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Patented Oct. 15, 1946
2,409,329
UNITED STATES PATENT OFFIC
2,409,329
n
'
ORGANIO ‘ THIOCYANO COMPOUNDS
Paul H. Williams,‘ Berkeley, Calif., assignor to
Shell Development Company, San Francisco,
Calif., a corporation of Delaware
No Drawing. ‘Application February 28, 1944,
'
‘
Serial N 0. 524,309
9 Claims. . (Cl. 260-454)
.
n
1
l
2
n
This invention relates to organic ‘thiocyano
critical importance, those compounds are pre
ferred wherein the alkyl groups contain less than
?ve carbon atoms, especially those wherein all of
the alkyl groups are methyl groups. Especially
desirable are those compounds in which‘there are
compounds, and more particularly , pertains to
compounds of the general formula
0
II
.
I
R—-‘O—C—X
‘ two methyl groups on the cyclohexyl radical, one
wherein
is an yalkyl-substit'uted cyclohexyl
radical containing at least two alkyl groups, ‘and
substituted in the 3 position and the other in the
5 position, and those wherethere are three sub
X is a thiocyano-substituted hydrocarbon radical.
stituent methyl groups, especially those where
The. organic thiocyano compounds of ‘the in 10 there are two methyl groups in the 3 position
vention have many importantluses. 'Theymay,
and one in “the 5 position. Thus 3,5-dimethyl
for example, be used as wetting agents,.‘as plas
ticizers, as addition. agents for rubber, and .as in
cyclohexyl thiocyanoacetate,
CH3
\oH-om
termediates in the synthesis “of, other valuable
organic compounds. They are particularly user 15
on;
ful, as insecticides, fungicides and parasiticides
since, in addition to possessing‘ unusually high
~
‘
‘
"
~
'
'
0
\OH-—O—g-—CHa—SON ‘
\CH—CHz
insecticidal activity, they havev an, inoifensive
odor, are light-stable, are‘compatible with or sol
.C‘ a
uble in light para?inic mineral oils such as kero 20 and 3,3,5-trimethylcyclohexyl thiocyanoacetate,
sene, and are not damaging in any way to fabrics,
‘
CH3
wall paper, painted walls, etc. This use of‘ the
Oil-CH:
compounds of the invention as insecticides, fungi
cides and parasiticides is described and ‘claimed
in the .copending application,v ‘Serial Number‘ 25
482,032, ?led April 6, 1943, of ‘which this applica
tionis‘acontinuation-impart.
“
p.
1 “
s
CH:
'
on-o-c'L-ora-sosr
\o~_om
'
on; on,‘
have been found to be especially desirable ‘com
‘ Theorganic thiocyano compounds or the in
vention have the general formula
’
pounds of this type when considered from‘ the’
30 standpoint of their general utility, their e?ective‘e
mass as insecticides, and their ease and economy
r
-
‘
_
‘
Ib-O-PJ-X
of preparation.
wherein R is an alkyl-substituted cyclohexyl
,
.
,
7
Although the radical represented by X in the
hereinabove de?ned general formula
radical which is, substituted ‘with at‘ least two
alkyl groups, and X is a ‘thiocyano-substituted 35
hydrocarbon radical.
‘
‘ '
'
Suitable alkyl group substituents on the cyclo
hexyl radical are, for example, the methyl, ethyl,
may be any thiocyano-substitutecl hydrocarbon
propyl, butyl, amyl, hexyl, heptyl, o‘ctyl, nonyl,
etc., radicals and theirhom‘ologues; aswell as
certain unsaturated radicals such as the allyl,
radical, it is preferably a mono-, die, or poly:
.40 thiocyano substituted aliphatic radical derived
methallyl, crotyl, etc.,.radica1s.v The said groups
may be substituted in any desired position on the
from the saturated or unsaturated aliphatic acid
of corresponding structure. The resulting pre
ferred compounds are, therefore, the alkyl-sub
cyclohexyl radical, although the third and ?fth ‘ stituted cyclohexyl esters of the mono” di-, or
carbon atoms relative to the carbon atom bearingv :45 poly-thiocyano substituted saturated or unsatu
the bond to the oxygen atom represent preferred
rated aliphatic acids. The aliphatic acid residue
positions. In‘ these preferred compounds the car—...
