Professional Documents
Culture Documents
1964
DEHYDRATION
OF ALCOHOLS
IN DIMETHYL
SULFOXIDE
123
PART WITH
TRAYNELIS,
HERQENROTHER,
HANSON,
AND VELICENTI
124
VOL.29
TABLEI
THEDEHYDRATION
OF 1-ALKYLCYCLOALKANOLS
Olefin yield, %
Aloohol
K;
Olefin composition"
88
B C H 3 (100)
D C H *
74.5
O C H 3 (95)
O C H Z (5)
(0)
6W
--
370
55.5
(5.4) O C H ( C H J z O C ( C H &
62
CH3
(78.3)
(16.3)
57
(72.8)
(0)
(27.2)
'The olefin composition was determinedby v.p.c. Iodine-catalyzed dehydration. 'Dehydration by a trace of p-toluenesulfonicacid
TABLEXI
THEDEHYDRATION
OF ~-PHENYL~-PROPANOL
I N VARYINQ
AMOUNTS
OF DIMETHYL
SULFOXIDE"
Product compositiona
0
Alc: dimethyl sulfoxide
mole ratio
OH
CsHaCH=CHCHs
CiHiCzHr
I/
CsHrCHCHiCHa
CsHsCCHiCHa
CsHiCHOCHCaHi
1:8
89
6
6
0
1:3
80
5.5
7
7
8
4
34
1:l
56
3:l
30
3
14
53
a Theae reactions were run at 175" for 9 hr. b The product composition waa determined by v.P.c., for the product residue isolated
in ementially quantitative yield. The starting alcohol was stable to the conditions used for V.P.C.
--t
.4
'I A
C&C-
-CsH6
OH
C& C E H ~
DMSO
__f
1900
CHz=C-C=CHz
bH
(CHI)%
vo
n = 2,3,4
CsHs
(5) B. T. Gillia and P. E. Beck, J . O w Cham., 48, 1388 (1963).
I11
CEHS
IV
125
DEHYDRATION
OF ALCOHOLS
IN DIMETHYL
SULFOXIDE
JANUARY,1964
TABLEI11
NUCLEAR
MAGNETIC
RESONANCE
SPECTRA
OF SOME
BENZYL
ETHERS"
Compound
c~H~CH~OCH~C~HK
Peak description
r-Values
Singlet
Singlet
A"
2.80
5.58
Bb
Proton
assignment
Weight
10
Benzene
Methylene
CHICH~
CeH6CHCC H C ~ H K
(meso and d l )
CHICHI
CHiCRi
c 6CHC CP6H 5
(meso and d l )
L A
C6H6 .HO
(solid product)
Singlet
Quartet center
Doublet center
2.82 2.76
5 . 5 6 5.85"
8.57c 8.67e
Cd
Dd
10
2
6
Benzene
Methine
Methyl
Singlet
Tri let center
Muftiplet center
Triplet center
2.95 2 . 8 5
5.86" 6 . 0 P
8 . 2 1 8.50
9.17' 9.25'
10
2
4
6
Benzene
Methine
Methylene
Methyl
Benzene
Multiplet center
3.03
10
Doublet center
5.880
0-Methine
6.94
8.66h
Ei Fi
2
6
C-Methine
Methyl
Multiplet center
3.03
10
6 .OP , 5 . 8 3
Doublet center
Benzene
0-Methine
2
C-Methine
7.00
Multiplet center
Methyl
9 . 1 l h 8.68*
6
Doublet center
* Analysis of coma These spectra were determined in carbon tetrachloride solution with tetramethylsilane aa an internal standard.
ponents A and B was by comparison of the relative peak areas for the methine proton. This waa found to be 37% A and 63% B.
Analysis of components C and D was by comparison of the relative peak areaa for the methine proton. This waa
c J = 6.8 c.p.8.
f o u n d t o b e 4 6 % C a n d 54% D. e J = 6.1 c.p.8. 'J = 7.3 c.p.8.
J = c.p.8. J = 7 c.p.8. Analysis of components E and
F waa by comparison of the relative peak areas for the 0-methine proton. This waa found to be 25% E and 75% F. 1 The unknown
solid from the dehydration of threo-1,2-diphenyl-l-propanolwas recrystallized several times from petroleum ether (b.p. 60-90' ) and had
m.p. 151-154.5'. Anal. Calcd. for CIoHaoO: C, 88.63; H, 7.44. Found: C, 88.60, 88.68; H, 7.40, 7.55.
M. Biguard.
Compt.
