e tic a l 2 :1 r a t i o .
th e form o f w h ite ,
su b lim ed .
in d icated
1:1
Of t h e
now 2 . 0 9 : 1 ,
or 3 .2 8
c e n t from th e
The c o m p l e x was
tals
of
w i t h m ore b o r o n f l u o r i d e .
a d d itio n a l boron f lu o r id e
of th e
The c r y s t a l s
ro d -lik e
m elted
crys­
a t about
7 1 ° C.
The d i s s o c i a t i o n
listed
in
T ab le X I, and r e p r e s e n te d
E v id en tly
sib le ,
p ressu re d ata
th e d is s o c ia tio n
sin ce
same o r d e r
th e
of
th e
of
the 2 :1
g rap h ically
com plex i s
tem p eratu res a re
listed
in
com plex a r e
in F ig u re 10.
re a d ily revereT a b le XI i n
i n w hich th e m easurem ents w ere t a k e n .
tem p eratu re la g
is
th e
A slig h t
in d ic a te d by th e d a ta .
If
ated
t h e com plex w e re c o m p l e t e l y v a p o r i z e d and d i s s o c i O
a t 9 6 . 5 C . , t h e d i s s o c i a t i o n p r e s s u r e s h o u l d b e 3 0 . 3 mm.
The d i s s o c i a t i o n p r e s s u r e a c t u a l l y
2 6 . 9 mm.
(see
T able X I ) .
from th e
t h e o r e t i c a l 3 0 . 3 mm.
T his v a lu e d i f f e r s
The c o m p l e t e d i s s o c i a t i o n
not
co m p letely c e r t a i n ,
i n F i g u r e 10
(P
observed
sin ce a t
2 4 . 7 m m .,
of
a t 9 6 . 5 ° C . was
by 11 p e r
the v apor i s ,
how ever,
the sh arp b re a k in
l / T as 0 . 0 0 2 8 0 5 )
cent
th e
th e p re s s u re
curve
is
D isso ciatio n P ressure
lOP
(ran®)
54
90
80
60
50
4-Q
30
-
XQ
os
T H a O o e i a t i O r t P r o s O u r on
f 2 : t Boron* T r i x l u i p r l 'd o
<k»aple5£
Z.S5
( l / T ° A . ) x ! 0‘
3.00
55
o n ly 84*5 p e r c e n t o f w hat i t
a tio n ,
w h ile a t a h ig h e r
0.002700)
th e p re s s u re
w ould be f o r
tem p eratu re
observed
is
co m p lete d i s s o c i ­
( P as 2 7 . 0 m m . ,
8 8 .8 p e r
l/T
cen t of th e
—
th eo ­
re tic a l*
TABLE X I
DISSOCIATION DATA OP THE 2 : 1 BORON TRIFLUORIDE—
1 ,4 -D I O X A N E COMPLEX
T em perature
°c.
6 0 .4
7 0 .7
7 5 .7
8 1 .0
8 6 .3
90*6
9 6 .5
8 5.2
8 0 .7
7 6 .3
7 0 .7
6 5.7
6 0.7
5 5.7
Exp’tl*
C alc.
mm*
mm*
5 .0
10.4
1 5 .0
2 1 .3
2 4 .9
2 5 .9
2 6 .9
2 4 .9
2 1 .0
15 .7
1 0.9
7.7
5 .6
4 .0
5.3
1 0 .8
1 5 .0
2 1 .0
—
—
—
- -
2 0 .7
1 5 .6
1 0 .8
7 .7
5 .5
3 .8
These d is c r e p a n c ie s
so c ia tio n pressures
so cia tio n
of
(l/T )1 0 3
T o tal
d isso ciatio n
pressure
and
v a n d e r W aals f o r c e s .
C alc.
l/°A .
atm . ^
a tm .^
2 .9 9 8
2 .9 0 9
2 .8 6 7
2 .8 2 4
2 .7 8 2
2 .7 5 0
2 .7 0 6
2 .7 9 1
2 .8 2 6
2 .8 6 2
2 .9 0 9
2 .9 5 2
2 .9 9 6
3 .0 4 1
0 .4 2
3 .7 8
1 1 .4
3 2 .6
0 .5 1
4 .2 7
1 1 .4
3 1 .3
C ertain ly
to
—
—
—
mt mm
—
3 1 .2
1 3 .0
4 .3 6
1 .5
0 .5 9
0 .2 2
betw een th e
calcu lated
t h e v a p o r may b e d u e
xlO 7
E x p 1t l .
ex istin g
th o se
atm .
