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Патент USA US3097138

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United States Patent 0 " "ice
Patented July 9, 1963
These compounds are well known in the art, various
classes thereof being ‘described in such United States
patents as U.S. 2,744,128; 2,788,358; 2,865,944; 2,867;
Charles R. Sprinkle, Bound Brook, Leo F. Sekula, Pater
646; 2,891,887; 2,894,014; 2,894,018; 2,895,982; 2,898,
son, Milton R. lohnson, Spring?eld, and Bertram I.
341; 2,913,367 and 2,956,073, and in such British patents
Sparr, Summit, NJ” assignors to Shell Oil Company,
as No. 783,697.
As indicated in these patents, the organic groups rep
resented ‘by the symbols, R and R’, preferably are low
molecular Weight hydrocarbon or substituted hydrocar
New York, N.Y., a corporation of Delaware
No Drawing. Filed Jan. 6, 1961, Ser. No. 80,996
7 Claims. (Cl. 167-22)
This invention relates to stabilized insecticide compo 10 bon groups, for example, containing from one to ten car
bon atoms each. They may be aliphatic, cycloaliphatic,
sitions and to methods for preparing them.
aromatic or of mixed structure. When aliphatic, they
The vinyl phosphates, such as dimethyl Z-carbo
may be either straight-chain or branched-chain in con
methoxy-l-methylvinyl phosphate and dimethyl 2,2-di
?guration. "l‘ype-wise, the preferred organic groups in
chloroyinyl phosphate, and related phosphonates and
phosphinates, constitute a general class of highly effective 15 clude alkyl, cycloalkyl, aryl, alkaryl, and like groups.
Illustrative examples include the methyl, ethyl, n- and
insecticides. For many =applications-as in baits, dusts
isopropyl groups, the various isomeric butyl, hexyl and
or the like-these insecticides must be used in the form
like alkyl groups; the cyclopentyl, cyclohexyl and like
of dry formulations wherein they are impregnated upon
cycloalkyl groups, the phenyl group; the na-phthyl group;
solid materials. Such formulations ‘have been prepared,
and it has been found that these insecticides tend to be 20 the benzyl, phenethyl, p-methylbenzyl and like aralkyl
groups; the isomeric tolyl groups, the isomeric xylyl
unstable when formulated in this manner. The reason
groups, the ethylphenyl group, the 2,4-dimethyl- and 3,5
for this instability has not been determined with cer
dimethylphenyl and like alkaryl groups, and the like. ~
tainty, but it is believed to involve in substantial part
Where n is 2—that is, in the phosphate insecticides
hydrolysis of the insecticides. It does not appear from
examination of a variety of typical members of these in 25 the two symbols, R, may together represent a divalent
hydrocarbon group, each of the symbols representing
secticides impregnated upon a variety of solid carrier
one valence bond thereof. In such insecticides, it is
materials that the instability of the insecticides is due to
preferred that the divalent group be an alkylene group
the nature of the carrier material, but that the instability
of up to 10 carbon atoms, with 1 to 5-—preferab=ly 2 to
occurs irrespective of the carrier material.
Because of this instability, the potential utility and 30 3-carbon atoms in the chain thereof which bonds to
gether the indicated oxygen atoms.
value of these insecticides has been seriously curtailed.
Further, the symbols, R’, together may represent such
Thus, it has been necessary in some cases to employ an
excess of therinsecticide to allow for decomposition be
a divalent hydrocarbon group.
v -
fore use, While in other cases it has even been necessary
The substituted hydrocarbon groups represented by R
these insecticides impregnated upon solid materials result
to prepare the formulation just prior to use, a procedure 35 and R’ are those of the above-mentioned hydrocarbon
groups which are substituted by one or more non-hydro—
which is not only more costly, but which requires that
carbon substituents. The preferred substituents are mid
the formulators employ special procedures for which
:dle halogen, the nitro group and amine groups repre
they ‘are not ordinarily equipped.
