CA1110656A - N-[[arylformimidoyl]methylamino]thio]-n- substituted sulfonamides] - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Novel pesticidal N-[[[arylformimidoyl)methylamino]thio]-N-substituted sulfonamides are disclosed with novel compositons thereof and methods for their use in controlling invertebrate arthropod pests, particularly insects, mites, and ticks.

Description

~ 5~ 3359 BACKGROUND OF I~ VENT~
1. Field of the Invention The invention concerns novel N-[~arylformimidoyl]methyl-amino]thio]-N-substituted sulfonamides, pesticidal compositions ~hereof, and their use for killing and otherwise controlling arthropod pests.

2. Description of the Prior Art A number of N-alkyl-N'-aryl formamidines have been pre-~
viously descr;bed as pesticides; see, for exampie, Belgian .Patents 760,141; 770,825 and German ~atents 1,172,081; 2,202,034.
N-sulfenylated chlorides of sulfonamides are known; for example, Ger~an Patents 1,101, 407 and 1,15~,403.
Arylsulfenylated formamidines and aminosulfenylated form-amid7nes are known and used as insecticTdes; for example, U.S.
Patents 3,887,~19 and 3,947,591 and 3,998,969.
SUMMARY OF THE INVENTION
;~ The Invention comprises compounds selected from those of the formula:
,~
: . 20 ,'` Rl , `
`: ~ H IH3 R9 . Rz_~/ \ ~ N=C- N - S-N -SO2 -R4 ,~:: \==/
~: : 25 ( l ) . . .

3 wherein Rl is chloro, bromo, or alkyl of one through four carbon ~` 2 .
,.'.. ` . ~

, . . .
:, : . 3359 ~ 5 ~ ;

atoms; R2 is hydrogen, chloro, bromo, or alkyl of one through four carbon atoms; R9 is (1) alkyl of one through etght carbon atoms,(2) cycloalky1 of five through eight carbon atoms J (3Jpi~n-alkyl wherein alkylis one ortwo methylene units in length, or (4) phenyl where the phenyl is unsubstituted or substituted with one through three substituents selected from the group consisting of methyl, chloro, bromo, nitro, trifluoromethyl, aikoxy of one or two carbon atoms, and cyano; and R4 is (1) alkyl of one through four carbon atoms3 (2) phenalkyl wherein alkyl is one or two methylene units in length and where.the phenyl is unsub-stituted or substituted with one through three substituents selected from the group consisting of methytJ chloro, bromo~
nitro, trifluoromethyl, alkoxy of one or two carbon atoms, and cyano, or ~3) phenyl where the phenyl is unsubstituted or sub-stituted with a substltuent setected from the group conslsting of methyl, chloro and bromo.
The invention atso comprises compounds of formuta I wherein :
R1 Is chloro or bromo; R2 is alkyl of 1 through 4 carbon atoms, . chloro, or bromo; and R9 and R~ are as defined above.
2G The invention atso comprises compounds of formuta I wherein ~ R1 and R8 are chtoro or bromo and R3 and R4 are as defined : above.
The invent7on also comprlses composTtions for arthropod con-trol whtch comprlse an acceptabte carrier and an effectlve amount of a compound of the invention.
The sulfonamidosulfenyl formamidine derivatives of this in-vention are particutarly advantageous commercially as inverte-brate pes~tcides because they are more stable than, for ex-ampte, the amtnosulfenylated formamidines both in storage and upon applicatlon in the field., thus provlding a long-last1ng .
:'`' .'. ~ - .
... . .
.

~ 6~ ~ . 3359 residual effectiYeness.
In addTtion to killing invertebrate pests on contact, the compounds of the invention are absorbed by the vascular.system of many plants, for example by cotton plants, and act systemi-. cally to kill the pests feeding upon the plant Thus their perlod of pesticidal activity is further extended and non-feeding arachnids and insects, e.g! insects not harmful to the plant, are not unnecessarily killed during the whole period of pesticidal activity.
Compounds of the invention are also ovicidal, and are partTcularly effective in the control of acarine pest popula-tions by this ovicidal action. Lepidopterous ova are also particularly susceptible to the compounds of the invention.
The compounds of the invention are also advantageous in that they exhlbit relatively low mammalian toxicity and are non-phytotoxic at effective concentrations.
Compounds of the inven.tion having the formula:

Rg ~ H CH3 R7 R~ y ~ N=C- N- S-N -SQ2 R4 ~ . (Il) : 25 wherein R5 is methyl or chloro; Re Is methyl or chloro; R7 is (1~ alkyl of one through four carbon atoms, (2) cyclo-alkyl of five through elght carbon atoms, (3) phenalkyl.
; wherein alkyl is one or two methylene units in length, or . (~) phenyl where the phenyl is unsubstituted or substltuted with one through three substituents selected f.rom the group ,, .

~ -4- .
.

consisting of methyl, chloro, and bromo; and R4 is (1) alkyl of one through four carbon atoms, (2) phenalkyl wherein alkyl is one or two methylene units in length and where the phenyl is unsubstituted or substituted with one through three substit-. uents selected from the group consisting of methyl, chloro,bromo, nitro, trifluoromethyl, alkoxy of one or two carbon atoms, and cyano,or O phenylwhere the phenyl is unsybstituted or substituted with a substituent selected from the group conslsting of methyl, chloro, and bromo are preferred for their greater pesticidal effect and chemical stability.
DETAILED ~ESCRIPTION OF T~E.lNVENTiON
. The compounds of this invention (I) can be synthesized ~ -by the reaction of an N-alkyl-N'^arylformamidine (III) with an N-substituted sulfonamide-N-sulfenyl chloride (IV) in an inert solvent, such as benzene, tetrahydrofuran, methylene ~
. chloride, or carbon tetrachlorideJ in the presence of an acid ~:
acceptor such as a tertiary amine. The reaction which occurs is illustrated by the schematlc formula:
'; ~.
~0 ;`
. , . R

R~ ~ N =t- N- H + tl -5- N -50~- R~
: .

~III) ~IV) . .
.':
.~ 5 '., , ,- ~ . ', 5~;

/ R

R2 ~-~=C--N--S--N--S02--R4 + HCl , ' : '' ( 1 ) ' .
,.,: ~ ~ " ' ' .~ .

;,, ~"~
whereln Rl ~ R2 ~ R3 ~ and R4 are as described above.
The above illustrated reaction i9 advanta~eously carried , out in the presence of an inert organic solvent~ An inert organic solvent is defined herein as a solvent for the for-~ . .
mamidine reactant ~111) which does not enter into reaction ; with the reaction mixture components or in any way alter the desired course of the reaction. Illustrative of inert organic solvents are tetrahydrofuran, benzene, diethylether! and ~^~ 10 methylene chloride. Preferred as the inert organic solvent ~.., is methylene chloride.
~;;
' .'``~ ' .~
~' .,.: ~, ; cg/

.

G5 Ei The proportion of solvent employed is not critical, but advantageously is a sufficient quantity to solubilize the re-actant formamidine (111).
During the course of the above illustrated reaction, hy- -drochloric acid is generated as a by-product. Preferably this -~
acid lS removed from the reaction mixture as it forms. This may be accomplished by conventional and known methods, for example by adding an acid acceptor compound to the reaction mlxture. Exampies of acid acceptor compounds are the terti-ary amines such as trimethylamine, triethylamine, tripropyl-amine, tributylamine, pyridine and the like. -Although the above reaction may be carried out over a broad range of temperature conditions, i.e., from about -30 C. to about reflux temperature for the reaction mixture, it is preferably carried out at about 0 to 20 C.
Progress of the above reactlon may be followed by con-ventional analytical methods, such as for example by nuclear magnetic resonance analysis which will show spectral char-acteristics of the product compounds (1) or by thin-layer chromatography which will show the appearance of product compounds. Upon completion, the desired compounds (1) are readily separated from the reaction mixture by conventional methods such as by filtration to remove solid residues, distilla-tion to remove solvents, and recrystalli7ation or silica gel chromatography.
Sulfonamide-N-sulfenyl chlorides (lV) are known in the literature and can be prepared by chlorination of an N,N'-dithiobissulfonamide, German Patent 1,101,~07 issued September 28, 1961, or by reaction of an N-substituted sulfonamide with sulfur dichloride in the presence of a tertiary amine, German Patent 1,156,403 issued October 31, 1963, N/N'-dithiobissul-,~, .

cg/
. .~ .
' ~ ' :: . '', ' ~^
6~6 fonamides can be generated by reacting an N-substituted sul-fonamide with sulfur monochloride in the presence of a terti-ary amine.
N-Alkyl-N ' -arylformamidines tlll) are also known in the literature and may be prepared by methods described in Belgium Patent 770,825 issued February 2, 1972, in U.S. Patent 3,72~,565 issued April 24, 1973, and in U.S. Patent ~,8~7,619 issued June 3, 1975.
The following examples describe the manner and process of making and using the invention and set forth the best mode contemplated by the inventor o~ carrying out the invention but are not to be construed as limiting.
All temperatures are in degrees centigrade.
Ambient temperature is in the range 20 to 25.
SSB refers to Skellysolve E'', anisomeric mixture of hex-anes.
NMR refers to nuclear magnetic resonance.
` Example 1 N-[[[N-(4-chloro-o-tolyl)- formimidoyl]methyl- -amino]thio]-N-methyl-p-toluenesulfonamide -~
; 20 To a stirred solution cooled to ~10 of 18,5 g. (0.1 mole) - of N-methyl-p-toluenesulfonamide and 10.1 g. (0.1 mole) of tri ethylamine in ~00 ml. of methylene chloride is added dropwise ` 10.3 g. (0.1 mole) sulfur dichloride. The reaction mixture ~ is stirred at ambient temperature for 0.5 hour and cooled ,~ to 10. A solution of 18.3 g. (0.1 mole) of N-methyl-N'-(4-chloro-o-tolyl)formamidine and 10.1 g. (0.1 mole) triethyl-~ amine in 100 ml. of methylene chloride is aaded rapidly with `~ stirring. The reaction mixture is stirred at ambient tem-perature for 0.5 hour and extracted successively with 300 ml.
' 30 of water, 300 ml. aqueous citric acid solution containing : ..
...
. ~.
'``

. ~:

~ ~ cg/
. - .

