Oxime carbamates

Abstract

Novel oxime-carbamates of the formula ##SPC1##WhereinR.sub.1 is --CH.sub.3, --CH(CH.sub.3).sub.2, ##EQU1## --C(CH.sub.3).sub.3, or --C.sub.6 H.sub.5 ; R.sub.2 is --H or --CH.sub.3 ;R.sub.3 is --CH.sub.3, --CH.sub.2 CH.sub.3, --(CH.sub.2).sub.2 CH.sub.3, --(CH.sub.2).sub.3 CH.sub.3, --CH.sub.2 CH.sub.2 Cl or --C.sub.6 H.sub.5 ;R.sub.4 is --H, --CH.sub.3, --CH.sub.2 CH.sub.3, --(CH.sub.2).sub.2 CH.sub.3, --CH(CH.sub.3).sub.2, --(CH.sub.2).sub.3 CH.sub.3, --CH.sub.2 CH=CH.sub.2, --CH.sub.2 C.tbd.CH, --C.sub.6 H.sub.5, ##EQU2## --CH (OH)CCl.sub.3, --CH.sub.2 CH.sub.2 X.sub.1, where X.sub.1 is --Cl, --Br, --NH.sub.2, --OH, --OCOCH.sub.3, --OCOCH.sub.2 Cl, or --OCONHCH.sub.3 ;R.sub.5 and R.sub.6 are each --H or --CH.sub.3, with the proviso that when R.sub.5 and R.sub.6 are both CH.sub.3 then both CH.sub.3 groups may be on either the same carbon atom or on different carbon atoms;R.sub.7 is H, --CH.sub.3 or --CH.sub.2 C.sub.6 H.sub.5 ;X.sub.2 is --Cl, --Br or --I; andn is O or 1, with the proviso that when n is 1 then Nbears a + charge and X.sub.2 bears a - charge.These compounds are useful as insecticides and acaricides.

Description

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel oxime-carbonates and their use as insecticides and acaricides.

2. Description of the Prior Art

A number of carbamates are known to exhibit insecticidal properties. Included among these are the following currently available in commerce: ##SPC2##

In addition, there is also a limited number of oxime-carbamates in use, such as, for example:Compound U.S. Patent No. Trademark______________________________________CH.sub.3 S.angle.C=NOCONHCH.sub.3 METHOMYLCH.sub.3CH.sub.3.vertline.CH.sub.3 SCC=NOCONHCH.sub.3 3,217,037 TEMIK.vertline..vertline..vertline.H.vertline.CH.sub.3______________________________________

However, the present oxime-carbamates, which may also be described as dihydropyrazinone oxime carbamates are novel compounds which display exceptional insectidical activity.

SUMMARY OF THE INVENTION

The present invention relates to novel oxime-carbamates and to the use of these compounds in the control of insects and acarids. The compounds of particular interest are those represented by the formula ##SPC3##

Where R.sub.1 is --Ch.sub.3, --CH(CH.sub.3).sub.2, ##EQU3## --C(CH.sub.3).sub.3, or --C.sub.6 H.sub.5 ; R.sub.2 is --H or --CH.sub.3 ; R.sub.3 is --CH.sub.3, --CH.sub.2 CH.sub.3, --(CH.sub.2).sub.2 CH.sub.3, --(CH.sub.2).sub.3 CH.sub.3, --CH.sub.2 CH.sub.2 Cl or --C.sub.6 H.sub.5 ; R.sub.4 is --H, --CH.sub.3, --CH.sub.2 CH.sub.3, --(CH.sub.2).sub.2 CH.sub.3, --CH(CH.sub.3).sub.2, --(CH.sub.2).sub.3 CH.sub.3, --CH.sub.2 CH=CH.sub.2, --CH.sub.2 C.tbd.CH, --C.sub.6 H.sub.5, ##EQU4## --CH(OH)CCl.sub.3, --CH.sub.2 CH.sub.2 X.sub.1, whereas X.sub.1 is --Cl, --Br, --NH.sub.2, --OH, --OCOCH.sub.3, --OCOCH.sub.2 Cl, or -- OCONHCH.sub.3 ; R.sub.5 and R.sub.6 are each --H or --CH.sub.3, with the proviso that when R.sub.5 and R.sub.6 are both CH.sub.3 then both CH.sub.3 groups may be on either the same carbon atom or on different carbon atoms. R.sub.7 is --H, --CH.sub.3 or --CH.sub.2 C.sub.6 H.sub.5 ; X.sub.2 is --Cl, --Br or --I; and n is 0 or 1, with the proviso that when n is 1 then N bears a + charge and X.sub.2 bears a - charge.

The present invention also provides a method for the control of insect and acarid infestation which comprises applying either to the locus of said infestation, or systematically, a pesticidally effective amount of an oxime-carbamate having the formula ##SPC4##

wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, X.sub.2 and n have the meanings hereinbefore disclosed.

Illustrative examples of the oxime-carbamates encompassed within the above described general formula are the following compounds: (Note -- the ##EQU5## group is indicated as ) ##SPC5##

As hereinbefore stated, the compounds of the present invention are useful as insecticides and acaricides. They are conveniently applied to the locus of infestation in a variety of ways, for example, as a solution in an organic solvent, as an emulsion, as a spray, on an inert carrier such as clay, kaolin, talc, bentonite, attapulgite, or diatomaceous earth and the like, or as a formulated product in liquid or solid form. The present compounds may also be applied systemically in the same variety of ways. Useful organic solvents are the aromatics such as toluene, xylene, benzene, cyclohexane, and alkylated coal tar distillates, aliphatics such as naphthas and petroleum distillates, and various combinations of alcohols, esters, ketones and chlorinated compounds. The present insecticides may be provided as concentrated wettable powders containing as much as 80-90% active ingredient, or as concentrates in solid, liquid, or paste form containing 25-75% by weight of toxicant which may be diluted for application as desired, or as formulated products containing as little as about 5-10% active ingredient.

PREPARATION

The oxime-carbamates of this invention are prepared by utilizing the following general reaction employing the indicated reactants: ##SPC6##

where R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 have the meanings hereinbefore described.

By varying Reactant B so that R.sub.5 and R.sub.6 are on the same or adjacent carbon atoms, it is possible to prepare compounds in which R.sub.5 and R.sub.6 are on the same or adjacent carbon atoms.

Reactants A (Chloro-oxime carbamates) are conveniently prepared by known methods. Reactants B (ethylenediamines), may be utilized as either the dihydrochloride salts or as the free bases. They too are prepared by known methods or purchased commercially.