We now have discovered that stable dry formulations of 40 sented by the formula:
when ‘a minor amount of at least one phenol is intimately
incorporated with the formulations and that the presence
of the phenol does not adversely affect the insecticidal
.properties of the formulations. As a result of these dis
and ether groups, R—O—-, wherein R, m and n have
coveries, we have found that the shelf life of typical dry 45 the respective meanings already set out herein.
formulations of these insecticides can be extended from
Illustrative examples of the non-hydrocarbon groups
a period so short as to prohibit use of those formulations
include monohaloalkyl groups, such as the chloromethyl
unless prepared immediately before use, to periods so
and bromomethyl groups, the 2-chloroethyl, l-bromo
long as to permit carry-over of the unused formulations
propyl, 3-chloropropyl and the like; polyhaloalkyl groups,
from one season to the next. Our discoveries thus sub
stantially extend the useful applications of these insecti
such as the dichloromethyl, tribromomethyl, 1,2-dichlor0
ethyl, 2,2 - dibromoethyl, 3,3 - dichloro - 2 - bromo'propyl
groups, and the like; nitroalkyl groups such as the 2
The insecticides which have been found to exhibit in
nitroethyl group; halo-substituted aromatic groups such
stability in dry formulations on solid carriers, and which 55 as the various isomeric chloro- and bromophenyl groups,
are stabilized according to this invention, have the for
the various isomeric polyhalophenyl groups, such as the
2,6-dichlorophenyl group, the 3,5-dibromophenyl group
and the like; amino-substituted groups, such as the 2
aminoethyl group, the Z-dimethylandnoethyl group and
60 the like; the aniline group; the p-dimethylaminophenyl
wherein R represents hydrocarbon or substituted hydro
carbon, R’ represents hydrogen, halogen or one of the
[groups represented by R, and R" represents halogen, one
group; the peethylaminobenzyl group and the like.
The symbol R", may also represent a functional or
ganic group, such as a carboaliphaticoxy group, particu
larly a carboalkoxy or an alkoxyalkyleneoxycarbonyl
of the groups represented by R or a functional organic 65 group of up to ten carbon atoms; it may represent an
group, n is 0, l or 2, and m+n=2, with the proviso
ether group, R——O-—, wherein R has the meaning already
that when‘ n=2, both of the symbols R, together can
set out; it may represent an acyloxyalkoxycarbonyl group
represent a ‘divalent organic group, each of R represent
wherein the acyl group is
ing one valence bond of that group.
In these insecticides, it is preferred that when vany of 70
R’ and R” represent halogen, the halogen be middle
halogen-that is, bromine‘ or chlorine.
or it may represent an amide group‘ having the amino
2-(ptmethoxybenzyloxycarbonyl)-1-methylvinyl dimethyl
moiety set out above.
The preferred organic groups represented by the symbol
2~phenoxyethoxycarbonyl-l-methylvinyl dimethyl phos
R" are those having the formulae:
2 - (p - chlorophenoxycarbonyl) - l-methylvinyl dimethyl
2 - (p - chlorobenzyloxycarbonyl) - 1 - methylvinyl di
wherein X represents oxygen or sulfur and R has the
meaning already set out herein.
Of particular interest because of their high insecticidal
activity and tendency toward instability are the phos 10
phates (n=2) of the foregoing generic formula wherein
each R is lower hydrocarbon-{particularly alkyl of up
to seven carbon atoms, aryl of up to ten carbon atoms
or aralkyl of up to 10 carbon atoms, particularly the
phenyl or benzyl group; R’ bonded to the alpha carbon 15
atom is hydrogen or one of the groups represented by
R and
(a) R’ bonded to the beta carbon atom is middle halo
gen and R" is middle halogen;
(b) R’ bonded to the beta carbon atom is hydrogen,
middle halogen or one of the preferred groups represented
by R, and R” is a group of the formula
methyl phosphate
Diethyl Z-carboethoxy-l-rnethylvinyl phosphate
Dimethyl 2-carbomethoxy-Z-phenylvinyl phosphate
Diethyl Z-carboethoxy-l-cyclopenten-l-yl phosphate
Diethyl 2-carbethoxy-2~chlorovinyl phosphate
Diethyl 1-ethoxy-2-carbethoxy-2-chlorovinyl phosphate
2-chloro-2-oarbethoxy-l-methylvinyl dimethyl phosphate
2-benzyloxycarbonyl-l-methylvinyl methyl phenyl phos
Z-carbethoxyvinyl dimethyl phosphate
2-chlorovinyl dimethyl phosphate
0,0-diethyl 0-2-(ethylthio)-carbonyl-l-methylvinyl phos
O-(p-chlorophenylsulfoxylethyl) O-ethyl O-l-methyl-Z
carbethoxyyinyl phosphate
Diethyl Z-carbethoxy-l-cyclopentenyl-yl thionophosphate
2-chloro-2-acetyl-1-methylvinyl diethyl phosphate
2,2-dichlorovinyl di-sec-b-utyl phosphate
2,2-dichlorovinyl ethyl phenylphosphonate
2,2-dibromovinyl dimethyl phosphate
2,2-dichloro-l-phenylvinyl dimethyl phosphate
2-chloro-1-phenylvinyl diethyl phosphate
2-chloro-2-carbethoxy-l-methylvinyl diethyl phosphate
2,2-dichlorovinyl ethyl 1,2-dichloropropyl phosphate
2 - chloro - 2 - (methoxycarbonyl)~1-methylvinyl dimethyl
wherein R is one of the preferred groups represented
by R.
