CARBAMATES, COMPOSITIONS CONTAINING THEM, THEIR INSECTICIDAL AND NEMATOCIDAL USE, AND A METHOD FOR THEIR PREPARATION

Abstract: Carbamates of the formula where R and R₁ are various organic imino groups, X and Y independently are NH, N Alkyl, 0 or S, and A can be various aliphatic or aromatic residues, exhibit insecticidal and nematicidal activities. They can be made e.g. by coupling an appropriate bisulfenyl chloride with two moles of a carbamate or with a mole each of two different carba­ mates, in the presence of an acid acceptor. The compounds can be formulated for use in conventional manner with a diluent and/or surfactant and applied in an effective amount to the locus to be protected.

Description: Insecticidal and nematicidal carbamates, and preparation and use thereof This invention relates to insecticidal and nematicidal carbamates, and preparation and use thereof. Insecticidal carbamates are known in the prior art, e.g. (a) Belgian BE 848,911 discloses compounds of the formula EMI1.1 (b) Belgian BE 848,914 discloses compounds of the formula EMI1.2 (c) Belgian BE 855,928 discloses compounds of the formula EMI1.3 (d) German DT 2,654,246 discloses compounds of the formula EMI2.1 In the above publications the R substituents are widely defined. SUMMARY OF THE INVENTION This invention relates to novel compounds of Formula I, to agriculturally useful compositions of these, and to the method of use of these compounds as insecticides and nematocides. EMI2.2 ¯ R2, R3, R5 and R8 are independently C1-C3 alkyl; and R7 are independently C1-C3 alkyl or CH3OCH2-; A is -(CT1T2)k(CT3T4Ll (CT5T6)m; EMI3.1 -CT1T2CT3T4-OCT1T2CT3T4-OCT1T2CT3T4 p X and Y are independently NR6, O or S; T1 to T6 are independently hydrogen or C1-C2 alkyl; R6 is H or alkyl C1-C3 R9 is alkyl C1-C3, EMI3.2 V is O, S(O) R10 is H, alpyl of C -C3, C1; T7is H, C1-C2 alkyl, carboalkoxy alkyl of 3-8 carbon atoms, C2-C4 carboalkoxy; T8 is H, alkyl C1-C4; T7 and T8 may be taken together to form a carbocyclic ring of 5-6 carbons; Q is 0-2; k,l, m are independently 0-3; n, p are independently 0-2, provided a) the sum of k, e and m is at least two; bL the total carbon content of -(CT1T2)R; (CT3T4)l (CT5T6)m-will not exceed 9; cl when A is EMI4.1 then X and Y are both oxygen and R = R1 d) when A is CT1T2CT3T4 -OCT1T2CT3Y4-lp -OCT1T2CT3T4, X and Y are both oxygen. DETAILED DESCRIPTION OF THE INVENTION Preferred Compounds Preferred for their ease of synthesis and/ór favorable cost are compounds of Formula I wherein R = R1, More preferred for their higher activity and/or more favorable cost are compounds of Formula I wherein R - R1; and EMI5.1 X and Y are both oxygen; A is (CT1T2)k (CT3T4)l (CT5T6)m or EMI5.2 and m are independently 0-3. Even more preferred are compounds within the preceding scope wherein R and R1 = R4-C = N S-R5 Most preferred for their excellent activity and/or most favorable cost. are compounds within the even more preferred scope wherein R2 P3 and R5 are methyl; R4 is C1-C2 alkyl; A is (CT1T2)k (.CT3T4) (CT5T6) m or EMI5.3 T1-T are hydrogen; provided the sum of k, ±, and m total not more than 5. Specific Examples are: dimethyl N,N-[[1,2-ethanediylbis[oxycarbonyl(Nmethylimino)thio(N-methylamino)carbonyloxy]]]bis [ethanimidothioatel; dimethyl N,N-[[1,3-propanediylbis[oxycarbonyl(Nmethylimino)thio(N-methylimino)carbonyloxy]]]bis [ethanimidothioate]; and dimethyl N,N-[[2,2-propanediylbis[4,1-phenyleneoxy carbonyllN^methyliminotthio(N-methylimino)carbonyl- oxy]]]bis-[etanimidothioate]. Methods of Preparation The compounds of Formula I wherein R = R1 can be prepared, as shown in Equation A, by reacting a bissulfenyl chloride of Formula II with two mole equivalents of a carbamate of Formula III, in the presence of an acid acceptor. Equation A EMI6.1 <tb> <SEP> 0 <SEP> 0 <SEP> 0 <tb> <SEP> ti <SEP> II <SEP> II <tb> ClSNCX-A-YCNSCl <SEP> + <SEP> ROCNHCH3 <SEP> acid <tb> <SEP> I <SEP> I <SEP> daccetor <tb> <SEP> R2 <SEP> R3 <tb> <SEP> 00 <SEP> 00 <tb> <SEP> II <SEP> III <SEP> II <SEP> IF <SEP> .. <SEP> ..II <tb> <SEP> ROCNSNCX-A-YCNSNCOR <tb> <SEP> . <SEP> . <SEP> . <SEP> . <tb> <SEP> CH3R2 <SEP> R3CH3 <tb> wherein R, R2, R3, X, Y, and A are as previously defined. The reaction represented in Equation A can be carried out in an inert organic solvent such as benzene toluene, the xylenes, ethyl acetate, methylene chloride chloroform, ethylene dichloride, tetrahydrofuran, dioxane, or dimethylformamide. Mixtures of these solvents may be used. The reaction can be performed at temperatures between -150 and 50 C, preferably between -50C and 3O0C. Pressure is not critical for the reaction procedure since pressures above and below atmospheric are suitable. For convenience, atmospheric pressure is preferred. The acid acceptor used in Equation A can be a tertiary organic amine, such as, trimethylamine, triethylamine, N,N-dimethylaniline, or pyridine The compounds of Formula I obtained via the reaction shown in Equation A may be purified by methods known to those skilled in the art, such as recrystallization, column chromatography, or another suitable procedure. The compounds of Formula I wherein R &num; R1 can be prepared as shown in Equation B by reacting a bissulfenyl chloride of Formula II with one mole equivalent of a carbamate of Formula III and one mole equivalent of a carbamate of Formula IV, in the presence of an acid acceptor. Equation B EMI7.1 <tb> <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <tb> ClSNCX-A-YCNSCl <SEP> + <SEP> ROC8NHCH3 <SEP> + <SEP> R1OCNHCX3 <tb> <SEP> R2 <SEP> R3 <tb> <SEP> 3. <tb> <SEP> II <SEP> III <SEP> I <SEP> IV <tb> <SEP> acid <SEP> acceptor <tb> <SEP> fi <SEP> , <tb> <SEP> O <SEP> O <SEP> 00 <tb> <SEP> ,I <SEP> .. <SEP> te <SEP> .. <tb> <SEP> ROCNSNCX-A-YCNSNCOR1 <tb> <SEP> I <SEP> I <SEP> I <SEP> I <tb> <SEP> CH3R2 <SEP> R3CH3 <tb> <SEP> I <tb> wherein R, R11 R2, R3, X, Y, and A are as previously defined. The reaction shown in Equation B can be carried out in an inert organic solvent, such as, benzene, toluene, the xylenes, ethyl acetate, methylene chloride, chloroform, ethylene dichloride, tetrahydrofuran, dioxane or dimethylformamide. Mixtures of these solvents may be used. The reaction can be carried out at temperatures between -15 and 500C, preferably between -5 and 3O0C. Pressure is not critical for the reaction procedure since pressures above and below atmospheric are suitable. For convenience, atmospheric pressure is preferred. The acid acceptor employed in Equation B can be tertiary organic amines, such as, trimethylamine, triethylamine, N,N-dimethylaniline, or pyridine. The compounds of Formula I obtained by the reaction shown in Equation B can be purified by suitable procedures, such as, high-pressure liquid chromatography. The bissulfenyl chlorides of Formula II used as intermediates in Equation-A and Equation B can be prepared, as shown in Equation C, by reacting a bisaminocarbonyl impound of Formula V with two mole equivalents of sulfur dichloride in the presence of an acid acceptor. Equation C EMI8.1 <tb> <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <tb> <SEP> II <SEP> II <SEP> II <SEP> II <tb> R2NHCX-A-YCNHR3 <SEP> + <SEP> SCl2 <SEP> acid <SEP> acceptor, <SEP> ClSMCX-A-YCNSCl <tb> <SEP> R2 <SEP> R3 <tb> <SEP> V. <SEP> II <tb> wherein R2, R3, X, Y, and A are as previously defined. The reaction shown in Equation C can be carried out in an inert organic solvent, such as benzene, toluene, ethyl acetate, methylene chloride, chloroform, or ethylene dichloride. Mixtures of these solvents may be used. The reaction can be carried out at temperatures between -250 and 150C, preferably between -10 and 50C. Pressure is not critical for the reaction procedure since pressures above and below atmospheric are suitable. For convenience, atmospheric pressure is preferred. The acid acceptor used in Equation C can be a tertiary organic amine, such as, trimethylamine, triethylamine, N,tJ-dimethylaniline, or pyridine. The carbamates of Formula III and Formula IV employed as reactants in Equation A and Equation B can be prepared by the methods taught in U.S. 3,576,834, U.S. 3,530,220, and U.S. 3,217,037. The compounds of Formula I wherein R = R1 and R2 = R3 = CH3 can also be prepared, as shown in Equation D, by reacting a compound of Formula VI with two mole equivalents of a carbamyl fluoride of Formula VII, in the presence of an acid acceptor. Equation D EMI9.1 <tb> <SEP> O <SEP> 0 <tb> HX-A-YH <SEP> + <SEP> ROCNSNCF <SEP> acid <SEP> acceptor <tb> <SEP> 6 <tb> <SEP> CH3 <SEP> CH3 <tb> <SEP> VI <SEP> VII <tb> <SEP> > <SEP> , <tb> <SEP> O <SEP> O <SEP> 00 <tb> <SEP> ,I <SEP> (I <SEP> II <SEP> .. <tb> <SEP> ROCNSNCX-A-yCNSNCOR <tb> <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <tb> wherein R, X, Y, and A are as previously defined. The reaction shown in Equation D can be carried out in an inert organic solvent, such as benzene, toluene, the xylenes, methylene chloride, chloroform, ethylene dichloride, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, acetonitrile, or dimethylformamide. Mixtures of these solvents may be used. The reaction can be carried out at temperatures between 0 and 1500C, preferably between 200 and 1000C. Pressure is not critical for the reaction procedure since pressures above and below atmospheric are suitable. For convenience, atmgspheric pressure is preferred. The acid acceptor used in Equation D can be a tertiary organic amine, such as, trimethylamine, triethylamine, N,N-dimethylaniline, or pyridine, or inorganic bases, such as, the alkali metal and alkaline earth metal hydroxides, carbonates, bicarbonates, and alkoxides, such as, sodium methoxide or potassium tertbutoxide. The compounds of Formula I obtained by the reaction described in Equation D can be purified by methods known to those skilled in the art, such as, recrystallization, column chromatography or another suitable procedure. Carbamyl fluorides of Formula VII can be prepared by the method taught in DT 2,654,246 and BE 848,914. The compounds of Formula I wherein R = R1 and R2 = R3 = CH3 can also be prepared, as shown in Equation E, by reacting a bis-carbamyl fluoride of Formula VIII with two mole equivalents of an oxime of Formula IX, in the presence of an acid acceptor. Eauation E EMI11.1 <tb> <SEP> o <SEP> o <SEP> 00 <tb> <SEP> II <SEP> II <SEP> II <SEP> II <tb> FCNSNCX-A-YCNSNCF <SEP> + <SEP> ROH <SEP> acid <SEP> acceptor <tb> <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <tb> <SEP> VIII <SEP> IX <tb> <SEP> O <SEP> O <SEP> 00 <tb> <SEP> re <SEP> CI <SEP> II <SEP> II <tb> <SEP> ROCiSNCX-A-YCNSNCOR <tb> <SEP> I <tb> <SEP> ?H3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <tb> wherein R, X, Y, and A are as previously defined. The reaction shown in Equation E can be carried out in inert organic solvents such as benzene, toluene, the xylenes, methylene chloride, chloroform, ethylene dichloride, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, acetonitrile, or dimethylformamide. Mixtures of these solvents may be used. The reaction can be carried out at temperatures between 0 and 100 C, preferably between 20C to 500C. Pressure is not critical for the reaction procedure since pressures above and below atmospheric are suitable. For convenience, atmospheric pressure is preferred. The acid acceptor employed in Equation E can be tertiary organic amines, such as, trimethylamine, triethylamine, N,N-dimethylaniline, or pyridine, or inorganic bases, such as, the alkali metal and alkaline earth metal hydroxides, carbonates, bicarbonates, and alkoxides, such as, sodium methoxide or potassium tertbutoxide. The compounds of Formula I wherein R &num; R1, R2 = R3 = CH3, can be prepared, as shown in Equation F, by reacting sequentially a bis-carbamyl fluoride of Formula VIII with one mole equivalent of an oxime qf Formula IX and one mole equivalent of an oxime of Formula X, in the presence of an acid acceptor. Equation F EMI12.1 <tb> <SEP> o <SEP> o <SEP> 00 <tb> <SEP> II <SEP> II <SEP> II <SEP> It <tb> FC?ISNCX-A-YCNSNCF <SEP> + <SEP> ROH <SEP> acid <SEP> acceptor <tb> <SEP> I <SEP> /1 <tb> <SEP> CH3 <SEP> CH3 <SEP> CH3CH3 <tb> <SEP> VIII <SEP> IX <tb> <SEP> O <SEP> 0 <SEP> 0 <SEP> 0 <tb> <SEP> II <SEP> II <SEP> IF <SEP> II <tb> <SEP> ROCNSNCX-A-YCNSNCF <tb> <SEP> 0 <SEP> 0 <SEP> 0 <SEP> O <SEP> CH3 <SEP> CH3 <SEP> CH <SEP> CH <tb> <SEP> II <SEP> li <SEP> . <SEP> II <SEP> II <tb> ROCNSNCX-A-YCNSSCOR1 <SEP> acid <SEP> acceptor <tb> <SEP> CH3 <SEP> CH3 <SEP> CH <SEP> +R1OH <tb> <SEP> -J <SEP> 3 <SEP> +R1OH <tb> <SEP> I <SEP> X <tb> wherein R, R1, X, Y, and A are as previously defined. The reaction shown in Equation F can be performed in an inert organic solvent, such as benzene toluene, the xylenes,. methylene chloride, chloroform, ethylene dichloride, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran4 acetonitrile, or dimethylformamide. Mixtures of these solvents may be used. The reaction can be carried out at temperatures between Oc and 100 C, preferably between 2O0-500C. Pressure is not critical for the reaction procedure since pressures above and below atmospheric are suitable. For convenience, atmospheric pressure is preferred. The acid acceptor -used in Equation F can be tertiary organic amines, such as, trimethylamine, triethylamine, N,N-dimethylaniline, or pyridine, or inorganic bases, such as, the alkali metal or alkaline earth metal hydroxides, carbonates, or bicarbonates, and alkoxides, such as, sodium methoxide or potassium tert-butoxide. The oximes of Formula IX and Formula X can be prepared by methods taught in U.S. 3,576,834, U.S. 3,530,220 and U.S. 3,217,037. The bis-carbamyl fluorides of Formula VIII, used as reactants in Equation E and Equation F, can be prepared as shown in Equation G, by reacting a carbamyl fluoride of Formula Y.I with two mole equivalents of a compound of Formula VI, in the presence of an acid acceptor. Equation G EMI13.1 <tb> <SEP> 00 <SEP> 00 <SEP> 00 <tb> <SEP> II <SEP> II <SEP> II <SEP> II <SEP> Fl <SEP> II <tb> F:ISSCF <SEP> + <SEP> HX-A-Y-H <SEP> acid <SEP> acceptor) <SEP> FCNSNCX-A-YCNSNCF <tb> <SEP> /I <tb> <SEP> CH3CH3 <SEP> C <SEP> 3 <SEP> CH3CH3 <tb> <SEP> XI <SEP> VI <SEP> VIII <tb> wherein X, Y, and A are as previously defined. The reaction shpwn in Equation G can be carried out in an inert organic solvent, such as benzene, toluene, the xylenes, methylene chloride, chloroform, ethylene dichloride, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, ethyl acetate, acetonitrile, or dimethyl formamide. Mixtures of these solvents may be used. The reaction can be carried out at temperatures between O and 100 C, preferably between 200 and 800C. Pressure is not critical for the reaction procedure since pressures above and below atmospheric are suitable. For convenience, atmospheric is preferred. The acid acceptor used in Equation G can be a tertiary organic amine, such as, trimethylamine, triethylamine, N,-dimethylaniline, or pyridine, or an inorganic base, such as, the alkali metal and alkaline earth metal hydroxides, carbonates, bicarbonates, and alkoxides, such as, sodium methoxide and potassium tert-butoxide. The carbamyl fluoride of Formula XI can be prepared by the methods taught in DT 2,654,246 and BE 848,914. In the following examples all parts and percentages are by weight and temperatures in degrees centi;rade unless otherwise specified. Example l .Dimethyl N,N'-[[1,3-propanediylbis[oxycarbonyl(Nmethylimino)thio(N-methylimino)carbonyloxy]]]bis lethanimidothioate] A suspension of 4.7g of N-methyl carbamic acid, diester with 1,3-propanediol, in 50 ml methylene chloride was cooled to .OcC and 5.2g of sulfur dichloride was added. To this mixture was added dropwise a solution of 5.0g of triethylamine in 20ml methylene chloride, maintaining the reaction temperature between o and 50C. When addition was complete, the yellow suspension was stirred 1 hr. at O to 50C. A solution of 8.lg of methyl N-l[(methylamino)carbonylaoxyZethani- midothioate and 4.9g pyridine in 50ml methylene chloride was added dropwise, maintaining the temperature between 0 and 50C. When addition was complete, the reaction mixture was allowed to warm to ambient temperature and stirred overnight. The reaction mixture was washed with three 300ml portions of water, a 200ml portion of saturated sodium chloride solution, and dried over anhydrous magnesium sulfate. Distillation of the solvent under reduced pressure gave a brown, viscous oil. The reaction product was dissolved in 100ml of l-chlorobutane, and the organic solution was washed with three 300ml portions of water, a small portion of saturated sodium chloride solution, and dried over anhydrous magnesium sulfate. Distillation of the solvent under reduced pressure afforded a brown, viscous syrup. The title compound was isolated from the crude reaction product by column chromatography on silica gel, eluting the