The foregoing General Reaction is illustrated by Example 1 which describes the preparation of Compound No. 1.

EXAMPLE 1

A solution of 20 g. (0.112 mole) of 1-acetyl-1-chloroformaldoxime-N-methylcarbamate (Reactant A) in 200 ml. methanol was stirred in an ice bath while 13.4 g. (0.224 mole) of ethylenediamine (Reactant B) was added. After stirring for 30 minutes at ambient temperature, the reaction mixture was evaporated to dryness under reduced pressure. Chloroform (200 ml.) was added and the precipitated ethylenediamine hydrochloride removed by filtration. The filtrate was evaporated to dryness and the residue extracted with boiling ethyl acetate. The extract was evaporated and the extraction process repeated with benzene. Cooling of the hot benzene extract and filtration provided 13.1 g. (63%) of Compound No. 1 as a light yellow solid, m.p. 129.degree.-130.degree.C.

EXAMPLES 2-7

The following table, Table 1, summarizes the preparation of Compound Nos. 2-7 by the same procedure as set forth in Example 1, with the exception that the reactants A and B were varied as indicated.

Table 1__________________________________________________________________________Reactants ProductExample A B (Compound No.)__________________________________________________________________________ OCl .parallel..vertline.2 CH.sub.3 C--C=NOCON(CH.sub.3).sub.2 H.sub.2 NCH.sub.2 CH.sub.2 NH.sub.2 2 OCl .parallel..vertline.3 CH.sub.3 C--C=NOCONH(CH.sub.2).sub.2 CH.sub.3 " 3 OCl .parallel..vertline.4 CH.sub.3 C--C=NOCONHC.sub.6 H.sub.5 " 4 OCl .parallel..vertline.5 (CH.sub.3).sub.2 CHC--C=NOCONHCH.sub.3 " 5 0Cl .parallel..vertline.6 C--C--NOCONHCH.sub.3 " 6 O Cl .parallel..vertline.7 C.sub.6 H.sub.5 C--C=NOCONHCH.sub.3 " 7__________________________________________________________________________

In those instances where the product does not solidify, it is purified by silica gel chromatography.

EXAMPLE 8

Compound No. 11 was prepared in the following manner: A solution of 5.0 g. (0.028 mole) of 1-acetyl-1-chloroformaldoxime-N-methylcarbamate (Reactant A) in 20 ml. of chloroform (or methanol) was added to a stirred mixture of 2.47 g. (0.028 mole) of N-ethylethylenediamine (Reactant B) and 10 g. of anhydrous potassium carbonate in 30 ml. of chloroform at 5.degree.-10.degree.C. The reaction was stirred 4 hours at room temperature, 2 g. of magnesium sulfate was added and the mixture filtered. The filtrate was evaporated to dryness giving 7.4 g. of an oil which was redissolved in chloroform, washed with water, and dried over magnesium sulfate. After removal of the solvent, the solid was slurried in petroleum ether to give 4.75 grams (80%) of Compound No. 11 as a cream-colored solid, mp 68.degree.-72.degree.C. In those instances where the product does not solidify, it is purified by column chromatography.

EXAMPLES 9-28

The following table, Table 2, summarizes the preparation of Compound Nos. 8-10, 12-18, 30-34, 40-44, and 52 by the procedure set forth in Example 8, except that the Reactants A and B were varied as indicated.

Table 2__________________________________________________________________________Reactants ProductExample A B (Compound No.)__________________________________________________________________________ OCl NH.sub.2 .parallel..vertline. .vertline. 9 CH.sub.3 C--C=NOCONHCH.sub.3 CH.sub.3 CHCH.sub.2 NH.sub.2 8 NH.sub.2 .vertline.10 " (CH.sub.3).sub.2 C--CH.sub.2 NH.sub.2 9 0Cl .parallel..vertline.11 CH.sub.3 C--C=NOCONHCH.sub.3 CH.sub.3 NHCH.sub.2 CH.sub.2 NH.sub.2 10 OCl .parallel..vertline.12 CH.sub.3 C--C=NOCON(CH.sub.3).sub.2 CH.sub.3 CH.sub.2 NHCH.sub.2 CH.sub.2 NH.sub.2 12 OCl .parallel..vertline.13 CH.sub.3 C--C=NOCONHCH.sub.2 CH.sub.3 " 13 OCl .parallel..vertline.14 CH.sub.3 C--C=NOCONH(CH.sub.2).sub.2 CH.sub.3 " 14 OCl .parallel..vertline.15 CH.sub.3 C--C=NOCONHCH.sub.2 CH.sub.2 Cl " 15 OCl .parallel..vertline.16 CH.sub.3 C--C=NOCONHCH.sub.3 CH.sub.3 (CH.sub.2).sub.2 NHCH.sub.2 CH.sub.2 NH.sub.2 1617 " (CH.sub.3).sub.2 CHNHCH.sub.2 CH.sub.2 NH.sub.2 17 OCl .parallel..vertline.18 CH.sub.3 C--C=NOCONHCH.sub.3 CH.sub.3 (CH.sub.2).sub.3 NHCH.sub.2 CH.sub.2 NH.sub.2 18 O Cl .parallel..vertline.19 CH.sub.3 C--C=NOCONHCH.sub.3 H.sub.2 NCH.sub.2 CH.sub.2 NHCH.sub.2 CH.sub.2 NH.sub.2 30 OCl .parallel..vertline.20 CH.sub.3 C--C=NOCONHCH.sub.3 HOCH.sub.2 CH.sub.2 NHCH.sub.2 CH.sub.2 NH.sub.2 31 OCl .parallel..vertline.21 CH.sub.3 C--C=NOCON(CH.sub.3).sub.2 " 32 OCl .parallel..vertline.22 CH.sub.3 C--C=NOCONH(CH.sub.2).sub.3 CH.sub.3 " 33 OCl .parallel..vertline.23 C-- C=NOCONHCH.sub.3 " 34 OCl .parallel..vertline.24 CH.sub.3 C--C=NOCONHCH.sub.3 CH.sub.2 =CHCH.sub.2 NHCH.sub.2 CH.sub.2 NH.sub.2 40 OCl .parallel..vertline.25 CH.sub.3 C--C=NOCON(CH.sub.3).sub.2 CH.sub.2 =CHCH.sub.2 NHCH.sub.2 CH.sub.2 NH.sub.2 41 OCl .parallel..vertline.26 CH.sub.3 C--C=NOCONHCH.sub.3 CH.tbd.CCH.sub.2 NHCH.sub.2 CH.sub.2 NH.sub.2 42 OCl .parallel..vertline.27 CH.sub.3 C--C=NOCON(CH.sub.3).sub.2 " 43 OCl .parallel..vertline.28 CH.sub.3 C--C=NOCONHCH.sub.3 C.sub.6 H.sub.5 NHCH.sub.2 CH.sub.2 NH.sub.2 44 OCl .parallel..vertline.28A CH.sub.3 C--C=NOCON(CH.sub.3).sub.2 CH.sub.3 CH.sub.2 CH.sub.2 NHCH.sub.2 CH.sub.2 NH.sub.2 52__________________________________________________________________________