may be of any desired-molecular weight, depend
bon atomsof the cyclohexyl‘nucleus maybe
ing upon the use to which the ester. is to be put.
linked to the alkyl groups in any possible manner
The alkylcyclohexyl esters of the lower thiocyano
of ‘distribution, ‘i. e., one alkyl group on each of 50 aliphatic acids having from 2 to 6 carbon atoms
the carbon atoms, in the 3 and 5 positions, one
may, for example, be particularly effective foruse ’
alkyl group on one of the indicatedcarbon atoms
as insecticidal toxicants while the cyclohexyl
and two on the other,“ or- two alkyl groups on
esters of the higher acids, i. e. those having up
either or both of the indicated carbon atoms.
to about 20 carbon atoms, may be more suitable
Although the" sizeof the ‘r alkyl group is 'notof 55
for use as wetting agents.
‘
2,409,329
3
Representative acids, which may be used in
forming the desired thiocyano esters include the
C2 to C20 straight chain and branched chain satu
rated and unsaturated aliphatic acids such as
acetic acid, propionic acid, butyric acid, valeric
acid, caproic acid, capric acid, undecylic acid, un
decylenic acid, lauric acid, myristic acid, palmitic
acid, oleic acid, stearic acid, arachidic acid, and
C1
4
substituted aliphatic carboxylic acids, including
monochloroacetic acid, dichloroacetic acid, tri
chloroacetic acid, alpha-chloropropionic acid,
beta-chloropropionic acid, the dichloropropionic
acids, the dichlorobutyric acids, the chloroiso
valeric acids, the chlorolauric acids, the chloro
myristic acids, the chlorostearic acids, the chlo
roleic acids, the chlororicinoleic acids, the chloro
malonic acids and the corresponding bromo- or
their homolo-gues and analogues together with
suitably substituted compounds thereof, such as 10 iodo-substituted acids. Mixtures may be utilized
if desired, as may the anhydrides of the halogen
hydroxyacetic acid, lactic acid, dehydro-xy-n
substituted carboxylic acids, or the acyl halides
butyric acid, d-hydroxyisovaleric acid, ricinoleic
of these halogen substituted carboxylic acids.
acid, etc.
The compounds of the invention may be pre
pared in a variety of ways. They may be pre
Suitable metal thiocyanates for use in the syn
15 thesis include those which are of a su?iciently re
active nature to undergo reaction with a halogen
pared, for example, by reacting metal thiocya
substituted aliphatic acid. It is also desirable
nates with the sulfated esters of the appropriate
that the metal thiocyanates be relatively soluble
alcohols. However, a preferred method of prep
in the reaction medium. In general, ammonium
aration generally comprises reacting an alkyl sub
stituted cyclohexanol, e. g. 3,3,5-trimethyl cyclo 20 thiocyanate, the thiocyanates of the alkali metals,
and the thiocyanates of the alkaline earth metals
hexanol (dihydroisophorol) in the presence of
represent suitable reagents for use in effecting
an esteri?cation catalyst, if desired, with a suit“
the conversion of the halogen substituted esters
able halo-gen substituted acylating agent, and re
to the thiocyano substituted esters. Ammonium
acting the ester so produced with a suitable metal
thiocyanate to obtain the desired thiocyano ester. 25 thiocyanate, sodium thiocyanate, ‘potassium thio
cyanate, are preferred members of this group.
These reactions may be represented by the follow
As examples of preferred methods of forming
ing equations wherein R=an alkyl substituted
the desired compounds of the present invention
cyclohexyl radical containing at least two alkyl
the following may be given:
groups:
0
0
¢
%
ROH + memo-0H —-> ClCHzC-OR + H10
0
0
§
\
no-oorncl + NHASCN A RO—CCHZ—SCN + NHlOl
As indicated, it may be desirable when effecting
the esteri?cation of an alkyl substituted cyclo
hexanol with an acylating agent, e. g. a halogen
substituted aliphatic carboxylic acid, to make use
of an esteri?cation catalyst to accelerate there
action. Almost any of the esteri?cation catalysts
known to the art may be used for this purpose.
