NO803467L - Isothioureas COMPOUNDS. - Google Patents

Description

L EPIDOPTERICIDE ISOTHIOURINE COMPOUNDS

Background for the invention

Lepidoptericidal isothiouronium compounds are described in the art, particularly those described in US patents 3,969,511 and 4,062,892 and having the formula

These compounds have a main disadvantage in that they exhibit a high

degree of phytotoxic activity and are thus, even if they fight lepidoptera in the growth to be protected, harmful to the growth itself. In order to remedy this problem, the applicants have discovered that replacing the active hydrogen on the above type of isothiouronium and urea compounds with certain specific, relatively easily cleavable groups, can reduce or eliminate phytotoxic effects of the starting compound while maintaining the compound's lepidoptericidal activity and in some cases is increased.

No literature has been discovered that teaches or suggests the results that the applicants have achieved.

Description of the invention

The present invention is a new group of compounds which can generally be described as certain isothioureas which are active lepidoptericides. The compounds according to the invention are represented by the general formula

where R and R^ independently of each other are selected from the group consisting of:<C>2~<C>10^^yl/ especially C^-Cg alkyl, more especially Cg-Cg- alkyl,

C" 2 -C 10 alkoxyalkyl, especially C 1 -C 4 alkoxyalkyl 1, more especially C 8 -C 8 alkoxyalkyl and

phenyl, and

R and R^ together contain from 12 to 22 carbon atoms;

where R2 is selected from the group consisting of:

C 1 -C 4 alkyl, especially C 1 -C 8 alkyl, more especially C 1 -C 4 alkyl

alkyl,

C^-C^q alkenyl, especially C^-C^alkenyl, more particularly

C2~C3alkenyl,

C3-C4alkynyl,

C2~C4hydroxyalkyl, especially C2~C3hydroxyalkyl, C^-Cg alkylthioalkyl, especially C^-C^ alkylthioalkyl1, C2-Cg alkyloxyalkyl, especially C2~C4alkylthioalkyl, (CH») [X(CH„) ] y where n = 1 or 2, X is 0 or S and 2 n 2 n J

y = 1-4, especially 1-2,

0

-(CH2)nCOH where n = 1-10, especially 1-5, more especially 1-3, phenyl and

phenethyl;

where R^ is selected from the group consisting of: carboalkoxyalkyl where the alkyl part is C^-C^alkyl, in particular

C1~C2alkyl1'

alkylketoalkyl wherein the alkyl part is C₁-C₁alkyl, in particular

C1~C2alkv1'

hydroxyalkenyl where the alkenyl moiety is C₁-C₋alkenyl, hydroxyalkyl where the alkyl moiety is C₂-C₁₂₂₂₂ especially C₂-C₂ alkyl, more particularly C₂-C₂ alkyl, formylhydroxymethyl,

hydroxyhalogenety1 where the halogen atom is chlorine, bromine or

iodine) especially chlorine or bromine, more especially chlorine,

substituted phenoxyalkyl where the alkyl part is C 1 -C 2 alkyl,

especially alkyl and the substituents are p-methoxy, Cl, NO 3 or CN,

where R"*" is -OH, ~NH 2 or C 1 -C 6 oxy, especially methoxy, where R, R 1 and R 2 are as defined above, where R, R 1 and R 2 are as defined above, or where B is a basic cation, especially an organic basic cation, more especially an organic basic cation selected from the group consisting of and

where R^ is selected from the group consisting of:

-H,

<_C>1~<C>22a-*-cyl' especially c1~c^2a^ y^-' more especially C^-Cg alkyl and most especially C1~C6 alkyl,

hydroxyethyl,

naphthyl,

phenyl,

substituted phenyl where the substituents are independently selected from the group of halogen, especially chlorine, C₁-C₂alkyl, especially C₁-C₂alkyl, C₁-C₂. alkoxy, especially C 1 -C 6 alkoxy, nitro,. cyano and"CF.,,

where R, R^ and R 2 are as above, where R, R^^ and R 2 are as above, where R, R^ and R 2 are as above, where R, R^ and Ry are as above, where R, R^ and R 2 are as indicated above, where x is 1 to 8, and R, R^ and R 2 are as indicated above, where m is 2 or 3 and R, R^ and R 2 are as indicated above, where R , R 1 and R 2 are as indicated above, where R, R 2 and R 2 are as indicated above, where X is selected from the group consisting of: 0,

S,

NH and

<NR>11'

Y is hydrogen or methyl; and

R-^q is selected from the group consisting of:

H,

C 1 -C 8 alkyl, especially C 1 -C 8 alkyl,

more particularly C^~ C2 a^- cooled C3-C4alkenyl,

C3-C4alkynyl,

C 2 -C 8 haloalkyl, especially C 1 -C 2 -haloalkyl,

C -CQ cycloalkyl,

C7_C20p°iycyki°aikyi'

C2-Ci6p°iyaikoksya^-ky^'

C2-C8 hydroxyalkyl,

C2~ <" io alkoxyalkyl,

C_-C0carboalkoxyalkyl,

C4~Cg cycloalkylalkyl,

C 1 -C 0 alkylcycloalkyl, especially C 1 -C 0 alkylcycloalkyl,

b o

C 1 -C 7 cycloalkyliraino,

C2~C10alky glue:i-no'