VI
126
TRAYNELIS,
HERGENROTHER,
HANSON,
AND
TABLE
IV
DIMETHYL
SCLFOXIDE
DEHYDRATION
OF ALCOHOLS
IN
Dimethyl
sulfoxide, moles
Alcohol (moles)
5-Butyl-5-nonanol
(0.053)
(0.0158)
(0.0158)
(0.158)
PMethyl-2-hexanol(O,0258)
0,371
0,110
0.110
0,110
0.181
(0,0058)
(0.40)
DMSO
1900
+ CHaCH=CHCHO
Yield, %
(0.005)
(0.0158)
(0,110)
n-CBH1TONa(0.0158)
(0.0026)
CHaCHCHzCHzOH -+
CHaCH=CHCHzOH
PRESENCE
OF BASE
Base (moles)
OH
THE
CsHsNHz
CeHsNHz
VOL. 29
VELICENTI
(0.0058)
Dielectric
constant,' E
Dipole
moment,* p
Recovered
alcohol, %
Dimethyl sulfone
Acetamide
Dimethyl sulfoxide
Nitrobenzene
Benzonitrile
Quinoline
Dip henylme thane
59
48.9"
36
25
9
2.7
4.4
3.7
3.95
3.98
3.94
2.25
2.95
90
100
3
82
85
93
91
a A. A. Maryott and E. R. Smith, National Bureau of Standards Circular, No. 514, 1951. * L. G. Wesson, "Table of Electric
Dipole Moments," The Technology Press, Cambridge, Mass.,
1948. c H. L. Schlafer and W. Schaffernicht, Angew. Chem.,
72,618 (1960).
DEHYDRATION
OF ALCOHOLS
IN DIMETHYL
SULFOXIDE
JANUARY,
1964
127
Experimentall o
128
TRAYNELIS,
HERGENROTHER,
HANSON,
AND VELICENTI
VOL. 29
fied by their infrared and n.m.r. spectra.24 In the n.m.r. specmethod B. Distillation of the condensate gave 8.5 g. (66%) of
trum, 1-isopropylcyclohexene had a doublet a t 9.04 with a weight
3-methyl-2-butanone, b.p. 92-96", 7 t Z o ~1.3968, 2,4-dinitroof 6 protons, a multiplet a t 8.20 with a weight of 9 protons, and a
phenylhydrazone derivative m.p. 118-119", and semicarbazone
singlet a t 4.60 7 with a weight of 1 proton, while isopropylidene
derivative m.p. 110-112" (lit.30 b.p. 93', n Z o1.3879,
~
2,4-dicyclohexane had two singlet absorptions a t 8.53 with a weight of 6
nitrophenylhydrazone derivative m.p. 117', semicarbazone deprotons and 8.38 r with a weight of 10 protons. 2-Cyclohexylrivative m.p. 113').
propene had the same retention time as the material identified in
2,3-Diphenyl-2,3-butanediol.-Using method A, 2,3-diphenylthe following experiment.
2,3-butanediol (2.0 g., 0.0082 mole) and dimethyl sulfoxide (9.0
2-Cyclohexyl-2-propanol (3.25 g., 0.0227 mole) and dimethyl
g., 0.116 mole) after 14 hr. at 190' gave 1.8 g. of a yellow oil
sulfoxide (12.5 g., 0.160 mole) were heated a t 175' for 15 hr., and
which upon chromatography on 100 g. of Alcoa F-20 activated
processed according to method A to give 1.60 g. (57%) of olefins.
alumina was separated into 0.30 g. (17%) of 2,3-diphenylbuWhen this mixture was analyzed by v.P.c., the composition was
tadiene, m.p. 44-46' (lit.31m.p. 49'), which exhibited strong ab72.8y0 2-cyclohexylpropene and 27.2% isopropylidene cyclohexsorption a t 11.05 M in the infrared spectrum, and 1.20 g. (65%) of
ane. The 2-cyclohexylpropene was collected from V.P.C. (cona mixture of ketones. The ketone mixture was analyzed by V.P.C.