5 ~ 3359 10.5 9. ~0.05 mole) of citric acid~ and 300 ml. of water.
The organic layer is dried and the solvent removed under reduced pressure. The residue is chromatographed over 100 9 silica gel using Hexane:EtzO:Et3N (18:2:3 by volumej to obtain 3.2 9. (8% yield) of N-[~[N-(4-chloro-o-tolyl)-for-mimidoyl]methylamino]thio]-N-methyl-p-toluenesulfonamide as a viscous oil.
Analysis: Calc'd for Cl7H20ClN90zS2 C, 51.31; H, 5.07; N, 10.56.
Found: C, 51 36; H, 5.23; N, 10.72.
NMR (CDCl3-tetramethylsilane) 7.~5, 7.3j ~.4, 3.25, 2.35, 2.2~.
ExamPle 2 N-[[[N-~4-chloro-o-tolyl)formimidoyl]-methyl-amino]thio]-N-isopropyl-p-toluenesulfonamide To 19.5 g. (0.04 mole) of N,N'-dithiobis[N-isopropyl-p-toluenesulfonamide] In 200 ml. of benzene is added dropwise 5.4 9. ~0.04 mole) sulfuryl chloride in 10 ml. of benzene.
The reaction mixture is heated at reflux for 1.5 hours un-til evolutton of gas ceases, purged w7th n-itrogen, and cooled to 10 . A solution of 14.~ 9. (o.o8 mole) of N-methyl-N'-(4-chloro-o-tolyl) formamTd!ne and 8.o8 9. (o.o8 mole) of trl-ethylamine in 100 ml. of benzene is added rapldly. The mix-ture is stirred 15 minutes at ambient temperature and ex-tracted consecuti~ely with 500 ml. water, 400 ml. aqueous citric acid solution containing 8 9. citric acidJ and 500 : . . . .
` ml water. The organic layer is drled and the solvent re-moved. The product is recrystallized from SSB to give 23.7 9.
(~8~ yield) of N-~[~N-(4-chloro-o-tolyl)formlmidoyl]-methyl-; aminoJthioJ-N-isopropyl-p-toluenesulfonamide as white crys-tals~ melting point (m.p.) 99.5-100.5.

:: _.9~
.

. .

65~ 3359 Analysis: Calc'd for C1~H24ClN302S2 C, 53.57; H, 5.68i N, 9.86.
Found: C, 53.97; H, 5.83; N, 9.80.
ExamP!e ~ N~ N-2,4-xylylformimidoyl]-methylamino]thio]-N-isopropyl-p-toluenesulf,onamide To a stirred solution cooled to -20 of 10.6 9. (0.05 mole) of N-isopropyl-p-toluenesulfonamide and 5.05 9. ~0,05 molej of triethylamine in 150 ml. of methylene chloride is added dropwise 3.4 g. (0.025 mole) of sulfur monochloride.
The reaction mixture is stirred at ambient temperature for one hour, A solution of 1.77 9. (0.025 mole) of chlorine in ; 50 ml. carbon tetrachloride is added rapidly and the reaction mixture stirred for 0.5 hour. 'The reaction mixture is cooled to 10 and a solution of 8.1 9. (0.05 mole) of N-methyl-N'-2,4-xylylformamidine and 5.05 9. (0.05 mole) of triethylamine in 75 ml, methylene chloride is added. The mixture is stirred at , ambient temperature for ~.5 hour and extracted with a solution of 10 9. citric acld in~200 ml. of water. The organic layer ,, is dried and the solvent removed. The product is recrystal-~" ~0 lized from ssa to give 11.5 9. (57~ yield) of N-L~N~2,4-xylylformlmidoyl]methylanllno]thio]-N-isopropyl-p-toluene-~ sulfonamide as white crystals, mp. 96-97.
,~; AnalYsfs~Calc'd for C20H27N 9252 s, C, 59.23; H, 6.71; N, 10.36.
, 25 Found: C, 59.07; H, 6.51; N, 10.45.
.:
` Exam,~le 4 N-~[tN-(4-chloro-o-tolyl)-formimidoyl]methyl-aminoJthlo]-N-methylmethanesulfonamlde ~................. .
Following the procedure of Example 1, but substitutlng N-methylmethanesulfonamide for N-methyl-p-toluenesulfonamide, the product Is prepared and recrystallized from ether to ob-"

~ S ~ 3359 tain 5.3 9. (16% yield) of N-[IlN-~4-chloro-o-tolyl)-form-imidoyl]methylamino]thio]-N-methylmethanesulfonam-tde as white ~
crystals, mp. 83-84. -Analysis: Calc'd for C~1H~GClNs02S2 C, 41.05; H, 5.01; N, 13.06.
Found: C, 41.07; H, 5.15; N, 1~.01. ~ :
Example 5 N~[[[N-(4-chloro-o-tolyl)-formimidoyl]me~hyl-amino]thi~]-N-isopropylmethanesulfonamide Following the procedure of Example 1, but substituting N-lsopropylmethanesulfonamide for N-methyl-p-toluenesulfon-, amide, the product is prepared. The residue is chromato-graphed over 800 9. silica gel using 19:1 benzene:ethyl acetate and recrystallized from isopropanol to obtain 5.5 9. (16% yield) of N-~[N-(4-chloro-o-tolyl)-formimidoyl]methylamino~thio]-N-isopropylmethanesulfonamide as white crystals, mp. 55-56 .
AnalYsis: Calc'd for C19HzoClN9025B
. C, 44.63; H, 5.7~; N, 12.00.
Found: C, 44.15; H, ~.01; N, 11.58.
ExamPle ~ N-[[[N-(4-chloro-o-tolyl)-formimidoy!]methylamino]-thio]-N-benzylmethanesulfonamide Following the procedure of Example 1, but substituting N-benzylmethanesulfonamide for N-methyl-p-toluenesulfonamide, the product is prepared. The product is recrystallized once from isopropanol followed by two recrystallizations from ether to obtaln 3.2 9. ~16~ yield) of N-[[[N-(4-chloro-o-tolyl)-~i~ formimtdoyl]methylamino]thio]-N-benzylmethanesùlfonamide as white crystalsl mp. 94-95.
Analysis: Calc'd for C~7H20ClNg02S2 .
C, 51.31; H, 5.07; N, 10.56.
Found: Cl 51.~4; H, 5.07; N, 10.63.
.

.. . .

.'''' .

: -:
~ 6~ ~ 3359 ExamPle 7 N-~[N-(4-chloro-o-tolyl)formimidoyl]methylamino~-thio]-N-isopropylbenzenesulfonamide Following the procedure of Example 1, but substituting N-isopropylbenzenesulfonamide for N-methyl-p-toluenesulfonamide, the product is prepared. The product is recrystallized from ;sopropanol to obtain 18.~ g. (44~ yield) of N-[~N-(4-chloro-o-tolyl)formimidoyl]methylamino~thio]-N-isopropylbenzene fonamide as white crystals, mp. 104-105 .
AnalYsis: Calc'd for C18H22ClN30252 C, 52.48; H, 5.38. N, 10.20.
Found: C, 52.72; Hr 5.51; N, 10.03.
ExamPle 8 N-[[[N-(4-chloro-o-tolyl)-formimidoyl]met~hylamino]-thio]-N-phenylmethanesulfonamide Following the procedure of Example 2, but substituting N,N'-dTthlobis[N-phenylmethanesulfonamide] for N,N'-dithiobis-[N-isopropyl-p-toluenesulfo~amide~, the product is prepared.
The product is recrystallized from isopropanol to obtain 5.0 9.
.
~ (16% yield) of N-[~[N-(4-chloro-o-tolyl)-formimidoyl]methyl-; amino]thio]-N-phenylmethanesulfonamide as white crystals, mp.
., o 120-121 .
AnalYsis; Calc'd for CI~HleClN~02S2 C, 50.06; H, 4 .72; N, 10.95.
Found: C, 50.01; H, 4.76; N, 10.64 ~`~ ExamPle 9 N-[[[N-(4-chloro-o-tolyl)-formim;doyl]methylamino~-thio]-N-cyclohexyimethanesulfonamlde Following the procedure of Example 2, but substituttng N,N'-dlthiobis~N-cyclohexylmethanesulfonamlde] for N,N'-dithio-bls~ lsopropyl-p-toluenesulfonamlde], the product Is prepared.
The product is recrystallized once from isopropanol and twice from ethyl acetate to obtain 1~.1 g. (20~ yield) of N-~[N-:.
:. ' ~ q6~ ~ 3359 (4-chloro-o-tolyl)-formimidoyl]methylamino]thio]-N-cyclohexyl-methanésulfonamide as white crystals, mp 1~5-127 .
AnalYsis: Calc'd for C~Hz4ClN902S2 C, 49.28; H, 6.20; N, 10.78.
Found: C, 49.22; H, 6.16; N, 10.77.
ExamPle 10 N-[[[N-(4-chloro-o-tolyl)formimidoyl]methylamine]-'thio]-N-isopropylbenzylsulfonamide Following the procedure of Example 2, but substituting N,N'-dithiobts[N-isopropylbenzylsulfonamide] for N,N'-dithio-bis[N-isopropyl-p-toluenesulfonamtde], the product is pre-pared. The product is recrystallized from ether to obtain 21.4 9. (51% yield) of N-~[N-(4-chioro-o-tolyl)formimidoyl]
methylamine]thio]-N-isopropylbenzyisulfonamide as white crys-tals, mp. 117-118 . ' AnalYsis: Cal'c'd for Cl~H2~ClN902S?
C, 53.57; H, 5.68; N, 9.86.
- Found: C, 53.75; H, 5.7~; N, 9.79.
ExamPle 11 N-[[[N-(4-chloro-o-tolyl)formimidoyl]methylam;no]-~ thio]-N-ethyi-p-toluenesulfonamide '~ ~o Following the procedure of Example 2, but substituting N,N~-dithiobis[N-ethy!-p-toluenesulfonamide] for NJN'-dithio-bis[N-isopropyl-p-toluenesulfonamide], the product is prepared.
~;' The product is recrystalllzed from isoproiianol to obtain 20.9 9 .. . .
~ (63% yield) of N-[[[N-(4-chloro-o-tolyl)formimidoyl]methyl- ~
.
amino]thio]-N-ethyl-p-toluenesulfonamide as white crystals, -' mp. 98-99 .
nalYsis: C~lc'd for C1 eH22C 1 N 92S2 C, 52.48; H, 5.38i N, 10.20.
' C~ 52.38; H, 5.44; N, 10.28.
ExamPle 12 N-[[[N-(4-chloro-o-tolyl)formimidoyl]methyl-' ~ ' . ; .
., .