C1~C3alkylamino'

C4~C12 dialkylaminoalkyl

C 1 -C 3 cycloalkenyl,

D IO

phenyl,

alkylphenyl where the alkyl part is C^-C^ , p-chloroalkylphenyl where the alkyl part is C^-C^,

naphthyl,

anthracenyl,

benzamidocycloalkyl1 where the alkyl moiety is

<c>1-<c>2,

pyranylmethyl,

tetrahydrofurfury1,

thiophenemethyl1,

benzhydryl,

vhalogenbenzhydry1,

polycyclic alcohol and substituted phenyl where the substituents are selected from the group consisting of:

C 1 -C 4 alkyl,

halogen,

nitrous,

trifluoromethyl,

form1,

chloracety1,

C 1 -C 4 alkoxy,

hydrogen,

benzyl,

chlorobenzyl,

phenethyl and

substituted phenethyl where the substituents are selected from the group: ci~c4alkyl1°9halogen, and

^11 is the va^-<3^- ^ra group consisting of: C1-C4 alkyl,

C₁-C₆ alkoxyalkyl and

C₁-C₁ alkenyl,

R^0and together form heterocyclic compounds selected from the group consisting of:

azepinyl,

morpholinyl,

piperidinyl,

C^-C^alkyl-substituted piperdinyl and

Y is hydrogen or methyl

provided that when X = 0 or S, then R^0 is different from hydrogen, and substituted phenyl where the substituents are selected from the group consisting of:

halogen,

C 1 -C 4 alkoxy,

phenoxy,

trifluoromethyl,

C1-C6thioalkyl1'

nitrous,

isocyanato,

C2~C4p°iyaikoxy'

C3~C7cycloalkyl,

C3_<~24 lower alkoxyalkyl, in particular

C₁-C₁₂ carboalkoxyalkyl,

C1~C8halogenalkyl'in particular

C1_G4nalo9enalkyl'

G3~^12alkenyl'in particular

C 1 -C 4 alkenyl,

C 1 -C 8 dialkylamino,

phenylamino,

C1~C24 alkyl'especially C^-C^ alkyl, C3~C12 hydroxyalkylamidoalkyl, C5-C10N,N-hydroxyalkylureidoalkyl1, isocyanatoalkyl where the alkyl part is C1~C5, C2~ ci2 aikyiami^oa^kyi'polyalkoxyamidoalkyl where the polyalkoxy part contains from 3-6 repeated C2-C.j~ alkoxy units and the amidoalkyl part contains from 4-12 carbon atoms,

-so2ci,

-SC>2 polyalkoxyamidoalkyl where the polyalkoxy part contains from 3-6 repeated C2~C3 alkoxy units and the amidoalkyl part contains from 4-12 carbon atoms,

R,, is selected from the group consisting of:

hydrogen,

C 1 -C 4 alkyl,

C₁-C₆ alkoxyalkyl.,

C 1 -C 4 alkenyl,

hydroxyethyl and

phenyl, R 1 and R 1 . taken together form heterocyclic compounds, particularly heterocyclic compounds selected from the group consisting of:

azepinyl,

morpholinyl,

piperidinyl and

C 1 -C , alkyl-substituted piperidinyl;

where X is 0 or S, n is 0 or 1,

Rg is selected from the group consisting of:

C1_C18alky1'especially C1~C12alkyl, more especially C1-C4alkyl,

C-j-C8 haloalkyl,

phenyl, and

substituted phenyl wherein, when N = 1, the substituents are selected from the group consisting of:

nitrous,

chlorine,

C1~C2alkyl,

C₁ -C₆ polyalkyloxyalkyl,

C3~Cg cycloalkyl,

C^-Cq alkenyl,

C₁-C₆ alkoxyalkyl,

C2~C8 hydroxyalkyl,

Ci-C3^arboksyaikyi,°g

C,--Cg trialkylammonium alkyl salts, and when n = 0, the substituents are selected from the group consisting of:

chlorine,

thiopotassium,

C1-C18alkyl>especially C1-C12alkyl, more

especially C 1 -C 4 alkyl,

benzyl,

ci~c2neteroai^yi'

C2~C4chlorocarboxyalkyl,

C₁-C₆ polyalkoxyalkyl, and

acetyl;

where R_ is selected from the group consisting of: -(CH„-) where n = 0 to 8

2 n

-CH=CH-,

where M is H or Cl,

-CC1=CC1-,

-CH2OCH2- and

-OCH2CH20-, and

d = 0 or 1,

and when d = 1,

Y is selected from the group consisting of: -0,

-S and

-NH,

Z is selected from the group consisting of: C1~CIQ alkyl, especially C1~C12alkyl, more especially C1~C4 alkyl,

hydrogen,

C₁-C₁₀ polyalkoxyalky1

C 1 -C 8 dialkylaminoalkyl,

C3-C5alkynyl,

phenyl,

substituted phenyl,

organic salts,

inorganic salts,

and when d 0 is Z

Cl or

where R, R₁ and R₂ are as indicated above, where R₂ is selected from the group consisting of: C₁-C₁₄ alkoxy, especially C₁-C₄₄ alkoxy, amino,

C₁-C₁₂ alkoxyamino, especially C₁-C₁ ₂ alkoxyamino, hydroxy and

organic base,

-SO^Rg where w = 0-2 and Rg is selected from the group consisting of:

amino,

C 1 - C 1 -C 1 alkyl, especially C 1 -C 1 . alkyl,

C-^-C^ haloalkyl,

phenyl,

C^-C^q dialkylamino,

C±~ CIQ alkylamino,

C 1 - C 1 -C 6 alkoxy, in particular C 1 -C 6 alkoxy, substituted phenyl where the substituents are selected from the group consisting of:

nitrous,

chlorine,

C^-C^, alkyl, and

methoxy.