for
0m mm
—
2 9 .6
1 2 .8
4 .2 7
1 .5
0 .5 5
0 .1 9
observed d i s ­
100 p e r c e n t d i s ­
ex perim en tal e rro r
or
to
t h e v a p o r s may b e c o n s i d e r e d
56
to behave
e s s e n tia lly as
pressures,
high*
2 :1
it
even though th e
A d e fin ite
th an
in to
so lid
curve
and
is
th at a
th e 1:1
2 :1
esta b lish ed
com plex
is
e v id e n tly very sm all,
in
th e neighb o rh o o d
of
as
sm all p o r tio n
th at
th e
( th e h e a t
th e
curve
vapor*
curve re p re s e n ts m erely th e
The lo w e r p o r t i o n
of
th e 'lo w e r
p o rtio n
e q u ilib r iu m betw een
of th e
com plex
shows no c h a n g e i n s l o p e
of
th e
com plex) and
The u p p e r p o r t i o n
th erm al expansion of
the
of the
N ev erth eless,
of fu sio n
the m e ltin g p o in t
d io x a n e and bo ro n f l u o r i d e
s u c h low
com plex and b o ro n f l u o r i d e
i n F i g u r e 10 r e p r e s e n t s
liq u id
at
are not p a rtic u la rly
in to dioxane and boron f lu o r i d e .
seems r e a s o n a b l y w e l l
of th e
how ever,
tem p eratu res
p o ssib ility
com plex d i s s o c i a t e s
ra th er
id eal gases,
curve
of the
th e v ap o rs.
i n F i g u r e 1 0 may b e
re p re s e n te d by the
T his
e q u a t i o n , l o g - j ^ P ( m m . ) =■ 1 0 . 9 5 9 - 3 4 1 2 /
O
e q u a t i o n g i v e s 149 C. a s t h e t e m p e r a t u r e a t w h i c h t h e
d isso c ia tio n pressure
o
m m . , o r 1 5 9 C. a s t h e
pressure
of
e q u a l s 3 8 0 mm.
(s , l )
4 7 ,0 0 0 * 3 0 0 0 g r a m - c a lo r ie s
eq u atio n ,
^atra. =
1 #4 " C4 H8 ° 2
p e r m ole,
l o S ^ K ^ ^ *=■ 2 3 , 3 7 4 -
P C4 H8 02 x P b F 3 •
p e r m ole*
com plex becom es
equal
*
to 760
te m p e r a tu re a t w hich th e p a r t i a l
of 1 ,4 -d io x an e
1 , 4 - C 4 Hq 0 2 * 2 B F 3
th e
t
( G)
as
10226/
AP2 9 8 “
AH f o r
th e r e a c tio n ,
2 BF3
calcu lated
t
(G) * i s
from th e
(see F ig u re
11),
w here
15,000*1000 g r a m - c a lo r ie s
Katm *x l u ‘
70
60
50
40
■<ffl !H,ea-<u;j , o n
ZPL
^ =^*r —3 o £ 5 3 t :
h
:
^ t l ^ i x r c n d id f e :
10
2.80
3.00
3.05
3.10
CHAPTER V
DISCUSSION
The r e s u l t s
in d icate
th at
o b tain ed
in
th e 1 :1 and 2 :1
th is
in v estig atio n
com plexes
seem t o
of boron f lu o r id e
and 1 ,4 -d io x a n e a r e
th e
su lfo trio x id e
the 2 :1
th an
com plex i s
th e
1:1
pressure
resu lt
p lex
is
is
q u a litativ ely
ju st
pounds.
tw ice
of th e
com plex i s
seems l i k e l y
th at
th e 2 :1
th at
of
th e
1:1
p ractically
th at
less
sta b le
of
of th e 2 :1
t h e same i n
com­
in d icates
th e
and
sin c e h eats
th an th e 1 :1
of
S in ce
p o in t
are
of vap­
th e
com plex,
the 2 :1
com pound.
compound h a s a h i g h e r m e l t i n g
th at
tw o com­
s i n c e b o t h AH v a l u e s
th e 1:1
in accord w ith th is
T his
ex p ectatio n s.
com plex a l s o
th e h e a t of v a p o riz a tio n
th an t h a t
sta b le
159 C.
com plexes w ere n o t c o n s i d e r e d .
slig h tly
of
However,
less
in accord w ith p rev io u s
larg e u n c e rta in tie s
g reater
compound i s
50
th e form er a t
only a rough ch eck,
to r a th e r
compound i s
1 :1
is
18 0 °C .,
case
producing a d ioxane p a r t i a l
th e h e a t of d is s o c ia tio n
energy is
T his
o riz a tio n
2 :1
th at
though s l i g h t l y ,
th e l a t t e r
o f 3 8 0 mm. a t
t h e B-0 bond
su b jec t
d e fin ite ly ,
com plex,
The f a c t
it
of s im ila r s t a b i l i t y , as in th e
50
com plexes
d i s c u s s e d on p a g e 1 8 .