... .
~, ,, ;. .

~ 3359 amino3thio~-N-t-butyl-p~toluenesulfonamide Following the procedure of Example 2, but substituting N,N'-dithiob'is[N-t-butyl-p-toluenesulfonamide] for N,N'-dithio;
bis~N-isopropyl-p~toluenesulfonamide], the product is prepared.
The product is recrystallized from isopropanol to obtain 33.6 9.
(76.4% yield) of N-~[[N-(4-chloro-o-tolyl)formimidoyl]methyl-amino]thio]-N-t-butyl-p-toluenesulfonamide as white crystals, mp. 85-86.
AnalYsis: Calc~d ~or c20H2~ClN302 S2 C, 54.59; H, 5 96; N, 9.55 Found: C, 54.47; H, 5.94; N, 9.58.
.ExamPle 13 N-[~[N-(4-chloro-o-tolyl)formimidoylJmethyl- .
amino]thio]-N-isopropy!-p-chlorophenylsulfon-amide Following the procedure of Example 2, but substituting N,N'-dithiobis[N~isopropyl-p-chlorophenylsulfonamide] for N,N'-dithiobis[N-isopropyl-p-toluenesulfonamide] and chlorine for sulfuryl chloride, the product is prepared. The product is recrystallized from SSB to give 11.5:9. ~64~ yield) of N-[~[N-~4-chloro-o-tolyl)formimidoyl]methylamino]thio3-N-iso-propyl-p-ch10rophenylsulfonamide as white crystals, mp.
80-81.5 .
AnalYsis: Calc'd for C1~H21Cl2N30zS2 C, 48.43; H, 4.74; N, 9.41.
. . .
Found: C, 48.51; H, 4.68; N, 9.52.
'~ Example 14 N~ N-2,4-xylylformimtdoyl]methylamino]thio]-N-cyclohexylmethanesulfonamTde Followlng the procedure for Example 2, but substituting ' NjN'-dithiobis[N-cyclohexylmethanesulfonamide] for N,N'-'' 30 dlthtobis~N-isopropyl-p-toluenesulfonamide], chlorine for .. . .

:' . ' , , .

SÇi 3359 sulfuryl chloride, and N-methyl-N'-2,4-xylylformamtdine for N^methyl-N'-(4-chloro-o-tolyl)formamidine, the product is pre-pared. The product is recrystallized from SSB containing a small amount of benzene to give 13.2 9. (45~ yield) of N-[[[N-2,4-xylylformimidoyl]methylamino]thio]-N-cyclohexylmethane-sulfonamide as white crystals, mp. 84-86 .
AnalYsis: Calc'd for Cl7H27N902S2 C, 55.23; H, 7.37; N, 11.~7.
Found: C, 54.95; H, 7.25; N, 11.~0.
ExamPle 15 N-[[[N-2,4-xylylformimidoyl]methylamino]thio]-N-phenylmethanesulfonamide Following the procedure for Example 2, but substituting N,N'-dithiobis~N-phenylmethanesulfonamide] for N,N'-dithiobis-[N-isopropyl-p-toluenesulfonamide], chlorine for sulfuryl chloride, and N-methyl-N'-2,4-xylylformamidine for N-methyl-N'-~4-~hloro-o-tolyl) formamidine, the product is prepared.
. The product is recrystallized from ethyl acetate to give 2.0 9. ~14~ yield) of N-~N-2,4-xylylformimidoyl~methyl-amino3thio3-N-phenylmethanesulfonamide as white crystals, ~ 20 mp. 120-121.5 .
- AnalYsis: Calc'd for C~H2~N302S2 C, 5~.17; H, 5.82; N, 11.56.
Found: C, 5~.06; H, 5.82; N, 11.40.
ExamPle 16 N-[[~N-2,4-xylylformimidoyl}methylamino]thio]-N-isopropylbenzylsulfonamide Following the procedure of Example 2, but substituting N,N'-dlthl~blsEN-lsopropylbenzylsulfonamide] for N,NI-diehio-bis[N-lsopropyl-p-toluenesulfonamlde], chlorlne for sulfuryl chloride, and N-methyl-N'-2,4-xylylformamldlne for N-methyl-~0 N'-(2-chloro-o-tolyl)formamidine, the product is prepared.

,, .
.~ ., .
` -15 -,.. -; . .
, , .

~ 5 ~ 3359 The product is recrystallized from SSB to give 9.0 g. (56%
yield) of N-[~[N-2,4-xylylformimidoyl]methylamino]thio]-N-isopropylbenzylsulfonamide as white crystals, mp. 82-83.5.
AnalYsls: Calc'd for C20H27N902S2 C, 59.23; H, 6 71; N, 10.76. .
Found: C, 59.34; H, ~.56; N, 10.51.
ExamPle 17 N-~[[N-2,4-xylylformimidoyl]methylamino]thio~-N-isopropyl-p-chlorophenyisulfonamide Following the procedure of Example 2, but substituting N,N'-dithiobis[N-isopropyl-p-chlorophenylsulfonamide] for N,N'-`
dithiobis[N-isopropyl-p-to.luenesulfonamide], chlorlne for sul-furyl chlorlde, and N-methyl-N'-2,4-xylyiformamidi~e for N-me.thyl-N'-(2-chloro-o-tolyl)formamidine, the product is ob-tained. The product is recrystallized from SSB to give 10.0 9. (59% yield) of N-~[N-2,4-xylylformimidoyl]methylamino]-thio]-N-isopropyl-p-chlorophenylsulfonamide as white crystals, mp. 93.5-95 AnalYsis: Calc'd for CI~H24CIN902S2 Cj 53.57; H, 5.68; N, 9.86.
; 20 Found: C, 53.43; H, 5.53; N, 10.01.
ExamP-le 18 N-~[tN-2,4-xylylform7midoyl]methylamino~thio~-N-p-chiorophenyl-p-toluenesulfonamide Followlng the procedure of Example 2, but substitutTng .~ N,N'-dithiobTs[N-p-chlorophenyl-p-toluenesulfonamide] for N,N'-2S dithlobis~N-isopropyl-p-toluenesulfonamide]~chlorine for sulfuryl chlorlde, and N-methyl-NI-2,4-xylylformamidine for N-methyl-NI-(4-chloro-o-tolyl)formamidine, the product is obtained. ~he pro-duct is recrystall7zed from a mTxture of SSB and cyclohexane to glve 5.5 9. (29% yield) of N-[~[N-2,4-xylylformimidoyl~methyl-amlno]thio]-N-p-chlorophenyl-p-toluenesulfonamtde as white ., ~16-., . . ~ . , . ~ :
.

. ~ . . . . . . . .

crystals, mp 86-87 ~ :
An~ysis: Calc'd for C2~H24CIN302S2 C, 58.28; H, 5.10, N, 8.86.
Found: C, 58.01; H, 5.19; N, 8.78.
ExamPle 19 N-[[[N-(4-chloro-o-tolyl)form-imidoyl]methylamino]-thio]-N-p-chloro~henyl-p-toluenes~lfonamide.
Following the procedu.re of Example 2, but substitt~ting N,N'-dithiobis~N-p-chlorophenyl-p-toluenesulfonamide] for N,N'-dithiobisEN-isopropyl-p-toluenesulfonamide~ and chlorine for sulfuryi chloride, the product is obtained. The product is re-crystallized from a mixture of ether and Skellysolve F ~ fol-lowed by two recrystallizations from cyclohexane to give 1.0 9.
(10~ yield) of N-[[~N-(4-chloro-o-tolyl)formimidoyl]me.thylamino]-thio]-N-p-chlorophenyl-p-toluenesulfonamTde as white crystals, mp. 103-104.
AnalYsis: Calc'd for C2zH2~Cl2N902S2 C, 53.44; H, 4.28; N, 8.50.
-~. Found: C, 53.48; H, 4.22; N, 8.og.
~ ExamPle 20 N-[[~N-(4-chloro-o-tolyl)formimidoyl~methylamTno]-.: ~ 20 thTo]-N-benzyl-p-toluenes~lfonamTde ;~ FolloWTng the procedure of Example 2, but substTtuting " .
N,N'-dlthTobTs~N-benzyl-p-toluenesulfonamide] for N,N'-dithTo-: bis[N-isopropyl-p-toluenesulfonamide] and chlorine for sulfuryl ~ chlortde, 8-8 9. (93~ yield) of N-~[[N-(4-chloro-o-tolyl)formimi-:~ 25 doyl]methylamino]~hio]-N-benzyl-p-toluenesulf~namlde is obtained as an oil.
: Analysls: Calc'd for C23H~ClN908S~
. . -. . C, ;8.28; H, 5.10; N. 8.86.
. Found: C, ~8.o5; H, 5.17; N, 8.81.
`;~ 3 N~R (CDCl9 - tetramethylsllane] 7.85, 7.25, 4.63, 3.1, ,. . .
;,. .
".; ~ , ., , , ' .

