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Патент USA US2122781

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lsatented July 5,) 1938 ‘
.‘ 2,122,781
'Paul I; Salzberg, Edge Moor, DeL, assignor, by
mesne assignments, to E. I. du Pont de Ne
mours & Company, Wilmington, Del., a corpo
ration of Delaware
No Drawing. Application May 16, 1935,
Serial No. 21,811 .
'16 Claims. . (01. 167-30)
The present invention relates to new cyclo al
siticides and I mention the following as belong;
kyl thio-cyano esters and their- uses as parasitici
ing to the group derived therefrom:
dal agents, particularly cycloalkyl thiocyanates.
My novel parasiticidal agents are broadly repre .bornyl-thiocyanate, and iso-thiocyanate
5 sented by the formula R(XCN)y in which R is terpineyl-thiocyanate, and iso-thiocyanate
an alicyclic hydrocarbon radical containing at menthyl-thiocyanate, and iso-thiocyanate .
least 10 carbon atoms,
X is selected from the group consisting of sul~
.fur, selenium and tellurium,
y is a simple digit corresponding tov the valency
of radical R.
My novel parasiticides are most conveniently
obtained from vthe alcohols R--OH in which Rv
has the same'characteristics as above.
These alcohols are ?rst transformed into the
corresponding halides or sulfates and these are
then allowed to react with salts of thiocyanic,
hydro-abietyl-thiocyanate, and iso-thiocyanate.
Hydrogenation of aromatic compounds pro
duces a number of alcohols and unsaturated 10
compounds from which novel parasiticides ac
cording to my invention are derived. I cite the
alpha-decahydro-‘naphthyl thiocyanate and ‘
beta-decahydro-maphthyi thiocyanate
- Particularly suitable from a practical stand
selenocyanic, tellurocyanic acid and their iso
point of availability as parasiticides are the CNS
esters of naphthenic alcohols obtained from the
The alcohols can also ?rst be dehydrated to naphthenic acids of petroleum oils.
the corresponding unsaturated compounds and
These naphthenic alcohols and the esters de
rived therefrom contain polymethylene rings of
these then reacted with thiocyanogen.
The most e?ective parasiticides were obtained various sizes, one being, for example, a cyclopen
according to my invention when the radicalR is tane ring to which is attached an aliphatic side
25 of the nature of a hydrogenated aromatic com
chain, the terminal carbon of which carried the
pound, R is a terpenic radical or R is a naph-' original carboxyl group.
‘ thenic compound.
Naphthenyl thiocyanates of this type are char
The character of R should be predominantly acterized physically by their high fluidity and ab
that of a cycle-alkyl hydrocarbon radical but the
30 presence of an aromatic group in the hydrocar
sence of crystalline or wax-like properties, even in
bon molecule does not detract or impair the para
siticidal e?iciency of the compoundprovided the
CNX group is directly attached to the aliphatic
the higher members of the series. Furthermore, 30
the naphthenyl thiocyanates and their corre-'
sponding iso and seleno and telluro analogs have
relatively little odor and are in this respect not
end of the hydrocarbon radical.
objectionable as are the alkyl thiocyanates de
While the CNX group is of decided in?uence ' rived from lower alkyl groups, such as methyl, 35
upon the effectiveness of my novel compounds
as parasiticides, the properties of the R radical
contribute to a dominant extent upon the prac
' tical usefulness of these new compounds.
40 bility, spreadability, and selective toxicity tolow
er forms of life depend upon the aliphatic-cyclic
character of this group. '
1n the practical embodiment of myinvention I
derive my novel parasiticides from the following
45 available raw materials:
'I start with naphthenic acids which are ob
tained from‘ certain petroleum oils. These acids
are submitted to catalytic hydrogenation and the
resulting alcohols are then reacted as above.
50 ' Terpenes are another source of my novel para
ethyl, propyl, etc.
These physical properties make the naphthenyl
esters of the formula R(CNS)y particularly de
sirable for use as parasiticides.
Similarly other esters of the formula R(CNS)1/ 40
are also characterized by a non-disagreeable
odor, especially;v those derived from terpenes and
having non-waxlike properties. In respect to
solubility and dispersibility my novel parasiticides
sumce all requirements for practical applications.- 45
I shall in the following give various speci?c em
bodiments of my invention:
Example 1.—Naphthenyl thiocyanate from
Russian naphthenic acids.
25 parts by weight of naphthenyl alcohols (hy
droxyl number 332), (boiling point Ell-141° C.
- My novel esters are especially useful as in- I
secticides against sgft bodied insects and as con-'
under 19 mm. pressure) obtained by catalytic hy
drogenation of the ethyl esteg of Russian naph
thenic acids were corryerted into the correspond
stituents of kerosene ?y sprays.
the sodium chloride and the butanol solvent a
light ,yellow limpid liquid hailing a characteristic
thiocyanate odor was obtained. This boiled fat
127-167° CCunder '31 mm. pressure and repre
4. Compounds of the formula’ memo, in'
\ghich Rjis an alicyclic hydrocarbon radical of
sents the naphthenyl thiocyanate corresponding
'-.;alence y and containing at least 10 carbonjatoms
and X is an elementselected from; Group”VI—B
The product
has). speci?c toxic effect against lower forms of
, life; particulfarly soft bodied insects.
2. An insecticidal composition comprising as 10
the toxic ingredient bornyithiocyanate.
3. An insecticidal composition comprising as
the toxic ingredient a naphthenyl thiocyanate.