General manufacturing methods

, The compounds according to the invention are derivatives of isothioureas containing a free hydrogen atom bound to nitrogen, i.e. as shown by the following formula:

The formation of the former isothioureas is well known in the art. They are derived by reaction of an isothiocyanate with a primary amine to form a thiourea, followed by reaction with an alkyl halide to form an isothiourea salt.

A non-reactive solvent such as ethanol can be used both for the formation of the isothiourea and for alkylation. step to form the isothiourea salt. Heat is usually used to speed up both reactions. The preparation of the isothiourea salt is shown below:

X = I, Br or Cl

The compounds according to the invention are produced by reacting the base of an isothiourea with an isocyanate or acid chloride. The free base can either be prepared by neutralizing an isothiourea salt with a cold aqueous solution of a base such as dilute sodium hydroxide, extracting the free isothiourea with a water-insoluble solvent such as hexane, benzene, toluene, etc., drying over a dehydrating agent such as magnesium sulfate, filtration and evaporation under vacuum. An alternative method is to dissolve the isothiourea salt in a non-reactive solvent such as benzene or toluene, then add an equal molar amount of an isocyanate and the equivalent amount of a soluble tertiary base or an acid chloride and two equivalent amounts of a soluble tertiary base such as triethylamine, completion of the reaction by stirring at ambient temperature for several hours or refluxing for a shorter time. An alternative method when a base such as triethylamine is used is to treat the isothiourea salt in a solvent such as benzene in which triethylamine hydrohalide is almost totally insoluble, filter off the triethylamine hydrohalide and treat the filtrate with the isocyanate or acid chloride, and complete the reaction as described earlier. Solvents suitable for the condensation of the isothiourea with an isocyanate or acid chloride are those which are unreactive towards any of the reaction components. These include hexane, benzene, toluene, tetrahydrofuran, dioxane, methylene chloride, diethyl ether and the like.

Depending on the reaction components, the reaction temperatures are usually in the range from -20 to 80°C, and the reaction time varies from 0.5 hours to 24 hours.

In some cases it has been found that the condensation of an isothiourea with an isocyanate or acid chloride can be accelerated by the addition of such catalysts as triethylamine and dibutyltin dilaurate.

Equations showing the reactions mentioned immediately above are as follows:

A) Using isothiourea base with an isocyanate

B) Use of isothiourea salt + a base C) Use of isothiourea base with an acid chloride

The isothiourea precursors according to the state of the art discussed above can generally be prepared by the methods described in US patents 3,969,511 and 4,062,892.

These compounds are useful as lepidoptericides when they used in a lepidoptericidally effective amount on insects of the order lepidoptera or their habitat or for. Some of the compounds also show phytotoxic effects which could make them useful as herbicides as well as lepidoptericides if such effects were desired. In addition, some of these compounds show biocidal and/or fungicidal effects.

By "lepidoptericidally effective amount" is meant the amount of

the lepidoptericidal compounds specified herein which, when applied in any ordinary manner to the habitation of lepidoptera, the food of lepidoptera, or the insects themselves, will "control" by killing or substantially injuring a substantial proportion of the lepidoptera.

These compounds are useful for the protection of foodstuffs, fiber crops and ornamental plants against damage by insects and larvae of the order lepidoptera. Examples of crops that can be protected include forest trees such as oak and pine, fruit trees such as peach, apple and walnut, vegetables such as tomatoes, other crops such as tobacco, cotton, lettuce, cabbage, corn and rice, and any growth, which lepidoptera feed on.

The compounds according to the invention can be prepared from the precursors described above by methods shown in the following examples.

Example 1

1, 3- diheptyl- 2- ethyl- 3-( 0, 0- dimethyl- phosphoro) isothiourea

6.0 grams (g) (0.02 mole) of 1,3-diheptyl-2-ethyl isothiourea and 200 milliliters (ml) of methylene chloride were mixed in a 500 ml 3-necked flask equipped with a stirrer, thermometer and dropping funnel. The solution was stirred and cooled to 0°C. 2.0 g (0.02 mol), triethylamine was added to the flask. Then 3.0 g (0.02 mol) of phosphorus oxychloride was dissolved in 25 ml of methylene chloride, added at such a rate that the temperature in the vessel was maintained at 0 to 5°C. After the addition was complete, the reaction mixture was stirred at 0°C for 30 minutes. Then a solution of 8.7 g (0.04 mol) of 25% sodium methoxide in methanol with 25 ml of methylene chloride was added over a period of 15 minutes while the vessel temperature was maintained at 0 to 5°C. The reaction mass was then stirred at 5°C for 30 minutes and then at room temperature for 30 minutes. The resulting mixture was then washed with two 200 ml portions of water and phase separated. The methylene chloride phase was dried with anhydrous MgSO 4 , filtered and evaporated in vacuo to give 7.4 g of the desired product, 1,3-diheptyl-2-ethyl-3-(0,0-dimethylphosphoro)isothiourea which had a nn 30 at 1.4528. The product iv identification was confirmed by infrared (IR), H nuclear magnetic resonance (NMR) and C 13 NMR spectra. Compound No. 229 in Table I.

