EP0000283B1

EP0000283B1 - Substituted carbamates, preparation and compositions thereof and use thereof as insecticides.

Info

Publication number: EP0000283B1
Application number: EP78300097A
Authority: EP
Inventors: Richard Frank Sauers
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 1977-07-01
Filing date: 1978-06-28
Publication date: 1981-10-14
Also published as: CA1107292A; IL55050A0; GR64548B; GB2001628A; IT7825229A0; GB2001628B; EG13741A; JPS5444614A; MX5138E; ES471280A1; DE2861154D1; IT1158872B; AR220138A1; PL208044A1; OA05999A; PH13803A; PL114208B1; BR7804185A; EP0000283A1; TR19962A

Description

This invention relates to substituted carbamates, preparation thereof and use thereof as insecticides for the control of pestiferous insects.
Belgian Patent No. 848,912, granted May 21, 1977, relates to insecticidal symmetrical bis- carbamoyl sulfide compounds of the following general formula:
wherein:

R is:
and
R' is alkyl containing from one to four carbon atoms. Among the numerous compounds which are included in the Belgian Patent are those wherein R₂ is alkyl, optionally substituted with one or more alkylthio groups, and wherein R₃ is hydrogen alkyl or alkoxy. The patentee states, however, that while compounds according to the above formula wherein R₂ is an alkylthioalkyl substituent and R₃ is hydrogen exhibit good pesticidal activity, their mammalian toxicity is unacceptably high.

U.S. Patent 4,004,031 issued January 18, 1977, discloses insecticidal compounds of the formula:
wherein R is an alkyl group of one to five carbons.
U.S. Patent 3,576,834 issued April 27, 1971, relates to insecticidal compounds having the structure:
such as methomyl.
This invention relates to compounds of Formula I, their preparation, to insecticidal compositions containing them and to the method of using said compounds as insecticides.
wherein

R is a branched or straight chain alkyl group of 1-3 carbon atoms or CH₂0CH₃;
R₁ is a branched or straight chain alkyl group of 1-3 carbon atoms;
and
Z is oxygen or sulfur.

Compounds which are preferred for their high insecticidal activity are those compounds of Formula I wherein

R is methyl or ethyl; and
R₁ is methyl.
More preferred for their higher insecticidal activity are those compounds of Formula I wherein R is methyl;
R₂ is -CH₂CH_2-; and preferably R₁ is methyl.

We prefer those compounds of Formula I wherein R₂ is
Specifically preferred for its outstanding insecticidal activity is dimethyl N,N'[[1,2-ethanediylbis[thio(methylimino)carbonyloxy]]]bis(ethaneimidothiate).
The compounds of Formula I can be prepared, as shown in Equation A,by reacting preferably at least two moles of a substituted N-(aminocarbonyloxy)-alkanimidothioic acid ester of Formula II with one mole of an alkane disulfenyl halide of Formula III in the presence of a base:
wherein R, R₁, and R₂ are as previously defined and X is halogen.
The reaction can be carried out in any organic solvent which is inert to the reactants and the reaction products, e.g. methylene chloride, dioxane, tetrahydrofuran, chloroform, 1,2-dichloroethane, acetonitrile, benzene, toluene, the xylenes, acetone or methyl ethyl ketone. Mixtures of such solvents can also be used. A base which will function as an acid acceptor can be used in synthesizing the compounds of this invention.
The process can be carried out at a temperature of between about -20° and 60°C, preferably between about -5° and 40°C. Pressure is not critical; for convenience, atmospheric pressure is preferred.
Preparation of the compounds of Formula II used as starting materials is described in U.S. Patents 3,574,736; 3,576,834 and 3,787,470.
In the compounds of Formula III, chlorine is the preferred halogen for economic reasons, and those compounds can be prepared by a suitable modification of the methods described in the Journal of Heterocyclic Chemistry, 6, 629 (1969). Alkane sulfenyl halides, such as those of Formula III wherein X is fluorine, bromine, or iodine, are also known and may be prepared by the methods reviewed in Synthesis, 11, 561-580 (1970).
In the examples which follow, which are illustrative only, temperatures are given in degrees centigrade.

