1792 NOTES VOL.

24

TABLE I an investigation being carried out in this labora-

PHYSICAL OF ISOMERIC
PROPERTIES tory.6
BIS(TRIMETHYLSILYL)-
XYLYLENES In striking contrast to the reaction of arene-
B.P., and alkane-sulfonates of secondary alcohols with
Isomer M.P., "C. OC./mm. di' ny dimethyl sulfoxide to yield olefins,' the sulfonates of
ortho 2-3 75-6/0.55 0.8686'' 1.4950
primary alcohols react with dimethyl sulfoxide
rneta 4.0 734/0.6 0.859524*7 1.4919 to yield, instead of the expected olefin, a mixture
para 61-3 73-4/0.3 ... ... of aldehyde, acetal, and the alcohol derived from
the starting ester. For example, hexyl tosylate
gave hexanal, the methyl hexyl acetal of hexanal,
EXPERIMENTAL and 1-hexanol. The corresponding aldehydes were
Bis( trzmethylsilyl)-o-rylylene. This compound was prepared
also identified as products from the reaction of
according to the procedure described in a previous article' butyl and octyl benzenesulfonates in dimethyl
from 0.75 mol. of o-xylylene dibromide, 6.0 mol. of tri- sulfoxide. Heating the alcohol or aldehyde with or
methylchlorosilane and 1.64 mol. of magnesium. The mate- without the sulfonic acid did not give the same
rial collected a t 75-6" (0.55 mm.) was identified as bis(tri- reaction products.
methylsily1)-o-xylylene, m.p., 2-3; d:' 0.8686 and n:
1.4950. The reaction was then extended to the production
Anal. Calcd. for C1&6Si~: c, 67.13; H, 10.46; Si, 22.40. of aldehydes from primary alkyl or aralkyl halides
Found: C, 67.28, 67.22; H, 10.02, 10.13; Si, 22.45, 22.40. and dimethyl sulfoxide or other sulfoxides. It was
Bis(dimethylchl0rosilyl)-p-sylylene. This compound was also found that ketones could be obtained in fair
also prepared by the same procedure' from 70.0 g. (0.40 mol.) yield in certain cases, e.g., benzophenone from
of pxylylene dichloride, 113.8 g. (1.05 mol.) of dimethyl-
dichlorosilane and 23.5 g. (0.97 g.-atom) of magnesium in diphenylmethyl chloride. Representative examples
tetrahydrofuran. Distillation yielded 35.8 g. (33% yield) are given in Table I. During the course of this in-
of bis(dimethylchlorosily1)-p-xylylene, m.p. 74-77'; b.p. vestigation the preparation of p-nitrobenzaldehyde
110-112° (0.47 mm.). by reaction of p-nitrobenzyl chloride with dimethyl
Anal. Calcd. for C12H20Si2Clz: C, 49.47; H, 6.92; Si,
19.26; C1, 24.34. Found: C, 49.35, 49.47; H, 7.07; 7.11; Si, sulfoxide was reported.2
19.26, 19.34; C1, 24.41,24.32. The reaction of sulfonates and halides with
sulfoxides can be carried out conveniently a t tem-
CHEMISTRY DEPARTXENT
FORD MOTORCo. peratures in the range 100-160" in a n excess of the
20000 ROTUNDA DRIVE sulfoxide as solvent, with or without an acid ac-
P. 0. Box 2053 ceptor such as sodium bicarbonate. With dimethyl
DEARBORN, MICH. sulfoxide, low-boiling products are formed which
(1) Present address: Department of Chemistry, Brown
University.
Reactions of Sulfoxides with Organic Halides. (2) N. Kornblum, J. W. Powers, G. J. Anderson, W. J.
Preparation of Aldehydes and Ketones Jones, H. 0. Larson, 0. Levand, and W. M. Weaver, J.
Am. Chem. SOC., 79,6562 (1957).
(3) R. T. Major and H. J. Hess, J. Org. Chem., 23, 1563
HAROLD ~ JOHN J. MONAGLE
R. N A C EAND (1958).
(4) J. M. Tien and I. M. Hunsberger, Abstracts of Papers,
Received M a y 11, 1959 A. C. S. 134th Meeting, Chicago, Illinois, September, 1958,
page 75P; Chem. and Ind. (London), 88 (1959).
(5) S. G. Smith and S. Winstein, Tetrahedron, 3, 317
The increasing i n t e r e ~ t ~
in-the
~ unusual behavior (1958).
of organic halides in the presence of dimethyl sulf- (6) U. S.Patent 2,888,488 (May 26, 1959).
oxide prompts us to publish preliminary results of (7) H. R. Nace, Chem. & Ind. (London), 1629 (1958).

TABLE I
OF ALDEHYDES
PREPARATION AND KETONES'

RIR2CHX + R3SR3 --f RIR2C0

Reaction Reaction
RI Rz R3 X Temp. Time-hr. To Yield
n-CaH7 H CHI -0SOzCeH6 100 2.0 ..
n-CE"i H CHI -oSo&eHs 100 2.0 Approx. 20
C6Hs H CHI -c1 100 10.0 58
C6Hs H C6H5 -c1 114-125 6.0 66
p-CHs-C6& H CH3 -Br 90-161 3.5 63
CeH6
. . CeH6 CH3 -c1 100 2.25 44
a Slight excess of sodium bicarbonate (based on halide) used as acid acceptor.
NOVEMBER 1959 NOTES 1793

include dimethyl sulfide, methyl mercaptan and Identities were confirmed by independent prepa-
dimethyl disulfide. If an acid acceptor is not used, ration of the m s o form by cis-hydroxylation6 of
large amounts of formaldehyde are also formed. cis-octadecene7 with hydrogen peroxide-osmium
With diphenyl sulfoxide, a high-boiling residue, tetroxide and of the dl form by ring opening, with
presumably diphenyl sulfide, is formed. Walden inversion,s performed on cis-9,lO-epoxy-
The formation of aldehyde can be conveniently ~ctadecane.~
accommodated by the following scheme: Since greater solubility has been correlated
with lower melting point and dl or threo configura-
0 tion in the case of stilbene dibromideg and vari-