Example 2

1, 3- diheptyl- 2- ethyl- 3- N-[ 4- methyl- 3-( carbowax- 350-carbamyl)]-phenylcarbamy1- isothiourea

The title compound was prepared as follows:

Intermediate product a)

3.56 g (0.02 mol) of 2-methyl-5-nitrophenyl isocyanate, 7.0 g (0.02 mol) of "Carbowax 350", 2 drops of triethylamine, 1 drop of dibutyltin dilaurate and 25 ml of methylene chloride were mixed with about -stirring in a 100 ml round bottom flask.- After the exothermic reaction had ceased, the solvent was removed in vacuo. The residue was dissolved in a 10:1 mixture of diethyl ether-toluene.

A white solid impurity was removed by filtration, and evaporation of the filtrate in vacuo gave 10.5 g of the desired compound N-(2-methyl-5-nitrophenyl)-carbowax (^50)-carbamate,

n^<0>1.4810. The structure was confirmed by C<13->NMR-spectr-a.•

Intermediate b)

7 g (0.013 mol) of intermediate a) were dissolved in 200 ml of ethanol in a glass Parr pressure bottle. 1 g of palladium-on-charcoal catalyst was added, and the mixture was shaken and reacted with hydrogen held at a pressure of 3.5 kg/cm 2 for 30 minutes. The reaction mass was then filtered, and the filtrate was evaporated in vacuo to give 6.0 g of the desired compound N-(2-methyl-5-aminophenyl)-carbowax (350)-carbamate.

13

The structure was confirmed by C -NMR spectra.

Intermediate c)

5.8 g (0.0116 mol) of intermediate b) were dissolved in

200 ml of toluene in a 250 ml 3-necked flask equipped with a condenser, stirrer and gas inlet tube. The solution was stirred, heated to 70°C and saturated with HCl gas. The mixture was then heated to reflux and the phosgene was bubbled in for 30 minutes. The reaction mass became clear. ^-gas was then bubbled in to remove excess phosgene. The solvent was removed in vacuo to give 6.1 g of N-(2-methyl-5-isocyanophenyl)-carbowax (350)-carbamate, n^° 1.5848. The structure was confirmed

13

by C -NMR spectra.

v

1, 3- diheptyl- 2- methyl- 3- N-[ 4- methyl- 3-( carbowax- 350-carbamy1)]-phenylcarbamy1- isothiourea

2.0 g (0.004 mol) of intermediate c), 1.2 g (0.004 mol) of 1,3-diheptyl-2-ethylisothiourea, 2 drops of triethylamine and 15 ml of methylene chloride were mixed in a 100 ml round bottom flask. After the exothermic reaction had ceased, the solvent was removed in vacuo to give 3.3 g of the desired product, 1,3-diheptyl-2-ethyl-3-N-[4-methyl-3-(carbowax -350-carbamyl)-phenylcarbamy1-isothiourea. The structure was confirmed by

13

C -NMR spectra. Compound No. 216 in Table I.

Example 3

1, 3-diheptyl-2-ethyl-3-[N-(3-tergitol' (15-S-7)-oxycarbamylphenyl)-carbamyl]- isothiourea

The title compound was prepared as follows:

Intermediate d)

In the same way as intermediate a) in example 2 above

became 3.28 g (0.02 mol) of 3-nitrophenyl isocyanate, 10.1 g of tergitol-

(15-S-7), 2 drops of triethylamine and 25 ml of methylene chloride mixed to give 13.2 g of the desired compound, N-(3-nitrophenyl)-tergitol (15-S-7)-carbamate. The structure was confirmed by IR spectra.

Intermediate e)

In the same way as intermediate b) in example 2 above

11.2 g (0.0166 mol) of intermediate d) was reduced with H 2 i ethanol using 1 g of palladium-on-charcoal catalyst to give 9.3 g of the desired compound, N-(3-aminophenyl) -tergitol (15-S-7)-carbamate. The structure was confirmed by IR spectra.

Intermediate product f)

In the same manner as intermediate c) in Example 2 above, 9.3 g (0.0145 mol) of intermediate e) was treated with excess HCl gas followed by excess phosgene to give 9.4 g of the desired compound , N-(3-isocyanophenyl)-tergitol (15-S-7)-carbamate. The structure was confirmed by IR spectra.

1, 3- diheptyl- 2- ethyl- 3-[ N-( 3- tergitol (15- S- 7)- oxycarbamylphenyl)-carbamyl]- isothiourea

In the same way as the title compound in example 2 above, 2 g (0.003 mol) of intermediate f) was mixed with 0.9 g

(0.003 mol) of 1,3-diheptyl-2-ethylisothiourea, 2 drops of triethylamine and 10 mL of methylene chloride to give 2.9 g of the desired product, 1,3-diheptyl-2-ethyl-3-[N-(3 -tergitol (15-S-7)-oxy-carbamylphenyl)-carbamyl]-isothiourea f , n^° 1.5710. The structure was confirmed by IR spectra. Compound No. 219 in Table I.