2.4, 2.18~.
ExamPle 21 N~ N-(4-chloro-o-tolyl)formimidoyl]~e.thylamino]-thio]-N-2,4-dichlorophenyl-p-toluenesulfonamide Following the proceduré of Exampie 2, but substituting N,N'~dithiobis[N-2,4-dichlorophenyl-p-toluenesulfonamide] for N,N'-dithiobi5[N-isopropyl-p-to!uenesulfonamide] and chlorine for sulfuryl chloride, the product is obtained. The residue .is triturated with methanol and recrystallized from a mixture ' of SSB and isopropanol to give 0.6 9. (5.7~ yield) of N-t[~N-(4-chloro-o-tolyl)formimidoyl]methylamino]thio]-N-2,4-dichlorophenyl-p-toluenesulfonamide as white crystals, mp.
97-98 .
Analysis: Calc'd for C22H20Cl9N302Sz C, 49.96; H, 3.81; N, 7.96 Found: C, 50.11; H, 3.73; N, 7.97.
ExamPle 22 N-[~[N-(4-chloro-o-tolyl)formimidoyl3methylamino]-. thio]-N-phenyi-p-toluenesulfonamide ~ Following the procedure of Example 2, but substituting : N,N'-dithiobis~N-phenyl-p-toluenesulfonamide] for N,N'-dithio-:: 20 bis~N-isopropyl-p-toluenesulfonamide] and chlorine for sul-'~ - .furyl chloride, the product is obtalned. The product is re-. crystallized from SSB to give 3.2 g. (40~ yield) of N-~E~N-(4-: chloro-o-tolyl)formimidoyl~methylamino]thio~-N-phenyl-p-tolu-"~: enesulfonamide as white crystalsJ mp. 95-96 .
. ~ 25 AnalYsis: Calc'd for C22H22ClN30eS8 '.~ C, 57.44; H, 4.8?; N, 9~13.
' Found: C. 5'7.79; H, 4.79; N. 9.17.
' ExamPle 23 N-[[[N-2,4-xylylformTmidoyl'JmethylaminoJthTo]-'. N-methylmethanesulfonamide FollowTng the procedure of Example 3, but substituting -18- .
.
.'; ' :

~ 3359 N-methylmethanesulfonamide for N-isopropyl-p-toluenesulfon-amide, the product is obtained. The product is recrystallized from SSB followed by recrystallization from isopropanol to give 8.o 9. (27% yield) of N-[[[N-2,4-xylylformimidoyl]methyl-amino]thio]-N-methylmethanesulfonamide as white crystals, mp.
63-64 .
Ana!Ysis: Calc'd for Cl2H19N30252 C, 47.82; H, 6 35; N, 13.94.
Found: C, 47.85; H, 6.53; N, 14.20.
ExomPle 24 N-[[~N-2,4-dTchlorophenylformimidoyl]methylamino]-thio]-N-isopropyl-p-toluenesulfonamide Following the procedure of Example 3, but substituting N-methyl-N'-2,4-d;chlorophenylformamidine for N-methyl-N'-2,4-xylylformamidine, the product Ts obtained. The product is re-crystallTzed from methanol to gtve 11.. 0 9. (49~ yield) of N-[~-` N-2,4-dichlorophenylformimidoyl]methylamino]thTo]-N-lsopropyl-p-toluenesulfonamide as white crystals, mp. 79-81 .
AnalYsis: Calc'd for CleH21Cl2N302Sz ` C, 48.43; H, 4.74; N, 9.41.: 20 Found: C, 48.~ ; H, 4.80 ; N, 9.55.
`; E~cple 25 N-[[~N-(2-chloro-p-tolyi)-formimldoyl]me~hylamino]-thio]-N-isopropyl-p-toluenesulfonamide Following the procedure of Example 3, but substituting N-methyl-N'-(2-chloro-p-tolyl)formamidine for N-methyl-NI-2,4-i~ 25 xylylformamidine, the product is obtained. The product is re-crystallized from methanol to give 8.o 9. (47% yield) of N-[~[N-(2-chloro-p-tolyl)formimidoyl]methylamino]thio]-N-isopropyl-` p-toluenesulfonamide as white crystals, mp. 101-103 .
`~ Analvsis: Calc'd for Cl~H24ClNgO2S2 ~0 C, 53.57; H, 5 68; N, 9.86.

~.. '` .
,. -19 -'.:
, ~ ~
.. . .

. 3359 ~ 5 ~

Found: C, 53.60; H, 5.71; N, 9.94.
ExamPle 2~
Following the procedure of Example 3, but substituttng N-methyl-N'-(4-chloro-o-tolyl)formamidine for N-methyl-N'-2J4-xylylformamidine and the appropriate N-substituted sul-fonamide (V) , IR5 H -N - SO2 -R'4 (V ) .

wherein R9 and R4 are as defined in Table 1 for N-isopropyl-p-toluenesuifonamide,the corresponding product of this in-vention (Vl) is obtained , ~ H CH3 R3 I Cl ~ N = C- N- S- N - S02 - R~
.
; .
(V l ) ; ' ~
'; .
~''' ' .

~. .
.

., , , 5 ~ 3359 wherein R3 and R4 are defined in Table 1.

. . .

5 Rg R4 1. methyl phenyl 2. ethyl methyl phenyl 3. ethyl methyl

4. n-propyl phenyl - 10 5. n-propyl p-tolyl 6. n-propyl 7. n-butyl methyl 8. n-butyl phenyl.
9. n-butyl p-tolyl 10. t-butyl phenyl ;~ 11. benzyl . phenyl ; 12. cyclohexyl ~ phenyl 13. cyclohexyl p-tolyl 14. phenyl phenyl 15. p-chlorophenyl methyl . phenethyl p-tolyl ' 17. e-nTtrophenyl methyl ; . 18. p-tr;f1uoromethylphenyl methyl g. p-methoxyphenyl methyl 20. p~cyanophenyl methyl ExamPle 27 ., ~
~ Following the procedure of Example 3, but substituting ., ~ .
the àpproprlate N-substituted sulfonamide (V) whereln R3 and R~
are as defined in Table 2 for N-isopropyl-p-toluenesulfonamide ~ 3 the corresponding product of thls invention (Vll) is obtained ,;.

., ... .
! . .
t~ -21- .
.r .
" .
:~ . .' ' ' ' , : :
, , : . ' , . ' '

5 6 . 3359 ~ H CH3 R3 CH ~ -N - C -N -S- N -S02- R4 , (V I I ) wherein R3 and R4 are as defined in Table 2.

' ' ' ' , ' .

B;~. B.~
1. methyl p-tolyi 2. methyl benzyl 3. ethyl methyl 4. ethyl phenyl . ethyl p-tolyl ~, n-propyl methyl ~ 7. n-propyl ~henyl ~.
-~ 8. n-propyl p-tolyl :
i, . .
c ~ 9, isopropyl methyl : 10 . I sopropy 1 phenyl 11. benzyl methyl : 12. benzyl . p-tolyl :~
13. cyclohexyl phenyi 14. cyclohexyl p-tolyl 15. phenyl p-tolyl 3 1~. phenethyl p-tolyl .. . .
~:

.

~359 5 ~

17. isopropyl phenethyl 18. methyl benzyl 19. methyl p-chlorophenyl 20. methyl p-nitrophenyl 21. methyl p-trifluoromethylphenyl 22. methyl p-methoxyphenyl 23. methyl p-cyanophenyl ExamPle 28 Following the procedure of Example 3, but substituting N-meth.yl-NI-(4-bromo-o-tolyl)formamidine for N-methyl-N'-2,4-xylylformamidine and the appropriate N-substituted sulfonamide : . (V) wherein R3 and R4 are ~as defined in Table ~ for N-isopropyl-p-toluenesulfo'namide, the corresponding product of this inven-, t70n'(VIII) is obtained ., 15 ' ,. . . .

; ~ .
' CH9 .: 20 ~ , ~ H fH9 l3 Br ~ ~ N= C-- N- S- N - S02 - R4 (V l l l ) ~: 25 ..

. ~.;
. ,:
,~ , .
" whereln R9 and R4 are as defined Tn Table 3.
,.,', 30 .'"" ' ' ' . .

, ~59 .

R3 . R4 1. methyl methyl 2. methyl p-tolyl 3. phenyl methyl 4. cyclohexyl methyl 5. i~opropyl . benzyl

6. isopropyl p-toiyl

7. phenyl p-tolyl

8. methyl phenyl ~ ExamPl_29 : Following the procedure of Example 3, but substituting N-methyl-N'-(4-chloro-2-ethylphenyl)formamidine for N-methyl-Nt-2,4-xylyiformamidtne and the appropriate N-substit~ted sul-fonamide (V) wherein R3 and R4 are as defined in Table 4 for N~isopropyl-p-toluenesulfonamideJ the corresponding product .
:~ of thls inventi,on (lX) is obtained . .
... .
~ .
~ CH2-CH3 : :-; : . ~ H CH3 Rl~ .
Cl ~ N= C-N- S- N- S02 -R4 ~.
.
: ~ 25 .~ . (IX) : :

wher~in R9 and R~ are as deflned tn Tabie 4.
., .