~
(lit.17n z o1.4586),
~
and was charditions as before), n Z 01.4575
(silicone QF-1 column a t 220' and a helium flow rate of 40 cc./
acterized by its infrared spectrum.
min.) and contained 11yo 1,2-dipheny1-2-methyl-l-propanone
1,2-Diphenylethanol .-A solution of 1,2-diphenylethanoI ( 1.OO
and 89% 3,3-diphenyl-2-butanone.
g., 0.0050 mole) and dimethyl sulfoxide (3.12 g., 0.040 mole)
A second experiment was performed using twice the quantities
waa heated a t 160" for 9 hr. and processed by method A to give
of reactants a t 190" for 7 hr. and gave, upon chromatography,
0.90 g. of solid material. Chromatography of this mixture on
0.50 g. (15%) of 2,3-diphenylbutadiene, 1.20 g. (33%) of a ketone
80.0 g. of Alcoa F-20 activated alumina and elution with petromixture (composition, 19% 1,2-diphenyl-2-methyl-l-propanone
leum ether (b.p. 30-60') gave 0.85 g. (93%) of trans-stilbene,
and 81% 3,3-diphenyl-2-butanone),and 1.90 g. (48%) of unm.p. 122-124" (lit.z6m.p. 125"). Elution with ether gave 0.05
reacted diol from which 1.3 g. (33%) of pure dl-2,3-diphenyl-2,3g. ( 5 % ) of starting alcohol, melting point and mixture melting
butanediol, m.p. 121-122", was obtained by recrystallization
point with an authentic sample 64-66",
from petroleum ether (b.p. 30-60').
1-Phenyl-1-propanol.-Four experimenta were performed using
A sample of the previous ketone mixture (0.50 9.) was treated
1-phenyl-1-propanol (5.0 g., 0.037 mole) and varying amounts
with sodium hypoiodite in dioxane and gave 0.10 g. (20%) of a
of dimethyl sulfoxide a t 175" for 9 hr. The reactions were procbrown oil with one carbonyl absorption in the infrared spectrum
essed according to method A and gave 4.44, 4.52, 4.80, and 4.75
a t 5.95 p . This wag converted to the oxime of 1,2-diphenyl-2g. of residue, respectively. The residue composition was determethyl-1-propanone, m .p. 190-192' (lit .e m .p. 192-193" ).
mined by V.P.C. (conditions same as described under l-phenyl-2When pure dl-2,3-diphenyl-2,3-butanediol(l
.O g., 0.0041 mole)
propanol). The results of this study appear in Table 11.
and dimethyl sulfoxide (4.5 g., 0.058 mole) were heated for 14
1,4-Butanediol.-A solution of 1,4-butanediol (36.0 g., 0.400
hr. a t 190" and similarly processed, 0.10 g. ( 12y0)of 2,3-diphenylmole) and dimethyl sulfoxide (15.6 g., 0.200 mole) was heated for
butadiene and 0.60 g. (65%) of a ketone mixture were isolated.
14 hr. a t 190' and processed according to method B to give 20.2
The ketone mixture was composed of 2% 1,2-dipheny1-2-methylg. (7070) of tetrahydrofuran, b.p. 64-65", n Z 01.4038
~
(lit.26b.p.
1-propanone and 98% 3,3-diphenyl-2-butanone. The oxime of
64-66', 72% 1.4040).
3,3-diphenyl-2-butanone,m.p. 149-150' (lit.lg m.p. 151), waa
1,5-Pentanediol (31.2 g., 0.300 mole) and dimethyl sulfoxide
prepared in the usual manner.
(23.4 g., 0.300 mole) were heated for 24 hr. a t 190" and processed
A second reaction identical with the preceding experiment exaccording to method B. Fractional distillation of the condensate
cept using the meso diol and reaction time of 7 hr. gave a 15%
(24.7 g.) which contained tetrahydropyran, dimethyl sulfide, diyield of 2,3-diphenylbutadiene and a 68% yield of ketones (2.4y0
methyl disulfide, and bismethylthiomethane gave 12 g. (47%) of
1,2-diphenyl-2-methyl-l-propanone
and 97.6% 3,3-diphenyl-2tetrahydropyran, b.p. 87-89', n Z 0 1.4255
~
(lit.,27b.p. 88", n Z 0 ~ butanone).
1.4205). This was contaminated with a small amount of byPinaco1.-Anhydrous
pinacol, m.p. 35-37' (11.8 g., 0.10
products containing sulfur and when a pure sample, 1 2 % ~1.4208,
mole) and dimethyl sulfoxide (54.6 g., 0.70 mole) were heated a t
waa collected from V.P.C. its infrared spectrum was identical with
160', 175', and 185" for 16 hr. and processed according to
method B. The condensates were analyzed by V.P.C. (mineral
that of an authentic sample.
oil column a t 75' and a helium flow rate of 40 cc./min.) and conEmploying the procedure of Franke, et ~ 1 . , 1,5-pentanediol
~*
tained 52%, 56%, and 55% 2,3-dimethylbutadiene and 20%,
(10.4 g., 0.10 mole) and 5070 sulfuric acid (100 ml.) were heated
2770, and 3Oy0 of pinacolone, respectively. Distillation gave
until tetrahydropyran ceased to distil. Redistillation gave 6.5
4,5pure 2,3-dimethylbutadiene, b.p. 68-69', n Z 1 . 41.4370;
~
g. (76y0) of tetrahydropyran, b.p. 86-88', n Z 01.4190.