Of most importance from the standpoint of this inven
tion are the dialkyl 2,2-dihalovinyl phosphates and the di
Ialkyl 1-alky1-2-carboa1koxyvinyl phosphates, having the
respective formulae:
a. (alky1-OliL—0—-é= —hal
wherein alkyl represents an alkyl group of from 1- to 4
carbon atoms and hal represents middle halogen-Le,
Formulations of these and similar insecticides on solid
carrier materials are stabilized by phenols, generally.
Thus, phenol itself is a suitable stabilizer, as are other
mononucle'ar phenols such as alkyl-substituted phenols.
The stabilizer suitably may be a polynuclear phenol, such
bromine or chlorine;
40 as alph - and beta-naphthols.
Polyphenols, such as hy
droquinone and 2,2’-bis(p-hydroxyphenyl)propane, also
are suitable. Those phenols which are known to be anti
oxidants are suitable. These include the so-called “kryp
wherein lalkyl represents alkyl of from 1 to 4 carbon
tophenols”--phenols substituted at one or both of the
45 carbon atoms of the aromatic ring in position ortho to
Typical species of these insecticides include:
Dimethyl 2-carbomethoxy-l-methylvinyl phosphate
Dimethyl 2,2-dichlorovinyl phosphate
Dimethyl 2~benz~yloxyoarbonyl~l-methylvinyl phosphate
Dimethyl Z-phenyloxycarbonyl-l-methylvinyl phosphate
Dimethyl 2 - (alpha-methylbenzyloxycarbonyl)-l-methyl
vinyl phosphate"
Z-carbomethoxy-l-methylvinyl methyl p-nitrophenyl phos
2 - (2 - acetoxyethoxycarbonyl) - l-methylvinyl dimethyl
the carbon atom thereof to which is bonded the phenolic
hydroxyl group-in which a stereo-chemical e?ect shields
or protects the phenolic hydroxyl group. These also in
clude the polyphenols with ortho and para hydroxyl
50 groups—which can undergo hydroquinone-quinone trans
formation. It must be noted, however, that the property
of being an antioxidant is not essential to the utility of
a phenol as a stabilizer in the present invention, since
phenol itself, and beta-naphthol, which are not considered
55 to be antioxidants, are quite suitable as stabilizers in
the present invention. Other speci?c phenols which may
be used to stabilize these insecticides include catechol,
2 - (2 - benzoyloxyethoxycarbonyl)-l-methylvinyl di
methyl phosphate
2 - (2-methoxyethoxycarbonyl)~1-methylvinyl dimethyl 60
Z-canbethoxy-l-methylvinyl ethyl 2-methoxyethyl phos
Methyl Z-carbethoxy-l-methylyinyl phenylphosphonate
Ethyl 2-methoxycarbonyl-1-methylvinyl dimethylamino
2,6-di~tert-butyl-alpha-methoxy-p-creso1, 2,6-di-tert-butyl
p-cresol, 2,2’-methylenebis(It-methyl-6-tert-butylphenol),
butylated hydroxyanisoles, propyl gallate, butyllated hy
droxytoluenes, 2-hydroxy-4-methoxybenzophenone, 3,5-di
tert-butyl-4-hydroxybenzyl alcohol, p-octylphenol, p~non~
ylphenol, p-tertabutylphenol, 2,6-di~tert-butyl-4-methyl
phenol, 2,6-diisopropylphenol, 2,6-di-tert-amylphenol,
2,4,6-trimethylphenol, 2,4,6-t1i-tert-butylphenol, 2,3,4,5
2 - (m - nitrobenzyloxycarbonyl) ~1-methylvinyl dimethyl
Dimethyl 1-methyl-2- (p-tolyloxycarbonyl)vinyl phosphate
Dimethyl Z-phenethyloxycarbonyl-l-me-thylvinyl phos
ethers, 2,6-di~tert-butylphenol, 2,6-di-tert-butyl-alpha-di
methylamino-p-cresols, the cresols, 4,4’-bis(2,6-di-tert
butylphenol), 4,4’ - methylene - bis(6-tentdbutyl-o-cresol),
2 - (2 - carbethoxyvinyloxy) - 4 - methyl - 2 - oxy - 1,3,2
2 - (p - nitrobenzyloxycarbonyl) 1 l-methylvinyl dimethyl
pyrogallol, resorcinol, phloroglucinol, sesamol, B-phenyl
isocoumarone, the tocopherols, p-aminophenol, phenol
tetramethylphenol, pentamethylphenol and the like.
As has already been pointed out, the available evidence
shows that the instability of these insecticides occurs with
out regard to the chemical nature of the solid carrier ma