Example 4

1, 3- diheptyl- 2- ethyl- 3-( 0, 0- diethylphosphorodithioylacety1)- isothiourea

Intermediate g)

30 g (0.1 mol) of 1,3-diheptyl-2-ethylisothiourea, 12.4 g (0.11 mol) of chloroacetyl chloride and 250 ml of toluene were mixed in a 500 ml 3-necked flask equipped with a stirrer, thermometer and dropping funnel . The solution was stirred and cooled to -30°C with a dry ice bath. 11.1 g (0.11 mol) of triethylamine was then added over a period of 30 minutes. After the addition was complete, the reaction mass was allowed to warm to room temperature, and stirring was continued for 1 hour. The reaction mass was then washed in turn with two 200 ml portions of water, 100 ml of saturated sodium bicarbonate solution and finally with two 200 ml portions of water. The toluene phase was dried with anhydrous MgSO 4 , filtered and evaporated in vacuo to give 36.1 g of the desired compound, 1,3-diheptyl-2-ethyl-3-chloroacetylisothiourea. The structure was confirmed by IR and NMR spectra.

1, 3- diheptyl- 2- ethyl- 3-( 0, 0- diethylphosphorodithioylacety1- isothiourea

2.2 g (0.012 mol) of 0,0-diethyldithiophosphoric acid was dissolved in 25 ml of acetone and treated with 5 g of anhydrous potassium carbonate. After neutralization, the acetone phase was decanted into a 250 ml flask containing a solution of 3.0 g (0.008 mol) of intermediate g) in 75 ml of acetone. The resulting mixture was stirred at room temperature for 2 hours and then poured into two 200 mL toluene. The resulting mixture was washed with two 200 mL portions of water. The toluene phase was then dried with anhydrous MgSO 4 , filtered and evaporated in vacuo to give 3.6 g of the desired product, 1,3-diheptyl-2-ethyl-3-(0,0-diethylphosphorodithioylacetyl)-isothiourea. n^° 1.5060. The structure was confirmed by IR and NMR spectra. Compound No. 261 in Table I.

Example 5

N, N'- diheptyl- S- ethyl- N- propane- sulfony1- isothiourea

1.8 g (0.018 mol) of triethylamine was added to 4.5 g

(0.015 mol) of N,N'-dihepty1-S-ethyl1-isothiourea in 50 ml of methylene chloride in a stirred, round-bottomed flask. A solution of propane sulfonyl chloride (0.018 mol, 2.6 g) in 8 mL of methylene chloride was added dropwise to the above solution at 0°C. The mixture was stirred for 1.5 hours at room temperature and then at 30-35°C for 1.5 hours. The cooled solution was washed twice with 20 ml of water, once with 25 ml of saturated sodium bicarbonate solution and two more times with 20 ml of water. The organic phase was dried over magnesium sulfate and evaporated in vacuo to give the product as a yellow oil. n^° 1.4805. The yield was 5.2 g (85.4% of the theoretical). The structure was confirmed by IR spectrum. Compound No. 203 in Table I.

Example 6

N,N'- diheptyl- S- ety1- N'- p- toluenesulfonyl- isothiourea

The reaction was carried out with 0.018 mol (3.4 g) of p-toluenesulfonyl chloride in the same way as in example 5 above. The product had an n^° of 1.517. The yield was 6.0 g (88% of the theoretical). IR, NMR spectra and mass spectroscopy confirmed the structure. Compound No. 206 in Table I.

Example 7

1, 3- di- n- heptyl- l- trichloromethylthio- 2- ethyl1- isothiourea

3 g (0.01 mol) of 1,3-di-n-hepty1-2-ethy1-isothiourea was mixed with 50 ml of tetrahydrofuran in a stirred, round-bottomed flask and cooled in an ice bath. 1.4 mL (0.01 mol) of triethylamine was added and the mixture was stirred for 10 minutes. 1.1 mL (0.01 mol) of trichloromethylsulfenyl chloride was added dropwise to the mixture over 2 minutes. A white precipitate formed and the mixture was stirred for 1 hour as it warmed to ambient temperature. The resulting reaction mixture was allowed to stand

overnight. The mixture was suction filtered to remove the white solid which was rinsed twice with 10 mL of fresh tetrahydrofuran. The filtrate was evaporated under vacuum,

which resulted in 4.55 g of the title product in a yield of 101.2 percent. The resulting liquid had a n^° on it

1.5084 and was identified as the title compound by IR spectrum and mass spectroscopy.. Compound No. 297 in

table I.

Example 8

1, 3- di- n- heptyl- 1-( 2'- fluoro- 1', 1', 2', 2'- tetrachloroethylthio-2- ethylisothiourea

2.0 g (0.007 mol) 1,3-di-n-heptyl-2-ethylisothiourea

was dissolved in 100 ml of tetrahydrofuran and introduced into a stirred, round-bottomed flask and placed in an ice bath. 0.7 g (0.0069 mol) of triethylamine was added and the mixture was stirred for 10 minutes. 1.68 g (0.0068 mol) 2-fluoro-1,1,2,2-tetrachloroethylsulfenyl-

chloride dissolved in 20 ml of tetrahydrofuran was added during approx. 15 minutes. A precipitate formed while the mixture was stirred for 2 hours. The mixture was suction filtered and the precipitate was washed twice with 20 ml of tetrahydrofuran. The filtrate

was vacuum evaporated. The yield of the title product was 3.53 g of a liquid with an n^° of 1.5091. Product identity was confirmed by IR spectrum and mass spectroscopy. Compound No. 298 in Table I.