product with ethyl acetate. By employing this procedure, there was obtained 2.4 g of substantially pure dimethyl N,N'-[[1,3-propanediyl- bis [oxycarbonyl (N-methyliinino) thio(N-methylimino) car- bonyloxy)]]bis-[ethanimidothioate] as a pale yellow glass. Calcd for C17H30N608S4: C,35.53; H,5.26; N,14.62; S,22.32 Found: C,34.5; H,4.93; N,13.9; S,22.7 C, 34.6; H,4.52; N,13.8; S,22.7 Example 2 Dimethyl N ,N N, [1, 2-ethanediylbis [oxycarbonyl (N-methylimino)thio(N-methylimino)carbonyloxy]]]bis-[ethanimidothioate] A suspension of 4.4g of N-methyl carbamic acid, diester with 1,2-ethanediol, in 50ml methylene chloride was cooled to 00C, and 5.2g of sulfur dichloride was added. To this mixture was added dropwise a solution of 5,0g of triethylamine in 20ml CH2C12, maintaining the temperature between -5 and OOC. When addition was complete, the yellow suspension was stirred at 0 C for 1 hr. A solution of 8.lg of methyl N-[[(methylamino)carbonyl]oxy]-ethanimidothioate and 4.9g of pyridine in 25ml methylene chloride was added dropwise at OOC. When addition was complete, the reaction mixture was allowed to warm to ambient temperature and stirred 66 hr. The reaction mixture was washed with three 300 ml portions of water and dried over anhydrous magnesium sulfate, Distillation of the solvent at reduced pressure gave a brown viscous syrup. The reaction product was dissolved in 50ml toluene; on addition of small amounts of ether with scratching, there was obtained 1.6g of a tan solid, mp 1170-1400C. The title compound was isolated from the crude reaction product by column chromatography on silica gel, eluting the product with ethyl acetate. Employing this procedure, there was obtained 0.3g of dimethyl-N,N'-[[l, 2-ethanediylbis loxycarbonyl- (N-methylimino) thio(N-methylimino) carbonyloxyl 1) bis- [ethanimidothioate], mp 150 -155 C. Example 3 Methyl 2-(dimethylamino)-N-[[[[[[N-methyl [[[[3-[[[N-methyl[[N-methyl[N-(1-methylthioethylidene)aminooxycarbonyl]aminothio]]aminocarbonyloxy]]]propoxycarbonyl]]]]aminothio]]]]]aminocarbonyloxy]]]]]] 2-oxo- [ethanimidothioatej. A suspension of 4.7g of N-methylcarbamic acid, diester with 1,3-propanediol, in 50ml methylene chloride was cooled to 0 C, and 5.2g of sulfur dichloride was added. To this mixture was added dropwise a solution of 5.0g of triethylamine in 20ml methylene chloride, maintaining the reaction temperature between 0 and 50C. When addition was complete, the yellow suspension was stirred 1 hr. at 0 to 50C. A solution of 4.0g of methyl N-[[(methylamino) carbonyl] oxy1ethanimidothioate, 5.5g of methyl 2-(dimethylamino)- N-[[(methylamino(carbonyl]oxy]-2-oxo-ethanimidothioate, and 4.9g of pryidine in 50ml methylene chloride was added dropwise maintaining the temperature between 0 and 50C. When addition was complete, the reaction mixture was allowed to warm to ambient temperature and stirred overnight. The reaction mixture was washed with three 300ml portions of water and a 200ml portion of a saturated solution of sodium chloride. The organic solution was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The title compound can be isolated from the crude reaction product by a suitable procedure, such as, high pressure liquid chromatography. Example 4 Dimethyl N,N'-[[1,2-ethanediylbis[aminocarbonyl(Nmethylimino)thio(N-methyliminocarbonyloxy]]]bis [ethanimidothioate J. A solution of 0.3g of 1,2-ethanediamine and 1.0g of triethylamine in 10ml of tetrahydrofuran was added dropwise at ambient temperature to a solution of 2.7g of methyl N-[[(N-[(N-fluorocarbonyl-N-methyl- amino)thio-N-methylaminocarbonyloxy]]ethanimidothioate in 40ml tetrahydrofuran; an exotherm of 50C occurred. When addition was complete, the turbid reaction mixture was stirred an additional one hour. The resulting white solid was collected, washed with two 50ml portions of water, a 50ml portion of ethanol, and dried to afford 1.4g of dimethyl N,N'-[I1, 2-ethanediylbis [aminocarbonyl (N-methylimino)thio(N-methylimino)carbonyloxy]]]bis [ethanimidothioate],mp 166-l680.C. Calcd for C16H30N806S4: C,34.52; H,5.07; N,20.13; S,23.04 Found: C,34.7; H,5.58; N,20.0; S,21.3 C,34.3; H,5.61; N,20.1; S,21.1 Example 5 Dimethyl N,N'-[[1,4-phnylenebis[oxycarbonyl (Nmethylimino)thio(N-methylimino)carbonyloxy]]]bis [ethanimidothioate]. A solution of 1.0g of triethylamine in 10ml tetrahydrofuran was added dropwise at ambient temper an ture to a solution of 2.7g of methyl N-[[(N-[(N-fluoro- carbonyl-N-methylamino)thio-N-methylamino]carbonyloxy]]ethanimidothioate and 0.55g of 1,4-benzenediol in 25ml tetrahydrofuran. The reaction solution was stirred 2 hr. at ambient temperature, heated at reflux for 2 hr, then stirred at ambient temperature for an additional 86 hr. The resulting solid was collected, washed with a small volume of tetrahydrofuran-ether (3:2 v/v), and dried to give 1,8g of dimethyl N,N'-[[1,4-phenylene bis-[oxycarbonyl(N-methyZinino)thio(N-methylimino)- carbonyloxy]]]bis-[ethanimidothioate),m.p. 175-178 C. Calcd for C20H28N603S4: C,39*46; H,4.63; N,13.80; S,21.07 Found: C, 39.2 ; H, 4.71; N, 14.3 S, 20.2 Example 6 N,N'-1[1,3-Propanediylbisloxycarbonyl(N-methylimino)- thio J-methylimino) ] Ibis- jcarbamic fluoride To a solution of 7.0g of N,N'-thiobis[Nmethyl carbamic fluoride and 1.44g of 1,3-propane diol in 100ml of acetonitrile was added dropwise at ambient temperature 4.0g of triethylamine. When addition was complete, a slow exotherm of 60C occurred. The reaction mixture was stirred at ambient temperature for 4 hrs. then heated at 800C for 0.5 hr. The yellow reaction solution was cooled to ambient temperature, and the solvent was distilled under reduced pressure. The crude reaction product was dissolved in 100ml of methylene chloride and the organic solution was washed with two 100ml portions of water followed by a 100ml portion of saturated sodium chloride solution. The organic solution was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure to 6.4g of substantially pure N,N'-[[1,3- propanediylibis[oxycarbonyl-(N-methylimino)thio(Nmethylimino)]]]bis-[carbamic-fluoride] as a yellow brown oil. Calcd for C11H18F2N40652: C,32.67; H,4.49;N,13.85; S,15.86 Found: C., 32.2 ; H, 4.37; N, 13.9; 5, 16.0 Example 7 Dimethyl N,N'-[[1,3-propanediylbis[oxycarbonyl(N- methylimino) thio (N-methylimino) carbonyloxy) 11 bis- !ethanimidothioate). To a solution of 6.0g of N,N'-1[1,3-pro- panediybis-(oxycarbonyl(N-methylimino)thio (N-methylimino)]]]bis-[carbamic fluoride] and 3.3g of methyl N-hydroxyethanimidothioate in 100ml tetrahydrofuran was added dropwise at ambient temperature 3.3g of triethylamine. When addition was complete, the reaction mixture was stirred at ambient temperature until thinlayer chromatography indicated that reaction was complete. The solvent was distilled under reduced pressure, and the residue was dissolved in 100ml methylene chloride. The organic solution was washed with two 100ml portions of water, and a 100ml portion of saturated sodium chloride. The organic solution was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The title compound can be isolated from the crude reaction product by an appropriate purification technique. Example 8 Methyl N-[[[[[[N-methyl[[[[[N-methyl-[[[[3-[[[N-methyl [[N-methyl[fluoro-carbonyl]-aminothio]]aminocarbonyloxy]]]-propoxy carbonyl]]]]aminothio]]]]]aminocarbonyloxy]]]]]]-ethanimidothioate. To a solution of 4.0g of N,N'-([l,3-pro- panediylbis[oxycarbonyl(N-methylamino)thio(N-methyl amino)jlbis-tcarbamiefluoride] and 1.0g of methyl Nhydroxyethanimidothioate in 75ml of tetrathydrofuran was added dropwise at ambient temperature 1.0g of triethylamine. When addition was complete, the reaction mixture was stirred at ambient temperature until thin layer chromatography indicated that reaction was complete. The solvent was distilled at reduced pressure, and the crude reaction product was dissolved in 100ml methylene chloride. The organic-solution was washed with two 100 ml portions of water followed by a 100ml portion of saturated sodium chloride. The organic solution was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The title compound can be isolated from the crude reaction product by an appropriate purification technique. Example 9 Methyl 2-(dimethylamino)-N-l[lt[lN-methyl[[[[[N- methyl [[[[3-[[[N-methyl[[N-methyl[N-(1-methylthioethylidene)-aminooxycarbonyl]aminothio]]aminocarbonyloxy]]]propoxycarbonyl]]]]aminothio]]]]]aminocarbonyloxy]]]]]]-2-oxo-[ethanimidothioate]. A