EXAMPLE 29

Compound No. 19 was prepared in the following manner: A suspension of 5.0 g. (0.028 mole) of 1-acetyl-1-chloroformaldoxime-N-methylcarbamate (Reactant A), 5.75 g. (0.029 mole) of N-(2-chloroethyl)-ethylenediamine dihydrochloride (Reactant B) and 2.5 g of magnesium sulfate in 30 ml. of tetrahydrofuran was stirred at 5.degree.-10.degree.C. and treated slowly with a solution of 12.5 ml. of triethylamine in 20 ml. of tetrahydrofuran. After the addition was completed, the reaction mixture was stirred 4 hours at room temperature, filtered and the filtrate evaporated to dryness giving 6.8 g. (98.5%) of oil which solidified on standing. The crude product was purified by redissolving in chloroform, washing with water, drying over magnesium sulfate, concentrating and slurrying the resulting solid with diethyl ether to give 3.9 g. (57%) of Compound No. 19 as a light yellow solid, m.p. 98.degree.-100.degree.C.

EXAMPLES 30-39

Compounds 20-29 were prepared according to the procedure set forth in Example 29, except that the Reactants A and B were varied as indicated in Table 3.

Table 3__________________________________________________________________________Reactants ProductExample A B (Compound No.)__________________________________________________________________________ OCl .parallel..vertline.30 CH.sub.3 --C--C=NOCONHCH.sub.3 ClCH.sub.2 CH.sub.2 NHCH.sub.2 CH.sub.2 NH.sub.2.2HC l 20 OCl .parallel..vertline.31 CH.sub.3 --C--C=NOCONHCH.sub.2 CH.sub.3 " 21 OCl .parallel..vertline.32 CH.sub.3 --C--C=NOCONH(CH.sub.2).sub.2 CH.sub.3 " 22 OCl .parallel..vertline.33 CH.sub.3 --C=C=NOCONH(CH.sub.2).sub.3 CH.sub.3 " 23 OCl .parallel..vertline.34 CH.sub.3 --C--C=NOCONHCH.sub.2 CH.sub.2 Cl " 24 OCl .parallel..vertline.35 (CH.sub.3).sub.2 CH--C--C=NOCONHCH.sub.3 " 25 OCl .parallel..vertline.36 C--C=NOCONHCH.sub.3 " 26 OCl .parallel..vertline.37 (CH.sub.3).sub.3 --C--C=NOCONHCH.sub.3 " 27 OCl .parallel..vertline.38 CH.sub.3 --C--C=NOCONHCH.sub.3 BrCH.sub.2 CH.sub.2 NHCH.sub.2 CH.sub.2 NH.sub.2.2HB r 28 OCl .parallel..vertline.39 CH.sub.3 C--C=NOCON(CH.sub.3).sub.2 " 29__________________________________________________________________________

EXAMPLE 40

Compound No. 36 was prepared in the following manner: A suspension of 2.28 g. (0.01 mole) of Compound No. 31 in 40 ml. of dichloromethane was cooled to 0.degree.C. and treated with 1.39 ml. (1.01 g., 0.01 mole) of triethylamine. A solution of 0.79 ml. (1.13 g., 0.01 mole) of chloroacetyl chloride in 5 ml. of dichloromethane was then added dropwise, the reaction temperature being maintained at 0.degree.C. After the mixture was allowed to warm to room temperature the solvent was evaporated. The residue was taken up in tetrahydrofuran and the amine salt removed by filtration. Evaporation of the solvent from the filtrate produced 3.8 g. of oil which was purified by chromatography over Florisil (20 g. packed in benzene) using chloroform as the eluting solvent. The product fractions were evaporated to dryness giving 0.94 g. of Compound No. 36 as a colorless oil. Alternatively the product could be purified by extraction of a benzene-dichloromethane (2:1) solution thereof with water followed by drying and concentrating the organic phase.

EXAMPLE 41

Compound No. 35 was prepared according to the procedure of Example 40, except that CH.sub.3 COCl was used instead of chloroacetyl chloride.

EXAMPLE 42

Compound No. 37 was prepared according to the procedure of Example 40 except that CH.sub.3 NCO was used instead of chloroacetyl chloride.

EXAMPLE 43

Compound No. 38 was prepared in the following manner: A mixture of 5.0 g. (0.027 mole) of Compound No. 1 and 4.0 g. (0.027 mole) of chloral in 30 ml. of benzene was stirred 12 hours at room temperature and filtered providing 8.7 g. (97%) of Compound No. 38 as a white solid, m.p. 155.degree.-156.degree.C.

EXAMPLE 44

Compound No. 39 was prepared according to the procedure of Example 43, except that Compound No. 2 (instead of Compound No. 1) was treated with chloral as set forth therein.

EXAMPLE 45

Compound No. 45 was prepared as follows: A solution of 3.0 g. (0.0134 mole) of Compound No. 40 in 30 ml. of chloroform was cooled to 0.degree.C. and treated cautiously with a solution of 1.4 g. of chlorine in 20 ml. of chloroform at 0.degree.C. After the excess chlorine as removed, the reaction mixture was cooled to 5.degree.C. and 20 g. of potassium carbonate was added followed by 5 ml. of water. The mixture was then filtered and evaporated to dryness leaving 3.8 g. of syrup which was purified by dissolving in 8 ml. of ethyl acetate and passing through a chromatographic column containing 40 g. of silica gel. The product was eluted with ethyl acetate-methanol (20:1). Evaporation of the solvent gave 1.4 g. of Compound No. 45 as a waxy semi-solid.

EXAMPLE 46

Compound No. 46 was prepared according to the procedure of Example 45, except that Compound 42 (instead of Compound No. 40) was treated with chlorine as set forth therein.

EXAMPLE 47

Compound No. 47 was prepared as follows: A solution of 5.0 g. (0.027 mole) of Compound No. 1 in 100 ml. of ethyl acetate was saturated with anhydrous hydrogen chloride. The resulting suspension was filtered and the hygroscopic solid dried in a vacuum desiccator affording 5.9 g. (99%) of Compound No. 47 as a cream-colored solid, m.p. 150.degree.-155.degree.C.

