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Патент USA US2404425

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2,404,425
Patented July 23, 1946
‘UNlTED stares PATENT caries
2,404,425
PROCESS FOR PRODUCTION OF ALKYL
‘
MERCAPTAN S
Joy E. Beanblossom, Niagara Falls, and Richard
H. Kimball, Lewiston, N. Y., assignors to Hooker
Company, Niagara Falls,
Electrochemical
N. Y., a corporation of New York
N 0 Drawing.
Application November 30, 1944,
Serial No. 566,022
11 Claims.
(Cl. 260-609)
1
Our invention relates more particularly to a
2
in a solvent with which the water solution of hy
drosulphide has a. limited miscibility, and which
process for production of alkyl mercaptans by
reaction of the corresponding alkyl chloride with
sodium hydrosulphide, in accordance with the
following reaction:
boils preferably above the reaction temperature
and-below the boiling point of the mercaptan.
This permits of the use of relatively cheap com
mercial flake NaI-IS, containing water of crystal
the
lization, in place of NaI-IS or KI-IS formed in
reaction mixture, and affords the further very
in which R may be any alkyl radical of the group
practical advantage that the reaction can be car
ried out in an iron reactor.
herein. de?ned.
'
As a typical example of ouixprocess, we will
It is known that alkyl chlorides may be reacted 1.0
with an alkali metal hydrosulphide in methyl or
describe production of a mixture consisting of
decyl to octadecyl mercaptan inclusive, from the
ethyl alcohol, at 125° to 150° C., and under sub
corresponding chlorides, obtainable by treatment
stantial pressure. Some of the alkyl chloride is
hydrolyzed to the alcohol and some of it is de 15 of the mixture of alcohols known by the trade
name of “Lorol,” which is derived from cocoanut
hydrochlorinated to the ole?n. A considerable
oil. This mixture of mercaptans will hereafter
quantity of dialkyl sulphide is formed. The alco
be referred to as “Lorol mercaptan” and the chlo
hol must be recovered from the aqueous phase.
It is also known that decyl to pentadecyl chlo
rides from which it is produced as “Lorol chlo
RCl-l-NaHSeRSH-l-NaCl
rides may be reacted. with potassiumhydrosul
phide in a medium of blutanol, at atmospheric
pros-sure, by re?ux'ng the reagents together.
ride.”
~
1 '
“Lorol” chloride will not react to any practica-j
ble extent with solutions of sodium ,hydrosulphide
process is open to the serious objection that
is not a commercial product and must
therefore be formed in situ in the butanol by re
action of HzS with KOH, a process which is sim
ple enough if performed in glass on a laboratory
in water‘ alone or in methyl or ethyl alcohol solu-,
scale, but di?icult on a plant scale. For each mol
of Kl-IS one mol of H20 is formed, but ‘the quan
pletely with sodium hydrosulphide at atmospheric
of water to butanol. is within the limit of its solu
ess is very 10W, a large proportion. of the product
a water solution of the hydrosulphide and a
solvent for the Lorol chloride with which the
water solution‘has a limited miscibility, such as
butanol. For this purpose we mix the NaI-IS in
?ake form, containing 30 per cent water of crys
consisting of the dialkyl sulphide.
One object of our process is to make possible
the use of sodium hydrosulphide in place of po
tallization, or ‘£3 per cent water, based on hydro
sulphide, with butalnoL-which may have been re
cycled from a previous cycle of the process and
tions at temperatures attainable at ordinary
pressures, even with vigorous agitation. We have ‘
found, however, that with mechanical agitation
Lorol chloride can be made to react very com
pressure and at a temperature below its refluxing
tity of butanol used is such that the proportion 30 temperature in a two-phase medium comprising
bility inythe reaction mixture. The reaction is
therefore performed in a single-phase medium.
Nevertheless, the yield of mercaptan in this proc
‘
tassium hydrosulphide, and in particular. the use '
of commercial ?ake sodium hydrosulphide, con
taining water of crystallization, without involv
butanol. We heat these materials to fromy70° to
110° C. and agitate them thoroughly together.
This causes the NaI-IS to dissolve largely in its
ing super atmospheric pressure or recovery of
alcohol from an aqueous medium.
Another object of the invention is to avoid the
complications involved in , re?uxing.
