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Патент USA US2406410

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Patented Aug. 27, ‘1946
Frank Kerr Signaigo,‘ Wilmington, DeL, assignor
to E. I. du Pont de Nemourslé’c Company,‘ Wil
mington, Del., a corporation of- Delaware
No Drawing. Application March‘ 2,1944,
Serial No. 524,811‘
9. Claims. (01. 26019609,)‘
Example I
There-is placed in a steel hydrogenation auto
clave‘ '70 parts of heptaldehyde, 56 par-ts of bu
tanethiolll; and 15 parts of a cobalt trisulphide
catalyst prepared by’ precipitating a solution of
cobalt- clil‘oride with sodium trisulphide. The
washed‘ precipitated C‘oSa is dried in an inert at
phides from carbonyl compounds.
Aliphatic thiols, aldehydes: and ketones. are
useful intermediates for chemical‘ syntheses. It
has. been discovered that organic sulphides, can
be- readily synthesized in good yields from thiols
and either aldehydes or ketones. Since sulphides
are. attractive as‘ intermediates in the prepara
tion‘ of chemicals useful in the ?elds of insecti
cides, pharmaceuticals, rubber chemicals, sur
face-active agents, and the like, methods which
make. such materials available are of consider
able practical importance.
This invention has as one of its primary ob
jects the preparation of such sulphides by a new
and improved method. Another object is to pro
vide a simple and direct process for preparing
plea, wherein- parts are, by weight unless. other
wise stated:
Thisv invention relates to the production‘ of or
ganic. sulphides or thioethers‘,v and more particu
larly to; novel processes for producing such. sul
10 mosphere since it ispyrophoric and made into a
paste with dioxane. The autoclave is then
charged with hydrogen, at superatmospheric
pressure and: agitated and heated at 175° C. The
initial total‘, pressure in the autoclave at 175° is
15 2500‘ lbs/sq. in; During 3 hours, the pressure
decreases to 2,000 lbs/sq. in. and no further
pressure’ dro-pis'j observed during a second 3-hour
, heatin'g'period. The autoclave is cooled, the con
aliphatic sulphides which are‘ useful as such or as 20
intermediates in the synthesis. of important com- ’
mercial products. Still another object is the
preparation of sulphides from readilyv available
raw carbonyl compound materials. Other ob
jects will be apparent from a reading of the de
scription which follows:
These'and other objects are accomplished by
the following invention which comprises cata
tents- separated from the catalyst by ?ltration
and’ subjected to vacuum distillation. The fol
lowing products are obtained?
- -
‘ parts ’ »
Bo?mg pomt
Per cent
Per cent.
S‘ (H)
l‘. ____ _.
2 _____ __
86°’ (1/50 mm.»to 77F’ C./27
lasso/27mm ___________ -_
17. 0
3 _____ __
1269- C./2.6 min“ _ _ a. ____ __
l4. 9
18. 5
lytically hydrogenating an organic compound
containing a carbonyl group in the presence of a 30
thiol over a sulphactive hydrogenation catalyst.
In adapting the invention to practical applica
tion, a suitable organic carbonyl compound, such
as an aldehyde or ketone, is charged into a con
Product No; 1’, appears to comprise a-_ mixture of
unreacted heptaldehyde and heptanethiol-l.
The principal product, No. 2, comprises heptyl
butyl sulphide The high boiling by-product is
probably diheptyl sulphide.
ventional type of high pressure reactor together 35
- Example II
with hydrogen, an equivalent amount of a thiol,
hydrogenation autoclave
and a sulphactive hydrogenation catalyst pre
there‘ are‘ charged 79- parts- of dodecanethiol-l,
pared in accordance with the methods described
25 parts of acetone‘ and 15 parts of cobalt tri
in U. S. Patents Nos. 2,221,804. and 2,230,390. The
sulphide catalyst prepared‘ as in Example I and‘
reactor is then closed, agitated and heated to a
parts of acetic acid. As a diluent, 50 parts of
temperature at which reaction occurs at a suit
able, desired rate. Hydrogen is added or‘ intro
duced as needed, to maintain the total pressure
within the reaction vessel in the neighborhood of
about 1,000 lbs/sq. in. After the reaction is
complete, as evidenced by no further pressure
dioxane are also added. The autoclave is charged
with hydrogen at ,sjuperatmospheric pressure and
heated’ at 200°‘ C; with agitation for 5 hours, at a
total pressure of 2,000-1_bs,-./sq. in. The contents
of the autoclave arev then cooled, ?ltered from »
the catalyst and vacuum distilled. There is re
decrease, the vessel is cooled, opened, the catalyst
covered 43 parts of unreacted dodeoanethiol
separated from the resulting product and the lat
which is followed by 13 parts of dodecyl-l iso
ter is then isolated and recovered by methods 50 propyl sulphide boiling at 109° C‘. at 0.5 mm.