EXAMPLE 48

Compound No. 48 was prepared according to the procedure of Example 47 except that Compound No. 19 (instead of Compound No. 1) was treated with anhydrous hydrogen chloride.

EXAMPLE 49

Compound No. 49 was prepared as follows: A solution of 1.0 g. of Compound No. 1 in 5 ml. of ethyl acetate (or acetonitrile) and 2 ml. of methyl iodide was stirred overnight at room temperature, diluted with ethyl ether and the precipitated solid collected by filtration yielding 1.5 g. of Compound No. 49 as a light yellow solid, m.p. 185.degree.-190.degree.C.

EXAMPLE 50

Compound No. 50 was prepared according to the procedure of Example 49, except that Compound No. 19 (instead of Compound No. 1) was treated with methyl iodide as set forth therein.

EXAMPLE 51

Compound No. 51 was prepared by the procedure of Example 49, except that Compound 19 (instead of Compound No. 1) was treated with C.sub.6 H.sub.5 CH.sub.2 Br.

EFFICACY

The insecticidal and acaricidal activities of representative and typical oxime carbamates of this invention were determined according to the following described methods.

Test formulations of candidate samples were prepared by dissolving each candidate compound in acetone containing small amounts of emulsifier. The test formulations (solutions) were then diluted with water to obtain the desired active ingredient concentration. Where solubility was a problem, the diluted test formulation was wet ball-milled.

EXAMPLES 52-153A

TEST ORGANISMS

Southern Armyworm -- (Prodenia eridania), and Mexican Bean Beetle -- (Epilachna varivestis)

Lima bean leaves dipped into test solutions of the respective compounds were offered to ten larvae of the Southern Armyworm (late third instar) and the Mexican Bean Bettle (late second instar) for a 48-hour feeding period. Mortality data were recorded. In these tests, as in tests against all other organisms, untreated controls were included for comparative purposes.

Tables 4 and 5 summarize the activity of the indicated oxime carbamates against Southern Armyworms and Mexican Bean Beetles respectively. Blank spaces in these subsequent Tables mean that no tests were conducted at the corresponding particular concentrations.

TABLE 4______________________________________Test Organism: Southern Armyworm (Prodenia eridania) Percent MortalityExample Compound Application ConcentrationNo. No. 0.1 0.05 0.01 0.005______________________________________52 1 100 100 053 2 054 3 055 4 056 5 057 6 4058 7 059 8 100 100 90 4060 9 100 100 2061 10 100 100 062 11 100 90 063 12 8064 13 90 90 1065 14 066 15 067 16 100 100 80 5068 17 6069 18 7070 19 100 100 70 4071 20 4072 21 3073 22 074 23 075 24 076 25 077 26 078 27 079 28 100 80 60 080 29 081 30 082 31 5083 32 084 33 085 34 086 35 087 36 088 37 089 38 090 39 091 40 100 90 092 41 093 42 100 100 60 2094 43 095 44 096 45 097 46 1098 47 5099 48100 49 100 80 0101 50 100 60 0102 51 0102A 52 60Untreated -- 0 0 0 0______________________________________ TABLE 5__________________________________________________________________________Test Organism: Mexican Bean Beetle (Epilachna varivestis) Percent MortalityExample Compound Application ConcentrationNo. No. 0.1 0.05 0.01 0.005 0.001 0.0005__________________________________________________________________________103 1 100 90 0104 2 0105 3 0106 4 0107 5 70108 6 60109 7 0110 8 100 100 100 100 10111 9 100 100 50112 10 100 100 100 100 0113 11 100 100 50114 12 100 90 10115 13 100 90 70 50116 14 100 100 50 50117 15 0118 16 100 100 100 90 50119 17 20120 18 80121 19 100 100 100 100 80 40122 20 80123 21 70124 22 100 40125 23 0126 24 40127 25 100 20128 26 0129 27 0130 28 100 100 60 50131 29 60132 30 0133 31 0134 32 0135 33 0136 34 0137 35 0138 36 0139 37 0140 38 0141 39 0142 40 100 100 40 20143 41 70144 42 100 100 100 100 40145 43 80146 44 0147 45 0148 46 80149 47 80150 48151 49 70152 50 0153 51 0 153A 52 100 20Untreated -- 0 0 0 0 0 0__________________________________________________________________________

EXAMPLES 154-255A

Test Organism -- Pea Aphid -- (Macrosiphum pisi)

Contact Test

Ten adult pea aphids were sprayed with representative compounds of this invention diluted to the desired concentration and transferred to similarly sprayed pea plants. After a culture period of 48 hours, mortality determinations were made. The results are set forth in Table 6.

Systemic Test

To the vermiculite substratum of potted pea seedlings there is applied 25 ml. of the candidate chemical which has been diluted in a suitable non-phytotoxic solvent. Three days after treatment the pea plants are infested with ten adult pea aphids (Macrosiphum pisi). Mortality determinations are made after five days. The results are set forth in Table 7.

