2,611,729”
Patented Sept. 23, 1952
~ UNITED STATES PATENT OFFICE
INSECTIGIDAL COMPOSITIONS CONTAINING
HYDROCARBON ESTERS OF DIET'HYL DI
‘THIOPHOSPHORIC ACID
Jeffrey H. Bartlett, West?eld, Harry W. Rudel,
Roselle Park, and Elmer B. Cyphers, Cranford, ‘
N. J., assignors to Standard Oil Development
Company, a corporation of Delaware
No Drawing. Application Novemberil, 1949,
Serial No. 124,951
5 Claims.
(Cl. 167-30) .
1
2
provements in parasiticidal preparations and
phosphoric acid, and test results obtained on the
active compounds used as parasiticides.
more particularly to improved fungicides and in
secticides. This invention also relates to methods‘
of protecting organic material subject to attack‘
Example 1.—Preparati‘0a of alpha pinene ester of
This invention relates to new and useful im
by low orders of organisms. More speci?cally,
this invention is concerned with parasiticidal
compositions containing as the active ingredient
a hydrocarbon ester of diethyl dithiophosphoric
diethyl dithiophosphoric acid
A l-liter, 3-necked ?ask equipped with a"
. stirrer, re?ux condenser, and thermometer was '
charged with 276 'g. (6 mols) of absolute ethanol
and 333 g. (1.5 mols) of PzSs. The temperature
acid.
It has now been found that hydrocarbon esters
of diethyl dithiophosphoric acid are extremely ef
rose to 70° C. within 15 minutes. After heating
for an additional 20 minutes at 80° C. the product
was ?ltered to remove a small amount of in-n
fectlve for checking the growth of insects and
fungi.
These compounds may thus be used as
novel ingredients of parasiticidal compositions.
soluble material. A portion of the diethyl die‘
15 thiophosphori-c acid thus formed (2.4 mols) was‘
added to 326 g. (2.4 mols) of alpha pinene in "a
4-necked, 3-liter ?ask equipped with a stirrer,
Suitable compounds of the indicated type are
thus illustrated by Formula I below:
re?ux condenser, thermometer, and dropping
funnel over a period of 11/2 hours, during which;v
20 time the temperature rose from 25° to 36° ‘C.
The product was then heated at 115'” C. for 2
hours, after which it was permitted to stand
wherein R is a. hydrocarbon radical.
overnight. The product was then washed suc-I
cessively with 200 cc. of distilled water, two 200
25 cc. portions of 10% aqueous NazCOs-solution' to
remove any unreacted acid and ?nally washed»
fective. In compounds of .the cyclic ester pre
with 200 cc. of distilled water. The cloudyor
ferred type, R may thus be an alicyclic or
ganic layer was transferred to a 1-liter beaker‘
aralkyl radical. Some of the compounds of the
Those compounds wherein the hydrocarbon
ester is a cyclic ester, 1. e., is either a cyclic radi
cal or contains a cyclic group, are especially ef
preferred type contain cyclic hydrocarbon radi
cals derived from the following cyclic hydro
carbons: ethyl benzene, propyl benzene, toluene,
diphenyl ethane, cymene, cyclohexane, cyclo
pentane, para men'thane, methyl cyclohexane,
thujane, dicyclopentane, etc.
Especially effective and desirable compounds 35
of the present class of compounds are the alpha
and blown with nitrogen for 20 minutes at 110° .
C., followed by ?ltration to remove a small amount
of insoluble material. A clear reddish liquid was
obtained, which upon analysis was found to con—
tain 10.4% phosphorus and 19.3% sulfur. '
Example 2.-—Preparation of styrene ester of 1 Y
diethyl dithiophosphoric acid
pinene and styrene'esters of diethyl dithiophos
A cylindrically shaped glass reactor was
phoric acid.
charged with equimolecular quantities of 'vacuum
It is especially surprising to ?nd that the cyclic
distilled diethyl dithiophosphoric acid and styr
hydrocarbon esters possess extreme activity in 40 ene which had been washed free of inhibitors.
view of the fact that non-cyclic esters show dis
The mixture was placed in the sunlight for 2
tinctly less activity. Thus the Wax ester of
hours where the temperaturerose from 23° C. to‘
diethyl dithiophosphoric acid shows distinctly in
49° C. during the ?rst 30 minutes then gradually.
ferior insecticidal activity as compared to the
subsided to 44° C. during the next 11/2 hours.
cyclic hydrocarbon esters tested.