Example 9

1, 3- di- n- hepty1- 1- o- nitrophenylthio- 2- ethyl isothiourea

1.9 g (0.01 mol) of 2-nitrobenzene sulfenyl chloride was dissolved

in 50 ml of tetrahydrofuran. A mixture of 3 g (0.01 mol) of 1,3-di-n-hepty1-2-ethylisothiourea in 30 ml of tetrahydrofuran was added to the mixture in a round-bottomed, stirred glass flask. cooled in an ice bath. 1.05 g (0.01 mol) of triethylamine in 10 ml of tetrahydrofuran was added over a period of 10 minutes.

A white precipitate immediately formed, and the reaction mixture was stirred in the bath for 3 hours while warming to ambient temperature, then filtered with suction. The filtrate was vacuum evaporated to give a light brown sticky residue which was redissolved in approx. 100 ml of diethyl ether and filtered through magnesium sulfate and "Dicalite 4200" by suction. The filtrate was subjected to vacuum stripping to give 4.2 g of a liquid with an n_, of 1.546 3. The product was identified as the title product by IR spectrum. Compound No. 300 in Table I.

Example 10

S- ethyl- 1, 3- dihepty1- 3-( 2- carboethoxy)- ethyl- 2- isothiourea

3 g (0.01 mol) S-ethyl-1,3-diheptyl-2-isothiourea and

3 g (0.03 mol) ethyl acrylate was introduced into a 100 ml glass flask. A catalytic amount of base (0.1 g NaH) was added and the mixture was heated from 25 to 85°C and held at 85°C for 5 hours. The reaction mixture was cooled and 150 ml of ether was added. The ether was washed with 100 ml of water, then dried and

operated to give 2 g of the title product. The structure was confirmed by IR and NMR spectra. Compound No. 199 in Table I.

Example 11

S- ethyl- 1, 3- dihepty1- 3-( 3- oxobuty1)- 2- isothiourea

The procedure was the same as for Example 10, except that ethyl acrylate was replaced by methyl vinyl ketone, and the reaction was carried out at room temperature for 4 hours. Up-processing of the product was the same. 2 g of the title product was prepared and identified by IR and NMR spectra. Compound No. 200 in Table I.

Example 12

N,N- di- n- heptyl- N'- ethyloxalyl- S- ety1- isothiourea

5.0 g (16.6 mmol) of S-ethyl-1,3-diheptyl-2-isothiourea and 1.8 g (18.3 mmol) of triethylamine in 50 mL of methylene chloride were mixed together in a 100 mL one-necked round-bottom flask equipped with magnetic stirrer and cap. The clear pale yellow solution was cooled to 0°C in an ice bath. To this stirred, cooled solution was added 2.50. g (18.3 millimoles) of ethyl oxalyl chloride dropwise while maintaining the temperature between 5 and 15°C.

A large amount of white precipitate was formed within seconds,

and stirring was continued for 1 hour at 0°C. The cooling bath was removed and the mixture was stirred at room temperature for 3 hours. The precipitate was dissolved by adding 50 ml of water, and the mixture was transferred to a separatory funnel containing 50 ml of methylene chloride. The layers were separated and the organic phase was washed once with 10 ml saturated NaHCO 3 , 3 times with 10 ml portions of water, once with 10 ml saturated sodium chloride and dried over Na 2 SO 4 . The dried clear yellow organic solution was filtered through Na 2 SO 4 , and the solvent was removed under vacuum to give 6.63 g (99.7% yield) of the title product as a clear yellow oil with an nj of 1.4757. The product was identified as the title product by IR and NMR spectra and mass spectroscopy. Compound No. 6 71 in Table I.

Example 13

Bis- N'-( N, N'- n- hepty1- S- ethylisothiourey1)- oxalate

The procedure in Example 13 is the same as in Example 12 above, except that a 200 mL one-necked round-bottom flask was used instead of a 100 mL flask, and 1.16 g (9.13 mmol) of oxalyl chloride was used instead of the ethyl oxalyl chloride in the previous example. The reaction resulted in a clear, yellow solution which was stirred at 0°C for 1 hour and then stirred at room temperature for 20 hours. The clear, yellow solution was then transferred to a separatory funnel containing 50 mL of water and 50 mL of methylene chloride. The layers were phase separated and the organic phase was washed once with 10 ml of 10% potassium carbonate, 5 times with 10 ml portions of water, once with 10 ml of saturated sodium chloride and dried over Na 2 SO 4 . The dried organic solution was filtered and the solvent removed as in Example 12 to give 5.55 g (102.1% of theoretical yield) of an orange oil with an n^° of 1.4932. The product was identified as the title product by IR and NMR spectra and mass spectroscopy. Compound No. 688 in Table I.

