CA1139770A - Insecticidal carbamoyl sulfides - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Carboamoyl sulfides such as dimethyl N,N'-[2,3-butanediylidenebis[nitrilooxycarbonyl(N-methylimino]thio-(N-methylimino)carbonyloxy]]bis[ethanimidothioate] useful for control of insects and nematodes.

Description

~A-83Q7-A

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1~3~7'~ , TITLE
Insecticidal Carbamoyl Sulfides BACKGROUND OF THE INVENTION
This invention relates to insecticidal and nematicidal carbamate~.
Insecticidal carbamates are known in the prior art, e.g.
a) Belgian B~ 848,912 discloses pesticidal symmetrical bis-N-substituted carbamyl sul~ides of the formula . O O
.. ..
ROCNSNCOR
.- -R'R' where R and Rl represent subs~ituents o varying scope;
b) Belgian ~E 848,ql3 discloses pesticidal ~: uns~mmetrical bis carbamyl sulfides of the formula O O
i, RlOCNSNCOR2 R R
where R, Rl and R2 represent substituents of varying scope;

.

: .
.

: . - .
.
, ~ -. ~.~ . :

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c) Ger~an DT 2,813,281 discloses pesticidal bis-carbamoyl-oximino-disulfides of ~he formula OR RO
,., ....
OCN-S-S-NCOR

where ~ and Rl represent substituents of ~arying scope.

SUMMARY OF THE INVENTION
~his i`nvention relates to novel compounds of Formula I, to ayriculturally useful compositions of these compounds and to the method of use o~ these compounds as insecticides and nematicides.
O Rl R2 O
ROCN-S-NCON=C(CH2)nC=NOCN-S-NCOR
3 CH3 - .
tI~
wherein o 20 ~ and ~ are 3 > (CH3)2NC >
independentlyR4S R4S

2S C~3 or ~ C~3 %1 is hydrogen, Cl~Cg lkyl~ C5-C6 cyclo-alkyl, Cl-~3 alkylthio, chlorine, O O
~hloromethyl, -CN(CH3)~, R5SCH2-, -COR6, phenyl or phenyl subs~ituted with C1-C4 all~yl R2 is hydrogen, Cl-C4 alkyl, C~-C6 cyclo-alkyl, chlorine, Cl-C3 alkylthio, phenyl or phenyl substituted with Cl-C4 alkyl;

. ~ .

Rl and R2 can be taken together to ~orm a carbocyclic bridge of three t~ five carbon atoms, or a bridge of the formula R3 is Cl-C3 alkyl;
R4 is Cl-C3 alkyl;
R5 is Cl-C3 alk~l;
R6 is Cl~C~ alkyl; and n is Oj 1 or 2;
10 provided that~ is 0 when 1) Rl is chloromethyl or R4SCH2, or

2) Rl and R2 are taken together to form a carbocyclic bridge or a bridge of the formula -SCH2CH2S , or

3) at least one o~ R1 and R2 is alkylthio;
and provided that when n is 0, one of Rl and R~ cannot be H when the other is phenyl or phen~l substituted with Cl-C4 alkyl; 0 and further provided that when n is 1, R1 and R2 cannot both be t-butyl, phenyl, phenyl substituted with Cl-C4 alkyl or combination thereof.
Also, this invention relates to novel inter-25 mediates of Formula II useful for preparation of com-pounds o~ Formula I
O o R R O O
" " ll .2 " ., F-C-N-S-N-C-O-N=C-(CH2)n-C=N-O-C-N-S-N-C-F
CH3 CH3 CH~ CH3 II
wherein Rl, R2 and n are as previously defined.

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, , '7'7 DETAILED DESCRIPTION OF THE INVENTION
Preferred Compounds Preferred for their high activity and/or favorable cost are compounds of Formula I wherein 1) R and R' are identical; or 2) R3 is CH3; o~
3) Rl and R~ are independently hydrogen, Cl~C4 alkyl, o CN(CH3)2, phenyl, phPnyl substituted with Cl-C4 alkyl, Dr where R1 and ~2 are taken together to form a carbocyclic bridge of three to five carbon atoms, or

4) n is O.
More preferred for their higher activity and/or more favorable cost are the preferred compounds of Eormula I wherein CH3 ~
R and R' are ~ C-N- ;
CH3S ~
R1 and R2 a~e independently h~drogen or Cl-C4 alkyl; a~d n is 0; pro~ided at least one f ~ï and R2 is other than h~drogen.
2S S~ecifically preferred for their excellent activity and/or most favorable cost are dimethyl N,N'-l2,3-butane~iylidenebis~nitrilo-oxycarbonyl(N-methylimino)thio(N-methylimino)-carbonyloxy]]bisrethanimidothioate]
30 dimethyl N,N'-rl,2-propanediylidenebisrnitrilo-oxycarbonyl(N-methylimino)thio(N-methylimino)-carbonyloxy]]bisEethanimidothioate}
dimethyl N,N'-r2,4-pentanediylidenebislnitrilo-oxycarbonyl(N-methylimino)thio(N-methylimino)-carbonyloxy~]bis~ethanimidothioate~

.

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7'7~
s dimethyl N,N'-~2~5-hexanediylidenebis[nitrilo-oxycarbonyl~N-methylimino)thio(N-methylimino)-carbonyloxy]~bis[ethanimidothioate~
N-methyl-N-[N-methyl-N-(2-methyl-2-methylthio-propylideneaminooxycarbonyl)aminothio]carbamic acid, diester with 2,3-butanedione, dioxime N,N'-[2,3-butanediylidenebis[nitrilooxycarbonyl-(N-methylaminothio-(N-methylimino)carbonyloxy]-bis]-2-(dimethylamino)-2-oxoethanimidothioic acid, dimethyl ester.
Synthesis

5~2 novel oo~xN=~s of Fo~mLla I m ~ich R and R' are identical can be pre~ by the reaction sh~ m E~uation A.
Equation A

~., , 3 .. ,1 y2 2ROCN-S-N - CF + HoN-c(c~2~nc=NoH -(II) ~III) acid acceptor ," 3 , 3 ,, ,1 R2 CH3 CH3 o ROCN-S-N - CON=C~CH2~nC=NOC-N-S-N - COR