' R9 R~
1. methyl methyl 5 2. methyl p-tolyl . cyclohexyl methyl 4. phenyl, p-tolyl ExamPle ~0 Following the procedure of Example 3, but substituting ' N-methyl-N'-(2,4-dichlorophenyl)formamidine for N-methyl-N'- , ` : 2~4-xy!ylforma!nidine and the appropriate N-substituted sulfon-amide (V) wherein R3 and R4 are as defined in Table 5 f'or N-~' isopropyl-p-toluenesu!fonamide, the corresponding product of this invention (X) is obtained.
'' ' ,;: .
.
.. ' ' C l ~; 2 ~ N = ~ -N- S- N - 52 - R~

(X) .,. ~ , .
'' ~
~. 25 wherein R9 and'R4 are as deftned in Table 5.

~ . ~
~ TABLE 5 ,~ R~ ' R4 1. methyl methyl `' 30 2. methyl . phenyl :;!i ,: 25 65 ~

. methyl p-tolyl 4. ethyl phenyl ::
5. ethyl p-tolyl 6. isopropyl methyl 7. isopropyl phenyl 8. isopropyl p-tolyl

9. benzyl methyl

10. benzyl phenyl : :

11. benzyl p-tolyl :~:
, 12. cyclohexyl methyl 13. cyclohexyl phenyl . 14. cyclohexyl p-tolyl 15. pheny ! methyl 16. phenyl phenyl 17. phenyl p-tolyl . 18. isopropyl benzyl 19. isopropyt phenethyl 20. p-chlorophenyl . methyl 21. phenethyl p-tolyl ~ 20 22. p-nitrophenyl methyl ;~ 23. p-trifluoromethylphenyl methyl 24. p-methoxyphenyl methyl ~ ~ : . 25. p-cyanophenyl methyl : ~ 26. methyl benzyl 27. methyl ,p-chlorophenyl 28. methyl p-nitrophen 29. methyl p-trlfluoromethylphen ;- 30. methyl p-methoxyphenyl 31. methyl p-cyanophenyl . . .

:

~, . , . 335~ -~ 6 - ExamPle 31 Following the procedure of Example 3, but substituting N-methyl-N'-(2-chloro-p-tolyl)formamidine for N-methyl-N'-2,4-xylylformamidine and the appropriate N-substituted sulfonamide (V) wherein R3 and R~ are as defined in Table 6 for N-isopropyl-p-toluenesulfonamide, the corresponding pr.oduct of this in-vention (Xl) is obtained Cl -~ H CH9 ~9 CH9 ~ N= C- N- S- N -S02- R4 (Xl) ;;
... .

.
~ 20 ;`~ wherein R9 and R4 are def!ned in Table 6, ,, .
- ' TABLE 6 ~ R~ R4 :` 25 . 1. methyl .methyl . 2. methyl phenyl 3. methyl . p-tolyl 4. ethyl phenyl 5. ethyl p-tolyl ~' .
- : ' ~' 6. isopropyl methyl 7. isopropyl phenyl 8. isopropyl p-tolyl 9, benzyl methyl 10. benzyl phenyl ~:
11. benzyl p-tolyl

12. cyclohexyl methyl . 13. cyclohexyl phenyl 14. cyclohexyl p-tolyl 15. phenyl methyl 16. phenyl pheny1 17. phenyl p-tolyl 18. isopropyl . benzyl 19. isopropyl phenethyl ; 15 20. p-chlorophenyl ~ methyl : 21. phenethy ! p-to 1 y 1 . 22. p-nltrophenyl me~hyl 2~. p-trifluoromethylphenyl methyl 24. p~methoxyphenyl methyl 25. p-cyanophenyl methyl 26. methyl benzyl 27. methyl p-chlorophenyl 28. methyl p-nltrophenyl . ~ . .
~ 29. methyl p-trifluoromethylphenyl ~ : .
25~ 30, methyl p-methoxyphenyl ~1. methyl p-cyanophenyl , .
ExamPle 32 Following the procedure of Example 3, but substituting ~ N-methyl-N'-(2-bromo-p-tolyl)formamidine for N-methyl-N'-2,~-, ' .

. ~ . .
,~

:. . . ~ .

~ 6 3359 x.ylylformamidine and the appropriate N-substituted sulfonan.ide (V) wherein R3 and R4 are as defined in Table 7 for N-isopropyl-p-toluenesulfonamide, the corresponding product of this inven-tion (Xll) is obtained.

B~
~ "
~ H CH3 R9 CH3 ~ N= C -N- S- N - S2 - R4 .. .
(X l l ) ~Iberein R9 an~ R~ are as defined in Table 7.
, .

~- TA8LE 7 ,. ~

R9 R,~
1. m~thyl methyl ,~ 2. metliyl p-tolyl .j 3. phenyl me~hyl . 4. cyclohexyl methyl ~` 25 5 isopropyl benzyl . isopropyl p-tolyl 7. phenyl p-toly B. methyl phenyl ExamP ! e 33 3 Follow;ng the procedure of Example 3, but substltuting .

.. .
.: ' -~ 5 6 N-methyl-N'-(2-chloro-4-ethylphenyl)formamidtne for N-methyl-N'-2,4-xylylformamidine and the appropriate N-substit~uted sul-fonamide (V) wherein R3 and R4 are as defined in Table 8 for N-isopropyl-p-toluenesulfonamide, the corres.ponding product of this invention (Xlll) is obtained.

Cl ~ H fH3 R3 CH9-CH2 ~ N= C-N- S- N- S02 - R4 .
(X I I I ) wherein R3 and R4 are.as de~ined in Tabie 8. . .
`'.~: ' .

~ . . .

1. methyl . methyl 2. methyl p-tolyl : .
.: 3. cyclol-exyl n!ethyl ~ 4. phenyl p-tolyl : 25 ~ ' .
; The compounds of Formula I are particularly advanta-.. ~ geous commercially as arthropodal pesticides. For example, they are relatively stable both in storage and upon applica-tion in the field thus providing long-lasting residual effec-.~ .

-3~
. .

- ' ' .
.'.

1~ 6S~ 3359 tiveness.
In addition to ki lling arthropod pests on conta~t, the compounds of the invention are absorbed by the vascular system ~f many plants, for example by cotton plants, and act systemically to kill the pests feedinq upon th~ plant.
Thus, their period of pesticidal activity is further ex-tended and non-feeding arthropods, e.g., insects not harmful to the plantJare not unnecessar~ly killed dur~ng the whole period-of pesticidal activity.
Compounds of the invention are also ovicidal, and are particularly effective in the control of acarine pest popu-lations~by this ovicidal action. Lepidopterous ova are also particularly susceptible to the compounds of the invention.
~he compounds o~.the Formula l are also advantageous in thdt they exhibit relatively low mammalian tox~city and are non-phytotoxic at e~fective concentrdtions.
The invention also campr;ses compositions for arthropod ~ control which comprise an acceptable carrier and an effective ;~ amount of a compound of the invention. The compositions are useful in the method of the invention which is a process for ~ controlling invertebrate pests, which comprises applying to a - situs, effective amounts of the compounds of the invention.
By the term "situs" is meant plants such as ornamentals, food crops, fruit trees, textile producing plants, berry bushes, and lumber forests; animals, particularly domestic animals; farm yards; animal shelters; buildings; santtary land-fill areas;
ponds and standing water; and like s;tes which are Infected wIth or are potential infestation sites for invertebrate pests con-trollable with the compounds of the invention.
~0 The novel`compounds of the invention are useful in .. .
.' .
... .

.. . .

~ &5 ~ ~359 controlling inverteb~ate pest populations, e.g., in killing adu~s, Iarvae, and ova of invertebrate pests oranimals of the Phylum Arthropoda, for example those of Class Insecta such as those of the order Coleoptera as illustrated by the cotton boll weevil (~nthonomus grandis Boheman)i those of the order Lep~doptera as illustrated by the southern army worm (Spodoptera eri~ania Cramer); those of Class Arachnida such as those o~ the order Acarina as illustrated by the two-spotted spider mite (~etranychus telarius Linnaeus or Tetranychus urticae Kocii).
In addition to controlling pest populations through their lethal effect, the compounds are also useful in control through their effect as behavioral modifiers. For example, young lepidopteran larvae, aphids, ticks, and mites are repelled ; 15 by the chemicals or by treated foliage or animals, resultTng in a marked reduction in population density. Adult moths ;
i are affected and ovipost less on treated plant parts.
In addition to being repelled, mites exhibit spindown and .,. ~ .
walkdown activity from treated fol;age.
~The compounds of this invention may be employed in - their pure forms to control invertebrate pest populations.
However, it is preferred that they be applied to a situs in the form of a composition, comprising the compound and an acceptable diluent or carrier. The concentration of the . i -active compound can range from about 0.001~ to about 96~
w/w dependlng on the type of composition, the solubility of the compound, the pest to be controlled, etc. Accept-;` able carriers or diluents are well known in the art. For example, those compounds which are solids at ambient tem-`30 peratures may~be formulated as granulars, dusts, wettable :.','. ' . -32-,,, ' .