terial used—the instability exists with all solid carrier
persible synthetic resin, mineral oil, or equivalent adhe
materials. The investigation has included such common
carrier materials as various clays, including attapulgite
clays, such as those sold commercially under the trade
names of Attaclay and Diluex; montmorillonite clays‘,
sives all of which, are well known in the art.
agents and dispersing agents which may be employed in
clude the various naturally occurring or synthetic surface
acting materials known for the purpose, such as, inter
such as those sold commercially under the trade names
alia, soaps, saponins, lecithins, fatty acid salts, long-chain
Pike‘s Peak clay 9T66‘ and FF absorptive clay; dusting
sulfur; cornstarch; calcium carbonate; crushed corn cobs;
alcohols, sulfonated aliphatic and/ or aromatic hydrocar
bon derivatives, hydroxy esters, such as sorbitan mono
perlite; silicas, such as those sold under the trade names
laurate, pine oil, and the like. There may be employed
Silikil and Hi-Sil 233; kaolin clays, such as those sold
under the trade names Barden AG, ASP-105 and ASP 10 other insecticidal agents of natural or synthetic, of mineral
or organic origin, among which come into consideration
200; pyrophyllite, such as that sold under the name Pyrex
sulfur, copper arsenate, pyrethrum, allethrin, DMC,
ABB; talc, such as is sold under the trade name Emtal
23A; sand; crushed granite; sugar and diatomaceous
earths, such as those sold commercially under the trade
name Diacron.
HETP, malathion, DDT, BHC, lindane, and others well
known to those skilled in the art.
Suitable fertilizers
15 would include ammonium sulfate, urea, ammonium phos
The invention thus is applicable to the stabilization of
solid formulations of the herein de?ned insecticides, im
‘pregnated upon such carrier materials as kaolin clays,
phate, potassium nitrate, and the like. The concentration
talc, powdered calcium carbonate, lime, gypsum, pyro
can be as great as 50% or even more, in the case of the
of the insecticide in the ?nal formulation can vary wide
ly, depending upon the use to which the formulation is to
be placed. Thus, the insecticide concentration can be as
attapulgite clays, diatomaceous earths, vermiculites, syn
thetic calcium silicates, crushed rock, rock ?our, sand, 20 little as 0.1 percent of the weight of the formulation or it
Because of their characteristics, the preferred carrier
so~called “concentrated” formulations which are to be
diluted before use. Typically, a granular formulation
may contain from about 2% to about 35% insecticide by
weight. This type of formulation is generally'used as
such without further dilution with an insecticidally inert
materials for use with those insecticides de?ned in For
mula I, column 3, are the montm-orillonite clays, par
insecticide up to about 75% insecticide by weight. Fre
phyllite, powdered carb0n—-i.e., charcoal—~and the like,
upon sugar or like solid materials which are useful as
baits, upon organic ?brous materials, such as crushed
corncobs, bagass'e, crushed or powdered nut shells, or the
" Typically, a dust formulation can contain about 0.25%
ticularly‘that known 'as Pike’s Peak clay. ‘Sand, sugar, 30 quently, the dust formulations are ?rst prepared as so
I called “concentrates” which contain typically from about
pyrophyllites, particularly that known as Pyrax ABB and
10% to about 50% insecticide dispersed in the dust, and
talc, particularly that known as Emtal 23A, are preferred
such “concentrate” is further diluted to a so-called “?eld
carriers foruse with those insecticides de?ned in'Formula
strength” dust typically having an insecticide concentra
II, column 3.
