Patented Mar.

13, 1951 2,545,285

UNITED STATES PATENT OFFICE
CHILOROMETHYL MERCAPTAN AND ITS
SEPARATION FROM THE WARIOUS SUL
FUR COMPOUNDs
Mortimer J. Kamlet, Chattanooga, Tenn., as
signor to Tennessee Products & Chemical Cor
poration, Nashville, Tenn., a corporation of
Tennessee
No Drawing. Application December 5, 1949,
Serial No. 31,248
6 Claims. (C. 260-543)
1. 2
The present invention relates to a process for tetrachloride, sulfur dichloride, SCI2, and Sulfur
the formation of perchloromethyl mercaptan, and monochloride, S2Cl2, is distilled to remove the
of equal importance, comprehends an improved carbon tetrachloride (B. Pt. 77° C.) and most of
Simplified procedure for the separation of per the sulfur dichloride (B. Pt. 59 C.). The Sulfur
chloromethyl mercaptain from by-product sulfur monochloride (B. Pt. 136°C.) boils too close to
monochloride and sulfur dichloride. The inven the perchloromethyl mercaptain to be separated
tion leads to a maximum yield of the desired per by ordinary fractionation. The residue is then
chloromethyl mercaptain, with a minimum by subjected to steam distillation, during which Op
product formation of carbon tetrachloride. eration the sulfur monochloride is decomposed by
It has for its purpose to provide a simple, in G the steam, giving, among other products, copious
expensive and comparatively safe means for the deposits of elementary sulfur. The oil layer, still
renoval of Sulfur monochloride and Sulfur dichlo containing traces of undecomposed Sulfur mono
ride from perchloromethyl mercaptain so that chloride, is then dried over a suitable drying
this valuable Diesel fuel additive can be made agent and vacuum fractionated to give the pure
from cheap and readily available raw materials S product.
e.g., carbon disulfide and chlorine, without the The method of Dyson (Org. Syn. Coll. Vol. 1,
necessity of submitting any of the intermediate pp. 506 to 510, Wiley, New York, 1941) differs
reaction mixtures of said process to an expensive only in that the preliminary distillation to re
and Sometimes hazardous separation by means of move low boiling fractions is eliminated and the
Steam distillation and vacuum fractionation. 2) chlorination is carried out at a slightly lower
Ferchloromethyl mercaptain, Cl3C - S - C1, temperature (25 C. maximum).
When pure, is a lemon yellow oil, boiling with The decomposition of the Sulfur monochloride
slight decomposition at 149 C. at atmospheric by steam treatment is quite difficult. A large
pressure. Its odors are la chrymatory and toxic Wolume of steam is required to decompose Small
in moderate concentrations, extremely annoying 25 amounts of the S2Cl2 and the considerable
even in Slight concentrations. It has been used amounts of elementary sulfur, liberated in the
as an additive for Diesel fuels or as a starting decomposition, present a serious cleaning prob
material in the preparation of additives for Diesel lem in view of the rather low Solubility of sulfur
fuels and high pressure lubricants. The presence in most commonly used Solvents. In addition,
of even traces of the various sulfur chlorides im this procedure, on a large Scale, Would necessi
parts to the liquid a distinct reddish coloration. tate the decontamination of rather large, mal
Perchloromethyl mercaptain is formed by the odorous quantities of water before disposal. The
reaction: present invention permits the entire reaction to
2CS + 5C1 - 2CsCl + S,C). These reactions be carried out in one vessel, thereby eliminating
are fatalyzed
2CS2 -- 6Cl2 - 2C S Cl4 - 2S Cl by iodine. 35
much of the difficulty attendant in transferring
and handling large quantities of this noxious ma
Too much chlorination leads to the undesirable terial. The present invention also eliminates the
carbon tetrachloride: necessity of steam distillation.