Still an
other object of ‘the invention is to improve the
yield by minimizing production of the dialkyl sul
phides. A further object is to improve the qual
ity of the product by preventing decomposition
and by the removal of colloidal impurities.
We have now found that by the aid of mechani
cal agitation, and without re?uxing, alkyl chlo
rides can be reacted with sodium hydrosulphide
in a'two-phase medium, one phase comprising a
Water solution of the hydrosulphide, the other
phase comprising a- solution of the alkyl chloride
water, in the typi
40 cal proportions of 970' lbs. of NaI-IS to 1,500 lbs. of
water of crystallization and results in formation
of two distinct liquid phases, the aqueous phase
containing most of the Nal-ISI and the butanol a
small part of the NaI-IS or NaHSl solution mixed
therewith or dissolved therein. We preferably
pass in HzS until both phases are thoroughly
50 saturated therewith and excess Hrs bubbles
through the mixture. We then charge in 1,700
lbs. of Lorol chloride at room temperature, with
stirring. ‘This is about two-thirds of the molecu
lar equivalent of the NaI-IS.~ The addition of the
55 Lorol chloride having cooled‘ themixture, we heat
45
2,404,425
3
lit again and agitate it, preferably while continu
4
lution, acting as an electrolyte, will serve the same
‘ing to pass in 1-128, until the reaction is substan
1tially complete with respect to the Lorol chloride,
about one-third of the hydrosulphide remaining
‘unreacted. During the reaction the temperature
‘ is held at 100° C. After about one hour, the sup
purpose. After the impurities have been modi?ed
in this way they cease to be troublesome. We
then draw oil“ the aqueous phase again, and distill
off the butanol from the crude mercaptan for
reuse. The weight of crude mercaptan is ap
proximately equal to the weight of Lorol chloride
used. Finally we fractionate the product. In this
@ply of H28 may be diminished.
Although the NaI-IS used is practically free
from NazS, NaI-IS has a tendency to give up H28
and form NazS, which then reacts with the alkyl lo latter step any di-Lorol sulphide is left behind,
as well as any other high boiling impurities. The
chloride to form the unwanted dialkyl sulphide.
distilled mercaptan boils typically at l20°to 186° C.
The latter may also be formed directly, or by loss
at 5 m. m. and contains about 0.35per cent chlo
of H23 from two molecules of the mercaptan.
rine and 14.3 per cent sulphur combined as SH,
Saturation of the alcohol medium containing
or mercaptansulphur.
NaHS with H28 before addition of the Lorol
The ?nished product is much‘more uniform
chloride andaddition of HzS to the reaction mix
and lower in impurities than that of the prior
ture during the reaction, and in particular addi'-'
art,
tion of a very great excess during the ?rst hour,
'
‘
‘medium of methyl or ethyl alcohol.“ It is also
are therefore very important, and have been
comparatively free from the decomposition prod-v _.
found to increase the mol ratio of mercaptan to ‘:0 nets of the prior art. Our product has on this
dialkyl sulphide in the product substantially.
account been found very superior for use in the
‘The time required for the reaction depends
reactions requiring a uniform high grade mate
upon the temperature and the vigor of the agita-
rial.
tion. - Our process, as ordinarily conducted, start-
’
;
In the process of the prior art in which a wa
ing at 85° C. and ?nishing at 100° (7.,requires '25 ter miscible solvent is used, the recovery of the
eight hours. The product contains less than one
solvent from the aqueous phase constitutes an ad
per cent~of chlorine. By using a greater excess
ditional expense. In our process, the organic
of NaHS or continuing the process longer, the‘
phase, containing the butanol and product, forms
residual chlorine can be cut down still lower.
‘
‘a layer so distinct that the aqueous phase may be
‘It should be noted that in our process the water 30 drawn off without di?‘iculty. The latter contains
present during the reaction is that which is inless than 4 'per. cent'butanol and no recovery of '
troduced with the ?ake NaHS and butanol. This
the butanol from the aqueous phase is necessary.
amounts to7 to 15 per cent of the total weight of
the reaction mixture. Any water in excess of this '
In our process the choice of an organic solvent
is determined bythe considerations that it must
proportion is a hindrance.