~
1,6-Hexanediol-When a solution of 1,6-hexanediol (23.6 g.
dimethyl-l,2,3,6-tetrahydrophthalicanhydride, m.p. 76-78',
~
(lit.33m.p. 78"); and pinacolone,
lit.32b.p. 69-70", n Z 01.4377
0.200 mole) and dimethyl sulfoxide (7.8 g., 0.100 mole) was
b.p. 104-105", n Z 0 D 1.3970, 2,4-dinitrophenylhydrazonederivaheated a t 190" for 24 hr. according to method B, 9.5 g. of liquid
was collected. Distillation of this condensate gave 4.7 g. (24%)
~
2,4-dinitrotive m.p. 124-125" (lit.33b.p. 105", n Z 01.3956,
phenylhydrazone derivative m.p. 126-127" ).
~
(lit.z7b.p. 116', n Z 01.4355).
~
of oxepane, b.p. 116", n Z o1.4547
When pinacol was heated without dimethyl sulfoxide for 16
A pure sample, n 2 0 ~
1.4393, was collected by V.P.C. and had an
hr. a t 185', no product collected in the cold trap and pinacol waa
infrared spectrum identical with that of an authentic sample.
recovered quantitatively.
Dehydration of 1,6-hexanediol (6.4 g., 0.050 mole) also was
Bicyclohexyl-1 , l '-diol.-A solution of bicyclohexyl-1, l '-diol
~ gave 3.0 g.
accomplished by the method of Franke, et U Z . , ~and
(5.0 g., 0.025 mole) and dimethyl sulfoxide (16.4 g., 0.210 mole)
~
was
of distillate from which a sample of oxepane, n Z 01.4387,
was heated a t 160' for 16 hr. and processed according to method
isolated by V.P.C.
A. The resulting yellow oil (4.0 9.) was chromatographed on 150
1-Phenyl-1,2-ethanedio1.-Froml-phenyl-l,2-ethanediol (13.8
g. of Alcoa F-20 activated alumina and gave 3.4 g. (85y0)of big., 0.100 mole) and dimethyl sulfoxide (54.6 g., 0.700 mole) a t
~
(eluted with
cyclohexyl-1,l'-diene, n% 1.5282 (lit.84n z o1.5287)
190" for 48 hr., 9.0 g. of a black liquid was obtained by procedure
petroleum ether), and 0.60 g. of a mixture (eluted with ether)
A . A sample (1.00 9.) of this substance was treated with 2,4from which wag prepared spiro [5.6]dodecan-7-one semicarbadinitrophenylhydrazine and gave 2.0 g. of phenylacetaldehyde
zone, m.p. 206-208', and 2,4-dinitrophenylhydrazone,m.p. 1112,4-dinitrophenylhydrazone,m.p. 119-120.5" ( l k Z 9m.p. 121').
113" (lit." semicarbazone m.p. 20&209', lit.%2,4-dinitrophenylBased on this analysis the yield of phenylacetaldehyde in the dehydrazone m.p. 114'). The diene was characterized by its inhydration reaction was 67%.
frared spectrum and by a Diels-Alder reaction with maleic anZ-Methy1-2,3-butanediol.-A solution of 2-methyl-2,a-butanediol (15.6 g., 0.150 mole) and dimethyl sulfoxide (93.4 g., 1.20
mole) was heated for 36 hr. a t 190" and processed according to
(24) The n.m.r. spectra were measured in a carbon tetrachloride solution
with tetramethylsilane as an internal standard.
(25) W. Schlenk and E . Bergmann, Ann., 468, 116 (1928).
(26) R . Paul, Bull. 8oc. china. France, 2, 2220 (1935).
(27) A. Kirrmann and X. Hamaide, d i d . , 789 (1957).
(28) A. Franke, et al.. Monatah.. 69, 167 (1936).
(29) G . D . Johnson, J . A m . Chem. Soc.. 76, 2720 (1953).
JANUARY,1964
DEHYDRATION
OF ALCOHOLS
IN DIMETHYL
SULFOXIDE
129