(I) wherein R, Rl, R2 and n are as previously defined.
The reaction can be cax~ied out in an inert solvent ~uch as acetonltri`le, tetrahydrofuran ! toluene, sylene, ~ethylene.chloride, chloroform and the like at temperatures between -20 and 80C, preferably, at -5 to 40C. The acid acceptor used in this reaction can be an organic tertiary amine such as triethylamine, N,N-dimethylamiline, pyridine, and the like.
The reaction of a dioxime (III) and the carbamoyl fluoride (II) can be carried out in a heterogeneous system such as toluene-water, '~ , methylene chloride-water mixture and the like in the presence of a quaternary ammonium or phos-phonium salt as a phase transfer catalyst at -15C to 60~C. An eauivalent or a slight excess of metal hydroxide can be used as acid scavenger.
It is preferred that the reaction be conducted at 10C to 30C by using sodium hydroxide or potassium hydroxide as acid acceptor in the presence of 10 to 30 mole percent of phase transfer aatalyst such as cetyltrimethylammonium bromide or benzyltri-methylammonium hydroxide.
The reaction can also be carrie~ out in the absence of acid acceptor by directly reacting the carbamyl 1uoride of Formula II with a dianion of 15 Formula III in an aprotic solvent such as tetrahydro-furan, toluene, a~etonitrile, methylene chloride and the like at ~emperat~res between -50 and 40C, preferably, at -30 to ~5C. The dianion of Formula III is preferably genarated in situ by reaction o~ the dioxime 20 III with a metal hydride or metal amide in a proper solvent.
An alternate method to prepare the compounds o~ Formula I is shown by Equation B.
Eguation B
OCH3 CH3 Rl ,2 ,O,C~3 CH3 o ROH + FCN-S-N - CoN=c(cH2~nc=NocN-s-N - CF
(V) tI~) 1 OCH CH Rl R OCH CH O
", 3 , 3 " , ,2 "~ 3 , 3 "
ROCN-S-N - CON=C(CH2)nC.-NOCN---N COR
(I) wherein R, Rl~ R2 and n are as previously defined.

The compounds o Formula I (R=R') can be obkained by treatment of the bis-carbamyl fluoride of Formula IY
with eith~r the metal salt of an oxime of Yormula V
or the oxime of ~ormula V itsel~ in the presence of an organic tertiary amine.as an acid acceptor under the conditions described previously. The metal salt of an oxime of Formula V as previously described can ~e generated and used in situ by reaction o~ the oxime with metal hydride in an aprotic solvent, e.g. tetra-hydrofuran, toluene, acetonitrile, etc. r at -5 to 20C, Compounds of Formula I where R and R' are different can be conveniently prepared as E~uation C.
Equation C
" C,H3 ,CH3 o Rl R2 CH3 CH3 O
ROH ~ F-C-N-S-N - C-O-N=C(CH2)n-C=N-O~C-N-S-N - C-F

(V) (IV) acid acceptor O CH3 ~H3 Rl ,R2 CH3 CH3 o 25 R-O-C-N-S-N- C-O-N=C(C~2)n-C=N-O-C-N-S-N - C-F

(VII) ¦ R'OH (VIII) acid acceptor \ ~
O CH3 CH3 R~ R2 CH3 C~3 O
R-O-C-N-S-N - C-O-N=C(CH2)n-C=N-O-C-N-S-N - C-O-R' (I) The intermediate VII can be prepared preferably by mixing an equivalent of an oxime V, bis-carbamoyl fluoride rv and an acid acceptor such as triethylamine at -15C to 40~C in an inert solvent such as chloroform. Under similar reaction conditions, the subsequent reaction of the compound of Formula VII
with another oxime VIII in the presence of, for example, triethylamine, wou~d give the product of Formula I (R~R').
Reguired intermediates of Formula IV can be prepared by the reaction as give~ in Equation D.
Equation D

", , 3 " ,1 ,2 FCN-S-N C~ + HoN-c(cH2)nc=NoH -~VI) ~III) acid acceptor ~CH CH3 O R R2 OCH CH O
n 1 3 ~ " ~1 ~ n ~ 3 ~ 3 "
FCN-S-N--CON=C ~CH2 ) nC 5NOCN-S-N - CF
(IV) ~ he reaction ~hown in Equation D can be carried out in an inert solvent such as toluen~, xylene, tetrahydrofuran, ac~tonitrile, methylene chloride at temperatures between -20 and 80C, preferably, at -5 to 40~C. An organic tertiary amine such as triethylamine,N,N-dimethyl~
aniline, or pyridinei or an inorganic metal bicarbonate or carbonate can be used as an acid acceptor.
The carbamyl fluoride of Formula II and bis(N-methyl-N-fluorocarbonylamino)sulfide ~VI) can be prepared by the methods tauqht in DT 2654282.
~ In the above reaction proced~xes! ~Xe~sure is ~ot critical, but, for convenience, atmospheric pressure is preferred.

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~ he preparation of compounds of Formula I
can be more clearly illustrated by the following examples. A11 temperatures are in degrees centigrade and ~11 percen~ages are by weight unless otherwise 5 stated.

,.

E~ample 1 Dimethyl N,N' 12,3-butanediylidenebis~nitrilooxy-carbonyl(N-methylimino)thio(N-methylimino)carbonyloxy~]-bis~ethanimidothioate~
. ~_ Two grams of dimethylglyoxime disodium salt octahydrate was added in portions to a solution of 3.7 g of 0-[N-methyl-N-~N'-methyl-N'-fluorocarbonyl-aminosulfenyl)carbamoyl]-l-methylthioacetaldoxime in 10 30 ml of dry tetrahydrofuran (THF) at tempexatures below -20C. The mixture was stirrea on an ice bath for 3 hours after the additionO Then ether and water were added into the reaction mixture. ~he precipitate -was collected by filtration, washed with water, acetone 15 and air-dried ~o give 2.6g of dimethyl N,N'-~2,3-butanediylidenebisInitrilooxycarbonyl(N-methylimino)-thio(N-methylimino)carbonyloxy~]bis~ethanimidothioate~, m.p. 204-206C.
` Alternatively, a solution of 5.5 g of O-IN-methyl-M-(N'-~luorccarbonyla~mosulfenyl)carbam~yl~-l-methyl-thioacetaldoxime in a mixture of 40 ml of toluene and 20 ml of tetrahydrofuran was added dropwise in 5 min. to a mixture of 3 g of dimethylglyoxime disodlum salt octahydrate and 1 g of cetyltrimethyl-2S ammonium bromide in 50 ml of water at 15C to 20Cwith vigorous stirring.
After stirring at room temperature for 30 minutes, the solid was collected by filtration, washed with water, toluene, and air-dir~d to give 2.6 g of dimethyl N,N'-~2,3-butanediylidenebis-[nitrolooxycarbonyl(N-methylimino)thio(N-methyl-iMino)carbonyloxy~]-bis[ethanimidothioate] .