. . , , ~. . , .: .

powders,emulsifiable concentrates, aqueous dispersions, solu-tions, and flowable creams for application to insects, mites, ticks, objects, or other situs. Those compounds which are liquids at ambient temperatures may be formulated as emulsifi-able concentrates, aqueous dispersions, suspensions, solutions, aerosols, dusts, granulars, and the like.
The compounds (I) of the invention may also be admixed with other known pesticides to form compositions of the in-vention. For example~ they may be mixed with malathion, azin-phosmethyl, carbaryl, methoxychlor, and like pesticidal com-pounds.
Illustratively, dusts are readily formulated by grind-ing a mixture of the solid compounds (l~ and a pulverulent carrier in the presence of each other. Grindlng is con-veniently accomplished in a ball mill, a hammer mill, or by air-blast micronization. A preferred ultimate particle size is less than 60 microns. Preferably, 95~ of the particles are less than 50 microns, and about ?54 are 5 to 20 microns. Dusts of that degree o~ comminution are conven-iently free flowing and can be applied to inanimate matter, ~ fruit trees, crop plants, animals, and soil so as to effect - thorough distribution and coverage. Dusts are particularly adapted ~or effectively controliing invertebrate pests such as insects and mites over wide areas when applied by airp1ane. They are also indicated for application to the undersides of piant foliage.
.. . .
Representative pulverulent diluent carriers ~hich are ac-ceptable are the natural clays such as attapulgite, kaolin (e.g., China and Barden), and montmorillonite (e.g., bentonite); min-erals in their natural forms as they are obtained ... .

i~ 6s6 from the earth such as talc, pyrophyllite, quartz, diato~
maceous earth, fuller's earth, chalk, rock phosphates and sul$ates, sulfur, silica and silicates; chemically modified minerals such as washed bentonite, precipitated calcium silicate, synthetic magnesium silicate, and colloidal silica, and organic flours such as wood, walnut shell, soybean, cottonseed, and tobacco flours, and free-flowino hydrophobic starches.
Dusts may also be prepared by dissolving a compound (1) in a volatile solvent such as methylene chloride, mixing the solution with a pulverulent dlluent carrier and evaporating the solvent.
The proportions of pulverulent carrier and compound (1) may be varied over a wide range depending upon the pests to be controlled and the conditions of treatment.
In general, dust formulations contain up to about 50~
(on a weight basis) of the compound (1) as the active ingredient. Dusts having as little as O.uOl~ of the active ingredient may be used, but a generally pre-ferred proportion is from about 1% to about 10% of thecompound.
- Wettable powder formulations are prepared by ; incorporating a surfactant in a dust composition prepared as described above. By incorporating from 0.1% to about 12% of a surfactant in a dust, a wettable powder is obtained which is particularly adapted for further admix-ture with water for spraying on inanimate matter and products, - fruit trees, field crops, animals, and soil. Such wet-. , .
table powders may be admixed with water to obtain any deslred concentration of compound (1) and the mixture may ,:

' cg/
. :

~ iS~

be applied in amounts sufficient to obtain predetermined rates of application and uniform distribution, Preferably wettable powders contain from about 10 percent to about 80 percent by weight of compound (1) as the active in-gredient.
The surfactants employed may be characterized as capable of reducing the surface tension of water to less than about 40 dynes per centimeter in concentrations of about 1% or less.
Representative surfactants conventionally employed for preparing wettable powder formulations include alkyl sulfates and sulfonates, alkyl aryl sulfonates, sulfo- !
succinate esters, polyoxyethylene sulfate, polyoxyethylene-sorbitan monolaurate, alkyl-aryl polyether sulfates, alkyl-aryl polyether alcohols, alkyl naphthalene sulfonates, alkyl quaternary ammonium salts, sulfated fatty acids and esters, sulfated fatty acld amides, glycerol mannitan laurate, polyalkylether condensates of falty acids, and tne like. The preferred class of surfactants for preparing compositions of this invention are blends of sulfonated oils and polyalcohol carboxylic acid esters such as the commercially available Emcol H-77~, blends of polyoxyethylene ethers and oil-soluble sulfonates such as commercially available Emcol H-40 ~, blends of alkyl aryl sulfonates and alkylphenoxy polyethoxy ethanols such as the commercially available Tritons X-151, X-161, and X-171~ e.g. about equal parts of sodium dodecyl~enzene-:
sulfonate and isooctylphenoxy polyethoxy ethanol containingabout 12 ethoxy groups, and blends of calcium alkyl-aryl sulfonates and polyethoxylated vegetable oils such as ,.......................... .
''`

,.:

cg/

commercially available Agrimul N~ ~ The sulfate and sulfonate surfactants discussed above are preferably used in the form of their soluble salts, ror example, tneir sodium salts.
If desired, dispersants such as methyl cellulose, poly- -vinyl alcohol, sodium ligninsulfonates, and the like may be in-cluded in the wettable powder compositions of this invention.
Adhesive or sticking agents such as vegetable oils, naturally occurring gums, casein, and others may also be included. If un-lined storage or shipping drums are to be used a corrosion inhi-bitor may be added. Likewise, anti-foaming agents such as stearic acid may be added.
Granular compositions of this invention are convenient for application to soil when persistence is desired. Such compositions are reaaily applied by broadcast or by local-ized, e.g., in-the-row applications. The individual granules may be any desired size from 30 to 60 mesh up to ; 20 to 40 mesh, or even larger. Granulars are prepared by dissolving the active compound in a solvent such as methylene chloride, xylene, or acetone and applying ~he solution to a quantity of a granulated absorbent carrier. Representative granulated absorbent carriers are ground corn cobs, ground walnut shells, ground peanut hulls, and the li~e. ~hen ; desired, the impregnated granulated absorbent carrier may be coated with a coating that will preserve the integrity of the granular until it is applied to an object or situs . .
favorable for release of the actlve ingredienl. Such coat-ngs are well known in the art.

The compounds (1) of the invention may be applled to the pests themselves or to a situs in aqueous sprays with-r ~, ~ -36-''"' /

~ 5~ 3359 out a solid carrier. Such aqueous sprays are advan~ageous for certain types of spray equi~nent and conditlons of application as is well known in the art. They are also ad~antageous when uniform dispersions, homogeneous solu-tions, or other easily mixed aqueous sprays are desired.
Aqueous sprays without a solid carrier are prepared from concentrated solutions of the compounds (I) of the invention in an inert organic solvent carr;er. The inert organic solvent carrier may be one that is miscible or immlsclble with water. The compounds (I) that are somewhat soluble in water may be dissolved in a water miscible solvent carrier, e.g., ethanol, and mixed with water to 9~ve homogeneous solutions. The compounds (I) that are less soluble in water may be dissolved ln a solvent carrier that is imm~scible with water and the solution dispersed in water to give a uniform dispersion, e.g., an emulsion.
In an oi1-in-water emulsion, the solvent phase is dispersed in the water phase and the dispersed phase con-tains the compound (I~. In this way, uniform distr;bution of a water insoluble compound (I) is achieved in an aqueous spray. A so1vent carrier in which the compounds (I`) are highly so1uble i5 desirable so that relatively high concen-tràtions of the compound (I) can be obtained. One or more solvent carriers with or without a co-solvent may be used in ~5 order to obtain concentrated solutions of the compounds (I), the main consideration being to employ a water-immiscible solvent for the compound (I) that will hold the compound in solution over the range of concentrations useful for applying to invertebrate pests or a situs.
~o The emulsifiable concentrate compositions of the inven-, ~~7~
' , :

~ 3~59 tion are preferred compositions prepared by dissolving the compound (I) as the active ingredient and a surfacta~t such as one of those previous1y described, in a substantially water-immiscible solvent carrier (i.e., a solvent carrier which is soluble in water to the extent of less than 2.5%
by volume at temperatures of the order of 20 C. to 30 C.), for example: sum~er oils (a paraffinic, intermediate distilla-tion fraction having a viscosity range from 40 to 85 seconds Saybolt and an unsulfonatable residue over 90 percent); ethyl-ene dichloride; aromatic hydrocarbons such as benzene, tolu-ene, and xylene; and high-boiling petroleum hydrocarbons such as kerosene, diesel oil, high flash (>38 C.) xylene-range solvent (e.g., Tenneco 500-100 @D ), and the like. When de-sired, a co-solvent such as methyl ethyl ketone, acetone, iso-propanol, and the like may be included with the solvent carrier in order to enhance the solubilTty of the compound (I). Aque-ous emulsions are prepared by mlxing the concentrate with water to give the desTred concentration of compound.
Advantageous1y, the concentration of compound (I) in emulsifiable concentrates will range from about 5 percent to about 50 percent by weight, preferably from about 10 percent to about 40 percent. A concentrate compr~sing 20 percent by weight of the compound ~I) dissolved in a water-immiscible solvent of the kind noted abave may be admixed with an aqueous medium in the proportions of 13 ml. of con-centrate with 1 gal. of medium to give a mixture containing .... .
~; 700 parts of compounds (I) per million parts of liquid carrier. Similarly, 1 qt. of a 20 percent concentrate mixed .. ~ .
:i with 40 gals. of water provides about 1200 ppm (parts per million) of a compound (I). In the same manner, more concen-;, .

i.~ .;
?;
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65 ~ 3359 trated solutions,of active ingredient may be prepared by adj U5 ting upward the proportion of compound (I).
The above described concentrate compositions of the invention which are intended for use in the form of aqueous dispersions or emulsions may a.lso advantageously contain a humectant, i.e., an agent which.will delay the drying of the composition in contact with mdterial to which it has been applied. Conventionally used humectants are exempli-fied by g'lycerol, diethylene g1ycol, solubilized lignins such as calcium ligninsu1fonate, and the like.
For use in an aerosol, the compound (I) may be dissolved in acetone or a mixture of acetone and a heavy petroleum oil and mixed in a thick-wall.ed canister or bomb with a propellant such as methyl chloride or dichlorodifluoromethane .
The compositions contalning compounds (I) of the invention may be app'lied to invertebrate pests or pestiferous sites by con-ventional methods. ~or example, an area of soil~ buildings, ~ animals~ or plants may be treated by spraying emu!sions., or solu-tions from hand-operated knapsack sprayers. Creams and ointment formulations may be applied to a sltus for prolonged protection from insects, mites,and tlcks. As an alternatlve to spraying, an appropriate situs may be treated by dipping; e.g., domestic animals can be walked through a bath of a composition of the invention.
. It will of course be appreciated by those ski!led in the art that the conditi'ons encountered when applying the method and com-~ . positions of this invention to actual practice can vary widely.
; Among the varlables that may be encountered are the degree of in-festation by pests ? the particular pest to be controlled, the specific compound (I) employed, the particular situs being treated, the age or degree of development of plants to be protected, the ~39~

.