This sulphide has the iollowing analysis:
Well known to the art.
Since the exact manner of practicing the in
vention will vary somewhat depending upon the
particular compound processed, the invention is
Calculated vfor C15H32$t
best illustrated by means of the following exam 56
‘ G=74.4%.;
tations of the reaction vessel. It is preferred to
operate at temperaturesin the range of 150° to
While the foregoing examples indicate that
certain speci?c compounds may be readily con
225° C. and under a total pressure of from 100 to
verted to sulphides, in accordance with the in
5,000 lbs/sq. in. and particularly at pressures of
vention, it will be obvious that my invention is
not limited thereto.
in from 500 to 2,000 lbs/sq. in. When the reac
tants involve aryl thiols or aryl carbonyl com
In general catalytic hydrogenation of all alde
pounds it is desirable to operate at the minimum
hydes and ketones is contemplated ‘as falling
temperature at which reaction proceeds at a rea
within the scope of this invention. Speci?c ex
sonable rate in order to minimize hydrocarbon
:amples of such carbonyl compounds include ‘ali
phatic ketones, such as methyl ethyl ketone, d1“ 10 formation.
ethyl ketone, methyl butyl ketone, diisopropyl
' sulphactive catalysts utilizable in this inven
tion comprise those Which'are active for the cata
lytic hydrogenation of sulphur in organic multi
tanone, cyclohexanone, menthone, camphor, etc.;
sulphides, organic compounds having carbon to
aryl ketones such as acetophone, benzophone,
etc., aliphatic aldehydes such as‘formaldehyde, 15 sulphur unsaturation. and organic sulphur com
- pounds having sulphur to oxygen unsaturation.
acetaldehyde, butyraldehyde, heptaldehyde,‘ '2
ethyl-hexanal, etc.; and aryl aldehydes such as» -‘ ' They may be prepared by precipitation methods
or by sulphidation of the metals of their com
benzaldehyde, paratoluic aldehyde, etc. As will
ketone, etc.; alicyclic ketones such‘ as cyclopen
' pounds at ordinary or at elevated temperatures
Examples of 20 by means of sulphur, hydrogen sulphide or other
be apparent, these carbonyl compounds may con
tain one or more carbonyl groups.
sulphur compounds ‘and the latter may-be done
compounds containing more than one carbonyl
group are glyoxal, diacetyl, cyclohexanedione,
in situ.
with hydrogen at elevated temperatures. More
speci?c methods for preparing such catalysts.
comprise those disclosed in U. S. Patents Nos.
2,221,804 and 2,230,390. The type of sulphactive
catalyst employed may be variedconsiderably.
or linkages, such as hydroxy as in hydroxyalde
hydes and ketones, such as glycol-aldehyde,
sugars, etc. ; amine as in amino ketones such as
triacetoneamine and aminoacetophenone, etc.;
As a rule the subsulphides, sulphides and poly
sulphides of the common hydrogenating metals
are eifective. Especially useful are the sulphides
nitro as in nitro aldehydes and ketones such as
nitrobenzaldehyde, etc.; halogen as in chloroal
dehydes and ketones such as chloroacetone, etc.;
and polysulphides of iron, nickel, cobalt, and
carboxyl and its salts, esters, and amides such as
keto- and aldehyde-acids such as pyruvic acid,
molybdenum. The ?nely-divided metal or metal
sulphide may be supported on suitable inert car
.levulinic acid, ketostearic acid,’ acetoacetic ester,
riers such as kieselguhr, magnesia, alumina, etc. i
glyoxylic acid, and carboxy valeric aldehyde, etc.; .
unsaturated aldehydes and ketones such as cro
The proportion of catalyst employed may be var
ied considerably. In general, an amount that
tonaldehyde, citronaldehyde, methyl vinyl ,ke
tone, phorone,.acrolein, tiglic aldehyde, geranial
will bring about reaction at a suitable rate will
and citronellal, etc.; alkoxy and aryloxy alde
be found Within the range of 1 to 10% by Weight
hydes and ketones such as methoxybenzaldehyde 40
of the'combined reactants.