‘
- ‘
"'5 be miscible with the alkyl chloride and the water
‘It should also be noted that the butanol is not
* a mutual solvent for the reagents, in the ordinary sense, since the solubility of NaHS of NaHS
solution in butanol is slight and miscibility of wa-
solution of hydrosulphide must be slightly mis- '
cible with it, yet not so miscible as to result in a
single phase system or require a distillation to
‘separate it from the wash Water; also the organic
teri therewith limited. Nevertheless, we believe 40 solvent should preferably boil above the preferred
that it is the NaI-IS in the butanol that reacts
reaction temperature, to avoid the necessity for
with the Lorol chloride, and that this is replenre?uxing or pressure, but substantially below the
ished, as fast as used up, by NaHS from the,
mercaptan, ‘to facilitate recovery of the product
7
aqueous layer.
'
,
_
7
7
from the solvent.
These properties are possessed
‘After completion of the reaction in the manner 45 or lacking in varying degrees by the alcohols used
above described, the NaCl produced as a by-prodin the following series of experiments:
‘
1
2
s
N aHS in
Alcohol used as medium
l‘ggggbgf 31,3513}
.
.
RM
4
’
5
NgiHS i-n mac‘
6
7
Per cent
Per cent
-
Q‘t’if‘i’fté‘fi ,gggggggn fggégg militia
g. p. 1. _,
—
6hrs.
%hr. I ems.
'
8
,
’
by SH
'
11161“
_
n-Butanol ___________________ __
Isopropanol _________________ __
97-98
82-84
17. 40
57.10
2.7
' 3.15
13.00
4.80
96.2
89.7
83
55
88
54
IsobutanoL.
97-98
14.19
1. 30
1. 75
80.0
78
68
0.91
0. 45
55. 5
38.7
76
to
46
25
0.67
31.0
as
21
____ _.
Active amyl
“Lomr’?n
97-98
97-98
Getaniol____
97-98
8.75‘
8.50
.
0.54
0.61
5.30 ______ _.
1 After addition of ?ake NaSH, but before addition‘or Lorol chloride.
uct adheres to the sides and bottom of the reac- ~ ~
tor. {To remove this we add water and agitate.
The lower. aqueous phase containing NaCl and
is then drawn off.
The organic .
the butanol, product and any
65
All the above experiments were carried out un
der comparable conditions, and with reagents in
thesame proportions, which are those used in our
preferred process. ‘ In a ?ask provided with an
agitator were placed 180 grams of the alcohol, 10
grams of water, and 120 grams of 70% ?ake NaSH.
The temperature was raised to‘ 85° (3;, with stir
highly objectionable colloidal impurities formed
in the product. Acidifying with an acid, such 70 ring, and held there for a half hour.- In all cases
' two liquid layers were formed, the shallow'lower
as HCl, is also'e?ective in breaking down the col
unreacted Lorol chloride, is then washed with
strong brine solution. This breaks down certain
' loidal fimpu'rities.
' We believe that the breaking
down of these impuritiesis an electrochemical ef
' feet and that any strong aqueous salt or acid s0
layer containing most of the hydrosulphide and
water. From the upper alcohol layer a small'sam
ple was drawn off‘ and analyzed" for NaHS, giving
the values shown in column 3, which represent
2,404,425
1. The solubility of the solvent in the water and. VP
brine used for washing the product should prefer
the solubility of NaHS, solution in the organic
layer under the conditions of the reaction. The
ably be so low that recovery of alcohol from the
wash‘ water may be dispensed with. This is
notably true of the n-butanol, but not of iso
propanol, as 95% of the latter solvent is carried
away in the washes, necessitating a recovery of
mixture was then saturated with H25 and: 205
grams of Lorol chloride were added.
’
During the ensuing reaction, the mixture was
agitated vigorously, at the temperature indicated
in the table, while a current of His was bubbled
through. it. The temperature was necessarily
lower in the case of the isopropanol, because of
the2. alcohol.