45 After allowing the mixture to stand overnight
The active cyclic hydrocarbon ester compounds
at room temperature the resulting product had
of this invention may be prepared in general by
a neutralization number of 11.0.
-1
.
addition or condensation reactions of suitable de
The compounds prepared in Examples 1 and 2:
rivatives of the indicated hydrocarbons with
were tested for parasiticidal activity. The values »~
diethyl dithiophosphoric acid. The latter, in 50 given in column I of the following table, represent >
turn, can be prepared by reacting ethyl alcohol
the percentage-mortality of the test insects after
with sul?des ‘of phosphorus. ‘
.
_The following examples are given to illustrate
this invention and include both the preparation "
of cyclic hydrocarbon esters of diethyl dithio 55
96 hours following a two-minute immersion in an "
0.25% aqueous solution or suspension of thetest
compound.
The results in column 11 are given as per cent
t
2,611,729
3
4
mortality of the test insect after 96 hours fol
compounds with clays such as fuller’s earth, china
clay, kaolin, or bentonite. Solid wettable powders
for aqueous dispersion contain about 75% active
ingredient, 24%. clay, and.ahout_1.%_wetting agent.
lowing bloodstream injection of 0.002 cc. of a 5%
solution of the test compound.
The ?gures incolumn III list theresultsob
tained onrth'e-Nelsonv Drop test for house-fly
Clay itself . also‘ acts as a spreading agent.v
toxicity.‘ At full‘ dosage, 5 mg. of test mate
The term “dispersing agent” is consequently
rial/gm. body weight is placed on fly’s body
. used hereafter to connote generically, the various
(0.002 cc. of a 5% solution per fly). Standards:
0.01 mg. DDT/gm. gives 65%"~kill"(0.002 cc. of a
“wetting agents” and “spreading agents” includ
"ingclays, that are adapted to be admixed with
0.01% solution per ?y). 0.038:mg. pyrethrin/gm. 10 the'active compounds of this invention in order
gives 40% kill (0.002 cc. of an 0.038% solution
to secure! better wetting and spreading of the
per ?y).
sprays of the active ingredients in liquid vehicles
Not all the tests were performed on each com
.i-n-whichthey are insoluble. (See Frear—“Chem
pound. The blank spaces indicatethatthatpar
ticular test was not performed.
istry oflnsecticides;‘Fungicides, and Herbicides,”
15 second :edition; page 280.)
;Golumn_II; Blood
stream Insect
Column I, Contact
- Activity, Per-
luselrgtieidaiig?vitm
ercen
v
‘
I‘
.
pcentll?ill
erip an ma
_
1 1
C1£Luse_l;g'
Americana
' "Compound
-
lwnwmkmh)
'
-
-
'
->
--
r
-~
Blatiellc
Omelpeltus
,Getmanicw
' (German
Sociatus
‘(Milkweed
Roach)
Bug)
l~
" Toxicity
NelsonDrop
»
. Female
A
'Test
_
Male
B
A
Alghapineneester-otdiethi’l di-
-.t_Aicphosphcncacid__,_,.__.., ............... _-
100
100
_
100_'{
'
D '—100
D75
—100'
D/lllm95‘
"
Sm8~:e5ter:0f
diethyl smirk
.uhqspoltic 8cijd.---—. -------
.
7
100
Ohloro-wax;ester ot‘diethyl, dithio-
i 30"
D , l .......................... __
_
,
a
.
_
100
.
'
‘m0:
100
100"
'
_20
401 ............. _
gggsgg
100
100.
‘are
/
4
‘
pjh’losplioncacidun, ........... -Pyrethrin_...-.--.
.
a. as
5_
100
.................. __
D/500- 65
fD/132-1i0v
"These : ?gures indicate that the hydrocarbon
Among the water soluble wetting agents that
esters of ‘this invention :are especially-and surpris
can be used are the sulfates of long chain alcohols
ingly effective contact insecticides as goodas DDT
such as dodecanol upto' octadecanol, sulfonated
andipyrethrin. The chloro wax ester, on the other
amide and ester derivatives',.sulfonated aromatics,
hand,_exhibited a contact insecticide activity. only
and mixed alkyl-aryl sulfonatederivatives, ‘esters
one-twentieth as great as the other compounds
of fatty acids such as thetricinoleic'acid ester'of
tested.
sorbitol, and petroleum sulfonateso'f C10 to ‘020*
The compounds of this invention which in most 45 length. The non-ionic emulsifying agentstsuch as?~
casesare liquids, are best distributed in the form
the-ethylene oxide condensation‘products of‘al-v
of ‘sprays, such as in aqueous dispersions or
kylatedphenols may also be used.