Example 1

Ethane-1,2-bisthioacetate

To a solution of 141 g of sodium methoxide in 1 of absolute ethanol, under a dry nitrogen atmosphere, was added 200 g of thiolacetic acid dropwise with stirring over a period of 20 minutes. Ethylene dibromide (229.2 g) was then added and the reaction heated to reflux for five hours. The reaction mixture was cooled, sodium bromide was filtered off, and the ethanol was removed under vacuum. The residue was taken up in diethyl ether, washed with water, dried over anhydrous magnesium sulfate and the crude product isolated by distillation of the diethyl ether solvent. After recrystallization from hexane, the product, ethane-1,2-bisthiolacetate, melted at 68-70°.

Example 2

Ethane-1,2-Disulfenyl Chloride

Sulfuryl chloride (54 g) was added dropwise to a solution of 35.6 g of ethane-1 ,2-bisthiolacetate in 200 ml of methylene chloride at ambient temperature. After stirring for 45 minutes at room temperature the methylene chloride solvent and volatile by-products were removed by vacuum distillation of 0°. The yellow product, ethane-1,2-disulfenyl chloride, melted at 32-34^0.

Example 3

Dimethyl N,N'[[1,2-ethanediylbis[thio(methylimino)carbonyloxy]]]bis(ethanimidothioate)

A solution of 6.5 g of N-(methylaminocarbonyloxy)ethanimidothioic acid, methyl ester, in 50 ml methylene chloride and 2.0 ml of pyridine was prepared. To that solution was added dropwise 28 gm of ethane-1,2-disulfenyl chloride, dissolved in 25 ml of methylene chloride, with stirring over a period of 10 minutes. The reaction was slightly exothermic. After stirring for about 16 hours at ambient temperature, the reaction mixture was washed with water, dried over anhydrous magnesium sulfate, and the crude product isolated by distilling off the methylene chloride solvent. After recrystallization from ethyl alcohol followed by recrystallization from acetonitrile, the product, dimethyl N,N'-[[1,2-ethanediylbis[thio(methylimino)carbonyloxy]]]bis(ethanimidothiate), melted at 176-179°.
By reacting equivalent amounts of other compounds of Formula II with compounds of Formula III using the procedures of Examples 1, 2 and 3, the following compounds of Formula I can be prepared.

Formulation

Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, 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 litres to several thousand litres per hectare (from a few pints to several hundred gallons per acre). High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain e.g. about 1% to 99% by weight of active ingredient(s) and at least one of (a) e.g. about 0% to 20% surfactant(s) and (b) e.g. about 1% to 99% solid or liquid diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:
Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. 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 0°C. "McCutcheon's Detergents and Emulsifiers Annual," McCutcheon Division, MC Publishing Co., Ridgewood, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents," Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc.
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 "Perry's Chemical Engineer's Handbook," 4th Edn., McGraw-Hill, N.Y., 1963, 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, 1971, Col. 5, line 36 through Col. 7, line 70 and Exs. 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 Exs. 3-9, 11-18.
E. Somers, "Formulation," Chapter 6 in Torgeson, "Fungicides," Vol. I, Academic Press, New York, 1967.

Example 4

Wettable Powder

The ingredients are thoroughly blended, passed through an air mill, to produce an average particle size under 15 µm, reblended, and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) before packaging.
All compounds of the invention may be formulated in the same manner.

Example 5

The ingredients are blended, coarsely hammer milled and then air milled to produce particles of active ingredient essentially all below 10 µm in diameter. The product is reblended before packaging.

Example 6

The ingredients are thoroughly blended. The liquid surfactant is added by spraying upon the solid ingredients in the blender. After grinding in a hammer mill to produce particles essentially all below 100 µm, the material is reblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged.

Example 7

The ingredients are ground together in a ball or roller mill until the solid particles have been reduced to diameters under 10 µm.

Example 8

The ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 µm. The resulting thick suspension may be applied directly, but preferably after being extended with oils or emulsified in water.

Example 9

A slurry of wettable powder containing 50% solids is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged.

Example 10

The ingredients are blended, hammer-milled and then moistened with about 12% water. The mixture is extruded as cylinders about 5 mm diameter which are cut to produce pellets about 3 mm long. These may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm opening). The granules held on a U.S.S. No. 40 sieve (0.42 mm opening) may be packaged for use and the fines recycled.

Exam_Dle 11

The ingredients are blended and ground in a hammer mill to produce a high-strength concentrate essentially all passing a U.S.S. No. 50 sieve (0.3 mm opening). This material may then be formulated in a variety of ways.