Suitable catalysts include, for example, the min
eral acids such as sulfuric acid or phosphoric
acid. Para-toluene sulfonic acid represents a
preferred catalyst, since it exerts the desired cata
lytic action without producing any substantial
charring of the constituents of the reaction mix
30
In a, 250 ml. flask equipped with a, re?ux con
denser was placed 142 g. (1.0 mol) of 3,3,5-tri
methylcyclohexanol (dihydroisophorol) and while
maintaining the temperature of the reaction mix
ture at 80° C., 124 g. (1.1 mols) of chloroacetyl
chloride was added dropwise. After reaction had
ceased, the mixture was cooled and washed with
water and 5% aqueous sodium carbonate and
then distilled. 3,3,5-trimethylcyclohexyl chloro
acetate, having a. boiling point of 109° C. to
110° C. at 5 mm. pressure and by analysis a
16.25%
chlorine content (16.25% theoretical
chlorine content) was obtained.
Into a one liter
?ask was placed 164 g. (0.75 mol) of the resultant
3,3,5-trimethylcyclohexyl chloroacetate, '76 g. (1.0
mol) of ammonium thiocyanate, and 400 cc. of
ethanol (95%). The mixture was re?uxed for
about one hour and then the ammonium chloride
formed was ?ltered off. The ethanol was re
ture. The catalysts are active in small amounts,
moved by distillation and the remaining material
an amount of catalyst which is equal to but about 50 was distilled through a Claisen ?ask at reduced
1% by weight of the alcohol used being a suificient
pressure to obtain 3,3,5-trimethylcyclohexyl thio
amount in most cases.
cyanoacetate having a boiling point of 134° C. to
Either step or stage of the above-described pre
138° C. at ca. 3 mm. pressure, which material
ferred method for preparing the presently dis
gave on analysis a sulfur content of 13.27%
closed thiocyano esters may be carried out in the 55 (13.1% sulfur-—theoretical for C12H19O2SN).
presence of an inert solvent, such as methanol,
In another .case the 3,3,5-trimethylcyclohex
ethanol, isopropanol, butanol, isobutanol, ace
anol was ?rst separated into its cis and trans
tone, ethyl acetate, benzene, toluene, xylene, hex
forms. One isomer had a boiling point of
anes, octanes, isopropyl ether, hydrocarbon frac
108.1° C. to 108.4" C. at 50 mm. pressure, and the
tions, such as gasoline, etc. It is usually preferred 60 other isomer had a boiling point of 117.2° C. to
to carry out the second step, i. e. the conversion
118.0° C. at 50 mm. pressure. Since the evidence
of the chloro ester to the thiocyano ester, in an
is not conclusive as to which is the cis and which
alcoholic medium. Each step may be carried out
is the trans form, these forms are herein referred
at any temperature within the range of between
to as the “low boiling” and the “high boiling”
about 0° C. and about 250° C., and preferably in 65 types. The thiocyanoacetates of both of these
the range of between about 50° C. and about
isomers were prepared as in the above example.
The isomer of 3,3,5-trimethylcyclohexyl thiocy
150° C. It may be desirable to carry out the re
anoacetate prepared from the “low boiling” prod
actions of either step in the absence of oxygen,
uct had a boiling point of 134° C. to 142° C. at 3
as, for example, in an atmosphere of carbon di
oxide. The products of each stage are preferably 70 mm. pressure and a sulfur content by analysis of
vacuum distilled, although if only a crude prod
13.6% (13.27% su1fur—theoretical) , and the 3,3,5
trimethylcyclohexyl thiocyanoacetate isomer pre
uct is desired, no distillation is needed.
pared from the “high boiling” form had a boiling
Suitable halogen substituted acylating agents
point of 130° C. to 131° C. at 3 mm. pressure and
include the halogen substituted aliphatic car
boxylic acids, e. g. the chloro-, bromo- or iodo 75 a sulfur content by analysis of 13.6%.