4
dust ‘compositions of the active ingredient with a.
Solvents forthe compounds‘of this invention,"
powderedclay.
Since the-compounds of 'this invention are in 50 may be utilized as auxiliary ‘agents if desired.‘
Among the solvents for the compounds of this"
soluble in water, it is preferable to use them ad
invention are: naphtha, kerosene, aromatics
mixed with wetting or emulsifying agents so as
(toluene, etc.) alcohols, k'etonessuch as acetone
to be ableatosecure aqueous-emulsions and con
or methyl ethylketone, .estersand halogenated.
sequent uniformity of dispersion in the resulting
colloidal‘system. The use of these wetting agents 55 hydrocarbons.
also increases the spreading action of the spray
The compounds of Qthisinvention may .also - be
bydecreasingits Surface tension. This results in
admixed with carriers that arethemselvesactive, ‘
the securing of better contact of the spray with
such as other parasiticides, hormones, herbicides;
the surface being, treated, and consequently
fertilizers; and‘ wetting-agents; - Stomach and con
brings ‘the activeingredient into intimatecon 60 tact insecticides such asthemarsenates,z?uorides,.
tact withthe parasite life. The concentration of
rotenone, and the various ‘?sh poisons and‘organic
active ingredient in the aqueous emulsions varies
insecticides, such . as di (no chloroph'enyl-trichlo- i
with the insect pests to be treated. Ingeneral, the
roethane, benzene-hexachloride, and similar
aqueous emulsion contains about 5% active in,
gredient, and'_1% wettingpagent by weight. Thus, 65 products may also be advantageously added.
a typical ‘emulsion concentrate formulation con
It is to be understood that the invention ‘is'not '
limited to the specific exampleswhich have been
oifered merely as illustrations, since many other
derivatives-can be "prepared, and that modi?ca;
then be diluted with about 94 parts of water to 6 70 tions may be‘ made .withoutdeparting from the.
sists of 83% alpha-pinene'ester of diethyl dithio
phosphoric acid, and 17% petroleum sulfonate of
about‘Cm-Czo length by weight. This mixture can
parts of. concentrate.
‘
v'I'he active compounds of this invention may‘
also vdesirably 1be made up in solid compositions.
spirit of the invention.
What'is claimed ‘is:
'
,7
.
1. An insecticidal dust composition comprising
the styrene ester. of ~diethyl i-dithiophosphoricacid
Adust composition containing about 5% active
ingredient is made up by admixing the active 75 admixed
withjapowdered clay»
~ .
2,611,729
5
2. An insecticidal dust composition comprising
the alpha -pinene ester of diethyl dithiophosphoric
acid admixed with powdered clay.
6
REFERENCES CITED
The following references are of record in the
?le of this patent:
3. An insecticidal dust composition as in claim
UNITED STATES PATENTS
2 in which the clay is bentonite.
4. An insecticidal composition comprising the
Number
Name
Date
styrene ester of diethyl dithiophosphoric acid ad
1,939,951
Buchanan ________ __ Dec. 19, 1933'
mixed with a petroleum sulfonate of C10 to C20
2,063,629
Salzberg __________ __ Dec. 8, 1936
lengths, said sulfonate being present in an amount
2,143,639
Caprio __________ __ Jan. 10, 1939
corresponding to about one ?fth by weight of the 10 2,269,396
Jayne _________ __,___ Jan. 6, 1942
styrene ester.
OTHER REFERENCES
5. An insecticidal dust composition comprising
Schrader, Development of New Insecticides,
a hydrocarbon ester selected from the group con
B. I. O. S. Trip No. 1103; pages 1, 2 and 33 to 35
sisting of the styrene and alpha-pinene esters of
diethyl dithiophosphoric acid as the active in- 15 at hand’ and considered Pertinent (Publication
date April 23, 1948, Bibliography of Science and
gredient, admixed with a powdered clay.
Ind. Reports, volume 9, number 4, page 284.)
Fiat Final Report 949, “Organic Chemical Inter
JEFFREY H. BARTLETT.
mediates for Insecticides, Fungicides and Rodenti
HARRY W. RUDEL.
cides, pages 19 to 20. PB 60890 October 14, 1946.
ELMER B. CYPHERS.