Example 14

N,N'-di-(1-heptyl)-N'-(ethylmercapto- carbony1)-S-ethyl1- isothiourea f

Procedure and equipment were the same as in Example 12 above, except that 5.0 g (16.6 mmol) of N,N'-di-(1-heptyl)-S-ethyl1-isothiourea and 1.85 g (18 .3 mmol) of triethylamine and 50 mL of methylene chloride were added to the flask, followed by the addition of 2.28 g (18.3 mmol) of ethyl thiochloroformate.

The resulting product was phase separated, washed and dried as in Example 12. The solvent was removed under vacuum to give 6.55 g (101.5% of theory) of a collected yellow oil with an n^° of 1 ,4922. The product was identified as the title product by IR and NMR spectra and mass spectroscopy. Compound No. 300 in Table I.

Example 15

1, 3- diheptyl- 2- ethyl- 3-[ 3'- 2''- ethoxyethoxycarbonylamino)-4'- methylphenylaminocarbonyl)- isothiourea

The title product was prepared as follows:

Step a) 1,3-dihepty1-2-ethyl-3-(3-isocyanato-4-methylphenyl-aminocarbonyl)-isothiourea f (intermediate product)..

125 cm 3 of methylene chloride was pipetted under a stream of argon into a 200 cm 3 3-necked flask with stirring, and 15.1 g (0.86 mol) of toluene-2,4-diisocyanate was then added to the methylene chloride.

Then 25.8 g (0.086 mol) of 1,3-dihepty1-2-ethyl-isothiourea was added without cooling over a period of 5 minutes. The temperature rose from 20 to approx. 30°C during the addition. The reaction mixture was then heated to reflux temperature (41°C) and held at reflux temperature for 1 hour. The resulting reaction mixture was then concentrated on a rotary evaporator under high vacuum. The reaction gave 39.8 g of product with an n^<0> of 1.5318, which was identified as the intermediate title compound by IR and carbon 13 NMR spectra.

Step b) Preparation of 1,3-dihepty1-2-ethyl-3-[3<1->(2<1>'-ethoxyethoxycarbonylamino)-4<1->methylphenylaminocarbonyl]-isothiourea f .

4.74 g (0.010 ml) of the intermediate from step a), 0.95 g (0.0105 mol) of 2-ethoxyethanol, 2 drops of triethylamine, 1 drop of dibutyltin dilaurate and 25 cm 3 of tetrahydrofuran dried over a Linde molecular sieve 3A were introduced in a 3-necked flask. The mixture was brought to reflux (67 to 68°C) and held under reflux for 2 hours. The solvent was then removed under high vacuum at a pressure of 0.3 mm or less and at a bath temperature of 80 to 90°C. 5.6 g of a viscous oil was recovered and identified as the title compound by IR-

and carbon 13 NMR spectra analyses. Compound No. 419 in Table I.

Example 16 1,3-dihepty1-2-ethyl1-3-[3'-(3''-chloro-4''-methylphenyl-ureido)-4'-methylphenylaminocarbonyl]- isothiourea

The reaction and reaction components were identical to the reaction according to example 15 b), with the exception that 1.49 g (0.0105 mol) of 3-chloro-4-methylaniline is used instead of 2-ethoxyethanol. An insoluble by-product was formed which was removed by filtration before evaporating the solvent. The reaction gave 3.5 g of a product identified as the title compound by IR and NMR spectra analyses. Compound No. 429 in Table I.

Example 17

1, 3- dihepty1- 2- ethyl1- 3-[ 3'- propylurea ido- 4'- methylphenylamino-carbonyl]- isothiourea

4.74 g (0.010 mol) of the intermediate product as prepared in example 15 a) and 25 cm~* of dry tetrahydrofuran were introduced into a 3-necked flask. 0.62 g (0.0105 mol) of propylamine was added at room temperature without cooling. The reaction was exothermic and the temperature rose approx. 10 to 20°C. No heat was added to the mixture and the reaction was complete within 1 hour. The mixture was filtered from a small amount of solid by-product and worked up as in example 15 b). The reaction gave 5.0 g of a liquid with an nQ of 1.5312 and was identified as the title compound by IR and carbon 13 NMR spectra analyses. Compound No. 431 in Table I.

Example 18

1, 3- dihepty1- 2- ethyl1- 3[ 3'- p- chlorobenzylthiocarbonylamino- 4'-methylphenylaminocarbonyl1- isothiourea f

The reaction components were the same as in Example 15 b), except that 1.66 g (0v.0105 mol) of 4-chlorobenzylmercaptan was used instead of 2-ethoxyethanol. The reaction gave 6.5 g of a viscous liquid which was identified as the title product by IR and NMR spectra analyses. Compound No. 43 3 in Table I.

Example 19

1, 3- dihepty1- 2- ethyl1- 3-( 3'- phenoxycarbonylamino- 4'- methylpheny1-aminocarbonyl1)- isothiourea

The reaction components were the same as in Example 15 b), except that 0.99 g (0.0105 mol) of phenol was used instead of 2-ethoxyethanol. The reaction gave 5.2 g of a liquid with an nD 2 ° of 1.5488 which was identified as the title product by NMR and IR spectra analyses. Compound no. 452 in Table I. Example 20 1-octyl-2-ethyl-3-sec-heptyl-3-[3-(1-octyl-2-propyl-3-sec-heptyl-3-carbonylamino)-4 - methylphenylcarbonylamino]- isothiourea Step a) Preparation of 1-octyl-2-ethyl-3-sec-heptyl-3-(3-isocyanato-4-methylphenylaminocarbonyl)-isothiourea (intermediate product).