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E ~
~imethyl N,N'-~1,2-propanediylidenebisEnitrilooxycarbonyl (N-methylimino)thio(N-methylimino)carbonyloxy]]bis-Iethanimidothioate]
~_ In a flask was charged 1 g of 50~ of sodium hydride dispersed in mineral oil. Mineral oil was removed by washing the hydride with dry hexane under a nitrogen atmDsphere, and the hex~ne solution was decanted.
10 Then ~Q ml. of dry THF was added. ~o the su~-pensi~n 0.9 g of methylglyoxime was added in portions at temperatures below 20C. After stirring for 1 hour, a solution of 5 g of o-~N-methyl-N-(Nl-methyl~Nl-fluorocarbonylaminosulfenyl)carbamoyl~ me~ylthio-15 acetaldoxime in 30 ml. of dry THF was ad~ed rapi~lyat -20 to 30C. The mixture was stixred on an ice bath for an hour. Then ether was added. The excess of sodium hydride was quenched by careful addition of water~ The precipi~ate was collec~ed by filtrationl 20 washed with water, then hexane, and was air-dried to giva 2~5 g of dimethyl N,N'-tl,2-propanediylidenebis~nitrilooxy-carbonyl(N-methylimino)thio(N-methylimino)carbonyloxy]]-bis[ethanimidothioate]l m.p~ 175-178C (dec.).
Example 3 25 Dimethyl N,N'-Eethanediylidenebis[nitrilooxycarbonyl-(~-methylimino)thio(N-methylimino)carbonyloxy~3bis-tethanimidothioate~

A solution of 1.5 g o~ triethylamine in 10 ml.
30 of dry acetonitr1le was added dropwise to a mixture of 0.6 g. of glyoxime and 3.9 ~ of 0-~N-methyl-N-(N'-methyl-N'-fluorocarbonylaminosulfenyl)carbamoyl]-l-methylthioacetaldoxime in 30 ml. of dry acetonitrile on an ice bath with stirring. The mixture was allowed to warm up slowly and st1rred at embient temperature '7~

~or 17 hours. The precipitate was collected by fil-tration, washed with water, acetonitrile and air-dried to give 1 g of dimethyl N,N'-[ethanediylidenebis~ni-trilooxycarbonyl~N-methylimino)thio~N-methylimino)car-bonyloxy]]bis~ethanimidothioate], m.p. 167-168.5C
(dec.).
Example 4 N,N'-~2,3-butanediylidenebis~nitrilooxycarbonyl(N-methylimino)thio~bis~N-methylcarbamic fluoride]

A solution of 4.1 g of triethylamine in 10 ml of dry acetonitrile was added dropwise to a mixture of 2.3 g of dimethylglyoxime and 7.4 g of bis(N-methyl-N-fluorocarbonylamino)sulfide in 40 ml 15 of dry acetonitrile at 0 to 5C. The mixture was stirred on an ice bath for 30 minutes and a~ ambient temperature for 3 hours. To the suspension, water and ether were added. The precipitate was collected by filtration, washed with water, a mixture of ether and n-chlorobutane, and air-dried to give 6 g of N,N'-~2,3-butanediylidenebis~nitrilooxycarbonyl(N-methylimino)thio~bis~N-methylcarbamic fluoride], m.p. 212-215C (dec.).

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Example 5 Methyl N-~N-[N-EN-~1,2-dimethyl-2[[N-methyl-N-[N-methyl-N-~[l-(methylthio~ethylidene~aminooxycarbonyl]~
aminothio3amino]carbonyloxyimino~ethylidene3amino-oxycarbonyl]-N-methylaminothio]-N-methylamino-carbonyloxy]-2-(dimethylamino)-2-oxoethanimidothioate A solution o~ 1.1 g of triethylamlne in 10 ml of methylene chloride was added dropwise to a suspension of 4.5 g of N,N'-~2,3-butanediylidene-10 bisEnitrilooxycarbonyl(N-methylimino)thio]~bis[N
methylcarbamic fluoride] and 1.1 g of methyl N-hydroxyethanimidothioate in 90 ml of methylene chloride at 0 to 5O in 30 minutes. The mixture was stirred on an ice bath 3 hours. The unreacted 15 starting material was separated by filtration. The filtrate was washed with three 80 ml portions of water and the oxganic layer was dried over anhydrous magnesium sulfate. The mixture was filtered and the filtrate was evaporated to give an oil, which was 20 triturated with ether and methylene chloride mixture to give 3.1 g of methyl N-~N-~N-~N- ~2-`E ~N-~N-(fluoro-carbonyl)-N-methylaminothio]-N-methylamino]-carbonyl-oxyimino]-1~2-dimethylethylidene]aminooxycarbonyl3-N-methylaminothio]-N-methylaminocarbonyloxy]ethanimido-25 thioate.IR (Nujol): 5.6~ , 5.7~
NMR ~CDC13) ~2.13, 2.33 and 2.40 (3S, 12H), 3.4 and 3~47 ~S, 12H).
This crude carbamic fluoride was used in the next 30 reaction without further purification.

A solution of 1 g o~ tri~thylamine in 10 ml of me~hylene chloride was added dropwise to a solution of 3 g of the crude carbamic fluoride and 1.1 g of methyl 2-(dimethylamino)-~-hydroxy-2-oxoethanimido-thioate in 50 ml of methylene chloride at 10 to20~C and stirred at room temperature for ~.5 hours.
The solution was washed with three 50 ml portions of water, and the organic layerlwas dried over anhydrous magnesium sulfate. The mixture was filtered, and the filtrate was evaporated. Ether was added to the crude product ~ollowed by dilution ~ith methylene chloride until the mass could flow freely. The solid was separated by filtration to give a mixture.
The mother liquor was concentrated and diluted with ethers to give 0.5 g of the title compound, m.p.
87-110C (glass).
IR (Nujol): 5.7Sy , and 6.08y NMR (CDC13): ~2.3, 2.33 and 2.4 ~S, 15~), 3.02 and 3.08 l25, 6H), 3.42 and 3.48 (2S, 12H).