The bases of the present invention are the dis
coveries that the complete and rapid decomposi
Temperatures over 30.C., and Sunlight or actinic 40 tion of sulfur monochloride can be effected by
radiation favor carbon tetrachloride formation. treatment With lower aliphatic alcohols Such as
The chlorination is, therefore, effected under 30° ethanol, methanol, propanol, isopropanol, bu
C., and in the absence of sunlight or actinic radi tanol, isobutanol, sec-butyl alcohol and mix
ation, but in the presence of an iodine catalyst. tures thereof; that the complete and rapid de
There are, in the art, two commonly accepted composition of sulfur dichloride is effected by
methods for the preparation of perchloromethyl treatment with the lower aliphatic alcohols Such
nercaptain. According to the method of Hellfi'ich
and Reid (Journ. Anner. Chen. Soc. 43 591. as are recited above, as well as with lower ali
(1921)), carbon disulfide, containing about 0.3- phatic ethers such as dimethyl ether, methyl
(0.4% by weight of iodine is chlorinated in the 50 ethyl ether, diethyl ether, dipropyl ether, diiso
absence of direct sunlight, at a temperature main propyl ether, isopropyl ethyl ether and mixtures
tained between 29 C. and 30° C., until the vol thereof; and that chlorination to a volume
Unine of the reaction mixture has just doubled. equivalent to from about 2.0 to 2.5 times the
The crude reaction product, containing in addi original volume and preferably about 2.25 times
tion to the perchloromethyl mercaptain, carbon 55 the original volume, of the carbon disulfide con
 2,545,285
3 4.
verts most of the sulfur monochloride formed to The mixture is then distilled at atmospheric
sulfur dichloride without appreciably lowering pressure taking off all that comes over below 135
the yield of perchloromethyl mercaptain. C. (still-pot temperature). The still-head tem
The sulfur monochloride and sulfur dichloride perature remains at about 55-57 C. and about
react as follows with alcohols and ethers: s 450 cc. of deep red SCI2 is collected. The tem
perature is then allowed to fall to about 60° C.
and a vacuum of 70 mm. Hg is applied. An ad
ditional 10 cc. SCI2 comes OWer.
The light red residue is then allowed to cool
It will be seen that all of the by-products of this ) to 45° C., and a mixture of 25 cc. methanol with
decomposition are either highly volatile (alkyl 100 cc. diethyl ether is added dropwise over a
chloride, gaseous HCl, gaseous SO2) or Solid period of about ten minutes. An immediate and
(sulfur) and remain behind in the still when the vigorous reaction is noticed With appreciable
perchloromethyl mercaptain is distilled. The per lightening in the color of the Solution. When
chloromethyl mercaptain is completely unaffected addition is complete the mixture is vigorously
by the alcohol and/or ether treatment. agitated for an additional fifteen minutes (effec
I have found that pure perchloromethyl mer tive agitation can be applied by disconnecting
captain can be obtained by the sequence of steps the chlorine and pulling air through the Sparger
involved in: Via the vacuum take-off).
(a) Chlorinating carbon disulfide to from 30 The low boilers are then taken off by distilla
about 2.0 to 2.5 times its original volume and tion at atmospheric pressure, about 75 cc. being
preferably about 2.25 times its original volume, collected, after which the residue is vacuum dis
i.e., chlorinating carbon disulfide until the volume tilled at a pressure of about 50 mm. Hg. Frac
of the chlorinated product is from 2.0 to 2.5 times, tionation is not necessary. The first 10 cc. Of
and preferably 2.25 times the volume of the Origi 25 condensables are discarded and the next por
nal carbon disulfide, in the presence of 0.2-0.4% tion is collected as the pure product. This prod
by weight of iodine as catalyst and in absence of uct is lemon yellow in color containing not the
direct sunlight, and maintaining the tempera slightest reddish tinge characteristic of the Sul
ture by cooling to between about 5° C. and 30 fur chlorides and comes over at 72-73° C./50 mm.
C., preferably around 15 C., 30 The last 20 cc. is left in the still pot to keep dis
(b) Distilling to remove most of the Sulfur solved the Sulfur formed in the decomposition.
chlorides produced in the form of the lower boil The last 30 cc. distilling over is collected sepa
ing sulfur dichloride, rately and has a slight reddish tinge which can
(c) Treating the pot residue with one or a be removed by treating with ether and redis
mixture of the lower aliphatic alcohols above 3. 5 tilling. The yield of pure perchloromethyl mer
mentioned or, preferably, a mixture of a lower captain is 831. g. (490 cc., 62%).
aliphatic alcohol or mixture of the same with one An even purer product can be obtained by
or a mixture of lower aliphatic ethers as above treating this first distillate with a further por
recited, to decompose any residual Sulfur di tion of ether (50 cc.) returning to the cleaned
chloride and the Sulfur monochloride, still pot and redistilling. This cuts the yield
(d) Distilling again to remove reaction prod down by about 3%. The product thus prepared
ucts of this decomposition as well as the exceSS does not develop any color on Standing for Over
of the compounds used in decomposition and low a month.
boiling fractions, and The reaction Wessel and all fittings can easily
(e) Wacuum distilling. 45 be cleaned out With acetone.