2,409,829"
In a ‘like manner 3,3,5‘-trimethylcyclohexyl
thiocyanoacetate was prepared from a mixture of
the cis and trans forms of 3,3,atrimethylcyclo
hexanol by reacting the latter with chloroacetic
clohexanol and chloro acetic acid; 3,3-dimethyl-"
5-ethyl-5 - propyl - cyclohexyl thiocyanoacetate
from 3,3 - dimethyl-5-ethyl-5-propyl-cyclohex
acid in the presence of toluene as an entraining
agent for water and then reacting the resulting
product with ammonium thiocyanate. This prod
anol and chloro acetic acid; 3-methyl-3-ethyl-5,5
dibutyl-cyclohexyl thiocyanoacetate from 3
uct had a boiling point of 137.5° C. at 3.0 mm.
pressure and a sulfur content by analysis of
‘chloro acetic acid; 3-methyl-3-ethyl-5-propyl-5
13.5%.
methyl-3-ethyl -' 5,5 - dibutyl-cyclohexanol- and
10 butyl - cyclohexyl
In a similar manner 3,3,5-trimethylcyclohexyl
thiocyanoacetate
from
3 -
methyl-3-ethyl-5-propyl - 5 - butyl-cyclohexanol
alpha-thiocyano propionate was prepared by
and chloro acetic acid; 3,3,5--trimethyl-5-ethyl
esterifying 3,3,5-trimethylcyclohexanol ‘with
alpha-chloropropionic acid and reacting the
cyclohexyl
thiocyanoacetate
from
3,3,5 - tri
methyl-5-ethyl-cyclohexanol and chloro acetic
product thus obtained with ammonium thiocy 15 acid; 3,3,5,5-tetramethyl-cyclohexyl thiocyano
anate. The 3,3,5-trimethylcyclohexyl alpha-thio
acetate from 3,3,5,5~tetramethyl-cyclohexanol
cyano propionate product had a boiling point of
and chloro acetic acid; 3,3,5,5—tetraethyl-cyclo
149° C. to 151° C. at 4.7 mm. and a sulfur content
hexyl thiocyanoacetate from 3,3,5,5-tetraethyl
by analysis of 12.6% (12.55%-—theoretical).
Similarly, 3,5-dimethyl cyclohexyl thiocyano
acetate was prepared by heating 3,5-dimethyl
cyclohexanol and chloro acetic acid.
20
I claim as my invention:
1. 3,5-dimethylcyclohexyl thiocyanoacetate.
2. 3,3,5-trimethylcyclohexyl thiocyanoacetate.
3. The 3,3,5-trimethy1cyclohexy1 thiocyanopro
pionates.
cyclohexanol with a 10% molar excess of chlor
acetic acid, a small amount of an esteri?cation
catalyst comprising para-toluene sulfonlc acid
and a su?icient amount of benzene to serve as an 25
4. An ester of a polyalkyl cyclohexanol and a
entraining agent for the water formed during the
thiocyano-substituted aliphatic carboxylic acid,
course of the reaction. Distillation of the reac~
tion product under subatmospheric pressure re
which ester contains no more than three alkyl
radicals directly linked to nuclear carbon atoms
sulted in the isolation of a good yield of 3,5-di
of the cyclohexyl radical, and wherein all of the
methylcyclohexyl chloro acetate. The chloro 30 alkyl radicals are directly linked to nuclear car
acetate was then converted to the corresponding
bon atoms by means of primary carbon atoms,
thiocyano acetate by reacting it with a 10%
only one of the alkyl radicals being directly
molar excess of ammonium thiocyanate in a so
linked to the nuclear carbon atom in the 5 posi
lution of ethyl alcohol. After removal of the al
tion relative to the acid radical, and the other
cohol, the thiocyano acetate product was dis 35 alkyl radicals being directly linked to the nuclear
tilled. Its boiling point was 114° C. to 119° C./1
carbon atom in the 3 position relative to the acid
mm. It contained 13.8% sulfur (calculated for
radical.
3,5 - dimethylcyclohexyl
thiocyano
acetate,
5. An ester of a trialkyl cyclohexanol and a
14.1%).
thiocyano-substituted aliphatic carboxylic acid,
In a like manner are prepared: 3-methyl,5
ethyl-cyclohexyl
thiocyanoacetate
from
3
methyl,5 - ethyl - cyclohexanol and chloroacetic
acid; 3-butyl,5-methyl-cyclohexyl thiocyanoace
tate
from 3-butyl,5-methyl-cyclohexanol and
chloroacetic acid; 3-methyl,5-isopropyl-cyclo
heXyl alpha-thiocyano-oleate from 3-methyl,5
isopropyl-cyclohexanol and alpha~bromo oleic‘
40 which ester contains only three alkyl radicals
directly linked to nuclear carbon atoms of the
cyclohexyl radical, two of the alkyl radicals be
ing directly linked by means of a primary carbon
atom to the nuclear carbon atom in the 3 position
relative to the acid radical, and the other alkyl
radical being directly linked by means of a pri
mary carbon atom to the nuclear carbon atom
acid; 3-ethyl,5-propyl-cyclohexyl thiocyanopro
in the 5 position relative to theyacid radical.