solution of 4.9g of methyl N-[[[[[[N- methyl [[[[[[N-methyl-[[[[3-[[[N-methyl[[N-methyl[fluorocarbonyl]aminothio]]amino-carbonyloxy]]]propoxycarbonyl]]]]aminothio]]]]]aminocarbonyloxy]]]]]]ethanimidothioate and l.6g of methyl 2- (dimethylamino) -N- hydroxy-2-oxo-ethanimidothioate in 50ml of triethyl amine in 5ml of tetrahydrofuran was added dropwise at ambient temperature. When addition was complete, stirring was continued at ambient temperature until thin-layer chromatography indicated the reaction was complete. The solvent was distilled under reduced pressure, and the residue was dissolved in 100ml of methylene chloride. The organic solution was washed with two 100 ml portions of water followed by a 100ml portion of saturated sodium chloride solution. The organic solution was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The title compound can be isolated from the crude reaction product by an appropriate purification technique. EXAMPLE 10 Dimethyl N,N'-C2,2-propanediylbisC4,1-phenylene- oxycarbonyl(M-metilylimino)thio(-methylimino)- carbonyloxy]]]bis[ethanimidothioate]. To a solution of 2.7 g of methyl N-[[[N- [[(N-fluorocarbonyl-N-methylamino)thio]]-N-methyl aminocarbonyloxy]]]ethanimidothioate and 1.1 g of 4,4'-(2,2-propanediy1bis(phenol) in 40 ml of tetrahydrofuran was added dropwise at ambient temperature 1.1 g of triethylamine. The reaction solution was stirred overnight at ambient temperature then refluxed 6 hrs. The reaction mixture was diluted with 100 ml of water, and the aqueous mixture was extracted with 100 ml of ethyl acetate. The organic phase was washed consecutively with 100 ml of 5% sodium hydroxide solution, two 100 ml portions of water, and 100 ml of saturated sodium chloride solution. The organic solution was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The title compound was isolated from the crude reaction product by column chromatography on silica gel. Elution of the column with a mixture of ethyl acetate-hexane (1:1, v/v) gave unreacted starting materials. Elution with ethyl acetate afforded the title compound as a colorless viscous oil. Trituration with ether gave a white solid which was suspended in a mixture of ether-hexane (1:1, v/v), collected, and dried to give 1.6 g of dimethyl N,N'-[[2,2-propanediyl-bis[4,1-phenyleneoxycarbonyl (N-methylimino)thio(N-methylimino)-carbonyloxy]]] bis[ethanimidothioate], m.p. 146 -150 C. Caled. for C29H38N6O8S4; C, 47.92;H,5.27;N,11.56; S, 17.65 Found: C,47.6;H,5.32;N,11.9; S, 17.0; S, 17.4 By employing the appropriate procedures as described in Examples 1-10, the compounds shown in Tables I-VIII can be prepared. TABLE I EMI25.1 EMI25.2 <tb> <SEP> A <SEP> Physical <SEP> Property <tb> <SEP> CH2 <SEP> C1H <SEP> - <SEP> C=O <SEP> (5.82p) <tb> <SEP> CH3 <tb> <SEP> CH2 <SEP> CFH <SEP> <tb> <SEP> C2H5 <tb> - <SEP> CH2 <SEP> CH2 <SEP> C1H <SEP> <tb> <SEP> CH3 <tb> <SEP> - <SEP> (CH2) <SEP> 4 <SEP> - <SEP> m.p. <SEP> 148-1500C <tb> <SEP> - <SEP> (CH2).5 <tb> <SEP> - <SEP> (CH2) <SEP> 8 <SEP> 8 <SEP> - <SEP> m.p. <SEP> 118-122"C <tb> <SEP> - <SEP> (CH2) <SEP> 9 <tb> <SEP> - <SEP> CH2 <SEP> C <SEP> CH2 <SEP> - <SEP> C=O <SEP> (5.83it <tb> <SEP> (CH3) <SEP> 2 <tb> <SEP> CH2 <SEP> C <SEP> CH2 <SEP> C=O <SEP> (5.84p <tb> <SEP> (C2 <SEP> Hg)2 <tb> <SEP> CH <SEP> - <SEP> CH <SEP> - <SEP> CH <tb> <SEP> ' <SEP> ' <SEP> ' <SEP> C <SEP> n <SEP> (5.84 <SEP> ) <tb> <SEP> CH3 <SEP> CH3 <SEP> CH3 <tb> <SEP> I? <SEP> ¯ <SEP> m.P. <SEP> l75-1780C <tb> <SEP> r.D <SEP> l46-l500C <tb> <SEP> (cH3)2 <tb> <SEP> - <SEP> < &commat; <SEP> - <SEP> S <SEP> - <SEP> i)- <SEP> C=O <SEP> (5.81 <SEP> ) <tb> <SEP> - <SEP> &commat; <SEP> - <SEP> so2- <SEP> o) <SEP> - <SEP> C=n <SEP> (5.80H <SEP> ) <tb> <SEP> Qo-o <SEP> - TABLE I CONTINUED EMI26.1 <tb> <SEP> A <tb> <SEP> CC22-0- <SEP> CCH2)1 <SEP> <tb> <SEP> (CH2L2-N-tCH2I-2 <tb> <SEP> h2 <tb> <SEP> Th <tb> <SEP> C. <tb> <SEP> coo <SEP> C=O <SEP> (5.80p) <tb> <SEP> CH3 <SEP> CH <SEP> < <SEP> CH3 <tb> <SEP> CH, <SEP> C=0 <SEP> (5.80ii) <tb> <SEP> CH3 <tb> - <SEP> (CH2) <SEP> 2-N- <SEP> (CH2) <SEP> 2 <tb> <SEP> 0 <SEP> 0 <tb> <SEP> tI <SEP> II <tb> <SEP> (CH2)2-O-CN-S-NCON=CCH3 <SEP> C=O <SEP> (5.82p) <tb> <SEP> CH3 <SEP> C1 <SEP> H3 <SEP> SCH3 <tb> <SEP> CH <tb> <SEP> Cb <tb> <SEP> TCH2N2Co2cH3 <tb> <SEP> H <tb> <SEP> ThocC:¸ <tb> <SEP> cl <tb> <SEP> CH <tb> <SEP> < , <SEP> a <tb> <SEP> CH <SEP> *E3 <tb> <SEP> CHCH3 <tb> TABLE. I CONTINUED EMI27.1 TABLE II EMI28.1 EMI28.2 <tb> R4 <SEP> * <SEP> R7 <SEP> R2 <SEP> R3 <SEP> 9 <SEP> R8 <SEP> A <tb> <SEP> 4 <SEP> L <tb> <SEP> CR <SEP> CH3 <SEP> CH3 <SEP> CH3 <tb> <SEP> 02R5 <SEP> OH3 <SEP> CR3 <SEP> OH3 <SEP> .3 <SEP> 3 <SEP> 22 <tb> C2R5 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH2,CH <tb> <SEP> CH3 <tb> C2ss5 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> - <SEP> (CH2)3 <tb> C2 <SEP> H5 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> - <SEP> -O <tb> <SEP> (CH3)2 <tb> CH3 <SEP> CH3 <SEP> C2H5 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CR2 <SEP> OH2 <tb> CH3 <SEP> CH3 <SEP> O2H5 <SEP> CR <SEP> 3 <SEP> CH3 <SEP> OH3 <SEP> CR <SEP> OH <tb> <SEP> 21 <tb> <SEP> CH3 <tb> CH3 <SEP> CH3 <SEP> 3 <SEP> 3 <SEP> 02H5 <SEP> 3 <SEP> (CH2)3 <tb> CH3 <SEP> CH3 <SEP> 3 <SEP> CR3, <SEP> C2H5 <SEP> CH3 <SEP> - <SEP> &commat; <SEP> -C- <SEP> <tb> C <SEP> 3H7 <SEP> CH3 <SEP> 3 <SEP> OH3 <SEP> CH3 <SEP> CH3 <SEP> CH,CH2L <tb> O <SEP> 3H7 <SEP> CH3 <SEP> 3 <SEP> 3 <SEP> CH3 <SEP> CH3 <SEP> CH <SEP> CH <tb> <SEP> CH3 <tb> C3H7 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> (CH2)3 <tb> 03H7 <SEP> CH3 <SEP> OR3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> 3 <SEP> 0 > - <SEP> <tb> <SEP> 1 <SEP> I <tb> CH3 <SEP> CH3 <SEP> 3 <SEP> 7 <SEP> 3 <SEP> CH3 <SEP> OH3 <SEP> (CH3)2 <tb> CH3 <SEP> CH3 <SEP> C <SEP> 3H7 <SEP> 3 <SEP> CH3 <SEP> CH3 <SEP> CH2,CH <tb> <SEP> CH3 <tb> II continued EMI29.1 <tb> 4 <SEP> 7 <SEP> 2 <SEP> R3 <SEP> Pe <SEP> A <tb> ¯ <SEP> ¯ <tb> C2H5 <SEP> C2H5 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <tb> <SEP> CCH312 <tb> C3R7 <SEP> C3R7 <SEP> CH3 <SEP> .CH3 <SEP> CH3 <SEP> CH3 <tb> <SEP> (CH3)2 <tb> C2H5 <SEP> C3H7 <SEP> CH3 <SEP> CR3 <SEP> CH3 <SEP> CH3 <tb> <SEP> (CH3) <SEP> 2 <tb> TABLE II cont'd EMI30.1 <tb> <SEP> R4 <SEP> R7 <SEP> R2 <SEP> R3 <SEP> R5 <SEP> R8 <SEP> A <tb> <SEP> 9 <SEP> 2 <SEP> 3 <SEP> 5 <tb> <SEP> CH3 <SEP> CH3 <SEP> C <SEP> 3117 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> (CH2)3 <tb> <SEP> CH3 <SEP> CH3 <SEP> 03117 <SEP> CH3 <SEP> CH3 <SEP> CH-C <tb> <SEP> (cm3)2 <tb> <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CR <SEP> CH3 <tb> <SEP> 3 <SEP> 3 <SEP> 3 <SEP> 03R7 <SEP> 3 <SEP> 20112 <tb> <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> Ç3H7 <SEP> CH3 <SEP> CH2C,H <tb> <SEP> CH3 <tb> <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> 03117 <SEP> CH3 <SEP> (or2)3 <tb> <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> 03117 <SEP> CH3 <SEP> ¯ <SEP> C-(O)-,C <tb> <SEP> (CH3)2 <tb> CH3OCH2 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH2CH2 <tb> CH3OCH2 <SEP> CH3 <SEP> C <SEP> 3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH2,CH <tb> <SEP> CH3 <tb> CH30CH2 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> (CH2)3 <tb> <SEP> CH3 <SEP> CH3 <SEP> 0 <SEP> H <SEP> OH3 <SEP> cH3 <SEP> CH3 <SEP> (OH2)3 <tb> <SEP> CH3 <SEP> CH3 <SEP> 02115 <SEP> CH3 <SEP> 0113 <SEP> 0113 <SEP> -C <tb> <SEP> (CH3)2 <tb> <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> 02115 <SEP> CH3 <SEP> CH2CH2 <tb> <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> 02H5 <SEP> CH3 <SEP> CH2,CH <tb> <SEP> CH3 <tb> EMI31.1 <tb> <SEP> R4 <SEP> R7 <SEP> R2 <SEP> R3 <SEP> R5 <SEP> R8 <SEP> A <tb> <SEP> CH3OCH2 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> C112-01CH2 <tb> <SEP> 0 <tb> <SEP> I( <tb> II <tb> (CH3)2NC <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH2CH2 <tb> <SEP> 'O <tb> CH3 <tb> <SEP> CH3 <tb> <SEP> o <tb> " <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> 0113 <SEP> CH3 <SEP> 0113 <SEP> (OH2)3 <tb> <SEP> o <tb> <SEP> It <tb> <SEP> 2 <SEP> 3 <SEP> 3 <SEP> e <tb> (CH3)2Nc <SEP> CH3 <SEP> CH3 <SEP> 3 <SEP> 3 <SEP> CH3 <SEP> CH-c-c <tb> <SEP> 0 <SEP> 0 <tb> <SEP> O <SEP> (C <SEP> O <SEP> 011 <SEP> (0113)2 <tb> <SEP> II <SEP> II <tb> ( <SEP> 3)2NC <SEP> (CH3)2NC <SEP> CH3 <SEP> CH3 <SEP> eCH3 <SEP> CH3 <tb> <SEP> (1 <tb> (CH3) <SEP> NC <SEP> (CH <SEP> 3) <SEP> NC <SEP> CH3 <SEP> CH3 <SEP> CH, <SEP> .CH <SEP> CH2CH <tb> (CH3)2NC <SEP> (0113) <SEP> NO <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH2,CH <tb> <SEP> CH3 <tb> <SEP> O <SEP> O <tb> II <tb> 32NC <SEP> (CH3)2NC <SEP> CH3 <SEP> CH3 <SEP> - <SEP> CH3 <SEP> CH3 <SEP> (CH2)3 <tb> <SEP> 9 <SEP> 011 <SEP> <tb> (CH3)2Nc <SEP> (CH3)2NC <SEP> CH3 <SEP> CH3 <SEP> CH3 <SEP> . <SEP> 3 <SEP> CH <tb> <SEP> (0113)2 <tb> <SEP> m.p. <SEP> 111-115 <SEP> C <tb> TABLE III EMI32.1 EMI32.2 <tb> <SEP> R4 <SEP> A <tb> CH3 <SEP> CH2CH2 <tb> CH3 <SEP> CH2C,H <tb> <SEP> o <SEP> CH3 <tb> CH3 <SEP> (CH2)3 <tb> <SEP> 011 <SEP> C-OH <tb> CH3 <SEP> 2t <SEP> 2 <tb> <SEP> (cm3)2 <tb> <SEP> OH <SEP> 0-OH <tb> CH3 <SEP> CH2C-CH2 <tb> <SEP> -(C2E5)2 <tb> <SEP> OH <SEP> - <SEP> CH <SEP> - <SEP> CH <tb> 0113 <SEP> 1 <SEP> 1 <tb> <SEP> CH3 <SEP> CH3 <SEP> CH3 <tb> CR3 <SEP> mm <tb> <SEP> o <SEP> (CH3)2 <tb> (CH3)2NC <SEP> CR20112 <tb> <SEP> 0 <tb> <SEP> It <tb> (CH3)2NC <SEP> 01120tH <tb> <SEP> CH3 <tb> <SEP> 0 <tb> (CH3)2 <SEP> (CH2)3 <tb> <SEP> 0 <tb> (CH3)2NC <SEP> 2, <SEP> CH,C-CH, <tb> <SEP> (CH3)2 <tb> <SEP> 0 <tb> <SEP> II <tb> (CH3)2NC <SEP> 2, <SEP> 2 <tb> <SEP> (C2H5)2 <tb> (TABLE III CONTINUED) EMI33.1 <tb> R <SEP> A <tb> <SEP> 0 <tb> <SEP> II <tb> (CH3)2NC <SEP> CH <SEP> - <SEP> CH <SEP> - <SEP> CH <tb> <SEP> CH3 <SEP> CH3 <SEP> CH3 <tb> <SEP> 0 <tb> (CH3)2NC <SEP> < <SEP> C <SEP> 9 <tb> <SEP> (CH3 <SEP> 2 <tb> TABLE IV EMI33.2 EMI33.3 <tb> <SEP> 5 <SEP> R7 <SEP> R6 <SEP> A <SEP> .PhYsical <tb> <SEP> K <SEP> K6 <SEP> A <SEP> Physical <tb> <SEP> Properties <tb> <SEP> 0113 <SEP> 11 <SEP> OH <SEP> 011 <tb> CH3 <SEP> CH3 <SEP> 2 <SEP> 2 <tb> CH3 <SEP> CH3 <SEP> CH3 <SEP> CH2C82 <tb> CH3 <SEP> CH3 <SEP> C3117 <SEP> -CH2CH2 <tb> CH3 <SEP> CH3 <SEP> H <SEP> CH2CH <tb> <SEP> CH3 <tb> CH3 <SEP> CH3 <SEP> H <SEP> 2, <tb> <SEP> (CH3)2 <SEP> m.p. <SEP> 172-1760C <tb> CH3 <SEP> CH3 <SEP> H <SEP> ç <tb> CH3 <SEP> CH3 <SEP> H <tb> CH3 <SEP> CH3 <SEP> H <tb> <SEP> o <tb> <SEP> II <tb> t <SEP> 3)2 <SEP> CH3 <SEP> 2 <SEP> 2 <tb> CH3 <SEP> CH3 <SEP> CH3 <SEP> -(CH2)3 TABLE IV CONTINUED EMI34.1 <tb> <SEP> R4 <SEP> R7 <SEP> R <SEP> A <tb> <SEP> 0 <SEP> 6 <tb> <SEP> II <tb> (O113)2NC <SEP> CH3 <SEP> 0113 <SEP> CH2CH2 <tb> <SEP> 0 <tb> <SEP> II <tb> (CH372NC <SEP> CH3 <SEP> - <SEP> C3H7 <SEP> CH2CH2 <tb> <SEP> 0 <tb> <SEP> II <tb> (C113)2NO <SEP> OH3 <SEP> H <SEP> CH,CH <tb> <SEP> 0113 <tb> <SEP> 0 <tb> (CH3)2NC <SEP> CH3 <SEP> H <SEP> 011201 <tb> <SEP> (cm372 <tb> <SEP> 0 <tb> <SEP> II <SEP> Th <tb> (cm3) <SEP> H <SEP> H <tb> <SEP> 0 <tb> (CH,)2NC <SEP> H; ;)O <tb> <SEP> 0 <tb> (3)2NO <SEP> CH3 <SEP> 3 <SEP> 1 <SEP> OH <tb> <SEP> O <SEP> 0 <SEP> 3 <tb> (CH3)2NC <SEP> (CH3)2NC <SEP> H <SEP> OH2OH2 <tb> <SEP> O <SEP> 0 <tb> (CH3)2NC <SEP> (CH3)2NC <SEP> CH) <SEP> CH2CH2 <tb> <SEP> O <SEP> 0 <tb> (CH3)2NC <SEP> (CH3)2NC <SEP> O2H5 <SEP> CH2CH2 <tb> <SEP> 0 <SEP> 0 <tb> <SEP> II <SEP> It <tb> (CH3)2NC <SEP> fOH3)2NO <SEP> H <SEP> CH2CH <tb> <SEP> CH3 <tb> <SEP> 0 <SEP> 0 <tb> (CH3)2NC <SEP> (OH3)2NO11 <SEP> H <SEP> 01120tH <tb> <SEP> (CH3)2 <tb> <SEP> 0 <SEP> 0 <tb> <SEP> It <SEP> II <SEP> H <tb> (CH3)2NC <SEP> (CH3)2NC <tb> TABLE IV CONTINUED EMI35.1 <tb> <SEP> R4 <SEP> ¯¯¯¯¯ <SEP> Rx <SEP> a <tb> <SEP> O <SEP> O <tb> <SEP> o <tb> CCH3 <SEP> r <SEP> 2AC <SEP> CC11312N0" <SEP> H <tb> <SEP> O <SEP> 0 <tb> <SEP> IF <SEP> It <tb> (CH322NC <SEP> (CH3)2NC <SEP> H <SEP> B11 <tb> TABLE V EMI35.2 EMI35.3 <tb> R, <SEP> R6 <SEP> A <tb> CH3 <SEP> H <SEP> CH2CH2 <tb> CH3 <SEP> CR3 <SEP> CR <SEP> CR <tb> CH3 <SEP> C2H5 <SEP> CH2CH2 <tb> 0113 <SEP> II <SEP> CHZCH <tb> <SEP> 21 <tb> <SEP> CH3 <tb> CH3 <SEP> H <SEP> CR20 <tb> <SEP> (0113)2 <tb> CH3 <SEP> 11 <tb> CH3 <SEP> 11 <tb> 0113 <SEP> 11 <SEP> ¸' <tb> <SEP> 0 <tb> <SEP> .. <tb> (CH3)2NC <SEP> H <SEP> CH2CH2 <tb> <SEP> 0 <tb> <SEP> Ir <tb> (ca <SEP> )2NC <SEP> CH3 <SEP> CH2CH2 <tb> <SEP> 0 <tb> <SEP> II <tb> (CH3)2Nc <SEP> C2E5 <SEP> CH2CH2 <tb> TABLE V CONTINUED EMI36.1 <tb> <SEP> R4 <SEP> R6 <SEP> A <tb> <SEP> 0 <tb> <SEP> o <tb> CH3)2NC <SEP> H <SEP> CHZCH <tb> <SEP> CH3 <tb> <SEP> 0 <tb> (CH3)2NC <SEP> H <SEP> CHIC <tb> <SEP> (cm.3)2 <tb> <SEP> 0 <tb> .(0H3)2N10' <SEP> H <tb> <SEP> 0 <tb> (CH3)2Nc <SEP> H <tb> <SEP> 0 <tb> (CH3)2NC <SEP> H <SEP> H <tb> TABLE VI EMI36.2 EMI36.3 <tb> R4 <SEP> R7 <SEP> X <SEP> Y <SEP> . <SEP> A <SEP> Physical <tb> CH3 <SEP> CH3 <SEP> NH <SEP> NH <SEP> - <SEP> CH2CH2 <SEP> Properties <tb> CH3 <SEP> CH3 <SEP> NOR3 <SEP> NOR3 <SEP> CH2CH2 <SEP> m.p. <SEP> 166-168 <SEP> 0C <tb> CH3 <SEP> CH3 <SEP> NH <SEP> NH <SEP> (cm2)3 <tb> CH3 <SEP> CH3 <SEP> NH <SEP> NH <SEP> (cm2)6 <tb> CH3 <SEP> CH3 <SEP> NCH3 <SEP> NCH3 <SEP> t <tb> CH3 <SEP> CH3 <SEP> NH <SEP> NH <tb> CH3 <SEP> CH3 <SEP> NH <SEP> NH <tb> CH3 <SEP> CH3 <SEP> NH' <SEP> NH <SEP> CH2,CH <tb> <SEP> 2, <tb> <SEP> CR3 <tb> TABLE VI CONTINUED EMI37.1 <tb> R, <SEP> R7 <SEP> X <SEP> Y <SEP> A <tb> CH3 <SEP> CH3 <SEP> NH <SEP> NC2H5 <SEP> CH2CH2 <tb> CH3 <SEP> CH3 <SEP> NHCH3 <SEP> NH <SEP> CSH2t3 <tb> CH3 <SEP> CH3 <SEP> NH <SEP> S <SEP> CH2CH2 <tb> CH3 <SEP> CH3 <SEP> NH <SEP> S <tb> CH3 <SEP> CH3 <SEP> O <SEP> S <SEP> ' <SEP> CH2CH2 <tb> CH3 <SEP> CH3 <SEP> S <SEP> S <SEP> CH2,CH <tb> <SEP> CH3 <tb> CH3 <SEP> CH3 <SEP> S <SEP> S <SEP> (CH2)4 <tb> <SEP> 0 <tb> (CH3)2NC <SEP> CH3 <SEP> NH <SEP> NH <SEP> CH2CH2 <tb> <SEP> 0 <tb> <SEP> It <tb> (CH3)2NC <SEP> CH3 <SEP> NCR3 <SEP> NCR3 <SEP> CH2CH2 <tb> <SEP> 0 <tb> (CH3)2 <SEP> 0113 <SEP> NH <SEP> NH <SEP> (CH2)3 <tb> <SEP> O <tb> <SEP> . <SEP> <tb> (CH3)2NC <SEP> CH3 <SEP> NH <SEP> ' <SEP> NH <SEP> (CH2)6 <tb> <SEP> 0 <tb> <SEP> II <SEP> NCR <SEP> NCR <tb> (0R3)2NC <SEP> NCH3 <SEP> 3 <SEP> 3 <tb> <SEP> 0 <tb> II <SEP> NH <SEP> NH <tb> (0113)2N0 <SEP> 0113 <tb> <SEP> o <tb> (CH3)2NC <SEP> CH3 <SEP> NH <SEP> NH <tb> <SEP> o <tb> (CH3)2NC <SEP> CH3 <SEP> NH <SEP> NH <SEP> CHUCK <tb> <SEP> CH3 <tb> <SEP> 0 <tb> (CH3)2 <SEP> 3 <SEP> NH <SEP> NC2H5 <SEP> CH2CH2 <tb> TABLE VI CONTINUED EMI38.1 <tb> R4 <SEP> R2 <tb> <SEP> 0 <tb> <SEP> II <tb> (CH3)2NC <SEP> CH3 <SEP> NH <SEP> . <SEP> NCH3 <SEP> (CH2ss3 <tb> <SEP> 0 <tb> C0113)2N0 <SEP> CH3 <SEP> NH <SEP> S <SEP> CH2CH2 <tb> <SEP> 0 <tb> (CH3)2 <SEP> 3 <SEP> NH <SEP> S <SEP> B <tb> <SEP> 0 <tb> (CH3)2NC <SEP> CH3 <SEP> S <SEP> S <SEP> CH2CR2 <tb> <SEP> 0 <tb> <SEP> II <tb> (CH3)2NC <SEP> CH3 <SEP> S <SEP> S <SEP> CUR21 <tb> <SEP> 3 <tb> <SEP> CR3 <tb> <SEP> 0 <tb> <SEP> II <tb> (CH3)2NC <SEP> CH3 <SEP> S <SEP> S <SEP> (cm224 <tb> <SEP> 0 <tb> <SEP> II <tb> (CH3)2NC <SEP> CH) <SEP> O <SEP> S <SEP> CH,CH, <tb> <SEP> O <SEP> 0 <tb> <SEP> II <SEP> 11 <tb> (CK3) <SEP> 2N <SEP> (CH3)2NC <SEP> NH <SEP> NH <SEP> CH2CH2 <tb> <SEP> O <SEP> 0 <tb> <SEP> II <SEP> it <tb> (CH3)2NC <SEP> (CH3)2NC <SEP> .3 <SEP> 3 <SEP> NOR <tb> (OR3)2N0 <SEP> (OR3)2N0 <SEP> .3 <SEP> 3 <SEP> CR2CH2 <tb> <SEP> .. <SEP> 0 <tb> <SEP> Ii <SEP> Fl <tb> (CH3)2NC <SEP> (CH3)2NC <SEP> NH <SEP> NH- <SEP> (CH2)3 <tb> <SEP> O <SEP> Pt <tb> <SEP> IF <tb> (Ctd3)2NC <SEP> (CH3)2NC <SEP> NH <SEP> NH <SEP> (CH2)6 <tb> <SEP> O <SEP> 0 <tb> <SEP> II <SEP> II <tb> (CH3)2NC <SEP> (CH3)2NC <SEP> NOR3 <SEP> NOR3 <tb> <SEP> 0 <tb> <SEP> 91 <SEP> II <SEP> NH <tb> (CH3)2NC <SEP> (CH3)2NC <SEP> NH <tb> <SEP> O <SEP> 0 <tb> <SEP> II <SEP> II <tb> (CH3)2NC <SEP> (CH3)2Nc <SEP> NH <SEP> NH <tb> TABLE VI CONTINUED EMI39.1 <tb> <SEP> R4 <SEP> R7 <SEP> as <SEP> y <SEP> A <tb> <SEP> O <SEP> 0 <tb> <SEP> re <SEP> II <tb> (SH3)2NC <SEP> (CH3)2NC <SEP> NH <SEP> NH <SEP> CR2CR <tb> <SEP> CH3 <tb> <SEP> O <SEP> 0 <tb> (CH3)2NC <SEP> (CH3)2NC <SEP> NH <SEP> NC2H5 <SEP> CH2CH2 <tb> <SEP> O <SEP> 0 <tb> (CH3)2NC <SEP> (CH3)2NC <SEP> NH <SEP> NCH3, <SEP> (.C)3 <tb> <SEP> o <SEP> 0 <tb> <SEP> o <SEP> (0H3)2N011 <SEP> o <tb> (CH3)2NC <SEP> (CH3)2 <SEP> NH <SEP> 5 <SEP> C82CB2 <tb> <SEP> o <SEP> O, <SEP> 0 <tb> II <SEP> II <tb> (CH3)2NC <SEP> (CH3)2NC <SEP> NH <SEP> S <tb> <SEP> o <SEP> 0 <tb> <SEP> II <SEP> <SEP> S <SEP> S <SEP> CH2CH2 <tb> (CH3)2NC <SEP> (CE3)2 <tb> <SEP> .. <SEP> OCt <SEP> S <SEP> S <SEP> CH2CH <tb> (CH3)2NC <SEP> (CH3)2NC <SEP> CH3 <tb> <SEP> O <SEP> 0 <tb> <SEP> II <SEP> II <tb> (OH3)2N0 <SEP> (cR3)2N0 <SEP> .. <tb> <SEP> S <SEP> (CR3)2NC <SEP> S <tb> <SEP> 0 <SEP> 0 <SEP> L <tb> <SEP> It <SEP> cm <tb> (CH3)2NC <SEP> (CH3)2NC <SEP> 0 <SEP> S <SEP> C112CH2 <tb> TABLE VII EMI40.1 EMI40.2 <tb> R4 <SEP> X <SEP> Y <SEP> A <tb> CH3 <SEP> NH <SEP> NH. <SEP> CH2CH2 <tb> CH3 <SEP> SCH3 <SEP> NCH3 <SEP> 01120112 <tb> CH3 <SEP> NH <SEP> NH <SEP> (CH2)3 <tb> CH3 <SEP> NH <SEP> NH <tb> CH3 <SEP> NH <SEP> NH <tb> CH3 <SEP> NH <SEP> NH <SEP> CH2CH <tb> <SEP> 0113 <tb> CH3 <SEP> NH <SEP> . <SEP> NC2Hs <SEP> CH2CH2 <tb> CH3 <SEP> NH <SEP> S <SEP> CH2CH2 <tb> CH3 <SEP> NH <SEP> S <SEP> X <tb> CH, <SEP> O <SEP> S <SEP> 0R20112 <tb> CH3 <SEP> S <SEP> S <SEP> CH2CH2 <tb> CH3 <SEP> S <SEP> S <SEP> CH2,CH <tb> <SEP> CHz <tb> CH3 <SEP> S <SEP> S <SEP> (CH2)4 <tb> <SEP> 0 <tb> (CR3).2N0 <SEP> NH <SEP> NH <SEP> CH2CH2 <tb> <SEP> 0 <tb> <SEP> CI <tb> (CH3)2NC <SEP> NOR3 <SEP> NCH3 <SEP> CH2CH2 <tb> <SEP> 0 <tb> <SEP> II <tb> (CH3)2NC <SEP> NH <SEP> NH <SEP> (cm2)3 <tb> <SEP> 0 <tb> (CH3)2NC <SEP> NH <SEP> NH <tb> <SEP> 0 <tb> (CH3)2NC <SEP> NH <SEP> NH <tb> TABLE VII CONTINUED EMI41.1 <tb> <SEP> R4 <SEP> x <SEP> Y <SEP> A <tb> <SEP> 0 <tb> <SEP> (( <SEP> NH <SEP> NH <SEP> CH2CH <tb> (CH3)2NC <SEP> CH3 <tb> <SEP> 0113 <tb> <SEP> 0 <tb> (CH3)2NC <SEP> NH <SEP> NC2HS <SEP> C1120H2 <tb> <SEP> 0 <tb> (CH3)2NC <SEP> NH <SEP> S <SEP> CH2CH2 <tb> <SEP> 0 <tb> (CH3)2NC <SEP> NH <SEP> S <SEP> e <tb> <SEP> 0 <tb> <SEP> O <SEP> S <SEP> CH <SEP> CH2 <tb> (CH3)2NC <SEP> O <SEP> S <SEP> CHZCHZ <tb> <SEP> , , <SEP> S <SEP> C <SEP> 2 <SEP> 2 <tb> (CH3)2NC <tb> <SEP> 0 <tb> <SEP> IF <SEP> S <SEP> S <SEP> CH2CH2 <tb> (CH3)2NC <SEP> CH3 <tb> <SEP> o <tb> (CH3)2NC <SEP> S <SEP> S <SEP> (CH2)4 <tb> TABLE VIII EMI42.1 EMI42.2 <tb> X <SEP> A <SEP> Y <tb> o <SEP> CR20112 <SEP> O <tb> O <SEP> CH,CH <SEP> O <tb> <SEP> CH3 <tb> <SEP> 0113 <tb> O <SEP> (CH2)3 <tb> O <SEP> ACS <SEP> 0 <tb> O <SEP> CB2CH, <SEP> NH <tb> C <SEP> 2 <SEP> 2 <SEP> CH2CH2 <SEP> NCH3 <tb> O <SEP> 01120tH <SEP> NH <tb> <SEP> OR <tb> O <SEP> z <SEP> NH <tb> O <SEP> S <SEP> NH <tb> NH <SEP> CH2CH2 <SEP> NH <tb> NH <SEP> CH2,CH <SEP> NH <tb> <SEP> CH3 <tb> NCH3 <SEP> CH2CH2 <SEP> NCH3 <tb> NH <SEP> t <SEP> NH <tb> NH <SEP> NH <tb> O <SEP> CR20112 <SEP> S <tb> WH <SEP> CH2CH2 <SEP> S <tb> S <SEP> 2 <SEP> 2 <SEP> S <tb> S <SEP> 2 <SEP> S <tb> Formulation Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few pints to several hundred gallons per acre. High strength compositions are primarily used as intermediates for further formulations. The formulations, broadly, contain about 1% to 99% by weight of active ingredientCs) 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 in the following approximate proportions: Active Ingredient Diluent(s) Surfactant(s) Wettable Powders 20-90 0-74 1-10 Oil Suspensions, 5-50 40-95 0-15 Emulsions, Solu tions (including Emulsifiable Concentrates) Aqueous Suspensions 10-50 40-84 1-20 Dusts 1-25 70-99 0-5 Granules and Pellets 1-95 5-99 0-15 High Strength 90-99 0-10 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. For Example, many of the compounds are relatively low melting solids or glasses. In these cases, the strength of wettable powders and granules must he limited because of physical handling considerations. Higher ratios of surfactant to active ingredient are sometimes desirable and are achieved by incorporation into the formulation or by tank mixing. Typical solid diluents are described in Watkins, et al., Handbook of insecticide Dust Diluents and Carriers", 2nd. Edn., Dorland Books, Caldwell, N.J. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide", 2nd. Edn., Interscience, New York, 1950. Solubility under 0,1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation.at OOC. McCutcheonts Detergents and Emulsifiers Annual", MC Publishing Col, Ridgewood, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publ. Co., Inc., New York, 1964, list surfactant and recommended uses. All formualtions can contain minor amounts of additives to reduce foam, caking, corrosion, microbioloqical qrowth, etc. Preferably, ingredients should be approved by the U.S. Environmental Protection Aqency for the use intended. The methods.of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. 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, U.S. Patent 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, pp. 147ff. and tPerrybs Chemical Engineer's HandbooR", 4th. Edn., McGraw-Hill, N.Y., 1963,pp. 8-59ff. and "Perry's Chemical Engineer's Handbook", 4th. Edn., McGraw-Hill, N.Y., 19.63, pp. 8-59ff. For further information regarding the art of formulation see for example: J. B. Buchanan, U.S. Patent 3,576,834, April 27, 19.71, Col, 5, Lines 36 through Col. 7, Line 70 and Ex. 1-4, 17, 106, 123-140; R. R. Shaffer, U.S. Patent 3,560,616, Feb, 2, 1971, Col. 3, Line 48 through Col. 7, line 26 and Examples 3-9, 11-18; E. Somers, "Formulation", Chapter 6 in Torgeson, "fungicides", Vol. I, Academic Press, New York, 1967. Example A Wettable Powder Dimethyl N,N'-[[2,2-propanediylbis[[4,1-phenyleneoxycarbonyl-(N-methylimino)thio[N-methylimino]-carbonyloxy]]]]]-bis[ethanimidothioate] 30% Dioctyl sodium sulfosuccinate 1.5% Sodium ligninsulfonate ¯ 3% Low viscosity methyl cellulose 1.5% Attapulgite 64% The ingredients are.thoroughly blended, passed through an air mill, to produce an average particle size under 15 microns, reblended, and sifted through a U,S.S. No. 50 sieve C0.3 mm opening) before packaging.. All compounds of the invention may be formulated in the same manner. Example B Wettable Powder Dimethyl N,N'-[[[1,2-ethanediylbis[oxycarbonyl- 50% (N-methylimino[thio(N-methylimino)carbonyloxy]]] bis-[ethanimidothioate] Sodium alkylnaphthalenesulfonate 2% Low viscositv meth.vl cellulose 2% Diatomaceous earth 46% The inaredients are blended. coarselv hammer-milled and then ar milled to produce particles of active essentially all below 10 microns in diameter. The product is reblended before packaging. Example C Dust Wettable powder of Example B 10% Pyrophyllite (powder) 90% The wettable powder a.nd the pyrophyllite diluent are thoroughly blended and then packaged. The product is suitable for use as a dust. Example D Solution Dimethyl N,N'-[[[2,2-propanediylbis[[4,1- 30% phenyleneoxycarbonyl-[N-methylimino]thio [N-methylimino]carbonyloxy]]]-bis ethanimidothioate Dimethylformamide 70% The ingredients are combined and stirred to produce a solution, which can be used for low volume applications. Example E Emulsifiable Concentrate Dimethyl N-N'-[[1,3-propanediylbis- 30% oxycarbonvl(N-methylìmino)thio- (N-methylimino)carbonyloxy]]]bis [ethanimidothioate) Blend of oil soluble sulfonates 4% and polyoxyethylene ethers Xylene 60% The ingredients are combined and stirred with gentle warming to speed solution. A fine screen rilter is include in packaging operation to insure the absence of any extraneous undissolved material in the product. Example F Granule Wettable powder of Example A 158 Gypsum 698 Potassium sulfate 16% The ingredients are blended in a rotating mixer and water sprayed on to accomplish granulation. When most of the material has reached the desired range of 1.0 to 0.42 mm. LUSS. No. 18 to 40 sieves), the granules are removed, dried, and screened. Oversize material is crushed to produce additional material in the desired range. These granules contain 4.5% active ingredient. Example G Extruded Pellet Dimethyl N,N'-[[[2,2-propanediylbis[[4,1- 25% phenyleneoxycarbonyl-[N-methylimino]thio [N-methylimino]carbonyloxy]]]]]-bis [ethanimidothioate] Anhydrous sodium sulfate 10% Crude calcium ligninsulfonate 5% Sodium alkylnaphthalenesulfonate 1% Calcium/magnesium bentonite 59% The ingredients are blended, hammer milled 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 directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20. sieve t0.84 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 recycled. Example R Aqueous Suspension Dimethyl N,N'-[[1,2-ethanediylbis[oxy carbonyl(N-methylimino)thio(N methylimino)-carbonyloxy]]]bis [ethanimidothioate] Hydrated attapulgite 3% Crude calcium ligninsulfonate 10% Sodium dihydrogen phosphate o-. Water 61.5% The ingredients are ground together in a ball or roller mill until the solid particles have been reduced to diameters under 10 microns. USE The compounds of this invention are useful for control of insects and nematodes which are detrimental to agriculture. As demonstrated in the following examples the compounds have provided a hish degree of control of important agricultural pests with minimization of side effects known in prior art compounds such as phytotoxicity. Only a slight effect has been noted on cotton with compounds within Formula I, i.e. dimethyl N,N-LEl,2- ethanediylbis[oxyzarbonyl-(N-methylimino)thio(N-methyl- imino)-carbonyloxy]]]-bis-[ethanimidothioate], dimethyl N,N'-[[1,3-propanediylbis[oxycarbonyl-(N-methylimino)thio(N-methylimino)-carbonyloxy]]]-bis-[ethanimidothio