The f a c t
th an has
the
rough d e d u c tio n .
C . M. S u t e r , P . B . E v a n s a n d J a m e s M. K i e f e r ,
" D i o x a n e S u l f o t r i o x i d e , a New S u l f a t i n g a n d S u l f o n a t i n g
A g e n t” , J o u r n a l of th e A m erican C hem ical S o c i e t y , 6 0 :5 3 8 -4 0
(1 9 3 8 ). ~ ( C hem ical A b s t r a c t s , 3 2 :3 4 0 5 1 1 9 3 8 ) ) .
59
The b e h a v i o r o f
d i o x a n e was
in ite ly
p u zzlin g .
esta b lish ed ,
prepared,
per
in d eed
cent
th e 1:1 a d d itio n
The c o m b i n i n g r a t i o
sin ce f iv e
(th e av erag e v alu e
com plex, a s i n g l e
F ig u re
of
of th e
curve is
and b o ro n f l u o r i d e .
of
to
f lu o r id e w ith
are
1:1 r a t i o
b e i n g 11
was 1 . 0 2 : 1 ) .
However,
lo g P— l / T
curve
(see
known t o b e t h e
one r e p r e s e n t i n g
of
th e
com plex i n t o
of th e
two
1 ,3 -d io x an e
B oth s o l u b i l i t y and d e c o m p o s itio n e f f e c t s
stu d y .
of
two d i o x a n e s
T herefore,
th e 1:1
com plexes
no co m pariso n
of boron
c a n b e made u n t i l f u r t h e r d a t a
o b tain ed .
A p p aren tly th e 2 :1
ex isten t,
w ork.
at
T his
le a s t under
is
in accord
th e 2 :1
com plexes
ing 1 :1
com pounds.
th e fo rm a tio n
com plex o f 1 , 3 - d i o x a n e
th e
w ith
co n d itio n s
the
sh o u ld be le s s
L ik ew ise,
of a 2 :1
w ith 1 ,4 -d io x an e,
in
compound w e r e
N eith er
sta b ilitie s
th e
def­
o b tain d is s o c ia tio n d ata w ith
in te r f e r e w ith th is
the r e l a t i v e
is
from th e d a t a .
th e r e v e r s ib le d i s s o c i a t i o n
appear
of th e
the r a t i o
straig h t-lin e
6) d i d n o t r e s u l t
p o rtio n s
sam ples
th e a v e ra g e d e v i a t i o n from th e
when t h e a t t e m p t was made t o
th e
compound o f 1 , 3 -
due
as
com plex i s
to
is
non­
em ployed i n
th is
o rig in al
sta b le
p red ictio n
th an
p red icted ,
less
w ith
th eir
the
th at
correspond­
ten d en cy f o r
1 ,3 -d io x an e
th e p ro x im ity of th e
than
two o x y g e n a to m s
th e form er c a s e .
The u n c e r t a i n t y
connected w ith
th e d is s o c ia tio n d a ta
of th e 1 ,3 -d io x an e
1 :1
from f u l l y
th e m ajo r pro b lem o f t h i s
so lv in g
com plex u n f o r t u n a t e l y p r e v e n t s
th esis,
one
nam ely,
60
th e n a t u r e and
atom s
in
each of
of a 1:1
ab le
least
to
ex ten t of
the
in te ra c tio n
th e d io x a n e m o lecu les..
com plex te n d s
t o make t h e
th e
in te ra c tio n
case
is
of th e
1 ,4 -d io x an e
th e
two o x y g e n
That th e fo rm atio n
o th er
sh are an e le c tr o n - p a ir fo llo w s
in
of
oxygen atom l e s s
from th e d a t a .
com plex,
At
how ever,
th is
not very g re a t.