pionate from 3-ethyl,5-propyl~cyclohexanol and
alpha-chloropropionic acid; 3»propyl,5-pentyl
cyclohexyl thiocyanostearate from 3 -propyl,5-v
pentyl-cyclohexanol and alpha-chloro stearic
6. An ester of a dialkyl cyclohexanol and a
50 thiocyano-substituted aliphatic carboxylic acid,
which ester contains only two alkyl radicals
linked to nuclear carbon atoms of the cyclohexyl’
acid; 3,5 - diethyl - cyclohexyl thiocyanoacetate
radical, one of the alkyl radicals being linked di
from 3,5-diethyl-cyclohexanol and chloro acetic
rectly by means of a primary carbon atom to the
acid; 3,5-dimethyl-cyclohexyl dithiocyanoacetate 55 nuclear carbon atom in the 3 position with respect
from 3,5-dimethyl-cyclohexanol and dichloro
to the acid radical, and the other alkyl radical
acetic acid; 3,5-dipropyl-cyclohexyl thiocyano
being linked by means of a primary carbon atom
acetate from 3,5 - dipropyl - cyclohexanol and
to the nuclear carbon atom in the 5 position with
bromo acetic acid; 3,5-dibutyl-cyclohexyl thio
respect to the acid radical.
cyanoisobutyrate from 3,5-dibutyl-cyclohexanol
and alpha-chloro isobutyric acid; 3,3-dimethyl,
5-ethyl-cyclohexy1 thiocyanoacetate from 3,3-di
60
methyl-5-ethyl-cyclohexanol and chloro acetic
7. An ester of a polymethyl cyclohexanol and a.
thiocyano-substituted aliphatic carboxylic acid,
which ester contains no more than three alkyl
radicals, all of which are methyl radicals, direct
acid; 3,3-diethyl-5~propyl-cyclohexyl thiocyano
ly linked to nuclear carbon atoms of the cyclo
propionate from 3,3-diethyl-5-propyl-cyclohex~ ‘35 hexyl radical, only one of the methyl radicals be
anol and alpha-chloro propionic acid; 3-methyl
5,5-dibutyl-cyclohexyl thiocyanovalerate from 3
methyl - 5,5 - dibutyl-cyclohexanol and alpha
ing linked to the nuclear carbon atom in the 5
position relative to the acid radical, and the other
methyl radicals being directly linked to the nu
clear carbon atom in the 3 position relative to the
bromo valeric acid; 3,3,5-tri-ethyl-cyclohexyl
thiocyanoacetate from 3,3,5-tri—ethyl-cyclohex 70 acid radical.
anol and iodo acetic acid; 3,3,5-tributyl-cyc1o
hexyl thiocyanoacetate from 3,3,5-tributyl-cyclo~
hexanol and chloro acetic acid; 3,3,5-tripropyl
cyclohexyl beta-thiocyanopropionate from 3,3,5
tripropylécyclohexanol and beta-chloro propionic 75
8. An ester of a trimethyl cyclohexanol and a
thiocyano-substituted aliphatic carboxylic acid,
which ester contains only three radicals, all of
which are methyl radicals, directly linked to nu
clear carbon atoms of the cyclohexyl radical,
2,409,329
7
one of the methyl radicals being directly linked
to the nuclear carbon atom in the 5 position with
respect to the acid radical, and the other two
methyl radicals being directly linked to the nu
clear carbon atom in the 3 position with respect
to the acid radical.
.
9. An ester of a dimethyl cyclohexanol and a
thiocyano-substituted aliphatic carboxylic acid,
which ester contains only two alkyl radicals, both
8
of which are methyl radicals linked to nuclear
carbon atoms of the oyclohexyl radical, one of
the methyl radicals being directly linked to the
nuclear carbon atom in the 3 position relative to
the acid radical, and the other methyl radical be
ing linked to the nuclear carbon atom in the5
position relative to the acid radical.
PAUL H. WILLIAMS.
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