ate); and methyl 2-(dimethylamino)-N-CCCCCCN-methyl- [[[[[N-methyl-[[[[3-[[[N-methyl-[[N-methyl-[N-(1 methylthioethylidene)-aminooxycarbonyl]aminothio]]- aminocarbonyloxy]]]propoxycarbonyl]]]]aminothio]]]]]- aminocarbonyloxy]]]]]]-2-oxo-[ethanimidothioate]. The compounds readily control pestiferous insects belonging to such orders as Lepidoptera, Coleoptera, and Diptera. More specifically, insects controlled by the compounds of this invention include but are not limited to: southern armyworm (Spodoptera eridania), fall armyworm (Spodoptera frugiperda), soybean looper (Pseudoplus'ia includens), Mexican bean beetle (Epilachna varivestis), the house fly (Musca domestica), budworm (Heliothis virescens) and bollworm (Heliothis zea). These compounds readily control pestiferous nematodes. More specifically nematodes controlled by compounds of this invention include, but are not limited to, the root-knot nematode, Meloidogyne incognita; lesion nematode, Pratylenchus spp. and dagger nematode, Xiphinima. The insects are controlled by applying one or more of 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 plant parts which are infested or which are to be protected. Effective amounts to be applied depend upon the specific compound used, the species to be controlled, its life stage, its size and location, the amount of rainfall, the time of year, moisture, temperature, type aof application plant spacing, and other variables. In general, .05 to 10 Kg/ha may be required for insect control in agriculture with rates of .15 to 5 Kg/ha usually being sufficient in many situations. In large scale field operations, rates in the range of .25 to 3 Kg/ha are generally used. Nematodes are controlled by applying the compounds to the locus of infestation; to the area to be protected or to the pest themselves. For the control of nematodes in agricultural crops, a compound of this invention is generally applied to a portion of the plant or surrounding soil which is infested or which is to be protected. Effective amounts to be applied depend upon the species to be controlled, its life stage, its size and location, the amount of rainfall, the time of year, 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 10 Kg/ha usually being sufficient in many situations. The compounds of this invention possess significant advantages over prior art compounds. For example1 their improved residual insecticidal activity can reduce the need for closely spaced multiply sprays re resulting in greater economy to the 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 can be mixed with fungicides, bactericides, acaricides, nematicides, insecticides, or other biologically active compounds in order to achieve desired results with a minimum expendi ture of time, effort and material. Amounts of these biologically active materials added for each part by weight of the composition of this invention may vary 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: Fungicides: methyl 2-benzimidazolecarbamate (carbendazim) tetramethyl thiuram disulfide (thiuram) n-dodecylguanidine acetate (dodine) manganese ethylenebisdithiocarbamate (maneb) 1,4-dichloro-2,5-dimethoxybenzene (chloroneb) methyl 1- (butylcarbamoyl) -2-benzimidazolecarbamate (benomyl) 2-cyano-N-ethylcarbamoyl- 2-methoxyimino acetamide CurzateO N-trichloromethylt:hiotetrahydrophthalimide (captan) N-trichloromethylthophthalimide (folpet) Bactericides: tribasic copper sulfate streptomycin sulfate Acaricides: : senecioic acid, ester with 2-sec-butyl-4,6-dinitro phenol ("MorocidE.11) 6-methyl-1,3-dithiolo[2,3-B]quinonolin-2-one ("Morestan") ethyl 4,4' (p-chlorophenyl)-2,2,2-trichlroethol (Kelthane#) bis(pentochloro-2,4-cyclopentadien-1yl) (Pentac#) tricyclohexyl tinSydroxide (Plictran) Nematicides: 2-[diethoxyphosphinylimino]-1,3-dithietanc (Nematak#) S-methyl l-(dimethylcarbamoyl)-N-(methylcarbamoyloxy)- thioformimidate S-methyl 1-carbamoyl-N-(methylcarbamoyloxy)thioformi date N-isopropylphosphoramidic acid, O-ethyl-O' E4- (methyl- thio)-m-tolyl]diester ("Nemacur") Insecticides: 3-hydroxy-N-methylcrotonamide(dimethylphosphate)ester (Azodrin#) methylcarbamic acid, ester with 2,3-dihydro-2,2 dimethyl-7-benzofuranol (Furadan&commat;) O-[2,4,5-trichloro-&alpha;-(chloromethyl)benzyl]phosphoric acid, O',O'-dimethyl ester (Gardona) 2-mercaptosuccinic acid, diethyl ester, S-ester with thionophosphoric acid, dimethyl ester (Malathion&commat;) phosphorothioic acid, O,O-dimethyl, O-E-nitrophenyl ester (methyl parathion) methylcarbamic acid, ester with a-naphthol (Servin#) methyl O-(methylcarbamoyl)thiolacetohydroxamate (methomyl) N'-(4-chloro-o-tolyl)-N,N-dimethylformamidine (Galecron&commat; ;) O,O-diethyl-O-(2-isopropyl-4-methyl-6-pyrimidylphos phorothioate (Diazinon) octachlorocamphene (toxaphene) O-ethyl O-2-nitrophenyl phenylphosphonothioate (EPN) cyano(3-phenoxyphenyl)-methyl-4-chloro-a-(1-methyl ethyl)-benzeneacetate (Pydrin&commat; ;) (3-phenoxyphenyl)methyl(#)-cis,trans-3-(2,2-dichloro- ethenyl)-2,2-dimethylcyclopropanecarboxylate dimethyl N,N'-[thiobis[(N-methilimino)carbonyloxy]] bis (ethanimidothioate] (Larvin#) (Ambush#) O-ethyl-S-(p-chlorophenyl)ethyphosphonodithioate (Curacron) phosphorothiolothionic acid, O-ethyl-0-E4- (methylthio) - phenyl]-S-n-propyl ester (Bolstar#) EXAMPLE I The foliage only of red kidney bean plants in the two-leaf stage is sprayed to run-off with dispersions of compounds of this invention at various concentrations. Dispersions are prepared by dissolving appropriately weighed quantities of the active ingredient in 10 ml of acetone and diluting to 100 ml of water containing surface active agent (DuponolE L-144 WDG) at 1:3000. After drying, leaves are excised and placed in covered 10 cm petri dishes along with moist filter paper td keep them fresh. Ten southern armyworm larvae are placed in each dish. The units are kept in a room maintained at 25 t 20C, 53 + 5% RH. Results are recorded at the end of two days. Compound Concentration % % Mortality dimethyl N,N-[[1,2ethanediylbis(oxycarbonyl- 01 100 (N-methylimino)thio(N- .005 85 methylimino)carbonyloxy]]]bis-(ethanimidothioate) dimethyl N,N'-[[1,3 propanediylbis[oxycarbonyl- .01 100 (N-methyliminÏ)thio(N- .005 85 methylimino)carbonyloxy]]]bis-[ethanimidothioate] dimethyl N,N'-[[1,5 pentanediylbisfoxycqrbonyl- .01 95 Compound (Continued) Concentration % 8 Mortality (N-methylimino)thio(N- .005 85 methylimino)carbonyloxy]ll- bis-lethanimidothioate] dimethyl N,N'-{2,2-profpanediyl- .01 10° bis-[4,1-phenyleneoxycarbonyl (N-methylamino)thio-(N-methyl- .005 100 iino)carbonyloxylis (ethan- imidothioate) Untreated O EXAMPLE tI The foliage of red kidney bean plants in the two-leaf stage infested with 20 soybean looper larvae (Wadmalaw strain)Ú)is sprayed to run-off with disper sions of compounds of this invention at various con centrations. Dispersions are prepared by dissolving appropriately weighed quantities of the active ingredi ent in 5 ml of acetone and diluting to 100 ml of water containing surfactant (Trem# 014) at 1:3000. After drying, plants are placed under individual cylindrical cages, and watered daily to keep them fresh. The units are kept on the laboratory bench at room temper an ture. Results are recorded at the end of three days. Compound Concentration z % Mortality dimethyl N,N'-[[1,3 propanediylbis(oxycarbonyl- .12 95 (N-methylimino)thio(N- .06 87 methylimino)carbonyloxy]]] bis-[ethanimidothioate] dimethyl N,N'-[[1,5 pentanediylbis[oxycarbony1' ,12 (N-methylimino)thio(N- .36 80 1) Obtained at Wadmalaw Island, Georgia, during 1977. Compound (Continued) Concentration * % Mortality methylimino)carbonyloxy]]] bis-Eethanimidothioate] Untreated - 10 EXAMPLE III The foliage of red kidney bean plants in the two-leaf stage is sprayed to run-off with dispersions of compounds of this invention at various concentra tions. Dispersions are prepared by dissolving appropri ately weighed quantities of the active ingredient in 10 ml of acetone and diluting to 100 ml with water con taining surface active agent (DuponolE L-144 WDG) at 1:3000. After drying, plants are placed under arti ficial light in a room maintained at 25 + 20C, 54 t 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 fresh. Ten southern armyworm larvae are placed in each dish. The units are kept in a room maintained at 25 + 20C, 54 # 5% RH. Results are recorded at the end of two days. Days (% Dead) Compound . Concentration % 2 7 9 dimethyl-N,N-[[1,2 ethanediylbis!oxycarbonyl .01 95 100 100 (N-methylimino)thio(N- .005 95 95 80 methylimino)carbonyloxy))l- bis-Iethanimidotflioatel dimethyl N-N'-[[1,3 propanediylbis[oxycarbonyl- .01 100 100 95 (N-methylimino)thio(N- .005 100 100 90 methylimino)carbonyloxy]]] bis-[ethanimidothioate] Compound (Continued) Concentration 8 Days (* Dead) 2 7 9 dimethyl N,N'-i2,2-propane- diylbis[4,1-phenyleneoxy- .01 100 100 carbonyl-(methylimino) thio-(N-methylimino)car- .005 95 95 - bonyloxy]ibis(ethanimido- thioate) Untreated Check O 0 O 0 EXAMPLE IV Potted cotton plants approximately 25 cm high having 3-4 true leaves are sprayed to run-off with aqueous dispersions of compounds of this invention at 500 ppm. The sprays contain surface active agent (DuponolS L-144 WDG) at a concentration of 1:3000. Another set of plants is similary treated with metho myl. After drying, plants are set out in the green house and held for observation. Compoound (500 ppm Ar)Ú/ Ratingê/ (6 Days) dimethyl-N,N-[[1,2 ethanediylbistoxycarbonyl- .2R (N-methylimino)thio(N methylimino)carbonyloxy]]] bis-[ethanimidothioate] dimethyl-N-N'-[[1,3 propanediylbis [oxycarbonyl- .1R 1Al = active ingredient. 