But a minor amount of ‘the phenol stabilizer ‘is re-I 35 tion of about 0.25 % to about 5'%, varying with the use
quired. Thus, in most cases, from. about 0.1 to about 10
'percent by weight of stabilizer, based upon the weight of
the insecticide carrier formulation, will be su?icient. This
desired and the potency of the toxicant.
The wettable powders typically contain a concentration
is not to say, however, that in some cases, moreor less of
the stabilizer may be used to. advantage. In the great
majority of cases, it will be found that at least 0.01 per
cent of the stabilizer will .be. required, and that seldom
will an amount of stabilizer in excess of 20 percent by
weight of the insecticide-carrier formulation be of such
additional advantage as to be desirable.
The phenol stabilizer is incorporated in the formulation
in any manner, which will enable it to be intimately con
tactedwith the insecticide therein. The phenol may be
of toxicant on the order of that contained in dust con
trates as above described. However, they are diluted to
“?eld strength” by dispersing in water rather than by
dispersing in dust.
The following data exemplify practice of this inven
tion and illustrates the benefits to be derived therefrom:
' In ‘these formulations, the insecticide was dimethyl
2,2-dichlorovinyl phosphate. It was ?rst formulated with
powdered sugar as a bait for houseflies. The insecticide
concentration was 1 percent by weight of the formulation.
In one formulation, no stabilizer was added. In two other
dissolved in the insecticide, or vice versa, depending upon 50
formulations, 2 percent by weight of the formulation of
the relative concentrations and solubilities of the two ma
a phenol was present as stabilizer. The amount of the
terials. Alternatively, and where the physical state of the
phenol permits, it- may be merely intimately mixed in
the already formed mixture of, carrier and insecticide.
insecticide remaining was determined by analysis after
the formulations were held at 130° F., for 2 weeks. The
Otherwise, the phenol, or the phenol and insecticide to 55 following data were obtained:
gether, can be dissolved in a suitable solvent, and the
solution mixed with the carrier or the carrier-insecticide
mixture, as the case may be. The solvent then may be
removed wholly, or in part; or in some cases, it may be
Percent of the insecticide
No stabilizer _______________________________ __ 90
2,6-di-tert-butyl-4-methylphenol added as stabilizer __ l0
desirable to include the solvent in the formulation.
60 Beta-naphthol added as stabilizer _______________ .._ 5
" The formulations are otherwise compounded by tech
niques well known and generally practiced by the art.
_ Further formulations were made employing a mixture
Thus, the formulation may be in'the form of a dust, in
of sand and granulated sugar as the solid carrier. In—
the form of granules, in the form of wettable powders, or
secticide concentration was 0.5 percent of the weight of
in other forms suitable to the intended use. The formula 65 the formulation. Where a stabilizer was used, the con
tion can contain other materials to provide necessary
centration was 1 percent of the weight of the formulation.
physical characteristics-thus, stickers, emulsi?ers, spread
The amount of the insecticide remaining was determined
ing or wetting agents, fertilizers, other insecticides, other
by analysis after the formulations were held at 130° F.
biocides (for example, fungicides or the like) can be in
for 2 weeks. The following data were obtained:
corporated in the formulation by known means. Suitably, 70
Percent of the insecticide
any of the materials known to the prior art can be used, as
desirable to impart the desired characteristic(s) to the
?nal formulation. As sticking agents, there may be used
casein, gelatine, cellulose derivatives such as carboxy
methylcellulose, sul?te waste liquor, a guru, a water-dis 75
No stabilizer _______________________________ __ 60
2,6-di-tert-butyl-4-methylphenol added as stabilizer .._
Beta~naphthol added as stabilizer _______________ __
Further data similarly obtained on other formulations
the amount of said phenol being su?‘icient to sta
is summarized in the following table:
bilize said insecticide against decomposition.