.10 parts re?uxing butanol. After separation from
' to ‘the naphthenic acid employed.
'nale which at ordinary temperature is a friquid
o? low ‘viscosity, boils in vacuo without substan
tial decomposition and has a speci?c toxicity
against soft bodiecfinsect's.
with 40 parts thionyl chloride in benzene. 18
parts of these naphthenyl chlorides in turn were
reacted with 10 parts sodium thiocyanate in 100
‘1. As a how compound a naphthenyl thiocya
ingnaphthenyl chlorides/KB. P. lid-‘13!;° C‘. under
18 mm.) (chiorine content 18.79%) by, treatment
of. the periodic table.
5; Compounds
Tests for the toxicity of these crude naphthenyl
of the
formula RHCNXM
wherein R1 is an alicycliic hydrocarbon radical 20
of valence y andjchosenfrom the group consist
20 » thiocyanates have shown the following results:
ing of naphtheriyl radicals and cyclic terpene
Gone. in
hydrocarbon radicals, and X is an element se
lected from Group VI-B of the periodic table.
' 6. Compounds of the formula RCNS 'fvherein
or .
B is an alicyclic hydrocarbon radical containing
' Permit
0.1% sulfonated ?sh C aphid.
at least 10 carbon atoms.
0.195, sulionated ?sh .-__. do ............... _.
o .
0.025% sulionated Nasturtium sip-hid---“
ilsh oil.
R1 is an alicyclic hydrocarbon radical chosen
from the group iconsistin?g ‘of naphthenyl radicals 30
and cyclic terpefhe hydrocarbon radicals.
Example 2.--Naphthenyl' thiocyanate from
35 number 2&3, B. P. 120-165" C. under 1 mm. pres
,X is an: element selected from Group ‘gI—B ofx
ithe periodic table.
sure) obtained by sodium reduction of the ethyl ’
ester of naphthenic acids from Californian pe
8. Compounds of the formula R2CN'X wherein
R2 is ajvcyclic terpene hydrocarbon radical and
42 parts of naphthenyl alcohols (hydroxyl
, W ,
9. Compounds of the formula RFCNS'wherein
.R’ is a cyclic terpene hydrocarbon radical.
troleum were converted into naphthenyl chlo
10. The compound bernyl thiocyanate.
rides by treatment with thionyl chloride in ben
0- zene.
7, 7. Compounds of the ‘formulafR‘CNS wherein
California naphthenic acids.
11. An insecticidal composition comprising as
the toxic ingredient a compound of the formula 40
These naphthenyllchloridés (12.47% Cl,
B. P. 120-160” C. under 11 mm. pressure) were
reacted with 10 parts sodium vthiocyanate in 100'
.R.(CNX)1, in which R is an alicyclic hydrocarbon
radicai: of valence y and containing at least i=3
c'arb'onatoms and X is an element selected from
parts re?uxing lintanol. A practically odorless
oil of a boiling
. point 155-487” C.’ under‘ 1 mm. E GroupVI-B of the periodic table.
45 pressure was obtained which represents the thio- . 7;
eyanate of the naphthenyl hydrocarboni corre
sponding’to the original naphthenic acids. The
product has a specific toxic 'Zeifect towards
Example 3.-Bornyl til‘iiocyanate.
12. An insecticidal composition comprising as 45
the toxic ingredient a compouriid of the formula
R1(CNX)u wherein R1 is an a'flicyclic hydrocar
bon radical of valence y and chosen from the
’ group consisting of :naphthenyl radicals and
cyclic terpenei hydrocarbon radicals, and X is
60 parts by weight of crude bomyl chloride, an element se?ected from Group VI—-B of the 60
120 parts n-butainol, 37 parts sodium thiocyanate' periodic table.
'and 0.5: part of sodium iodide were re?uxed;
13. "An insecticidal composition comprising as
for 92 hours. The crude reaction product was’ the toxic ingredient a compound of the formula
55,Vwashed with water, and the butyl alcohol dis-E RCNS wherein R is an alicyclic hydrocarbon 55
ftilled oif. The solid residue represents the bomyl radical containing at least 10 carbon atoms.
With a 5% kerosene solution this crude bomyl
thiocyanate showed a toxicity against the com
0 mon house ?y comparable with that of pyrethrum.
It will be understood that my invention is not
limited to these speci?c thiocyanates but that
it embraces broadly the parasiticides of the for;
mula 1%(CNXM ‘as explained above, particularly
those in which R is selected from naphthfenic and
terpene hydrocarbon radicals, which are
also distinguished by slight odor and :low vise
14.‘ An insecticidal jgcomposi'tion comprising as
the toxic ingredient compound of the formula
RICNS wherein R1 is an alicyclic hydrocarbon
radical chosen from the group consisting of
naphthenyl radicals and cyclic terpene hydro
carbon radicals.
15. An insecticidal composition comprising as
the toxic ingredient a‘compound of the formula
R'~’CNX wherein R2 is a cyclic terpene hydrocar 65
bon radical and X is an element selected from
Group VI--B of the periodic table.
cosity of the compounds themselves or their
16. An insecticidal; composition comprising as
solutions and? emulsions and consequent high the toxic ingredient a compound of the formula
penetrability. In, thisi respect they distinguish R’CNS wherein R2 is a cyclic terpene hydrocarbon
themselves particularly from the thiocyanates
and other .cyano esters of long carbon chain radical. .
aliphatic alcohols, such as for instance’the waxy
stearyi thiocyaiiate.
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