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~ ctive compounds of Formula I that can be p-epared according to the procedures demonstrated by the given examples are given, but not restricted, as follows:

.
' . . ' '' ~ ~ ~ ,.

Table 1 O CH3CH3 Rl R2 CH3CH3 O
R3c=Noc N S N - CON=C(CH~)nC=NOC ~ S N - CON=C R3 R3 _ R4 - 1 R2 n melting point C_ CH3 CH3 CH3 CH3 1 13:L-140 (dec.) CH3 CH3 C6H5 C6H5 214-216.5 (dec.) o CH3 CH3 CN(CH3)2 CH3 184-189 (dec.

CH3 CH3 Cl Cl 0 96 99.S
CH3 CH3 CH3S CH3S 200-202.5 (dec.) CH3 CH3 C2CH3 CH3 173-176.5 (dec.) CH3 CH3 C02(n-C6Hl3) CH3 CH3 CH3 ~ ~
CH3 CH3 n C3 7 n C3 7 0 180-183.5 (dec.) CH3 CH3 CH3SCH2 CH3 oil CH3 CH3 n-C3H7SCH2 CH3 100-115 (dec.) CH3 CH3 ClCH2 CH3 166-168.5 (dec.) CH3 CH3 n-C4Hg n C4H9 0 CH3 CH3 t-Bu ~ t-Bu ~ 0 CH3 ~H3 t-Bu CH~S 0 GH3 CH3 t-Bu H 0 CH3 CH3 -CH2CH2CH2CH2- 0 170-173 (dec.) CH3 CH3 ~ ~

CH3 CH3 CH~ ~ CH3 ~ 0 , ~' '.
.

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Table 1 continued - 3 - _ 4 _ R~2 - n melting~point 3C
CH3 CH3 ~ ~

CH3 CH3 (cH3)~cH(CH3)2CH 0 C~3 CH3 C6H5 CH3 167-170 (dec.

CH3 CH3 2CH2S 204-207 (dec.) CH3 CH3 CH3 C~3CH2 0 193-195.5 ~dec.) CH3 n-C3H7 CH3 CH3 0 n-C3H7 CH3 C~3 CH3 0 CH3 CH3 CH3 CH3(CH2)3 0 99-104 , L~ 7~

Table_2 ~Oj CH3 CH3 Rl R2 CEE3 CH3 0 R-O-C-N-S-N - CON=C(CH2) -C=N-O-C-N-S-N - C-O-R' R ___ R' 1 - R2- - n melting point C
O
Il ..
Me2NC-C=N Me2NCC=N CH3 CH3 185-188 (dec.) . .
O O
.. ..
Me2NCC=~NMe2NCC=N CH3 C02CH3 O

3 _ O O
Me2NCC=N Me2NCC=N CH3S 3 0 O
.. ..
15 Me2NCC=NMe2NCC=N CH3CH2 CH3CH2 0 o n .. ..
Me2NCC=N Me2NCC=N CH3(CH2)3- CH3 0 2 0 o O _ _ Me2NCC=N Me2NCC=N CH3 CH3 0 O O
~e2NCC=NMe2NCC-N CH3 CH3 0 2 5 n-C3H7S 3 7S
_~
CH3 ~
CE~3SCCN=NCEI3SCCH=N CH3 CH3 117-118 . 5 . CH3 CH3 3 0CH3SCCH=NCH3SCCH=N CH3CH2 CH3CH2 0 CH3SC-CH~N CaN- CH3 CH3 0 CEI3 CE~3S

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Table 2 continued R R' Rl R2 n melting pointC
CH
, 3 ..
CH3SccH=N- Me2NCC=N CH3 CH3 0 .
10 ~ ~ CH3 CH3 155-161 (dec.) _ _ _ . . . . . . .

15 ~ C=N- CH3 CH3 0 Me2NCC-N- CH3 CH3 0 25 ~ CH3 CH3SCCH=N- CH3 . CH3 0 CH3 ~ , 3 /C=N CH3SCCH=N CH3 CH3 0 __ . _ _ 3 ~ n ~ C=N ~e2NCC=N CH3 CH3 a :, ` ` ' .

7~a~

Table 2 Continued _ _ R__ _ R _ Rl - - 2-- n ~eltlng point C
,CH3CH3 CH3SCCH=N CH3SC-CH=N C6H5 C6H5 0 lQ

Formulation ~ seul ~ormulations of the com~ounds of Fsrmula I can be prepared in conventional ~ays. They include dusts, granules, pellets t solutions, wettable pow~ers, and the like. Many of these may be applied directly. Sprayable formulations can be exten~ed in suitable media and used at spray volumes of from a few pints to several hundred gallons per acre. High strength compositions are primarily usecl as intermediates lO for further formulations. The formulations, broadly, contain about 1~ to 99% by weight of active ingredient(s) and at least one of a) about 0.1~ to 20~ surfactant(s) and b) about 1% to 99% solid or liquid diluent(s).
More specifically, they will contain these ingredients 15 in the following approximate proportions:
Table 3 Active Dilu Surfac-Ingredient ent(s) tant(s) Wettable Powders 20-90 0-74 l-lO
20 oil Suspen~ionS,5 50 40-95 0-15 Solutions Aqueous Suspensions 10050 40-84 1-20 Dusts 1-25 70-99 0-5 - Granules and Pellets 1-95 5-99 0-15 25 High strength 90-99 0-lO 0-2 Compositions Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound.
30 ~igher ratios of Rurfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.