The solvent should not promote formation
its lower boiling point. In all cases a two-phase
chlorine reacted out is replaced by the SH or mer
of di-Lorol sulphide. With n-butanol, 83% of the
system formed and after one-half hour and a
brief settling the organic phase was sampled and
analyzed for dissolved NaHS, giving the values
captan group. Isopropanol, on the other hand,
promotes the formation of di-Lorol sulphide to .
such an extent that only 55% of the chlorine
shown in column 4. The reaction was continued
for 6 hours, and the same phase was analyzed
umn 'l.
reacted out is replaced by SH, as shown in col
again for NaI-IS, giving the values shown in col
3. The boiling point of the solvent should be
high enough to permit an adequate reaction tern»,
perature, without the use of pressure. This is
true of all the alcohols used in the above series
calculated. The results are given in column 6. 20 except isopropanol, which is unsatisfactory in this
The mixture was also analyzed for sulphur com
respect, as unless pressure is used it permits of
umn 5. The organic phase of the reaction mix
ture was then analyzed for chlorine and the per
centage of the chlorine that had been reacted out
bined as SH. or mercaptan sulphur, to show what
a reaction temperature of not over 82-84" (3.,
proportion of the chlorine reacted out had been
replaced by an SH group, i. e., the ef?cieney of
conversion of the Lorol chloride to Lorol mercap
tan, as distinguished from di-Lorol sulphide.
whereas a temperature, of 97-98" C. is desirable.
i. The boiling point of the solvent should be
suf?ciently below that of the mei'captan to allow
the solvent to be easily separated from it by
These results are shown in column 7. It is not
possible to express the yield of mercaptan as a
vacuum distillation. “Lorol” and geraniol are un
satisfactory in this respect because their boiling
points lie too close to that of the crude mercap
percentage of the theoretical yield, as the aver
age molecular weight of the‘mixture of mercap- :
tans making up Lorol mercaptan'is not precisely
tan.
known, hence the theoretical yield cannot be ex
actly calculated. However, it can be assumed that
the molecular weight of Lorol mercaptan is near
ly the same as that of Lorol chloride. On this 2"
assumption the yield of mercaptan was calculated
from the mercaptan sulphur. Hence in column 8
the yield of mercaptan is, arbitrarily given
a
Lorol and geraniol are not considered practical
percentage of the Lorol chloride used.
v
These results constitute conclusive evidence
that in our process the mercaptan is produced by
'
>
.
For these reasons, such solvents as isopropanol,
for our process.
These solvents were included
in the table to emphasize the particular advan~
tages of the other sol-vents. especially of n-butanol.
It is at interest to note that the presence of
the product a?ects the solubility of the hydro~
sulphide in some of'the alcohols much more than
49 in others, and that affects the ~speed of the re~
action. Hence the reaction requires much more
time in some alcohols than in others. In this
a mechanism differing entirely from that of the
respect'again n-butanol appears much superior
simple one-phase system of the prior art. In all
to the other alcohols for our purpose.
Although butanol has been used before for the
cases the alcohol used was miscible with Lorol
chloride, to form the upper organic phase of the
reaction mixture. At no time however did this
phase contain more than a small proportion of
the NaHS, which was continually reacting with
Lorol chloride to form the mercaptan, and being
reaction of dodecyl and tetradecyl chlorides and
bromides with KHS in a single-phase medium, it
ppears to be interior for this purpose to ethyl
alcohol. The discovery that n-butanol has pecul
iar advantages in our type of two-phase reaction
is therefore believed to be new and important.
We do not wish, however, to be limited to the
above mentioned alcohols as solvents for use in
our process, as other solvents have been found
end of the ?rst half hour, the reaction continued 55 suitable for our purpose, such as those known
by the trade name‘ of “C‘ellosolve,-”' which are
and used up some of the NaHS' content before the
replenished by agitation in contact with the lower '
aqueous phase containing the large excess of
NaHS. The reaction with Lorol chloride was so
rapid that when a sample was taken out at the
analysis could be completed. At the end of the 6
hour period the reaction had slowed down and
analysis then gave the true concentration of
NaHS in the organic phase. For this reason the
?gures in column 5 are ‘higher than in column 4',
and more reliable.
The higher the sustained concentration of
Hal-IS in the organic phase after the reaction
has proceeded for a time, the faster the reaction
should take place. Byarbitrarily limiting the
ether alcohols.
.