TABLE 6__________________________________________________________________________Test Organism: Pea Aphid (contact) (Macrosiphum pisi) Percent MortalityNo. No. 0.1 0.05 0.01 0.005 0.001 0.0005 0.0001 0.00005 0.00001__________________________________________________________________________154 1 100 100 100 20155 2 100 100 50156 3 60157 4 0158 5 90 20159 6 100 100 20160 7 40161 8 100 100 50162 9 100 100 100 100 50163 10 100 100 100 100 30164 11 100 100 100 100 100 100 100 40165 12 100 100 100 100 100 90 30 30166 13 100 100 100 100 100 70 50167 14 100 100 100 50168 15 100 100 80 40169 16 100 100 100 100 100 100 50170 17 100 100 100 100 100 90 20171 18 100 100 100 40172 19 100 100 100 100 100 100 80 15173 20 100 100 100 100 100 100 100 40174 21 100 100 100 100 70 50 20175 22 100 100 100 30176 23 100 80 60 10177 24 100 100 100 100 0178 25 100 100 60179 26 20180 27 100 80 0181 28 100 100 100 100 100 100 50182 29 100 100 100 100 100 40183 30 30184 31 100 100 60185 32 100 100 30186 33 100 40 0187 34 100 100 50188 35 100 100 100 10189 36 100 100 60190 37 100 50 0191 38 10192 39 0193 40 100 100 100 100 100 100 50194 41 100 80 50195 42 100 100 100 100 30196 43 100 100 100 100 100 30197 44 80198 45 100 100 100 60199 46 100 100 100 40200 47 100 100 60201 48 100 100 50202 49 10203 50 90 60 0204 51 100 100 90 50 204A 52 100 100 100 100 100 100 100 100Untreated -- 0 0 0 0 0 0 0 0__________________________________________________________________________ TABLE 7__________________________________________________________________________Test Organism: Pea Aphid (Systemic) (Macrosiphum pisi) Percent MortalityExample Compound Application ConcentrationNo. No. 0.1 0.05 0.01 0.005 0.001 0.0005 0.0001__________________________________________________________________________205 1 100 100 40206 2 0207 3 0208 4 0209 5 0210 6 0211 7 0212 8 0213 9 100 0214 10 0215 11 100 100 100 20216 12 100 100 50217 13 100 100 0218 14 100 40 10219 15 0220 16 100 60 0221 17 100 100 0 0222 18 80223 19 100 100 100 0224 20 100 100 100 100 100 40225 21 100 0226 22 0227 23 0228 24 0229 25 0230 26 0231 27 0232 28 100 100 40 0233 29 100 100 10 0234 30 0235 31 0236 32 0237 33 0238 34 0239 35 0240 36 0241 37 0242 38 0243 39 0244 40 100 100 60 30245 41 0246 42 100 100 100 0247 43 100 90 60 0248 44 0249 45 0250 46 90 0251 47 60252 48253 49 10254 50 0255 51 0 255A 52 100 100 100 100 10Untreated -- 0 0 0 0 0 0 0__________________________________________________________________________

EXAMPLES 256-306A

Strawberry Mite -- (Tetranychus atlanticus)

Excised lima bean plants were infested with 50 to 100 adults of the strawberry spider mite prior to testing. The infested plants were dipped into water dilutions of each test chemical. Treated test plants were allowed to dry and then cultured at room temperature. After 5 days, mortality counts were made. The results are noted in Table 8.

EXAMPLES 307-357A

Housefly -- (Musca domestica)

Diluted samples were applied to houseflies in a contact test by means of the Waters vertical spray tower. The spray tower is operated at 10 psi and discharges about 28 ml. of material per minute through a glass atomizer. The spray descends through an 8 inch stainless steel cylinder to the plant or test insects 44 inches below the atomizer.

Fifty adult houseflies were sprayed in a 2 inches high by 5 inches diameter stainless steel cage faced on top and bottom with 14 mesh screen. The insects were retained in the same cages for knockdown observations. The 24-hour mortality of houseflies may be from residual as well as from direct contact. The percentages of knockdown and kill are summarized in Table 9.

TABLE 8______________________________________Test Organism: Strawberry Mite (Tetranchus atlanticus) Percent MortalityExample Compound Application ConcentrationNo. No. 0.1 0.05 0.01 0.005______________________________________256 1 68 17257 2 0258 3 0259 4 0260 5 0261 6 0262 7 0263 8 34264 9 22265 10 21266 11 100 20 0267 12 86268 13 35269 14 15270 15 12271 16 76272 17 100 43273 18 54274 19 100 40 33 30275 20 73276 21 20277 22 0278 23 0279 24 21280 25 0281 26 0282 27 0283 28 90 95 77 30284 29 33285 30 0286 31 0287 32 0288 33 0289 34 0290 35 0291 36 15292 37 0293 38 0294 39 0295 40 88 52 10296 41 13297 42 95 43 25 0298 43 90 45 42 0299 44 0300 45 10301 46 83 87 15302 47 64303 48304 49 97 94 35305 50 0306 51 0 306A 52 86Untreated -- 0 0 0 0______________________________________ TABLE 9__________________________________________________________________________Test Organism: Housefly (Musca domestica) Percent Mortality Application ConcentrationExample Compound 0.1 0.05 0.01 0.005 0.001No. No. KD Kill KD Kill KD Kill KD Kill KD Kill__________________________________________________________________________307 1 100 100 100 100 0 16308 2 10 10309 3 0 0310 4 0 12311 5 0 0312 6 100 100 80 100 10 50313 7 0 12 -314 8 100 100 100 100 70 80 30 30315 9 72 62316 10 100 100 100 100 94 100 90 88 0 0317 11 100 100 30 96 0 0318 12 80 62319 13 98 86320 14 50 58321 15 0 0322 16 100 100 100 100 40 28 6 0323 17 90 38324 18 100 100 90 86 8 10 0 0325 19 100 100 90 82 0 6326 20 6 8327 21 0 0328 22 0 0329 23 0 0330 24 0 0331 25 0 0332 26 0 0333 27 0 0334 28 100 100 80 44 0 0 0 0335 29 0 0336 30 0 0337 31 0 0338 32 0 0339 33 0 0340 34 0 0341 35 0 0342 36 0 0343 37 0 0344 38 0 0345 39 0 90 0 0346 40 100 100 100 100 30 58 0 8347 41 0 0348 42 100 100 100 100 40 40 14 12349 43 0 0350 44 0 0351 45 0 0352 46 0 0353 47 96 100 24 96 0 0354 48355 49 30 96 0 0356 50 0 0357 51 0 0 357A 52 20 0Untreated -- 0 0 0 0 0 0 0 0 0 0__________________________________________________________________________

EXAMPLE 357-B

German Cockroach (Blatella germanica)

The procedure for testing against this species was the same as that employed for the housefly, except that twenty specimens were utilized (instead of fifty) and observations were made after 48 hours (instead of 24). In this test, Compound Nos. 9-10, 12-18, 21-22, 24, 29-30, 33, 35-37, 40-46, 48 and 52 were not tested. Compounds 1-8, 11, 19-20, 23, 25, 26-28, 31-32, 34, 38-39, 47, 49-51 were tested at a concentration of 0.1%, with the result that the only activity displayed was by Compound No. 11 which showed a 20% mortality.

EXAMPLES 358-382

Corn Earworm (Heliothis zea)

The procedure for testing against this species was the same as that employed for the Southern Armyworm. The Compounds tested were Compound Nos. 1-8, 11, 19-20, 23, 25-28, 31-32, 34, 38-39, 47, 49-51. The results are set forth in Table 10.