A c o n s id e r a b le amount of a d d i t i o n a l w ork c o u ld be p u t
in to
th e stu d y
of th is
w o rth w h ile r e s u l t s .
prob lem ,
M ost i m p o r t a n t
w o rk on t h e d i s s o c i a t i o n
an e f f o r t
to
in
th e a u t h o r ’s o p in io n , w ith
of a l l
w ould b e a d d i t i o n a l
of the 1 ,3 -d io x a n e
1:1
c l e a r up th e d o u b t c o n n e c te d w ith
com plex,
in
th e p re se n t
d ata •
A lth o u g h i t
is
q u e s tio n a b le w h eth er boron c h lo r id e ,
b o ro n b ro m id e , m e th y l b o ro n d ib ro m id e o r d im e th y l b o r o n brom ­
i d e w ould fo rm e l e c t r o n d o n o r - a c c e p t o r m o le c x ila r compounds
w ith
eith er
of
the d io x a n e s,
be m ost i n t e r e s t i n g
co m p ariso n s.
d id n o t re v e a l
not at a ll
the
compounds w ould
v alu ab le fo r
th e p re lim in a ry p a r t
compound o f s u l f u r d i o x i d e
ex isten ce
ex h au stiv e
of any com plex,
of th is
to form th e
su lfo trio x id e
made,
th e r e s u l t s
th o se a lre a d y d e sc rib e d
kept a t
com plexes
o b tain ed
in
th e
of
could
fu rth er
stu d y
and 1 , 3 - d i o x a n e
b u t t h e w o r k was
( s u l f u r d i o x i d e g a s was b u b b l e d
th ro u g h a sam ple o f 1 ,3 - d io x a n e
sin ce
th ese
and m ight p ro d u ce d a ta
An a t t e m p t i n
to form a m o le c u la r
w ork w ith
0 °C .).
slo w ly
An a t t e m p t
1 ,3 -d io x an e
sh o u ld be
th e n be com pared w i t h
literatu re
for
the
co rresp o n d in g
61
51
1 ,4 -d io x an e
com plexes
com pounds.
T he t w o l , 4 - d i o x a n e - - s u l f o t r i o x i d e
s h o u ld b e s t u d i e d m ore c r i t i c a l l y ,
tio n p re s s u re d ata
51 L o c .
c it.
for
them i s
lack in g .
sin ce d is s o c ia ­
CHAPTER VI
SUMMARY
The v a p o r
and found
to
ten sio n
fo llo w
c u r v e o f 1 , 3 - d i o x a n e was d e t e r m i n e d ,
the fo rm u la,
The 1 : 1 a d d i t i o n
te tra c h lo rid e
ab ly a
is
q u ite
la b ile ,
only s l i g h t l y
-40°C . as
co n tain in g
liq u id
o r im m e d ia t e ly on w arm ing
of
The 1 : 1
ied .
It
form s
lo ng w h ite n e e d le s
The 1 : 1
on s t a n d i n g f o r
(prob­
com plex
to form a 2 :1
th e
s e v e r a l hours
even g e n t l y w ith a n open fla m e .
ex isten ce
could n o t be o b ta in e d .
com plex w i t h 1 , 3 - d i o x a n e g av e
of any such seco n d ary a d d itio n .
c o m p le x o f 1 , 4 - d i o x a n e was p r e p a r e d
sm all w h ite n e e d le - lik e
a t a b o u t 5 0 C. a n d s u b l i m e r e a d i l y .
com plex i n t o
from c h lo ro fo rm -c a rb o n
ch lo ro fo rm ).
S a tis fa c to ry d is s o c ia tio n d ata
no e v id e n c e
t o 1 , 3 - d i o x a n e was
d eco m p o sin g u n d e r vacuum to a brow n, v i s c o u s ,
v o latile
A ttem pts
- 2169/T .
The co m p lex was a p p a r e n t l y l i q u i d
but cry stallized
so lu tio n a t
com plex a l s o
(mm.) ® 8 . 6 5 2
of boron f lu o r id e
s u c c e s s f u lly acco m p lish ed .
a t room t e m p e r a t u r e ,
lo g ^ P
cry stals
and s t u d ­
w hich m e lt
The d i s s o c i a t i o n
of
the
d i o x a n e a n d b o r o n f l u o r i d e was s t u d i e d .
The 2 : 1
c o m p le x o f 1 , 4 - d i o x a n e was a l s o
stu d ie d .
It
form s
a t 7 1 C.
The d i s s o c i a t i o n
boron f lu o r id e
sm all w h ite r o d - l i k e
was s t u d i e d .
to w ard d i s s o c i a t i o n
th an
is
of
th e
th e
c ry stals
com plex i n t o
The 2 : 1
1 :1
p r e p a re d and
com plex i s
com plex.
w hich m e lt
d io x a n e and
less
sta b le
BIBLIOGRAPHY
NOTE:
Books an d j o u r n a l a r t i c l e s c i t e d i n
n o t in clu d ed In th is b ib lio g ra p h y .
A.
T ables
I and
II
are
BOOKS
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E llis,
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New Y o r k :
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1153 p p .
1 .
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S u lf u r ic A cid .