2. A stable solid insecticidal composition comprising
in combination:
(a) a substantially toxicologically inert solid carrier
dosage decomposi
Stabilizer (percent by weight (percent tion after
of formulation)
by weight 2 weeks at
of formula-
130° F.
(b) an insecticide of the formula:
Pyrax ABB_ ___
None _____________ __
Alpha-naphthol (5%
N one ____________ __
phenol (5 ).
on 10
None _____________________ __
phenol (2%).
wherein “alkyl” is lower alkyl and “hal” is a
member of the group consisting of chlorine and
in w
Alpha-naphthol (5%) _____ __
Beta-naphthol (5%) _______ _.
(c) a phenol,
Phenol (5%) ______________ __
the amount of said phenol being su?icient to sta
bilize said insecticide against decomposition.
3. A stable solid insecticidal composition comprising
In a further series of investigations, dimethyl 2~carbo
in combination:
methoxy-l-methylvinyl phosphate Was employed as the
(a) a substantially toxicologically inert solid carrier
insecticide. The data obtained in these investigations is 20
summarized in the following table.
(b) an insecticide of the formula:
dosage decomposi
(percent tion after
by Weight 2 weeks at; 25
Stabilizer (percent by Weight
of formulation)
of formula
alkyl H ?
<a1ky1-o>—P-0—b=b- —O—alky1
130° F.
wherein “alkyl” is lower alkyl,
(c) a phenol,
. Pike’s Peak
None _____________________ __
stabilizer (5%).
2,2’;Bis(p-hydroxy-phenyl)propane (5%).
the amount of said phenol being su?icient to Sta
bilize said insecticide against decomposition.
4. A stable solid insecticidal composition comprising
in combination:
(a) a substantially tox-icologically inert solid carrier
It-is evident from a review of the above data that a small
quantity of the present phenol stabilizers unexpectedly
provides superior protection against deterioration of the
(b) dimethyl 2,2-dichlorovinyl phosphate,
(0) ‘a phenol,
the amount of said phenol being sufficient to sta
‘bilize said phosphate ‘against decomp-ositoin.
5. A composition according to claim 4 wherein the
insect toxican-t when in contact with the indicated carrier 40 phenol is phenol.
materials. So, too, when others of the previously de
6. A stable solid insecticidal composition comprising in
(a) a substantially toxicologically inert solid carrier
scribed carriers are used in the insecticide formulations
‘comparable results are obtained.
We claim as ourinvention:
l. A stable solid insecticidal composition comprising in 45
(a) ‘a substantially toxicologically inert solid carrier
(b) dimethyl
(c) a phenol,
the amount of said phenol being su?icient to sta
(b) an insecticide of the formula:
2-carbomethoxy-l-methylvinyl phos
bilize said phosphate against decomposition.
7. A composition according to claim 6 wherein the
‘phenol is phenol.
References Cited in the ?le of this patent
wherein R is a member of the group consisting of
low molecular weight hydrocarbon radicals and
low molecular weight substituted hydrocarbon
radicals, R’ is a member of the group con
sisting of hydrogen, chlorine, bromine, and
radicals represented by R, R" represents a mem
ber of the group consisting of chlorine and 60
bromine, radicals represented by R and func
tional organic radicals, n is an integer from
zero to two, with the proviso that m+n=2.
(c) a phenol,
Morris _______________ __ May 1, 1956
Stiles _______________ __ Dec. 23, 1958
Stiles ________________ __ July 7, 1959
Schring ______________ __ Aug. 4, 1959
Davison _____________ __ Nov. 17, 1959
Whetstone ___________ __ Oct. 11, 1960
King: U.S. Dept. Agr. Handbook No. 69 (1954), pp.
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