TABLE 10______________________________________Test Organism: Corn Earworm (Heliothis zea) Percent MortalityExample Compound Application ConcentrationNo. No. 0.1 0.05 0.01 0.005______________________________________358 1 100 50 0359 2 0360 3 0361 4 0362 5 0363 6 0364 7 0365 8 100 20 0366 11 100 20 0367 19 30368 20 0369 23 0370 25 60371 26 0372 27 0373 28 100 70 30 0374 31 0375 32 0376 34 0377 38 0378 39 0379 47 0380 49 40381 50 40382 51 0Untreated -- 0 0 0 0______________________________________

As hereinbefore stated, the oxime carbamates of the present invention are broadly effective as insecticides and acaricides. It should be understood, however, that each particular compound of the present oxime carbamate genus, although exhibiting insecticidal and acaricidal activity as indicated by the foregoing examples, may be not effective against each and every insect and acarid species.

Claims

1. Novel oxime-carbamates of the formula ##SPC7##

where

R.sub.1 is --CH.sub.3, --CH(CH.sub.3).sub.2, ##EQU6## --C(CH.sub.3).sub.3, or --C.sub.6 H.sub.5 ; R.sub.2 is --H or --CH.sub.3 ;

R.sub.3 is --CH.sub.3, --CH.sub.2 CH.sub.3, --(CH.sub.2).sub.2 CH.sub.3, --(CH.sub.2).sub.3 CH.sub.3, --CH.sub.2 CH.sub.2 Cl or --C.sub.6 H.sub.5 ;

R.sub.4 is --H, --CH.sub.3, --CH.sub.2 CH.sub.3, --(CH.sub.2).sub.2 CH.sub.3, --CH(CH.sub.3).sub.2, --(CH.sub.2).sub.3 CH.sub.3, --CH.sub.2 CH=CH.sub.2, --CH.sub.2 C.tbd.CH, --C.sub.6 H.sub.5, ##EQU7## --CH(OH)CCl.sub.3, --CH.sub.2 CH.sub.2 X.sub.1, where X.sub.1 is --Cl, --Br, --NH.sub.2, --OH, --OCOCH.sub.3, --OCOCH.sub.2 Cl, or --OCONHCH.sub.3 ;

R.sub.5 and R.sub.6 are each --H or --CH.sub.3, with the proviso that when R.sub.5 and R.sub.6 are both CH.sub.3 then both CH.sub.3 groups may be on either the same carbon atom or on different carbon atoms;

R.sub.7 is H, --CH.sub.3 or --CH.sub.2 C.sub.6 H.sub.5 ;

X.sub.2 is Cl, --Br or --I; and

n is 0 or 1, with the proviso that when n is 1 then N

bears a + charge and X.sub.2 bears a - charge.

2. The compound of claim 1 wherein R.sub.1 is --CH.sub.3 , R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4, R.sub.5 and R.sub.6 are each --H, and n is 0.

3. The compound of claim 1 wherein R.sub.1, R.sub.2 and R.sub.3 are each --CH.sub.3, R.sub.4, R.sub.5 and R.sub.6 are each --H, and n is 0.

4. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --(CH.sub.2).sub.2 CH.sub.3, R.sub.4, R.sub.5 and R.sub.6 are each --H, and n is 0.

5. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --C.sub.6 H.sub.5, R.sub.4, R.sub.5 and R.sub.6 are each --H, and n is 0.

6. The compound of claim 1 wherein R.sub.1 is --CH(CH.sub.3).sub.2, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4, R.sub.5 and R.sub.6 are each --H, and n is 0.

7. The compound of claim 1 wherein R.sub.1 is ##EQU8## R.sub.2 is --H, R.sub.3 is --CH.sub.3, and R.sub.4, R.sub.5 and R.sub.6 are each --H, and n is 0.

8. The compound of claim 1 wherein R.sub.1 is --C.sub.6 H.sub.5, R.sub.2 is --H, R.sub.3 is --CH.sub.3, and R.sub.4, R.sub.5 and R.sub.6 are each --H, and n is 0.

9. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --H, R.sub.5 is --CH.sub.3, R.sub.6 is --H, and n is 0.

10. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --H, R.sub.5 and R.sub.6 are each --CH.sub.3, and n is 0.

11. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 and R.sub.4 are each --CH.sub.3, R.sub.5 and R.sub.6 are each --H, and n is 0.

12. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.3, R.sub.5 and R.sub.6 are each --H, and n is 0.

13. The compound of claim 1 wherein R.sub.1, R.sub.2 and R.sub.3 are each --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.3, R.sub.5 and R.sub.6 are each --H, and n is 0.

14. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 and R.sub.4 are each --CH.sub.2 CH.sub.3, R.sub.5 and R.sub.6 are each --H, and n is 0.

15. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --(CH.sub.2).sub.2 CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.3, R.sub.5 and R.sub.6 are each --H, and n is 0.

16. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.2 CH.sub.2 Cl, R.sub.4 is --CH.sub.2 CH.sub.3, R.sub.5 and R.sub.6 are each --H, and n is 0.

17. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --(CH.sub.2).sub.2 CH.sub.3, R.sub.5 and R.sub.6 are each --H, and n is 0.

18. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH(CH.sub.3).sub.2, R.sub.5 and R.sub.6 are each --H, and n is 0.

19. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --(CH.sub.2).sub.3 CH.sub.3, R.sub.5 and R.sub.6 are each --H, and n is 0.

20. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 Cl, R.sub.5 and R.sub.6 are each --H, and n is 0.

21. The compound of claim 1 wherein R.sub.1, R.sub.2 and R.sub.3 are each --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 Cl, R.sub.5 and R.sub.6 are each --H, and n is 0.

22. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.2 CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 Cl, R.sub.5 and R.sub.6 are each --H, and n is 0.

23. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --(CH.sub.2).sub.2 CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 Cl, R.sub.5 and R.sub.6 are each --H, and n is 0.

24. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --(CH.sub.2).sub.3 CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 Cl, R.sub.5 and R.sub.6 are each --H, and n is 0.

25. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 and R.sub.4 are each --CH.sub.2 CH.sub.2 Cl, R.sub.5 and R.sub.6 are each --H, and n is 0.

26. The compound of claim 1 wherein R.sub.1 is --CH(CH.sub.3).sub.2, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is CH.sub.2 CH.sub.2 Cl, R.sub. 5 and R.sub.6 are each --H, and n is 0.

27. The compound of claim 1 wherein R.sub.1 is ##EQU9## R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 Cl, R.sub.5 and R.sub.6 are each --H, and n is 0.

28. The compound of claim 1 wherein R.sub.1 is --C(CH.sub.3).sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 Cl, R.sub.5 and R.sub.6 are each --H, and n is 0.

29. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 Br, R.sub.5 and R.sub.6 are each --H, and n is 0.

30. The compound of claim 1 wherein R.sub.1, R.sub.2 and R.sub.3 are each --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 Br, R.sub.5 and R.sub.6 are each --H, and n is 0.

31. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 NH.sub.2, R.sub.5 and R.sub.6 are each --H, and n is 0.

32. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 OH, R.sub.5 and R.sub.6 are each --H, and n is 0.

33. The compound of claim 1 wherein R.sub.1, R.sub.2 and R.sub.3 are each --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 OH, R.sub.5 and R.sub.6 are each --H, and n is 0.

34. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --(CH.sub.2).sub.3 CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 OH, R.sub.5 and R.sub.6 are each --H, and n is 0.

35. The compound of claim 1 wherein R.sub.1 is ##EQU10## R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 OH, R.sub.5 and R.sub.6 are each --H, and n is 0.

36. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 OCOCH.sub.3, R.sub.5 and R.sub.6 are each --H, and n is 0.

37. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 OCOCH.sub.2 Cl, R.sub.5 and R.sub.6 are each --H, and n is 0.

38. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 OCONHCH.sub.3, R.sub.5 and R.sub.6 are each --H, and n is 0.

39. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH(OH)CCl.sub.3, R.sub.5 and R.sub.6 are each --H, and n is 0.

40. The compound of claim 1 wherein R.sub.1, R.sub.2 and R.sub.3 are each --CH.sub.3, R.sub.4 is --CH(OH)CCl.sub.3, R.sub.5 and R.sub.6 are each H, and n is 0.

41. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH=CH.sub.2, R.sub.5 and R.sub.6 are each --H, and n is 0.

42. The compound of claim 1 wherein R.sub.1, R.sub.2 and R.sub.3 are each --CH.sub.3, R.sub.4 is CH.sub.2 CH=CH.sub.2, R.sub.5 and R.sub.6 are each --H, and n is 0.

43. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 C .tbd. CH, R.sub.5 and R.sub.6 are each --H, and n is 0.

44. The compound of claim 1 wherein R.sub.1, R.sub.2 and R.sub.3 are each --CH.sub.3, R.sub.4 is --CH.sub.2 C.tbd.CH, R.sub.5 and R.sub.6 are each --H, and n is 0.

45. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --C.sub.6 H.sub.5, R.sub.5 and R.sub.6 are each --H, and n is 0.

46. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is ##EQU11## R.sub.5 and R.sub.6 are each --H, and n is 0.

47. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is ##EQU12## R.sub.5 and R.sub.6 are each --H, and n is 0.

48. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4, R.sub.5 and R.sub.6 are each --H, R.sub.7 is --H, X.sub.2 is --Cl, and n is 1.

49. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 Cl, R.sub.5 and R.sub.6 are each --H, R.sub.7 is --H, X.sub.2 is --Cl, and n is 1.

50. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4, R.sub.5 and R.sub.6 are each --H, R.sub.7 is --CH.sub.3, X.sub.2 is --I, and n is 1.

51. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3 , R.sub.4 is --CH.sub.2 CH.sub.2 Cl, R.sub.5 and R.sub.6 are each --H, R.sub.7 is --CH.sub.3, X.sub.2 is --I, and n is 1.

52. The compound of claim 1 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 Cl, R.sub.5 and R.sub.6 are each --H, R.sub.7 is --CH.sub.2 C.sub.6 H.sub.5, X.sub.2 is --Br, and n is 1.

53. The compound of claim 1 wherein R.sub.1, R.sub.2, and R.sub.3 are each --CH.sub.3, R.sub.4 is --(CH.sub.2).sub.2 CH.sub.3, R.sub.5 and R.sub.6 are each --H, and n is 0.

54. A process for control of insect and acarid infestation which comprises applying either to the locus of said infestation or systemically a pecticidally effective amount of an oxime carbamate of the general formula ##SPC8##

where

R.sub.1 is --CH.sub.3, --CH(CH.sub.3).sub.2, ##EQU13## --C(CH.sub.3).sub.3, or --C.sub.6 H.sub.5 ; R.sub.2 is --H or --CH.sub.3 ;

R.sub.3 is --CH.sub.3, --CH.sub.2 CH.sub.3, --(CH.sub.2).sub.2 CH.sub.3, --(CH.sub.2).sub.3 CH.sub.3, --CH.sub.2 CH.sub.2 Cl or --C.sub.6 H.sub.5,

R.sub.4 is --H, --CH.sub.3, --CH.sub.2 CH.sub.3, --(CH.sub.2).sub.2 CH.sub.3, --CH(CH.sub.3).sub.2, --(CH.sub.2).sub.3 CH.sub.3, --CH.sub.2 CH=CH.sub.2, --CH.sub.2 C.tbd.CH, --C.sub.6 H.sub.5, ##EQU14## --CH(OH)CCl.sub.3, --CH.sub.2 CH.sub.2 X.sub.1, where X.sub.1 is --Cl, --Br, --NH.sub.2, --OH, --OCOCH.sub.3, --OCOCH.sub.2 Cl, or --OCONHCH.sub.3 ;

R.sub.5 and R.sub.6 are each --H or --CH.sub.3, with the proviso that when R.sub.5 and R.sub.6 are both CH.sub.3 then both CH.sub.3 groups may be on either the same carbon atom or on different carbon atoms;

R.sub.7 is H, --CH.sub.3 or --CH.sub.2 C.sub.6 H.sub.5

X.sub.2 is --Cl, --Br or --I; and

n is 0 or 1, with the proviso that when n is 1 then N

bears a + charge and X.sub.2 bears a - charge.

55. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4, R.sub.5 and R.sub.6 are each --H, and n is 0.

56. The process of claim 54 wherein R.sub.1, R.sub.2 and R.sub.3 are each --CH.sub.3, R.sub.4, R.sub.5 and R.sub.6 are each --H, and n is 0.

57. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --(CH.sub.2).sub.2 CH.sub.3, R.sub.4, R.sub.5 and R.sub.6 are each --H, and n is 0.

58. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --C.sub.6 H.sub.5, R.sub.4, R.sub.5 and R.sub.6 are each --H, and n is 0.

59. The process of claim 54 wherein R.sub.1 is --CH(CH.sub.3).sub.2, R.sub.2 is --H, R.sub.3 is --CH.sub.3, and R.sub.4, R.sub.5 and R.sub.6 are each --H, and n is 0.

60. The process of claim 54 wherein R.sub.1 is ##EQU15## R.sub.2 is --H, R.sub.3 is --CH.sub.3, and R.sub.4, R.sub.5 and R.sub.6 are each --H, and n is 0.

61. The process of claim 54 wherein R.sub.1 is --C.sub.6 H.sub.5, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4, R.sub.5 and R.sub.6 are each --H, and n is 0.

62. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --H, R.sub.5 is --CH.sub.3, R.sub.6 is --H, and n is 0.

63. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --H, R.sub.5 and R.sub.6 are each --CH.sub.3, and n is 0.

64. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 and R.sub.4 are each --CH.sub.3, R.sub.5 and R.sub.6 are each --H, and n is 0.

65. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.3, R.sub.5 and R.sub.6 are each --H, and n is 0.

66. The process of claim 54 wherein R.sub.1, R.sub.2 and R.sub.3 are each --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.3, R.sub.5 and R.sub.6 are each --H, and n is 0.

67. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 and R.sub.4 are each --CH.sub.2 CH.sub.3, R.sub.5 and R.sub.6 are each --H, and n is 0.

68. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --(CH.sub.2).sub.2 CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.3, R.sub.5 and R.sub.6 are each --H, and n is 0.

69. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.2 CH.sub.2 Cl, R.sub.4 is --CH.sub.2 CH.sub.3, R.sub.5 and R.sub.6 are each --H, and n is 0.

70. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --(CH.sub.2).sub.2 CH.sub.3, R.sub.5 and R.sub.6 are each --H, and n is 0.

71. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH(CH.sub.3).sub.2, R.sub.5 and R.sub.6 are each --H, and n is 0.

72. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --(CH.sub.2).sub.3 CH.sub.3, R.sub.5 and R.sub.6 are each --H, and n is 0.

73. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 Cl, R.sub.5 and R.sub.6 are each --H, and n is 0.

74. The process of claim 54 wherein R.sub.1, R.sub.2 and R.sub.3 are each --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 Cl, R.sub.5 and R.sub.6 are each H, and n is 0.

75. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.2 CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 Cl, R.sub.5 and R.sub.6 are each --H, and n is 0.

76. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --(CH.sub.2).sub.2 CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 Cl, R.sub.5 and R.sub.6 are each --H, and n is 0.

77. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --(CH.sub.2).sub.3 CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 Cl, R.sub.5 and R.sub.6 are each --H, and n is 0.

78. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 and R.sub.4 are each --CH.sub.2 CH.sub.2 Cl, R.sub.5 and R.sub.6 are each --H, and n is 0.

79. The process of claim 54 wherein R.sub.1 is --CH(CH.sub.3).sub.2, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is CH.sub.2 CH Cl, R.sub.5 and R.sub.6 are each --H, and n is 0.

80. The process of claim 54 wherein R.sub.1 is ##EQU16## R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 Cl, R.sub.5 and R.sub.6 are each --H, and n is 0.

81. The process of claim 54 wherein R.sub.1 is --C(CH.sub.3).sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 Cl, R.sub.5 and R.sub.6 are each --H, and n is 0.

82. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 Br, R.sub.5 and R.sub.6 are each --H, and n is 0.

83. The process of claim 54 wherein R.sub.1, R.sub.2 and R.sub.3 are each --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 Br, R.sub.5 and R.sub.6 are each --H, and n is 0.

84. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 NH.sub.2, R.sub.5 and R.sub.6 are each --H, and n is 0.

85. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 OH, R.sub.5 and R.sub.6 are each --H, and n is 0.

86. The process of claim 54 wherein R.sub.1, R.sub.2 and R.sub.3 are each --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 OH, R.sub.5 and R.sub.6 are each --H, and n is 0.

87. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --(CH.sub.2).sub.3 CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 OH, R.sub.5 and R.sub.6 are each --H, and n is 0.

88. The process of claim 54 wherein R.sub.1 is ##EQU17## R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 OH, R.sub.5 and R.sub.6 are each --H, and n is 0.

89. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 OCOCH.sub.3, R.sub.5 and R.sub.6 are each --H, and n is 0.

90. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 OCOCH.sub.2 Cl, R.sub. 5 and R.sub.6 are each --H, and n is 0.

91. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 OCONHCH.sub.3, R.sub.5 and R.sub.6 are each --H, and n is 0.

92. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH(OH)CCl.sub.3, R.sub.5 and R.sub.6 are each --H, and n is 0.

93. The process of claim 54 wherein R.sub.1, R.sub.2 and R.sub.3 are each --CH.sub.3, R.sub.4 is --CH(OH)CCl.sub.3, R.sub.5 and R.sub.6 are each H, and n is 0.

94. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH=CH.sub.2, R.sub.5 and R.sub.6 are each --H, and n is 0.

95. The process of claim 54 wherein R.sub.1, R.sub.2 and R.sub.3 are each --CH.sub.3, R.sub.4 is CH.sub.2 CH=CH.sub.2, R.sub.5 and R.sub.6 are each --H, and n is 0.

96. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 C.tbd.CH, R.sub.5 and R.sub.6 are each --H, and n is 0.

97. The process of claim 54 wherein R.sub.1, R.sub.2 and R.sub.3 are each --CH.sub.3, R.sub.4 is --CH.sub.2 C.tbd.CH, R.sub.5 and R.sub.6 are each --H, and n is 0.

98. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --C.sub.6 H.sub.5, R.sub.5 and R.sub.6 are each --H, and n is 0.

99. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is ##EQU18## R.sub.5 and R.sub.6 are each --H, and n is 0.

100. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is ##EQU19## R.sub.5 and R.sub.6 are each --H, and n is 0.

101. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4, R.sub.5 and R.sub.6 are each --H, R.sub.7 is --H, X.sub.2 is --Cl, and n is 1.

102. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 Cl, R.sub.5 and R.sub.6 are each --H, R.sub.7 is --H, X.sub.2 is --Cl, and n is 1.

103. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4, R.sub.5 and R.sub.6 are each --H, R.sub.7 is --CH.sub.3, X.sub.2 is --I, and n is 1.

104. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 Cl, R.sub.5 and R.sub.6 are each --H, R.sub.7 is --CH.sub.3, X.sub.2 is --I, and n is 1.

105. The process of claim 54 wherein R.sub.1 is --CH.sub.3, R.sub.2 is --H, R.sub.3 is --CH.sub.3, R.sub.4 is --CH.sub.2 CH.sub.2 Cl, R.sub.5 and R.sub.6 are each --H, R.sub.7 is --CH.sub.2 C.sub.6 H.sub.5, X.sub.2 is --Br, and n is 1.

106. The process of claim 54 wherein R.sub.1, R.sub.2, and R.sub.3 are each --CH.sub.3, R.sub.4 is --(CH.sub.2).sub.2 CH.sub.3, R.sub.5 and R.sub.6 are each --H, and n is 0.