I I . C o n s t i t u t i o n o f M eth y len e and G lyo x a l S u l f a t e s and th e R e a c tio n o f M eth y len e S u l f a t e w ith
T e r t i a r y B a s e s " , J o u rn a l o f th e C hem ical S o c i e t y , 86-91
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(1902).
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S ystem D io x an e and W a te r" , J o u r n a l o f t h e A m erican
C hem ical S o c i e t y , 5 8 :2 2 6 4 -7 (1 9 3 6 )•
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E ig e n b e rg e r, E r n s t, "O ccurrence of P ero x id e
J o u r n a l f u r p r a k t i a c h e C hem ie, 1 3 0 :7 5 - 8
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E v a n s , P . B . , J a m e s M. K i e f e r a n d C. M. S u t e r , " D i o x a n e
S u l f o t r i o x i d e , a New S u l f a t i n g a n d S u l f o n a t i n g A g e n t " ,
J o u r n a l o f th e A m erican C hem ical S o c i e t y , 6 0 :5 3 8 -4 0 (1 9 3 8 ),
F ra h m , Hermann a n d K u r t H e s s , " P r e p a r a t i o n a n d P r o p e r t i e s
o f P u re D io x a n e " , B e r i e h t e d e r D e u ts c h e n C hem ischen
G e s e l l s c h a f t , 7 1 B :2 6 2 7 - 3 6 (1938*H
"
G a l l a u g h e r , A. F , a n d H. H i b b e r t , " R e a c t i o n s R e l a t i n g t o
C a rb o h y d ra te s and P o ly s a c c h a r id e s .
LV. V a p o r P r e s s u r e s
o f th e P o ly e th y le n e G ly c o ls and T h e ir D e r i v a t i v e s " ,
J o u r n a l o f th e A m erican C hem ical S o c i e t y , 5 9 :2 5 1 4 -2 1
(1937).
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T e rtia ry -B u ta n o l" , R ecu eil des
927-30 (1 9 3 7 ).
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G r o s s , P h . and H. S u e s s , " T h e rm a l D e c o m p o s itio n o f D io x a n e " ,
M o n a tsh a fte , 68:207-14 (1 9 3 6 ).
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a D e s ic c a tin g A g e n t" , J o u r n a l of I n d u s t r i a l and E n g i­
n e e r i n g C hem is t r y , 2 5 : 6 5 3 - 9 Cl933T^
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f u r a n o r g a n i s c h e und a l l g e m e i n e C hem ie, 2 0 7 :2 4 2 -5 ( 1 9 3 2 ) .
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Boron F l u o r i d e ( 2 . W ith R e f e r e n c e to th e Q u e s tio n o f th e
E x i s t e n c e o f B o ro n H a l i d e - A d d i t i o n Compounds o f A nom olous
C o m p o sitio n )", Z e i t s c h r i f t f u r a n o rg a n is c h e und a llg e m e in e
C hem ie, 2 2 5 :2 7 0 - 2 ( 1 9 3 5 ) .
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t h e D e t e c t i o n a n d D e t e r m i n a t i o n o f S m a ll Amounts o f I o d i d e .
I t s A p p lic a tio n to the D e te c tio n of Io d id e in Io d iz ed
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65
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P ressure:
I I . A S im p le D ynam ic M e th o d , A p p l i c a b l e t o
B oth S o lid s and L iq u id s , f o r D e te rm in in g Vapor P r e s s u r e s ,
and A lso B o ilin g P o in ts a t S ta n d a rd P r e s s u r e s " , J o u rn a l
o f t h e A m erican C hem ical S o c i e t y , 3 2 :9 0 7 -1 4 (1 9 1 0 )•
C.
PATENTS
B i r c h a l l , T. and S . C o f f e y , " M e th y le n e E t h e r s " , B r i t i s h P a t e n t
3 3 8 ,6 2 4 , A u g u st 3 0 , 1929, to I m p e r i a l C hem ical I n d u s t r i e s ,
L td .
D re y fu s , H enry, " C y c lic E t h e r s " ,
M arch 2 , 1 9 3 7 .
U n ited
S tates
P a te n t 2 ,0 7 2 ,1 0 1 ,
N aw iask y , P a u l and G e rh a rd E . S p r e n g e r , " T h io x a n e S u l f u r
T r i o x i d e A d d i t i o n Com pounds", U n ite d S t a t e s P a t e n t
2 ,2 1 9 ,7 4 8 , O ctober 2 9 , 1940, to G e n e ra l A n ilin e and
F ilm C o rp o ra tio n .
D.
M a r t i n , M .A . t h e s i s ,
L i b r a r i e s , 1940.
THESES
The U n i v e r s i t y
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