, ~ 65 ~ 3359 prevailing weather conditions, such as temperature, relative hu-midity, rainfall, dew and like environmental conditions. Depen-dent upon the variables encountered in a given situation, the amount of compounds (I) to be employed as an effective amount, the frequency of application and the technique of application w~ll be adjusted for optimum effect, as those skilled ~n the art well appreciate.
In generali efficacy of the compounds (I) against inverte-brate pests has been demonstrated at concentrations of 1000, ~00, 100, 50 and even 30 ppm by weight of the novel compounds (I) depending upon the specific pest to be c0ntrolled. Some invertebrate animal pests w~ll be more sensitive to the compounds ~I) than others. Methods o~ testing a given compound (I) to determine the minimum effective concentra-t1cn required for killin~ a specific ~nvertebrate pest are well known; see for example U.S. Patents 3,474,170;
3,476,836; and 3,478,029. In general, effective amounts of the compounds (I) for pesticidal activity is obtained when . the compounds tI~ are applied at concentrations of about 30 to about 6000 ppm, preferably at concentrations of about-100 to about 4000 ppm.
;i~ The following examples illustrate composltions of the ; invention.
Example 34 A wettable powder formulatlon is obtained by blending and milling 327 ibs. of Georgia Clay, 4.5 lbs. of isooctyl-phenoxy ethanol (Triton X-100 ~) as a wetting agent, 9 lbs. of .` a polymerized sodium salt of substituted benzoid long-chain ^' sulfontc acid (Daxad 276~)as a dispersing agent, and 113 lbs.
., .
?r:: ~0 of N-[~[N-(~-chloro-o-tolyl)-formimidoyl]methylamino]thio]-. .
:' .

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~ 5 6 3359 N-isopropyl-p-toluenesulfonamide (Example 2). The resulting formulation has the following percentage composltion (parts herein ar~ by weight unless otherwise specified).
N-~[LN-(4-chloro-o-tolyl)-formimidoyl]methylamino]thio-N-isopro!pyl-p-toluenesulfonamide 25 Isooctylphenoxy polyethoxy ethanol 1 Polymerized sodium salt of sub-stituted benzoid long-chain sulfonic acid 2 Georgia Clay 72~
This formulation, when dispersed in water at the rate of 10 lbs. per 100 gals., gives a spray formulation contain-ing about 0.3~ (~000 ppm) active ingredTent which can be ap-plied to invertebrate pests, plants, or other ;nvertebrate pest habitats or invertebrate pest foods to kill such pests or control them through behavior modification.
Simiiarly, replacing the arylformamidine sulfonamide as used in the above example with an equal proportion of any other compound of the formula (I) as prepared in Examples ~ through 19 and-21 through 33, a pesticidal composition is obtained whlch wiil control Invertebrate pests.
. ~ ExamP l e 3~, 2~ An emulsif7able concentrate having the following per-centage composition:
N-L~[N-4-chloro-o-tolyl)-formimidoyl~-methylamino]thio]-N-methyl-p-toluene-sulfonamide (Example 1) 15.0 High-flash (~38 C.) xylene-range ,: :

:

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~ S~ 3359 solvent (e.g., Tenneco 500-100 ~ ) 80.0 Blend of alky1 aryl sulfonates and alkylphenoxy polyethoxy ethanols (Triton X-151 ~ ) 5 0~ -is obtained by mixing 15.0 pounds of N~ N-(4-chloro-o-tolyl)-formimidoyl~methylamino~thio]-N-methyl-p-toluenesulfonamide (Example 1), 80 pounds of Tenneco 500-100, and 5.0 pounds of Triton X-151.
6.67 Lbs. of the concentrate mixed with 10 gals. of water gives a spray emulsion containing about 11,000 ppm. of active ;ngredient which can be applied to invertebrate pests, plants, or other invertebrate pest habitats or invertebrate pest foods to kill such pests or control them through be-havior modification.
~ 15 Similarly, replacing the arylformamidine sulfonamide ; used in the above example with an equal proportion of the com-; pound prepared in Examples 2 through 33, a pesticidal com ; position is obtained which will control Invertebrate pests.

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Claims (2)

1. The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
   
   A compound of the formula (I) wherein R1 is chloro, bromo, or alkyl of one through four car-bon atoms;
   R2 is hydrogen, chloro, bromo, or alkyl of one through four carbon atoms;
   R3 is (1) alkyl of one through eight carbon atoms, (2) cycloalkyl of five through eight carbon atoms, (3) phenalkyl wherein alkyl is one or two methylene units in length, or (4) phenyl where the phenyl is unsubstituted or substituted with one through three substituents selected from the group consist-ing of methyl, chloro, bromo, nitro, trifluoromethyl, alkoxy of one or two carbon atoms, and cyano; and R4 is (1) alkyl of one through four carbon atoms, (2) phen-alkyl wherein alkyl is one or two methylene units in length and where the phenyl is unsubstituted or substituted with one through three substituents selected from the group consisting of methyl, chloro, bromo, nitro, trifluoromethyl, alkoxy of one or two carbon atoms, and cyano, or (3) phenyl where the phenyl is unsubstituted or substituted with a substituent selected from the group consisting of methyl, chloro and bromo.
   
   A compound according to claim 1 wherein R1 is methyl;
   R2 is selected from the group consisting of methyl, chloro, and bromo;
   R3 is (1) alkyl of one through four carbon atoms, (2) cycloalkyl of five through eight carbon atoms, (3) phenalkyl wherein alkyl is one or two methylene units in length, or (4) phenyl where the phenyl is unsubstituted or substituted with one through three substituents selected from the group con-sisting of methyl, chloro, and bromo; and R4 is (1) alkyl of one through four carbon atoms, (2)phen-alkyl wherein alkyl is one or two methylene units in length and where the phenyl is unsubstituted or substituted with one through three substituents selected from the group consisting of methyl, chloro, bromo, nitro, trifluoromethyl, alkoxy of one or two carbon atoms, and cyano, or (3) phenyl where the phenyl is unsubstituted or substituted with a substituent selected from the group consisting of methyl, chloro, and bromo.
   
   A compound according to claim 2 which is N-[[[N-(4-chloro-o-tolyl)-formimidoyl]methylamino]thio]-N-methyl-p-toluenesulfonamide.
   
   A compound according to claim 2 which is N-[[[N-(4-chloro-o-tolyl)formimidoyl]-methylamino]thio]N-isopropyl-p-toluenesulfonamide.
   
   A compound according to claim 2 which is N-[[[N-(2,4-xylylformimidoyl]-methylamino]thio]-N-isopropyl-p-toluene-sulfonamide.
   
   A compound according to claim 2 which is N-[[[N-(4-chloro-o-tolyl)-formimidoyl]methylamino]thio]-N-methyl-methanesulfonamide.
   
   A compound according to claim 2 which is N-[[[N-(4-chloro-o-tolyl)-formimidoyl]methylamino]thlol-N-isopropyl-methanesulfonamide.
   
   A compound according to claim 2 which is N-[[[N-(4-chloro-o-tolyl)-formimidoyl]methylamino]thio]-N-benzyl-methanesulfonamide.
   
   A compound according to claim 2 which is N-[[[N-(4-chloro-o-tolyl)formimidoyl]methylamino]thio]-N-isopropyl-benzenesulfonamide.
   
   A compound according to claim 2 which is N-[[[N-(4-chloro-o-tolyl)-formimidoyl]methylamino]thio]-N-phenyl-methanesulfonamide.
   
   A compound according to claim 2 which is N-[[[N-(4-chloro-o-tolyl)-formimidoyl]methylamino]thio]-N-cyclohexyl-methanesulfonamide.
   
   A compound according to claim 2 which is N-[[[N-(4-chloro-o-tolyl)-formimidoyl]methylamino]thio]-N-isopropyl-benzylsulfonamide A compound according to claim 2 which is N-[[[N-(4-chloro-o-tolyl)formimidoyl]methylamino]thio]-N-ethyl-p-toluenesulfonamide.
   
   A compound according to claim 2 which is N-[[[N-(4-chloro-o-tolyl)formimidoyl]methylamino]thio-N-t-butyl-p-toluenesulfonamide.
   
   A compound according to claim 2 which is N-[[[N-(4-chloro-o-tolyl]formimidoyl]methylamino]thio]-N-isopropyl-p-chlorophenylsulfonamide.
   
   A compound according to claim 2 which is N-[[[N-2,4-xylylformimidoyl]methylamino]thio]-N-cyclohexylmethanesul-fonamide.
   
   A compound accordlng to claim 2 which is N-[[[N-2,4-xylylformimidoyl]methylamino]thio]-N-phenylmethanesulfonamide.
   
   A compound according to claim 2 which is N-[[[N-2,4-xylylformimidoyl]methylamlno]thio]-N-isopropylbenzylsulfon-amide.
   