2"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, with 10 indicating total leaf area involvement. Compound (500 ppm AI)(Cont1d) Rating (6 Days) (N-methylimino)thio(Nmethylimino) carbonyloxy bis- Eethanimidothioate] methyl 2-(dimethylamino-N- Trace R [[[[[[N-methyl[[[[[N-methyl [[[[3-[[[N-methyl[[N-methyl[N (l-methylthioethylidene) aminooxycarbonyl]aminothio] ]- aminocarbonyloxy]]]propoxycarbonyloxy]]]]aminothio]]]]]aminocarbonyloxy]]]]]]-2-oxo-[ethanimido thioate] Methomyl 3K Untreated Control O EXAMPLE V Fall armyworm larvae are treated topically with compounds of the invention. One microliter of each concentration used is applied to the dorso-thoracic area of each larva tested. The stock solutions are prepared by dissolving appropriately weighed quantities of active ingredient ih predetermined quantities of acetone. Further diluting with acetone yields the desired concentrations. After treating the 15 fall armyworm larvae with each desired concentration, they are placed on artificial diet in 118 ml squat cups. The units are kept in a chamber at 27 + 2 C. Results are recorded 2 days after treatment. Concentration % Mortality Compound (g/larva) (48 hrs) dimethyl-N,N-[[1,2 ethanediylbis[oxycarbonyl- 4 93 (N-methylimino)thio(N- 2 87 methylimino)carbonyloxy]]] bis-[ethanimidothioate] dimethyl N,N'-[[1,3 propanediylbis[bxycarbonyl- 4 100 a (N-methyliminÏ)thio(N- 2 100 methylimino)carbonyloxy]]] bis- [ethanimidothioatel dimethyl N,N'-[[1,5 pentanediylbis[oxycarbonyl- 4 100 (N-methylimino)thio(N- 2 93 methylimino) carbonyloxy1 11- bis- [ethanimidothioate] Untreated - 13 EXAMPLE VI The under surfaces of four 4 cm red kidney bean leaf discs are treated with acetone solutions of compounds of this invention at various concentrations. Solutions are prepared by dissolving appropriately weighed quantities of the active ingredient in 10 ml of acetone and diluting further with the appropriate quantities of acetone. After drying, the. discs are placed into covered 10 cm petri dishes along with moist filter paper to keep them fresh. Seven Mexican bean beetle larvae are placed into each dish. The units are kept in a room maintained at 250 + 20 C, 50% RH. Results are recorded at the end of 5 days. Compound Concentration % % Mortality dimethyl-N,N'-[[1,3 propanediylbis[oxycarbonyl- .01 100 (N-methylimino) thia (N- methylimino)carbonyloxy]]] bis-[ethanimidothioate] dimethyl N,N'-[[1,5 pentanediylbis[oxycarbonyl- 01 84 (N-methylimino)thio(N methzylimino)carbonyloxy]]] bis-[ethanimidothioate] Untreated - 0 EXAMPLE VII Twenty-five house fly adults are secured in screened stainless steel ring cages and treated with acetone dispersions of compounds of this invention at various concentrations. The stock solution is pre pared by dissolving appropriately weighed quantities of active ingredient in predetermined quantities of acetone. Further diluting with acetone yields the desired concentrations. After treating, the units are kept in a room maintained at 250 + 2 C, 50% RH. Results are recorded at, the end of 1 day. Compound Concentration % % Mortality dimethyl-N-N'-[11,3- propanediylbis[bxycarbonyl- 0.2 100 (N-methylimino)thio(Nmethylimino)carbonyloxy]]]bis-[ethanimidothioate] EXAMPLE VIII Dimethyl N,N'-[[1,2-ethanediylbis[oxycarbonyl (N-methylimino) thio(N-methylimino) carbonyloxy]]]-bis-[ethanimidothioate], was dissolved in acetone and mixed into soil containing the rootknot nematode, Meloidogyne incognita- Dimethyl N,N' [[1,3-propanediylbis[oxycarbonyl (N-methylimino)thio (N-methylimino)carbonyloxy]]]bis-[ethanimidothioate], was similarly dissolved in acetone and mixed into soil containing the root-knot nematode, Meloidogyne incognita. The treated soil samples were planted with cucumber seeds. After two weeks, the roots were examined for nematode injury and the results are summarized below. kg/ha % Nematode Control dimethyl-N,N-[11,2- ethanediylbis[oxycarbonyl (N-methylimino)thio(N methylimino) carbonyloxy]] 1- bis- tethanimidothioatel dimethyl N-N'-[[1,3- 15 100 propanediylbis[oxycarbonyl (N-methyliminÏ)thio(N- methylimino)carbonyloxy]]]- bis-[ethanimidothioate] Untreated Control 0 * * * "Consisting essentially of" is intended to have its customary meaning: namely, that all speci- fied materials and conditions are very important in practicing the invention but that unspecified materials and conditions are not excluded as long as they do not prevent the benefits of the invention from being realized.

Claims: Claims: 1. A compound of the formula EMI61.1 R2, R3, R5 and R8 are independently C1-C3 alkyl; and R7 are independently C1-C3 alkyl or CH3OCH2-; A is -(CT1T2)k (CT3T4Ll(CT5T6)m; EMI62.1 -CT1T2CT3T4-OCT1T2CT3T4)-OCT1T2CT3T4 p X and Y are independently NR6, O or S; T1 to T6 are independently hydrogen or C1sC2 alkyl; R6 is H or alkyl C1-C3 R9 is alkyl C1-C3, EMI62.2 V is O, S(O)n, CT7T8; R10 is H, alkyl of C1-C3, Cl; T7 is H, C1-C2 alkyl, carboalkoxy alkyl of 3-8 carbon atoms, C2-C4 carboalkoxy; T8 isH, alkyl C1-C4; T7 and T8 may be taken together to form a carbocyclic ring of 5-6 carbons; Q is 0-2; k, l, m are independently 0-3; ; n, p are independently 0-2, provided al the sum of k, l and m is at least twot b) the total carbon content of -(CT1T2)K; (CTeT4)l (CT5T6)m- will not exceed H; c) when A is -CH2CH2NCH2CH2, R9 then X and Y are both oxygen and R - R1 d) when A is CT1T2CT3T4 [OCT1T2CT3Y4]n -OCT1T2CT3T4, X and Y are both oxygen. 2. A compound of Claim 1 where R = R1. 3. A compound of Claim 2 where R and R1 both are EMI63.1 X and Y are both oxygen; A is (CTlT2)k(CT3T4) l(CT3-T6 m or EMI63.2 k, t and mare independently 0-3. 4. A compound of Claim 3 where R and R1 both are EMI63.3 5. A compopnd of claim 4 where R2, R3 and K5 are methyl; R4 is C1-C2 alkyl; A is (CT1T2) (CT3T4)l (CT3-T6)m or EMI63.4 T1-T6 are hydrogen; provided the sum of k, t and m total not more than 5. 6. Dimethyl N,N'-[[1,2-ethanediylbis[oxycarbonyl(N-methylimino)thio(N-methylimino)carbonyloxy]]]bis-[ethanimidothioate]. 7. Dimethyl N-N'-[[1,3-propanediylbis[oxycarbonyl (N-methylimino)thio(N-methylimino)carbonyloxy]]] bis- [ethanimidothioatej. 8. Dimethyl N,N'-±[2,2-propanediylbis[4,l- phenyleneoxycarbonyl (N-methylimino) thio (N-methylimino) - carbonyloxy]]]bis-[ethanimidothioate]. 9. An agricultural'composition consisting essentially of a diluent, surfactant or mixtures thereof and a pesticide characterised in that said pesticide is a compound of any of claims 1-8. 10. A method for controlling insects or nematodes by applying to a locus to be protected an insecticidally or nematicidally effective amount of a pesticide characterised in that said pesticide is a compound of any of claims 1-8. 11. A method for preparing a compound of claim 1 which comprises (a) where R = R1, contacting in the presence of an acid acceptor EMI64.1 (b) contacting in the presence of an acid acceptor EMI64.2 (c) where K = R1 and R2 = R3 ¯ CH3, contacting in the presence of an acid acceptor (i) HX-A-YH EMI65.1 or EMI65.2 (d) where R is different from R1 and R2 R R3 = CH3, contacting in the presence of an acid acceptor EMI65.3

Inventors: HAY, JAMES VOLNEY
Applicants: E.I. DU PONT DE NEMOURS AND COMPANY
Application year: 1979
Main classification: C07C145
IPC codes: C07C381, C07C67, C07C325, A01N47