ItiCHaY + +
f
CHsSCH, +RiCHzO+S(CIL)z + X-
ous esters of the isomeric 9,lO-dihydroxystearic
acids,l0S1l it was interesting to make solubility
+RICH0 (CH3)zS HX.
X = R2S03- or halogen.
+ measurements (Table I) on the present diols and
two related compounds.
Evidence for the existence of the intermediate TABLE I
salt has already been presentedJ6 and Hunsberger SOLUBILITY OCTADECANES,
OF 9, 10-DISUBSTITUTED STEARIC
and Tien have proposed a similar mechanism for ACIDS AND OCTADECANOLS
ethyl bromoacetate with dimethyl ~ulfoxide.~ ~~

Solubility,
Complete details, including a study of reaction g./L of Soln.
variables and experiments with other halides and Compound M.P. Solvent a t 25'
sulfonates, mill be reported later. meso-Octadecanediol 130" 95% EtOH 11.9
E. I. DU P O N T DE PI'EMOURS & CO.,INC. dl-Octadecanediol 78" 95% EtOH 30.2
N'ILMINGTON 99, DEL. meso-Octadecanediol 130" Benzene 2.6
dl-Octadecanediol 78" Benzene 13.7
er ythro-Dihydroxy-
stearic acid' 131' 9570 EtOH 8.8
meso- and dZ-9,10-0ctadecanediols1 threo-Dihydroxystcaric
acid' 95" 95%EtOH 69.8
Dichloroocta-
A. X. ~VRIGLEY,F. D. SMITH,AND A. J. STIR TON^ decanolb 31' 05%EtOH 19.0d
Dichloroocta-
Received May 15,'1959 decanolC 12' 95%EtOH 843.d
~~ ~~

'Ref. (8). Presumably erythro since made by chlorin-

The 9,lO-octadecanediols were desired as ex-
amples of secondary glycols. Stereochemically
definitive syntheses of the meso- and dl-9,lO-
octadecanediols, by performic acid treatment of
the corresponding trans- and cis-octadecenes, have
been reported by Criegee and co-workers.a
Other workers4v5had reported the preparation
of the "high-melting" forms of such glycols by
catalytic hydrogenation of acyloins, but had ex-
perienced difficulty in isolating the "low-melting"
forms in a pure state. Our own experience with
platinum oxide hydrogenation of nonyloin was simi-
lar.
A more convenient method of preparation was
found to be the reduction of nonyloin with sodium
borohydride, which proceeded almost quantitatively
to a mixture of the two forms. Separation by
crystallization from aqueous ethanol gave yields
of 42% of the meso and 56% of the dl modification.
(1) Presented a t the 135th Xational Meeting of the
American Chcmical Society, Boston, Massachusetts, April 6,
1959.
(2) Eastern Utilization Research and Development Divi-
sion, Agricultural Research Service, U. S. Department of
Agriculture, 15astern Regional Research Laboratory, Phila-
delphia 18, Pa.
(3) R. Criegee, E. Hoger, G. Huber, P. Kruck, F. Markt-
scheffel, and 1%.Srhellenbrrger, Ann., 599, 81 (1956).
(4) V. L. Hansley, J . Am. Chem. Soc., 57, 2303 (1935).
(5) F. E. neatherage and H. S. Olcott, J . Am. Chem.
SOC.,61,630 (1939).
ation of elaidyl alcohol.12 Presumably threo since made by
chlorination of oleyl alcohol.12 Measurements made at 0".
In each case the dl or threo modification is
considerably more soluble, as well as lower melt-
ing.
EXPERIMENTAL
meso-9,lO-Octadecanediol by hydrogenation of nonyloin.
Hydrogenation at room temperature of 10 g. of nonyloin over
PtOz, gave a 30y0 yield of 9,10-octadecanediol, m.p. 130.0-
130.4' (reported5 127°,3 127.5-128'). On admixture this
substance did not change the melting point of meso-9,lO-
octadecanediol reference compound Its infrared spectrum
meaeured on a KBr disk was superimposable on that of the
reference compound.
meso- and dl-Octadecanediols by sodium borohydride reduc-
tion of nonyloin. In 235 ml. of 95y0 alcohol 18.7 g. of non-
yloin was reduced by treatment with 1.24 g. of sodium boro-
(6) R. B. Woodward, F. E. Bader, H. Bickel, A. J. Frey,
and R. W. Kierstead, Tetrahedron, 2, 28 (1958).
(7) L. L. Gelb, W. S. Port, and W. C. Ault, J . Org. Chem.,
23,2022(1958).
(8) D. Swern, J. Am. Chem. SOC.,70,1235 (1948).
(9) L. F. Fieser and M. Fieser, Organic Chemistry, 3rd ed.,
D. C. Heath & Company, Boston, 1956, p. 303.
(10) D. Swern, E. F. Jordan, Jr., and H. B. Knight, J .
Am. Chem. SOC., 68,1673 (1946).
(11) H. B. Knight, E. F. Jordan, Jr., and D . Swern, J.
A m . Chem. Soc., 69, 717 (1947).
(12) J. K. Weil, A. J. Stirton, and E. W.Maurer, J . Am.
oil Chmists' SOC.,32, 148 (1955).