'
Since Lorol chloride includes the chlorides from
decyl to octadecyl, it is obvious that our process
is applicable to any individual chloride oij this
series. For example, wehave produced cetyl mer~
captan from cetyl chloride by our process. How
ever, our process is‘ not limited to mercaptans of
10 to 18 carbon atoms, but is applicable to mer
captans of a somewhat wider range, namely those
of 8 to 20 carbon atoms.
reaction time to 6 hours, we have shown that this
is the case. The extent of the reaction, as indi
cated by the lowering of the chlorine content and
increase of the mercaptan sulphur content, as
well as the yield of the mercaptan, is a function
1. The process for production of alkyl mercap
tans of .10 to 18 carbon atoms by reaction of the
of the concentration of NaHS in the organic phase
agitating the hydrosulphide at 76° to 100° C. with
We claim as our invention: 7
corresponding alkyl chloride with sodium hydro
sulphide- in a two-phase system which comprises
water amounting to not less than substantially
The characteristics which the [solvent should
43 per cent of the weight thereof, and an alcohol
have in order to be useful in ourv process may be 75 boiling above 85° C. but below the boiling point
summarized as follows:
of the reaction mixture.
2,404,425
of the mercaptan and miscible with the alkyl
chlorideas well as with a minor proportion only
of the hydrosulphide and water, said alcohol con
taining up to 10 per cent of its weight of water
and the quantity of alcohol being less than that
with which the water and hydrosulphide would ‘
tans of 10 to 18 carbon atoms by reaction of the
corresponding alkyl chloride with sodium rhyé
drosulphide in a two-phase systemv which com
prises agitating the hydrosulphide at 70° to 110°
C. with water amounting to not less than substan
tially '43 per cent of the weight thereof, and an
be miscible; passing hydrogen sulphide into the
alcohol boiling above 85° C. but below the boiling
mixture to saturate it_ therewith; incorporating
the alkyl chloride with the mixture, the quantity ‘
point of the mercaptan. and misciblewith' the
of alkyl chloride being less than the molecular 10 alkyl chloride as well aswith a minor proportion
only of the hydrosulphide and water, said alcohol
equivalent of the hydrosulphide and such that
containing up to 10‘per'gcent of its weight of
the water content of both phases of the mix- ‘
water and the quantity of alcohol being less than
‘ ture is not less than 7 per cent of the total weight;
l
'
‘
1
that with which the water and hydrosulphide
agitating the mixture at 85° to 110° C. and simul
would be’ miscible; passing hydrogen sulphide
taneously- passing hydrogen sulphide into it to
15
intothe mixture to saturate it therewith;/in
maintain 'it saturated therewith; continuing the
corporating the alkyl chloride with the mixture,
operation until the reaction is substantially com- '
' ‘ plete with respect to the
alkyl chloride; and re
7 covering the product from the organic phase.
the quantity of alkyl chloride being less than
the molecular equivalent of the hydrosulphide
and such that the water contentv of both phasesv
'2. The process for production of alkyl mercap
tans of 10 to 18 carbon atoms by reaction of the 20 of the mixture is not less than 7 'per cent of
3 corresponding alkyl chloride with sodium hydro
. ‘ sulphide in a two-phase system which comprises
the total weight; agitating the mixture at 85°
to 110° C. and simultaneously passing hydrogen
‘ agitating the hydrosulphide at 70° to 110° C. with
sulphide into the, mixture to maintain ‘it satu
j, water amounting to not ‘less than substantially
‘43'per cent of thekweight thereof, and an alco
‘hol boiling above 85° but below the boiling point
of the mercaptan and miscible with the alkyl
rated therewith; continuing the operation‘ until
25 the reaction is substantially complete with respect '
to the alkyl chloride; washing the organic phase;
drawing off the aqueous phase; and recovering
the product‘ from'the organic phase.
5. The process for production of alkyl mercape
tans of 10 to 18 carbon atoms by reaction of the
corresponding alkyl chloride with sodium hy
drosulphide in a two-phase system which com
prises agitating thehydrosulphide at 70° to>110°
C. with water amounting to not less than sub
stantially 43 per cent of the weight thereof, and
an alcohol of the group consisting of normal butyl,
isobutyl, active amyl and beta butoxy ethyl alco
hols, said alcohol containing up to 10 percent
of its weight of water and the quantity of alco
is not less than~7 nor more than 15 per cent of
‘the total weight; agitating themixture at 85° 40 hol being less than that with which the hydro
to 110° C. and simultaneously passing hydrogen
sulphide into it to maintain it saturated there
sulphide and water would be miscible; passing
hydrogen sulphide into the mixture to saturate
it therewith; incorporating the alkyl chloride
with; continuing the operation until the reaction
is substantially complete with respect to the
alkyl chloride; and recovering the product from
the organic phase.