Example 12

The ingredients are thoroughly blended and packaged for use.

Example 13

The ingredients are combined and stirred to produce a solution which can be emulsified in water for application.

Example 14

The ingredients are combined and stirred with gentle warming to speed solution. A fine screen filter is include in packaging operation to ensure the absence of any extraneous undissolved material in the product.

Use

The compounds of this invention are useful for control of insects which are detrimental to agriculture.
As demonstrated in Examples 16 to 18 below, improved residual insecticidal properties as well as decreased phytotoxicity are obtained with a formulation containing a compound of Formula I.
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: cotton bollworm (Heliothis zeaJ, tobacco budworm (Heliothis virescens), southern armyworm (Spodoptera eridania), beet armyworm (Spodoptera exigua), soybean looper Pseudoplusia includensJ, Mexican bean beetle (Epilachna varivestis), and the house fly (Musca domestica).
The insects are controlled by applying the compound to the locus of infestation, to the area to be protected, or to the pests themselves. For the control of insects in agricultural crops, a compound of Formula I is 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 species to be controlled, its life stage, its size and location, the amount of rainfall, the time of year, moisture, temperature, type of application, and other variables. In general, 0.1 to 10 kg/ha may be required for insect control in agriculture with rates of .2 to 4 kg/ha usually being sufficient in many situations. In large-scale field operations, rates in the range of 1/4 to 2 kg/ha are generally used.
The compounds of this invention will generally be used in formulation with a carrier that commonly will contain oil or water. Applications may be made with concentrated or dilute suspensions of the insecticide in the carrier. Low-volume applications utilizing dispersions containing about 20% of the active ingredient may be preferred by some applicators while others may prefer dilute suspensions containing only 25 ppm in high-volume applications.
The compounds of this invention possess significant advantages over prior art compounds, e.g. fewer applications are required to provide a given level of insect control due to this distinctly longer residual insecticidal action. Use of fewer applications results in greater economy to the grower and dissemination of less insecticide in the environment. An additional advantage is lower phytotoxicity to cotton.
Conventionally, the compounds will be incorporated into a formulation in a known manner with incorporation of other components such as (a) surfactants, (b) diluents, (c) additives to reduce foam or corrosion, or (d) preservatives to control microbiological growth.
The compounds of this invention can be mixed with fungicides, bactericides, acaricides, nematicides, other insecticides, or other biologically active compounds in order to achieve desired results with a minimum expenditure 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; the terms "Monocide", "Morestan", "Folbex", "Kelthane", "Pentac", "Furadan", "Pyridin" and "Ambush" are Trade Marks, at least in Great Britain.
Fungicides:

methyl 2-benzimidazolecarbamate;
tetramethyl thiuram disulfide (thiuram);
n-dodecylguanidine acetate (dodine);
manganese ethylenebisdithiocarbamate (maneb);
1,4-dichloro-2,5-dimethoxybenzene (chloroneb);
methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate (benomyl);
N-trichloromethylthiotetrahydrophthalimide (captan);
N-trichloromethylthiophthalimide (folpet);

Bactericides:

tribasic copper sulfate;
streptomycin sulfate;

Acaricides:

senecioic acid, ester with 2-sec-butyl-4,6-dinitrophenol (Morocide);
6-methyl-1 ,3-dithiolo[4,5-b]quinoxalin-2-one (Morestan@); ethyl 4,4'-dichlorobenzilate (Folbex);
1,1-bis(p-chlorophenyl)-2,2,2-trichloroethane (Kelthane);
bis(pentachloro-2,4-cyclopentadien-1-yl) (Pentac);
tricyclohexyl tinhydroxide (cyhexatin);

Nematicides:

S-methyl 1-(dimethylcarbamoyl)-N-(methylcarbamoyloxy)-thioformimidate (oxamyl);
S-methyl 1-carbamoyl-N-(methylcarbamoyloxy)thioformimidate;
N-isopropylphosphoramidic acid, O-ethyl-O'-[4-(methylthio)-m-tolyl]diester (fenamiphos);