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Typical solid diluents are described in Watkins, et al., "~andhook o~ Insecticide Dust Diluents and Carriers"~ 2nd. Edn., Dorland Books Cal~ell, N.J. The more absorp~i.ve diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Sol~ents ~uide", 2nd. Edn., Intexscience, New York, 1950. Solubili~y under 001% is prefexred for suspension concentrates; solution concentrates are preferable stable against phase separation at 0C. McCutcheon's"D~ g~nts and Emulsifiers Annual", MC Publishing Co., Ridgewood, New Jer~ey, as well as Sisely and ~ood, "Encyclopedia of Surface Active Agents", Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses.
All formulations can contain minor amounts of additives to reduce foam, caking, corroslon, microbiological growth, etc. Preferably, ingredients should be approved by the U.S. Environmental Protection Agency for the use intended.
The method of making such compositions are well known. Solutions are prepared by ~imply mixing the lngredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, UOS. Patent 3,060,084~. Granules and pellets may be made by spraying the acti~e material upon preformed yranule carriers or by agglomeration techni~ues. See J. ~.
Browning, "Agglomeration", Chemical Engineering, Dec. ~, 1967, pp. 1~7ff. and "Perry's Chemical Engineer's ~andbvok", 4th Edn., ~cGraw-Ilill, N.Y., 1963, pp. ~-59ff.

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For ~uxther information regarding the art of formulation see for example:
J. B.... .........Buchanan, U~S~ Patent 3,576!834, ~pril 27, lg71~ Col. 5, lines 36 through Col. 7, Line 70 and Ex.
1-~, 17, 10.6, 1~3-140;
R. R. Sha~fer, U.S. Patent 3,560,616, Feb~ 2, lg71, Col. 3, L~ne 48 through Col. 7, line ~6 and Ex. 3-9, 11-18;
E. Somers, "Formulation", Chaptex 6 in Torgeson, "Fungicides", Vol. I, Academic Press, New York, 1967.
Example 6_ I~e ~ wd2r 15 ~imethyl N,Nll2l3-butanediylidenebis- 30 ~nitrilooxycarbonyl~N-methylimino)-thio(N-methylimino)carbonyloxy3]bis-lethanimidothioate~
Dicotyl sodium sulfosuccinate 1.5%
20 Sodium ligninsulfonate 3%
Low viscosity methyl cellulose 1.5 Attapulgite 64%
The ingredients are thoroughly blended, passed through an air mill- to produc~ an average 25 p~rticle size under 15 microns, reblended, and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) before packaging.
All compounds of the invention may be formulated in the same manner.

Example 7 Wettable Powder ~imethyl N,N'~ 2~propanediylidenehis-~ 50%
Initrilooxycaxbonyl(N~methyli~ino)-thio(N-methylimino)carbonyloxy~]bis-I ethanimidothioate]
Sodium alkylnaphthalenesulfonate 2 Low ~iscosity methyl cellulose 2%
Diatomaceous earth 46~
~he ingredients are blenaed, coarsely hammer-milled and then air milled to produce particles of active essentially all below 10 microns in diameter.
The produc~ is reblended before packaging.
Example_8 15 Dust Wettable powder of Example7 10%
Pyrophyllite (powder) 90 The wettable powder a~d the pyrophyllite diluent are thoroughly blended and then packaged.
20 The product is suitable for u5e as a dust.
Example 9 Solution_ Dimethyl ~,N'-~2,4-pentanediylid~ne~is- 30%
[nitxilooxycarbonyl ~N-methylimino) -thio(N-methylimino)carbonyloxy]]bis-~ethanimidothioate]
Dimethylformamid~ 70 The ingredients are combined and stirred to produce a solution, which can be used 30 for low ~olume applicatio~s.

Granule -Wettable powder of Example 6 15~
Gypsum 6 9%
35 Potassium sulfate 16%

~o..B~ P'~

The ingredient~are blended in a rotatin~
mixer and water sprayed on to accomplish granulation.
When most of the material has reached th~ desire~
range of 1.0 to 0..42 ~m. (U.S.S. No. 18 to 40 sievQs), 5 the granules are r~mo~ed, dried, and screened.
Oversize material is crushed to produce ad~itional material in the desired range~ These granules contain 4.5% active igredient.

10 Extruded Pellet Dimethyl N,N' r 2,S-hexanediylidenebis- 25 ~ni~rilooxycarbonyl(N-methyllmin~)-thio(~-methylimino)carbonyloxy]~bis--[ethanimidothioate~
15 Anhydrous sodium sulfate 10%
Crude calcium ligninsulfonate 5 Sodium alkylnaphthalenesulfonate 1 Calcium/magnesium bentonite 59~
The ingredients ara blended, hammex milled 20 and then moistened with about 12~ water. The mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long.
These may be used dire~tly aftex drying, or the dried pellets may ~e crushed to pass a U.S.S. No. 20 sieve 25 (0.84 mm opening). The granules held on a U.S.S. No.
40 sieve (0.42 mm opening) may be packaged for use and the fines recycledO
xample 12 Aqueous Suspension 30 Dimethyl N,NI;~2,3~butanediylidenebis- 25%
Initrilooxycarbonyl(N-methylimino)~
thio(N-methylimino)carbonyloxy~]bis-lethanimidothioate]
Hydrated attapulgite 3%
35 Crude calcium ligninsulfonate 10%
Sodium dihydrogen phosphate 0.5%
Water 61.5%

Th~ ingredients are ground to~ethex in a ball or ~oller mill until the ~olid par~icles ha~e been reduced to diame~ers under 10 microns.
Use The compounds of this invention of Formula I are useful for the control of arthropods and nema-todes which are detrimental to agricultural, animals important to man, forestry, horticulture, the house-hold, man-made structures, public health and stored 10 p~odUct5.
As demonstrated in the following examples, the compounds have provided a high degree of control of important pests with minimization of side effects known in prior art compounds such as phytotoxicity.
The compounds readily control pestiferous arthropods belonging to such orders as Acari, Lepi-doptera, ~ymenoptera, Isoptera, Coleoptera, and Diptera. More specifically, arthropods controlled by the compounds of this in~ention include, but are not 20 limited to, southern armyworm (Spodoptera eridanis), fall armyworm (SE~doptera frugiperda), soybean looper (Pseudoplusia includens), Mexican bean beetle (Ed~-__ lachna varivestis), the housefly (Musca domestica), tobacco budworm (Heliothis virescens~, bollworm tHeli zea), easte~n tent caterpillar (Mala-_ _ cosoma americanum), brown dog tick (Rhipicephalus sanguineus), and black carpenter ant (Camponotus _ pennsylvanlcus).
These compounds readily control pestiferous 30 nematodes. More ~pecifically, nematodes controlled by compounds of this invention include, but are not limited to, the root~knot nematode, Meloido~yne incoynita;
lesion n~matode, Pratylenchus spp. and dagger nematode, Xi~hi_ima.