The product obtained in this manner is pure Eacample II
enough for most purposes. An even purer prod
uct may be obtained by treating the distillate The crude perchloromethyl mercaptain, pre
with a further portion of a lower aliphatic ether pared as in Example I and distilled to remove
or mixture thereof and repeating the distillation 50 CCl4 and most of the SCl2, is treated with a mix
and vacuum distillation operations. . ture of 40 cc. ethanol and 75 cc. dimethyl ether.
The following examples are given to define Wigorous reaction is accompanied by a distinct
and illustrate the present invention, but in no color change to light orange. The low boilers are
way to limit it to proportions or conditions de then taken off by distillation at atmospheric pres
Scribed therein. Obvious modifications and im 55 Sure and the residue is distilled at reduced pres
provements will occur to any person skilled in Sure. The first 10 cc. coming over at 50 mm.
the art. In each instance, chlorination is con Hg are discarded and the next portion, B. Pt.
ducted in the absence of direct Sunlight. 71-72 C./49 mm. is collected as the pure product.
Eacample I Yield: 792 g. (59%).
60
Eacample III
To 450 cc. CS2 (567 g., 7.46 moles) in a 2-liter
3-necked flask fitted with thermometer, Sparger The crude perchloromethyl mercaptain, pre
(for chlorination) and fractionating column (60 pared as in Example I and distilled to remove
cm. column packed with glass helices leading CCl4 and most of the SCl2, is treated with a mix
through condenser to vacuum take-off and vapor ture of 60 cc. n-propanol and 60 cc. diethyl ether.
trap) is added i.6 g. iodine. The temperature Again, vigorous reaction is noted, but in this case
is brought down by means of an ice-salt bath the color change is considerably less distinct than
to 5 C. and chlorine is introduced at as rapid in the previous examples. The low boilers are
a rate as will give a temperature no higher than taken off by distillation at atmospheric pressure
20° C. (preferably around 15° C.) with the most 70 and the residue is vacuum distilled as before,
effective cooling possible. Chlorination is con The first 70 cc. comes off with a distinct pink
tinued until the reaction mixture attains a vol color at 70-72 C./52 mm. The next portion is
ume of about 1000 ml. This should take about collected as the pure product, B. Pt. 71-73° C./50
eight to nine hours. The purplish-brown mix mm. Yield: 740 g. (55%). The first fraction is
ture is then allowed to stand overnight. 75 treated with 15 cc, diethyl ether and redistilled.
 2,545,285
5
An additional 35 g. (2.5%) pure perchloromethyl the sulfur monochloride in the chlorination mix
mercaptain was recovered. r ture by reaction with a member of the group
I claim: ..", consisting of the lower aliphatic alcohols, the
1. A process for the manufacture of perchloro lower aliphatic ethers, and mixtures thereof, and
methyl mercaptain which comprises chlorinating separating the Substantially unreacted perchloro
carbon disulfide in the absence of actinic radia methyl mercaptain from the more volatile by
tion until the volume of the chlorinated product products formed by said decomposition.
is from 2.00 to 2.5 times the volume of the original 3. The process of claim 2 where the chlorina
carbon disulfide, thereafter decomposing the by tion is continued until the volume of the chlorina
product sulfur monochloride and sulfur dichloride ( tion mixture is 2.25 times the volume of the
by reaction with a member of the group consist Original carbon disulfide.
ing of the lower aliphatic alcohol, the lower ali 4. The process of claim 2 Where the chlorina
phatic ethers and mixtures thereof, and separat tion is effected in the presence of iodine.
ing the substantially unreacted perchloromethyl 5. The process of claim 2 where the chlorina
mercaptain from the more volatile by-products tion is effected at a temperature not in excess of
formed by said decomposition. . . . . 30° C.
2. A process for the manufacture of perchloro 6. The process of claim 2 where the chlorina
methyl mercaptain which comprises chlorinating tion product is distilled to remove low boiling
carbon disulfide in the absence of actinic radia Sulfur dichloride prior to reaction with a member
tion until the volume of the chlorination product : of the group consisting of the lower aliphatic
is from 2.00 to 2.5 times the volume of the original alcohols, the lower aliphatic ethers and mixtures
carbon disulfide, and thereafter decomposing the thereof.
Sulfur dichloride in the chlorination mixture by MORTIMER. J. KAMLET,
reaction with a member of the group consisting
of the lower aliphatic alcohols, the lower aliphatic No references cited.
ethers and mixtures thereof, and decomposing