with the mixture, the quantity of alkyl chloride
being less than the molecular equivalent of the
hydrosulphide and such that the water content
of both phases of the mixture is not less than 7
1 3. The process for production of alkyl mercap
per cent of the total weight; agitating the mix
tans cf 10‘ to 18 carbon atoms by reaction of
the corresponding alkyl chloride with crystal 50 ture at 85° to 110° C. and simultaneously pass
ing hydrogen sulphide into it to maintain it sat- V
line sodium hydrosulphide in a two-phase sys
tem which comprises agitating the hydrosulphide
at 70° to 110° C‘. with an alcohol
l‘ ‘
boiling above , '
urated therewith; continuing the 'operation'un
til the reaction is, substantially complete with
respect to the alkyl chloride; washing the organic
85° 0., but below the boiling point
the mer
phase; drawing off the aqueous phase; and recove
cant-an and miscible with the alkyl ofchloride
as 55 ering the product from the organic phase.
well as with a minor proportion only of hydro
6., The process for production‘of alkyl mercap
tans of 10 to 18 carbon atoms by reaction of the
corresponding alkyl chloride with sodium ‘hydro
60
incorporating the alkyl chloride with the mixture,
‘sulphide in a two-phase system which comprises
agitating the hydrosulphide at 70° to 110° 0. with
water amounting to not less than substantially
43 per cent of the weight thereof, and normal
the quantity of alkyl chloride being less than the I b-utyl alcohol ‘containing up ‘to 10 per cent of its
molecular equivalent of the hydrosulphide and 65' weight of water, the quantity of alcohol being
less than that with which the hydrosulphide and
such that the water content of both phases of the
water would be miscible; passing hydrogen sul
mixture is not less than 7 per cent of the total
weight; agitating the mixture ‘at 85° to 110° C.
phide into the mixture to saturate it therewith;
and simultaneously passing hydrogen sulphide
incorporating the alkyl chloride with the mixture,
the quantity of alkyl chloride being less than the
into it to maintain it saturated therewith; con-'
tinuing the operation until the reaction is sub
stantially complete with respect to the alkyl chlo
ride; and recovering the product from the organic
at 85° to 1105C‘.
v4. The process for production of alkyl mercap v7 5 iand simultaneously passing hydrogen sulphide 1
nto. it to maintain it saturated’therewith; con
phase.
»
7
2,404,425
'10
hydrosulphide would be miscible; passing hydro
tinuing the operation until the reaction is sub
stantially complete with respect to the alkyl chlo
ride; washing the organic phase; drawing off the
aqueous phase; and recovering the product from
the organic phase.
'7. The process for production of alkyl mercap
gen sulphide into the mixture to saturate it there
with; incorporating the alkyl chloride with the
mixture, the quantity of alkyl chloride being less
than the molecular equivalent of the hydrosul
phide and such that the water content of both
phases of the mixture is not less than '7 per cent
of the total weight; agitating the mixture at ‘85°
tans of 10 to 18 carbon atoms by reaction of the
to 110° C. and simultaneously passing hydrogen
corresponding allgvl chloride with sodium hydro
sulphide in a two-phase system, which comprises
sulphide into it to maintain it saturated there
agitating the hydrosulphide at 70° to 110° C‘. with 10 with; continuing the operation until the reaction
' is substantially complete with respect to the alkyl
water amounting to not less than substantially
chloride; washing the organic phase; drawing off
43 per cent of the weight thereof, and isobutyl
its weight
the aqueous phase; washing the organic phase
again with an electrolyte inert to the product;
of water, the quantity of alcohol being less than
that with which the hydrosulphide and water 15 drawing off the aqueous phase again; and recov
ering the product from the organic phase.