7i~

The insects are controlled by applying one or more or the compounds to the locus of infestation, to the area to be protected, or to the pests themselves.
For the control of insects on agricultural crops, compounds of this invention are generally applied to the foliage or other plan~ parts which axe infested or which are to he protected. Effecti~e ~mol~nt~ to be a~lied depend upon the specific compound used ! the species to be controllea, its life stage~ its size and location 10 the amount of rainfall, the time of year~ moisture, temperatu~e, type of application plant spacing, and other variables. In general, O.Q5 to 10.0 kg/ha may be required for insect ontrol in agriculture with rates of 0.15 to 5.0 kg/ha usually being sufficient in many 15 situations. In large scale field operations, rates in the range o 0.25 to 3.0 kg/ha are generally used.
For the control of pe.stifexous arthropods of animals important to man, the household, man-made structures and stored products, compounds of this 20 invention of formula I are generally applied to the item(s) which are infested or which are to be pro-tected. Effective amounts to be applied depend upon the specific compound used, the species to be con-trolled, its liXe stage, its size and location, 25 the amount of rainfall, the time of year, moisture, temperature, type of application and other variables.
In general, 0.001% to 10% (by weight) preferably 0.05 to 5~ and more preferably 0.01 to 2 . 5% of the compound of this invention will be applied in a com~
30 position such as in the form of a solution dispersion or dust.

D~

Nematodes are controlled by applying the compounds to the locus of infestation, to ~he area to be protected or to thP pest themselves. For the control of nemato~es in agricultural crops, a compound of this invention is generally applied to a portion of the plant or surrounding soil which is infeste~ or which is to be protected. ~ffective amounts to be applied depend upon the species to be controlled, its life stage, its size and location, the amount of rainfall, the tlme of year, 10 moisture, temperature, soil type, percentage of area treated, type of application, and other variables. In general, 3 to 30 kg/ha may be required for nematode control in agriculture with rates of 5 to lO kg~ha usually being sufficient in many ~ituations.
The compounds of this invention of formula I
possess signiicant advantages over prior art compounds.
For example, their improved residual insecticidal activity can reduce the need for closely spaced multiple sprays resulting in greater economy to the 20 grower and dissemination of less insecticide in the envirOnment. An additional advantage is the reduced side-effects on cotton. Treated leaves remain green and free of reddening.
The compounds of this invention of formula I
25 can be mixed with fungicides, bactericides, acaricides, nematicides, insecticides~ or other bioloqically active compounds in order to achieYe desire~ Yesults with a minLmum expenditure of ti`me~ effort And ~aterial.
Amounts of these biologically active materials a~de2 30 for each part by waight of the composition of this in~ention may ~ary from 0.05 to 25 parts by weight.
Suitable agents of this type are well-known to those skilled in the art. Some are listed below:

7~
~ 9 Fungicides methyl 2-benzimidazolecaxbamate (carbendazim), tetramethyl thiuram disulfide (thiram), n-dodecylguanidine acetate (dodine~, manganese ethylenebisdithiocarbamate (maneb), 1,4-dichloro-2,S-dimethoxybenzene (.chloroneb), mPthyl 1-(b~tylcarbamoyl)-2-benzimidazolecarbamate (benomyl), 2-cyano-N-ethylcarbamoyl 2-methoxyimino acetamide (cymoxamide), N-trichloromethylthiotetrahydrophthalimide (captan), N-trichloromethylthiophthalimide (folpet);
Bactericides:
tribasic copper sulfate, ~5 strr*ptomycin sulfate;
Acaricides:
senecioic acid, ester with 2-sec-butyl-4,6-dinitrophenyl (Mor~cide~),

6-methyl-1,3~dithiolol2,3-B~quinoolin-2-one (Morestan~), 20 ethyl 4,4'(.~-chlorophenyl)-2~2,2-trichloroethanol (~elthane~), bis(pentochloro-2,4 cyclopentadien-lyl) (.Pentac~)~
trichlohexyltin hydroxide (Plictran~);
~ematicides:
25 2-1diethoxyphoxphinylimino]-1,3-dithietane (~ematak~), S~methyl l-(dimethylcarbamoyl)-N-(methylcarbamoyloxy)-thio~ormimidate (Vydate~), S~methyl l-c~xbamoyl-N~(~ethylc~rba~o~lo~x)thioformidate~
N-isopropylphosphoramidic acid, 0-eth~1~0'14-(methyl-thio]-m-tolyl]die~ter (Nemacur~), Insecticides:
3-.hydro~y-N-methylcrotonamide~dimethylphosphate)ester (Azodrin~), methylcarbamic acid, ester with 2,3-dihydro-2,2-~imethyl-7-benzofuranol (Furadan~), ~. ~.a~ ~ 7~

0-12,~,5-trichloro-~ (chloromethyllbenzyl]phosphoric acid, 0',0'-dimethyl ester (:Gardona~), 2-mercaptosuccinic acid, diethyl ester, S-ester with thionopho~phoric acid, dimethyl ester (Mælathion~), phosphorothioic acid, 0,0-dimethyl, 0-~-nitrophenyl ester (methyl parathion) methylcarbamic acid, ester with a-naphthol (Sevin~), methyl O~(methylcarbamoyl)thiolacetohydroxamate (methomyl) 10 N'-(4-chloro-o-tolyl)-N,N-dimethylform~nidine (Galecron~), 0,0 diethyl-0-(2-isopropyl-4-methyl-6-pyrimidyl-phosphvrothioate ~Diazinon~), octachlorocamphene (toxaphene) 15 0-ethyl 0-~-nitrophenyl phenylphosphonothioate (EPN) cyano(3~phenoxyphenyl)~methyl-4-chloro-~ methylethyl)-benzeneacetate (Pydrin~), (3-phenoxyphenyl)methyl~ cis, ~rans--3-(2,2,-dichloro-ethenyl)-2,2~dimethylcyclopropanecarboxylate,(~b~5h~), 20 dimethyl N,N'-~thiobis~(n-methylimino)carbonylOxy]~-bis~e~hanimidothioate] (Larvin~), 0-ethyl-S-(p-chlorophenyl)ethylphosphonodithioate (Curacron~), phosphorothiolothionic acid, 0-ethyl-0-~4-(~ethyl~hio)-phenyl~-S-n-propyl ester (.Bolstar~)~