Insecticides:

methylcarbamic acid, ester with 2,3-dihydro-2,2-dimethyl-7-benzofuranol (Furadan);
O-[2,4,5-trichloro-α-(chloromethyl)benzyl]phosphoric acid, O',O'-dimethyl ester (tetrachlorvinphos);
0-ethyl-0-(4-nitrophenyl)phenylphosphonothioate (EPN); octachlorocamphene (toxaphene);
cyano(3-phenoxyphenyl)methyl-4-chloro-alpha-(1-methylethyl)benzeneacetate (Pyridin);
(3-phenoxyphenyl)methyl(±)-cis,trans-3-(2,2-dichloroethenyl-2,2-dimethylcyclopropanecarboxylate
(Ambush); 3-phenoxybenzyl-dl-cis,trans-chrysanthemate (phenothrin);
2-mercaptosuccinic acid, diethyl ester, S-ester with thionophosphoric acid, dimethyl ester (malathion);
phosphorothioic acid, O,O-dimethyl, O-p-nitrophenyl ester (methyl parathion);
methylcarbamic acid, ester with α-naphthol (carbaryl);
methyl N-(methylaminocarbonyloxy)ethaneimidothioate (methomyl);
N'-(4-chloro-o-tolyl)-N,N-dimethylformamidine (chlordimeform);
0,0-diethyl-0-(2-isopropyl-4-methyl-6-pyrimidylphosphorothioate (Diazinon);
O,S-dimethylacetylphosphoramidothioate (acephate);
O,S-dimethylphosphoramidothioate (methamidophos).

Example 15

The foliage only of red kidney bean plants in the two-leaf stage was sprayed to run-off with aqueous dispersions of dimethyl N,N'-[[1,2-ethanediylbis[thio(methylimino)carbonyloxy]]]bis(ethan- imidothioate) (I) at the dilutions indicated. The sprays contained Duponol L-144-WDG (sulfonated oleyl acetate surfactant) at a concentration of 1:3000. After drying, a single leaf from each treated plant was excised and placed in a covered 20 x 100 mm Petri dish containing a moistened filter paper and 10 southern armyworm (SAW) larvae approximately 13 mm in length. The test was conducted in duplicate. Insect mortality was evaluated two days later and is recorded below.

Example 16

The plants from the test described in Example 1 were kept in a growth room at 77 ± 2°F and 53 ± 5% relative humidity for 7 days. At the end of that period of time the remaining cotyledonary leaf from each bean plant was placed singly in a Petri dish with southern armyworms as previously described. Insect mortality was again read 2 days later and is set forth below:

Example 17

Cotton plants approximately 22 cm in height having 3-4 true leaves were sprayed to run-off with an aqueous dispersion of dimethyl N,N'-[[1,2-ethanediylbis[thio(methylimino)carbonyl- oxy]]]bis(ethanimidothioate) (I) at a concentration of 0.05%. The spray contained Duponol L-144-WDG at a concentration of 1:3000. Another set of plants was similarly treated with methomyl. Plant injury was evaluated 6 days after treatment and is recorded below.

Claims

1. A compound of the formula

wherein

R is branched or straight chain alkyl containing 1 to 3 carbon atoms or methoxymethyl;

R, is branched or straight chain alkyl containing 1 to 3 carbon atoms;

and

Z is 0 or S.

2. A compound of claim 1 wherein R is methyl or ethyl and R₁ is methyl.

3. A compound of claim 1 or 2 wherein R is methyl and R₂ is -CH₂CH_2-.

4. A compound of claim 1 wherein R₂ is ―CH₂CH₂― or

5. A compound of claim 1 which is dimethyl-N,N'-[[1,2-ethanediylbis[thio(methylimino)car- bonyloxy]]]bis(ethaneimidothioate) having the formula:

6. A composition suitable for control of pestiferous insects comprising an effective amount of an insecticidal compound and at least one of (a) an inert diluent and (b) a surfactant characterised in that said insecticidal compound is a compound of any of claims 1-4.

7. The composition of claim 6 wherein said insecticidal compound is the compound of claim 5.

8. A method for control of pestiferous insects by applying to a locus of infestation, to the area to be protected or to the pests themselves, an effective amount of an insecticidal compound characterised. in that said insecticidal compound is a compound of any of claims 1-4.

9. The method of claim 8 wherein said insecticidal compound is the compound of claim 5.

10. A process for preparing a compound of claim 1 characterised in that compounds of the formulae:

wherein

X is a halogen atom; and

R, R₁ and R₂ are as defined in claim 1, are reacted in an inert organic solvent in the presence of a base.