   A compound according to claim 2 which is N-[[[N-2,4-xylylformimidoyl]methylamino]thio]-N-isopropyl-p-chlorophenyl-sulfonamide.
   
   A compound according to claim 2 which is N-[[[N-2,4-xylylformimidoyl]methylamino]thio]-N-p-chlorophenyl-p-toluenesulfonamide.
   
   A compound according to claim 2 which is N-[[[N-(4-chloro-o-tolyl)formimidoyl]methylamino]thio]-N-p-chlorophenyl-p-toluenesulfonamide.
   
   A compound according to claim 2 which is N-[[[N-(4-chloro-o-tolyl)formimidoyl]methylamino]thio]-N-benzyl-p-toluenesuifonamide.
   
   A compound according to claim 2 which is N-[[[N-(4-chloro-o-tolyl)formimidoyl]methylamino]thio]-N-2,4-dichloro-phenyl-p-toluenesulfonamide.
   
   A compound according to claim 2 which is N-[[[N-(4-chloro-o-tolyl)formimidoyl]methylamino]thio]-N-phenyl-p-toluenesulfonamide.
   
   A compound according to claim 2 which is N-[[[N-2,4-xylylformimidoyl]methylamino]thio]-N-methylmethanesulfon-amide.
   
   A compound according to claim 2 wherein R2 is methyl.
   
   A compound according to claim 2 wherein R2 is chloro or bromo.
   
   A compound according to claim 1 wherein R1 is chloro or bromo;
   R2 is selected from the group consisting of methyl, chloro, and bromo;
   R3 is (1) alkyl of one through four carbon atoms, (2) cycloalkyl of five through eight carbon atoms, (3) phenalkyl wherein alkyl is one or two methylene units in length, or (4) phenyl where the phenyl is unsubstituted or substituted with one through three-substituents selected from the group con-sisting of methyl, chloro, and bromo; and R4 is (1) alkyl of one through four carbon atoms, (2) phen-alkyl wherein alkyl is one or two methylene units in length and where the phenyl is unsubstituted of substituted with one through three substituents selected from the group consisting of methyl, chloro, bromo, nitro, trifluoromethyl, alkoxy of one or two carbon atoms, and cyano, or (3) phenyl where the phenyl is unsubstituted or substituted with a substituent selected from the group consisting of methyl, chloro, and bromo.
   
   A compound according to claim 28 wherein R2 is chloro or bromo.
   
   A compound according to claim 29 which is N-[[[N-2,4-dichlorophenylformimidoyl]methylamino]thio]-N-isopropyl-p-toluenesulfonamide.
   
   A compound according to claim 1 wherein R2 is alkyl of one through four carbon atoms.
   
   A compound according to claim 31 which is N-[[[N-(2-chloro-p-tolyl)formimidoyl)methylamino]thio]-N-isopropyl-p-toluenesulfonamide.
   
   A process for controlling arthropodal pest populations which comprises applying to a situs an effective amount of a a compound of the formula:
   
   (I) wherein R1 is chloro, bromo, or alkyl of one through four car-bon atoms;
   R2 is hydrogen, chloro, bromo, or alkyl of one through four carbon atoms;
   R3 is (1) alkyl of one through eight carbon atoms, (2) cycloalkyl of five through elght carbon atoms, (3) phenalkyl wherein alkyl is one or two methylene units in length, or (4) phenyl where the phenyl is unsubstituted or substituted with one through three substituents selected from the group consist-ing of methyl, chloro, bromo, nitro, trifluoromethyl, alkoxy of one or two carbon atoms, and cyano; and R4 is (1) alkyl of one through four carbon atoms, (2) phen-alkyl wherein alkyl is one or two methylene units in length and where the phenyl is unsubstituted or substituted with one through three substituents selected from the group consisting of methyl, chloro, bromo, nitro, trifluoromethyl, alkoxy of one or two carbon atoms, and cyano, or (3) phenyl where the phenyl is unsubstituted or substituted with a substituent selected from the group consisting of methyl, chloro and bromo.
   
   The process of claim 33 wherein R1 in the compound ap-plied is alkyl of one through four carbon atoms.
   
   The process of claim 34 wherein the compound applied is N-[[[N-2,4-xylylformimidoyl]methylamino]thio]-N-substituted sulfonamide.
   
   The process of claim 34 wherein the compound applied is N-[[[N-(4-chloro-o-tolylformimidoyl ]methylamino]thio]-N-substituted sulfonamide.
   
   The process of claim 34 wherein the compound applied is N-[[[N-(4-chloro-o-tolyl)-formimidoyl]methylamino]thio]-N-methyl-p-toluenesulfonamide.
   
   The process of claim 34 wherein the compound applied is N-[[[N-(4-chloro-o-tolyl)formimidoyl]-methylamino]thio]-N-isopropyl-p-toluenesulfonamide.
   
   The process of claim 34 wherein the compound applied is N-[[[N-(2,4-xylylformimidoyl]-methylamino]thio]-N-isopropyl-p-toluenesulfonamide.
   
   The process of claim 34 wherein the compound applied is N-[[[N-(4-chloro-o-tolyl)-formimidoyl]methylamino]thio]-N-methylmethanesulfonamide.
   
   The process of claim 34 wherein the compound applied is N-[[[N-(4-chloro-o-tolyl)-formimidoyl]methylamino]thio]-N-isopropylmethanesulfonamide.
   
   The process of claim 34 wherein the compound applied is N-[[[N-(4-chloro-o-tolyl)-formimidoyl]methylamino]thio]-N-benzylmethanesulfonamide.
   
   The process of claim 34 wherein the compound applied is N-[[[N-(4-chloro-o-tolyl)formimidoyl]methylamino]thio]-N-isopropylbenzenesulfonamide.
   
   The process of claim 34 wherein the compound applied is N-[[[N-(4-chloro-o-tolyl)-formimidoyl]methylamino]thio]-N-phenylmethanesulfonamide.
   
   The process of claim 34 wherein the compound applied is N-[[[N-(4-chloro-o-tolyl)-formimidoyl]methylamino]thio]-N-cyclohexylmethanesulfonamide.
   
   The process of claim 34 wherein the compound applied is N-[[[N-(4-chloro-o-tolyl)-formimidoyl]methylamino]thio]-N-isopropylbenzylsulfonamide.
   
   The process of claim 34 wherein the compound applied is N-[[[N-(4-chloro-o-tolyl)formimidoyl]methylamino]thio]-N-ethyl-p-toluenesulfonamide.
   
   The process of claim 34 wherein the compound applied is N-[[[N-(4-chloro-o-tolyl)formimidoyl]methylamino]thio]-N-t-butyl-p-toluenesulfonamide.
   
   The process of claim 34 wherein the compound applied is N-[[[N-(4-chloro-o-tolyl)formimidoyl]methylamino]thio]-N-t-isopropyl-p-chlorophenylsulfonamide.
   
   The process of claim 34 wherein the compound applied is N-[[[N-2,4-xylylformimidoyl]methylamino]thio]-N-cyclohexyl-methanesulfonamide.
   
   The process of claim 34 wherein the compound applied is N-[[[N-2,4-xylylformimidoyl]methylamino]thio]-N-phenylmethane-sulfonamide.
   
   The process of claim 34 wherein the compound applied is N-[[[N-2,4-xylylformimldoyl]methylamino]thio]-N-isopropyl-benzylsulfonamide.
   
   The process of claim 34 wherein the compound applied is N-[[[N-2,4-xylylformlmidoyl]methylamino]thio]-N-isopropyl-p-chlorophenylsulfonamide.
   
   The process of claim 34 wherein the compound applied is N-[[[N-2,4-xylylformimidoyl]methylamino]thio]-N-p-chlorophenyl-p-toluenesulfonamide.
   
   The process of claim 34 wherein the compound applied is N-[[[N-(4-chloro-o-tolyl)formimidoyl]methylamino]thio]-N-p-chlorophenyl-p-toluenesulfonamide.
   
   The process of claim 34 wherein the compound applied is N-[[[N-(4-chloro-o-tolyl)formimidoyl]methylamino]thio]-N-benzyl-p-toluenesulfonamide.
   
   The process of claim 34 wherein the compound applied is N-[[[N-(4-chloro-o-tolyl)formimidoyl]methylamino]thio]-N-
2. 2,4-dichlorophenyl-p-toluenesulfonamide.
   
   The process of claim 34 wherein the compound applied is N-[[[N-(4-chloro-o-tolyl)formimidoyl]methylamino]thio]-N-phenyl-p-toluenesulfonamide.
   
   The process of claim 34 wherein the compound applied is N-[[[N-2,4-xylylformimidoyl]methylamino]thio]-N-methylmethane-sulfonamide.
   
   The process of claim 33 wherein R1 in the compound applied is chloro or bromo.
   
   The process of claim 60 wherein the compound applied is N-[[[N-2,4-dichlorophenylformimidoyl]methylamino]thio]-N-iso-propyl-p-toluenesulfonamide.
   
   The process of claim 60 wherein the compound applied is N-[[[N-(2-chloro-p-tolyl)formimidoyl)methylamino]thio]-N-iso-propyl-p-toluenesulfonamide.
   
   The process of claim 33 for controlling insect pest popu-lations.
   
   The process of claim 33 for controlling arachnid pest populations.
   
   The process of claim 33 for killing insect pest popula-tions.
   
   The process of claim 33 for killing arachnid pest popu-lations.
   
   The process of claim 33 for controlling ticks.
   A compound of the formula wherein R2 is chloro, bromo or alkyl of one through four carbon atoms;
   R3 is alkyl of one through eight carbon atoms or cycloalkyl of five or six atoms; and R4 is alkyl of one through four carbon atoms, phenyl or phenyl substituted by chloro or methyl.