would be miscible; passing hydrogen sulphide into
10. The process for production of alkyl mercap
the mixture to saturate it therewith; incorporat
tans of 10 to 18 carbon atoms free from colloidal
ing the alkyl chloride with the mixture, the quan
impurities by reaction of the corresponding alkyl
tity of alkyl chloride being less than the molecular
equivalent of the hydrosulphide and such that 20 chloride with sodium hydrosulphide in a two
phase system which comprises agitating the hy
the water content of both phases of the mixture
drosulphide at 70° to 110° C. with water amount
is not less than '7 per cent of the total weight;
ing to not less than substantially 43 per cent of
agitating the mixture at 85° to 110° C. and simul
the weight thereof, and an alcohol boiling above
taneously passing hydrogen sulphide into it to
maintain it saturated therewith; continuing the 25 85° C. but below the boiling point of the mercap
tan and miscible with the alkyl chloride as well
operation until the reaction is substantially com
as with a minor proportion only of the hydrosul
plete with respect to the alkyl chloride; washing
phide and water; said ‘alcohol containing up to
the organic phase; drawing oil the aqueous phase,
10 per cent of its weight of water and the quan
and recovering the product from the organic
30 tity of alcohol being less than that with which
phase.
_
the water and hydrosulphide would be miscible;
8. The process for production of alkyl mercap
passing hydrogen sulphide into the mixture to
tans of 10 to 18 carbon atoms by reaction of the
saturate it therewith; incorporating the valkyl
chloride with the mixture, the quantity of alkyl
agitating the hydrosulphide at 70° to 110° C‘. with 35 chloride being less than the molecular equivalent
corresponding alkyl chloride with sodium hydro
sulphide in a two-phase system which comprises
of the hydrosulphide and such that the water
content of both phases of the mixture is not less
than 7 per cent of the total weight; agitating the
mixture at 85° to 110° C‘. and simultaneously pass
that with which the hydrosulphide and water 40 ing hydrogen sulphide into it to maintain it satu
water amounting to not less than substantially
43 per cent of the weight thereof, and active amyl
alcohol containing up to 10 per cent of its weight
of water, the quantity of alcohol being less than
rated therewith; continuing the operation until
the reaction is substantially complete with respect
the mixture to saturate it therewith; incorporat
to the alkyl chloride; washing the organic phase;
ing the alkyl chloride with the mixture, the quan
drawing o? the aqueous phase; washing the or
tity of alkyl chloride being less than the molecular
equivalent of the hydrosulphide and such that 45 ganic phase again with strong brine solution;
the water content of both phases of the mixture
drawing off the aqueous phase again; and recov- >
ering the product from the organic phase.
is not less than '7 per cent of the total weight;
11. The process for production of Lorol mer
agitating the mixture at‘ 85° to 110° C. and simul
captan which comprises agitating crystalline so
taneously passing hydrogen sulphide into it to
dium hydrosulphide at ‘70° to 110° Ctwith normal
maintain it saturated therewith; continuing the
operation until the reaction is substantially com
' butanol containing up to 10 per cent water in the
proportions of substantially 970 to 1,500 parts by
plete with respect to the alkyl chloride; washing
weight; passing hydrogen sulphide into the mix
the organic phase; drawing off the aqueous
ture to saturate both phases therewith; ‘incor
phase; and recovering the product from the or
65 porating Lorol chloride in the proportion of sub
ganic phase.
stantially 1,700 parts by weight with the mixture;
9. The process for production of alkyl mercapé
agitating the mixture at 85° to 110° C. and simul
tans of 10 to 18 carbon atoms free from colloidal
taneously passing in hydrogen sulphide to main
impurities, by reaction of the corresponding alkyl
tain it saturated therewith; continuing the opera
chloride with sodium hydrosulphide in a two
phase system which comprises agitating the hy 60 tion untilthe reaction is complete with respect
to the Lorol chloride; washing the organic phase;
drosulphide at 70° to 110° C. with water amount
would be miscible; passing hydrogen sulphide into
ing to not less than substantially 43 per cent by
weight and an alcohol boiling above 85° C. but
below the boiling point of the mercaptan and
miscible with the alkyl chloride as well as with 65
a minor proportion only of the hydrosulphidev and
water, said alcohol containing up to 10 per cent
of its weight of water and the quantity of alcohol
being less than that with which the water and
drawing oif the aqueous phase; washing the or
ganic phase again with a strong brine solution;
drawing off the aqueous phase again; and recov
ering the product from, the organic phase.‘
JOY E. BEANBLOSSOM.
RICHARD H. KIMBALL.
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