Additional bioloyical acti~e agents which.
can be mixed with compounds of this invention of formula I include:
30 0,0-dimethyl 0-(2,4,S-trichlorophenyl)phosphorothioate (Ronnel~
0,O~diethyl 0-(3-chloro-4-methyl-2-oxo-2H-1-benzapyran-

7-yl)phosphorothioate (Co-Ral~);
Dimethyl 2,2-dichlorovinyl phosphate (Dichlorvos);
35 N-(mercaptomethyl~phthalimide S-(0,0-dimethyl phosphorodithioate (Imidan@~;

3~t 2,~-Bis(p~methoxyphenyl)-l,l,l-trichloroethane (Methoxychlorl;
Octachloro-4,7-methanotetrahydroindane (Chlordane);
O,O-diethyl-0-(2-isopropyl-6-methyl-5-pyrimidinyl) phosphorothioate (Diazinon);
5 DL-2-allyl-4~hydroxy-3-methyl-2-cyclopenten-1-one ester of dicistranschrysanthemum monocarboxylic acid (Allethrin).

Example l~ -The folia~e only o~ red kidney ~ean plants in the two leaf sta~e is sprayed to nln-off with dis-persions of compounds of this ~nvention at ~arious concentrati~ns. Dispersions are prepared by dissolving appropriately weighed quantities of the active ingredien~ in lO ml of acetone and diluting to 100 ml o wa~er containing surface active agent (~Duponol3 ~-144 WDG) at 1:3000. After drying, leaves are excise~ and lO placed in coverea lO cm petri ~ishes along with moist filter paper to keep them fresh. Ten southern armyworm larvae are placed in each dish. The units are kept in a room maintained at 25 + ~C. 53 + 5% RH. Results are recorded at the end of two days.
Concen-Compound tration % Mortality dimethyl N,N'-I2,3-butane- .0~4 9~
diylidenebis~nitrilooxy- .oo~ go car~onyl(N-methylimino)-20 thio(N-methylimino)carbonyl-oxy~]bis~ethanimidothioate]

dimethyl N,N'-rl,2-pxopane- .01 100 diylidenebis~nitrilooxy- 005 lO0 25 carbonyl(N-methylImino)thio- 0~25 95 (N methylimino~carbonyl-oxy]]bis~ethanimidothioate]

dimethyl N,N'-12 r 4-pentane~ ~1 100 30 diylidenebislnitrilooxy- 005 80 carbonyl(N-methylLmino)thio-(N-methylimino)carbonyl-oxy]]bisrethanLmidothioate]

'7'7 corlcen- -_ Com~o~nd _ tration ~ ~ ~ %
dimethyl N,N'-l2,5-h~xane- . Ø1 lQQ
diylidene~isInitrilooxy- ,005 90 carbonyl~N-~ethyliminol-thio(~n-metXyl~mino)carbonyl~
oxyJ]bisIethanimidothioate~

Vntreated ~
Example 14 The foliage of red kidney bean plants in the two-leaf ~tage is sprayed to run-off with dispersions of compounds of this invention at ~arious concentra-tions. Dispersions are prepared by dissolving appropriately weighed quantities of the active ingredient in 10 ml of acetone and diluting to 100 ml with wate:r containing sux~ace ac~ive (Duponol~ L-144 WDG) at 1:3000. After drying, plants are placed under arti-ficial light in a room maintained at 25 ~ 2C, 54 + 5~ RH. After the designated period, leaves are excised and placed in covered 10 cm petri dishes along with moist filter paper to keep them ~resh. Ten southern armyworm larvae are placed in each dish. The units are kept in a room maintained at 25 + 2C, 54 Results are recorded at the end of two days.

Concen- Days (%Dead) Com~ound tration % ~ 7 _ dimethyl N,N'- I 2,3-butane- .01 90 lO0 diylidenebis Initrilooxy- . 005100 95 car~onyl(N-methylimino)-thio(N-methylLmino)carbonyl-oxy~]bislethanLmidothioate~

Untreated Check 0 0 ot~

Example 15 _ _ _ Potte~ cotton plants appro~Lmately 25 cm high havi~g 3-4 true leaves are sprayed to run~off witX aqueous dispexsions of compounds of this invention at 500 ppm. The sprays contain surface active agent (Duponol~ L 144 WD~l at a concentration of 1:3000.
Another set of plants is similaxly treated with methomyl.
After drying, platns are set out in the greenhouse and held for obserations.
10 Co~ound (500 ppm AIlLRatin~2 (5 Days) dimethyl N,~ 2,3-butane-diylidenebis[nitrilooxy-carbonyl(Id-methylimino)-thio~N-methylimino)carbonyl 15 oxy~]bls[ethanimidothioate]
Methomyl 4R
Untreated Control 0 Example 16 Tobacco budworm ~~Ieliothis virescens) larvae are treated topically with compounds o~ the invention. One microliter of each concentration used is applied to the dorso-thoracic area of each larva tested. The Ctock solutions are prepared by dissolving appropriately weighed quantities of ac~ive ingredient in predetermined quantities of acetone. Further dituting with acet4ne yielas the desired concentrations.
Larvae were treated in individual l-oz. cups in which ~I = ac~ive ingredien~
"R" denotes typical methomyl effect, i.e.~ reddening of older leaves, slight puckering and black stippling of younger leaves. Rating is on the basis of 0 to 10, wi~h 10 indicating total leaf area involvement.

7'~

were reared on artificial diet, Fifte~n or twenty larvae w~re treated with each des.ired concen~ration and kept in a room at 25 + 2C. Result~ were recorded 2 days af~er treatment.
Concen- % Mort-tration ality ~ ~ (48_hrs) dimethyl N,N'-I2,3-butane- 0.25 93 diylidenebislnitrilooxy- 0.125 85 10 carbonyl(N-methylimino)-thio(N-methyllmino)carbonyl-oxy~ 3 ~is I ethanimidothioate]

~imethyl N,N'~¦2,4~pentane oS 87 15 diylidenebisLnitriloo~y- 0.25 73 carbonyl(N-methyliminolthio-(N-methylimino)carbonyl-oxy]]bisEethanimidothioate]
20 Untreated - 0 xample l?
Dimethyl N,N'-[[1,2-~thanediylidenebis[nitrilo-oxycarbonyl(N-methy}imino)thio(N-methylimino)carbonyl-oxy]J]-bis [ethanimidDthioate], was dissolved in acetone and mixed into soil containing the rootknot nematode, Meloido~yne ~ . Di-methyl N,N'-~1,3-propanediylbis~nitrilooxycarbonyl(N-methylimino)thio(N-methylimino)carbonyloxy]]]bis- -~ethanimidothioate], was similarly dissolved in acetone and mixed into soil containing the root-know nematode, Meloido~yne inco~nita. The treated soil samples were planted with cucumber seeds.
After two weeks, the roots were examined for 35 nematode injury and the results are summarized below.