The process of this invention may be carried
and ethoxyacetophenone, etc.; and compounds
containing sulpho acid groups.
out as a batch, semicontinuous or continuous op
p In the practice of this invention, any thiolcan
eration, in the absence of solvents, or in the pres
be used and speci?c examples include methane
ence of water or organic solvents such as ethanol,
dioxane,j or benzene. The presence ofiacids es
thiol, ethanethiol, propanethiol, hexanethiol, do
decanethiol, octadecanethiol, ethanedithiol, bu
tanedithiol-L4, hexanedithiol-1,6, decanedithiol
pecially organic carboxylic acid will generally fa
cilitate reaction‘ of the less reactive types of
1,10, cyclohexanethiol, pinanethiol, thiophenol,
thio-alpha-naphthol, thio-beta-naphthol, and
The activity of certain of the metal sul-.
phide catalysts may be improved by treatment
benzoylacetone, lA-dibenzoylbutane, etc. ; car
bonyl compounds containing unreactive groups
vI claim as my invention:
1. A method for producing an organic sulphide
thiosorbitol, etc. These may be used as such or 50
which comprises hydrogenating an organic com
‘formed in situ for use in the invention from com
pound containing a carbonyl group in the pres
pounds Which readily yield them.
ence of a thiol and a sulphactive hydrogenation
The amount of thiol component used should be
at least the chemical equivalent of the carbonyl
2. A method for producing an organic sulphide
which comprises hydrogenating at an elevated
temperature and over a sulphactive hydrogena
tion catalyst an organic" compound containing
To obtain an improved conversion
of the carbonyl compound, it is desirable and
preferable to use an amount of thiol which is in
excess of the chemical equivalent of said carbonyl
a carbonyl group and veffecting said hydrogena
‘compound. In the case of end-unsaturated car
bonyl compounds, an additional mol of thiol may 60 tion in the presence of an amount of a thiol at
add to the ethylenic bond.
least chemically equivalent to the amount of car;
bonyl compound present.
I Although the above examples set forth certain
3. A method for producing an organic sulphid
de?nite conditions with respect to temperature,
which comprises hydrogenating an aldehyde at
pressure, concentration, duration of reaction, cat
alyst, etc., it is to be understood that these values 65 an' elevated temperature in the presence ,of. a
thiol and a sulphactive hydrogenation catalyst.
can be varied somewhat within the scope of this
invention, since the conditions of each adapta
{1. ‘A' method for producing an organic sulphide
tion of the invention are determined by and de
which comprises hydrogenating a ketone at
pend upon the particular vcarbonyl compound
an elevated temperature in the’presence of a
treated,»the quantity employed, the catalyst, and 70 thiol and a sulphactive hydrogenation catalyst.
5. A method for producing an organic sulphide.
end product desired, etc.
In'general the process of this invention is op
which comprises hydrogenating ketonic acid at
erative at temperatures ranging from 100° to 300°
an elevated temperature in thepresence of a
C. and at pressures ranging from atmospheric
thiol and a sulphactive hydrogenation catalyst. "
to a maximum determined by’ the practical limi
‘6. A method for producing an organic sulphide
which comprises hydrogenating an aliphatic
aldehyde at an elevated temperature in the pres
ence of a chemically equivalent amount of a
thiol and a sulphactive hydrogenation catalyst,
the amount of said catalyst ranging from about
1-10% by weight of the combined reactants.
7. A method for producing an organic sulphide
which comprises hydrogenating an aliphatic
'which comprises hydrogenating ‘at an- elevated
temperature heptaldehyde in the presence of at
least a chemically equivalent amount of bu-‘
tanethiol-l and from about 1-10% byweight,
on the basis of the combined reactants, of a .v
sulphactive hydrogenation catalyst.
9. A method for producing an organic sulphide
which comprises hydrogenating at an elevated
temperature acetone in the presence of at
ketone at an elevated temperature in the pres
ence of a chemically equivalent amount of a 10 least a chemically equivalent amount of dode
canethiol-l' and from about 1-10% by Weight,
thiol and a sulphactive hydrogenation catalyst,
on the basis of the combined reactants, of a
the amount of said catalyst ranging from about
7 1-10% by weight of the combined reactants.
8. A method for producing an organic sulphide
sulphactive hydrogenation catalyst.
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