~7'7~

Nematode ~ a Control_ dimethyl N,N'-I2,3-butane-15 100 diylidenebis~nitrilooxy 5 carbonyl(N-methylimino)-thio(N-methylimino)carbonyl-oxy~]bis~ethanimidothioate]

Untreated Control - 0 1~
Example 1~
Four-ounce wide mouth jars, each containing 10 blacX carpenter ants (Camponotus pennsylvanic~s) were sprayed with 100 and 10 ppm concentration of the indicated compound in acetone solution. The ants were con~ined with caps which were also sprayed. Forty-eight hours later, percent mortality was determined.

_ Compound S~ray Concentration ~E~% ~ortalit~
dimethyl N,N'~[2,3-butane-100100 diylidenebis[nitrilooxy-10 100 carbonyl~N-methylimino) thio(N-methylLmino)-carbonyloxy]lbis[ethan-imidothioate]

Four-ounce wide mouth jars, each containing 10 brown dog ticks (_hi~icephalus sanguineus) were sprayed with 10 and S ppm concentration of the indicated compound in acetone solution. The ticks were confined with caps which were also sprayed. Forty-eight hours later, percent mortality was determined.

7~

Compound _ _ dimethyl N,N' [2,3-butane- ppm diylidenebis[nitrilooxy~ lO lO0 carbonyl(N-methylimino)~ 5 100 5 thio(N-methylimino)-carbonyloxy3]bi 5 [ ethan-imidothioate]

_x~ e 20 Uniform test units consisting of ~ut branche~ of wild cherry trees beaxing four eastern tent s:aterpillar nests in can-type vases were prepared and sprayed with dispersions of this rompound. They were kept out o~ doors and results were read 5 days after treatment.
Evaluation was made by counting all caterpillars inside and outside the nests.

Concentration Compound _ oz(ai)/lO0 ~al % Mortality 20 dimethyl N~N'~l2,3-butane- 1 99 diylidenebis[nitrilooxy- 0.25 99 carbonyl(N-methylimino)~
thio(N-methylimino)-carbonyloxy~]bislethan-25 imido~hioate~

Claims (14)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A compound of the formula wherein R and R' are independently , , or provided that R and R' are not the same when R is , or R1 is hydrogen, C1-C4 alkyl, C5-C6 cyclo-alkyl, C1-C3 alkylthio, chlorine, chloromethyl, , R5SCH2-,, phenyl or phenyl substituted with C1-C4 alkyl;
R2 is hydrogen, C1-C4 alkyl, C5-C6 cyclo-alkyl, chlorine, C1-C3 alkylthio, phenyl or phenyl substituted with C1-C4 alkyl;

R1 and R2 can be taken together to form a carbocyclic bridge of three to five carbon atoms, or a bridge of the formula -SCH2CH2S-;
R3 is C1-C3 alkyl;
R4 is C1 C3 alkyl;
R5 is C1-C3 alkyl;
R6 is C1-C6 alkyl; and n is 0, 1 or 2;
provided that n is O when 1) R1 is chloromethyl or R4SCH2, or 2) R1 and R2 are taken together to form a carbocyclic bridge or a bridge of the formula -SCH2CH2S-, or 3) at least one of R1 and R2 is alkylthio;
and provided that when n is 0, one of R1 and R2 cannot be H when the other is phenyl or phenyl substituted with C1-C4 alkyl;
and further provided that when n is 1, R1 and R2 cannot both be t-butyl, phenyl, phenyl substituted with C1-C4 alkyl or combination thereof.

2. A compound of Claim 1 where R and R' are identical.

3. A compound of Claim 1 where R3 is CH3,

4. A compound of Claim 1 where R1 and R2 are independently hydrogen, C1-C4 alkyl, , phenyl, or phenyl substituted with C1-C4 alkyl or where R1 and R2 are taken together to form a carbocylic bridge of three to five carbon atoms.

5. A compound of Claim 1 where n is 0.

6. A compound of Claim 1 where R and R' are identical, R3 is CH3, R1 and R2 are independently hydrogen, C1-C4 alkyl, , phenyl or phenyl substituted with C1-C4 alkyl or where R1 and R2 are taken together to form a carbocyclic bridge of three to five carbon atoms and n is 0.

7. A compound of Claim 6 where R3 is CH3, R1 and R2 are independently hydrogen, C1-C4 alkyl, , phenyl or phenyl substituted with C1-C4 alkyl or where R1 and R2 are taken together to form a carbocyclic bridge of three to five carbon atoms and n is 0.

8. A method for control of insects, acari, or nematodes which comprises applying to a locus to be pro-tected an insecticidally, acaricidally, or nematicidally effective amount of a compound of Claim 1.

9. A method for control of insects, acari, or nematodes which comprises applying to a locus to be pro-tected an insecticidally, acaricidally, or nematicidally effective amount of a compound of Claim 2.

10. A method for control of insects, acari, or nematodes which comprises applying to a locus to be protected an insecticidally, acaricidally, or nematici-dally effective amount of a compound of Claim 3.

11. A method for control of insects, acari, or nematodes which comprises applying to a locus to be protected an insecticidally, acaricidally, or nematici-dally effective amount of a compound of Claim 4.

12. A method for control of insects, acari, or nematodes which comprises applying to a locus to be protected an insecticidally, acaricidally, or nematici-dally effective amount of a compound of Claim 5.

13. A method for control of insects, acari, or nematodes which comprises applying to a locus to be protected an insecticidally, acaricidally, or nematici-dally effective amount of a compound of Claim 6.

14. A method for control of insects, acari, or nematodes which comprises applying to a locus to be protected an insecticidally, acaricidally, or nematici-dally effective amount of a compound of Claim 7.