This intermediate was prepared in the same way as the intermediate according to Example 15 a), except that 27.2 g (0.086 mol) of 1-octyl-2-ethyl 1-3-sec-hepty.1-isothiourea was used instead of the thiourea reaction component according to step 25 a). The conversion gave 41.5 g (98.8 weight percent of the theoretical) of

a liquid with an n^ of 1.5,280, which was identified as the title intermediate by IR and carbon 13 NMR spectra analyses.

Step b) Preparation of 1-octyl-2-ethyl-3-sec-heptyl-3-[3-(1-octyl-2-propyl-3-sec-heptyl-3-carbonylamino)-4-methyl-phenylcarbonylamino] - isothiourea.

The title product was prepared as in step 15 b), except that 4.87 g (0.010 mol) of the intermediate product prepared in step 20 a) and 3.29 g (0.010 mol) of 1-octyl-2-propyl- 3-sec-heptyl-isothiourea f . The reaction gave 7.9 g (96.3% by weight of theory) of a liquid with an n^ of 1.5185 which was identified as the title product by IR and carbon 13 NMR spectra analyses. Compound No. 558 in Table I.

Example 21

1,3-bis-n-hepty1-1-(carbamylsulfonyl chloride)-2-S-ethylisothiourea 50 ml of dry methylene chloride and 8.49 g of chlorosulfonyl isocyanate (Aldrich) were placed in a 200 ml flask equipped with a magnetic stirrer, thermometer and drip funnel. A solution of 18 g of 1,3-dihepty1-2-ethyl1-isothiourea (in 100 ml of dry methylene chloride) was added dropwise over 40-45 minutes. The reaction was slightly exothermic, so the flask was cooled in a water bath to keep the temperature below 28°C. The solution was then stirred at approx. 25°C overnight.

The solution was then filtered, and the filtrate concentrated under reduced pressure. 26.2 g (99% by weight of theory) of a thick liquid with an nQ of 1.4833 was recovered. The product was identified as the title product by IR and NMR spectra analyses. Compound No. 6 35 in Table I.

Example 22

1/ 3- bis- n- hepty1- 1- chlorocarbonyl1- 2- ethy1- isothiourea

100 ml of dry CH 2 Cl 2 was introduced into a 500 ml flask equipped with a thermometer and dropping funnel and cooled to 5 C in an ice bath. A solution of phosgene in benzene (170 g at 17.5% by weight concentration) was then added. Then a solution of 100 ml of dry CH 2 Cl 2 , 10.1 g of triethylamine and 30 g of 1,3-diheptyl-2-ethyl-isothiourea was added dropwise over a period of 1 hour at 5°C. The mixture was then stirred overnight at ambient temperature.

The next morning, the reaction mixture was heated to approx. 40°C for 2.5 - 3 hours to ensure completion of the turnover. The mixture was then subjected to reduced pressure to remove the CH 2 Cl 2 solvent. 100 ml of dry ether was added and the mixture was filtered by suction on a glass frit.

The solid was washed with a little more ether, and the combined filtrates were concentrated under reduced pressure to remove the ether. 38.6 g of a liquid (106% by weight of theory) with an n^° of 1.4613 was recovered. The product was identified as the title product by mass spectra analyses. Compound No. 643 in Table I.

Example 23

1, 3- bis- n- hepty1- 1- diethylcarbamy1- 2- ethy1- isothiourea

100 ml of dry benzene and 5.44 g of 1,3-dihepty1-2-ethyl1-isothiourea f-carbamyl chloride were introduced into a 200 ml flask equipped with a thermometer and dropping funnel. A solution of 12 ml of dry benzene and 2.19 g of diethylamine was added dropwise over 10-12 minutes. An exothermic reaction raised the temperature from 21 to 30°C. The mixture was then heated to 45-50°C for 3 hours. The reaction mixture was then cooled to 15°C and washed twice with 50 ml portions of cold water. The benzene phase was dried with MgSO 4 , filtered, and the solvent removed under reduced pressure. 5.75 g of a liquid (96% by weight of theory) with an n^° of 1.4568 was recovered. The structure was confirmed to be the title compound by mass spectra analyses. Compound No. 644 in Table I.

Example 2 4

1,3-bis-n-heptyl-1-(propargyloxycarbonyl)-2-ethyl1-isothiourea f 50 ml of dry tetrahydrofuran and 0.36 g of NaH were placed in a 200 ml flask equipped with a thermometer and dropping funnel. A solution of 10 ml of dry THF and 0.84 g of propargyl alcohol was added dropwise over 8-10 minutes. The reaction mixture released hydrogen and was somewhat exothermic. The mixture was then stirred for 3 hours to complete the reaction.

Then a solution of 15 ml of dry THF and 5.44 g of 1,3-dihepty1-2-ethyl-isothioureacarbamyl chloride was added dropwise over 10 minutes. The mixture was stirred and heated to 45°C for 2 hours. The reaction mixture was cooled to 25°C and filtered by suction on a glass frit and filter. The solvent was removed under reduced pressure. 5.0 g of a liquid (88% by weight of theoretical) with an nD 30 of 1.4553

was mined. The structure was confirmed as the title compound by NMR and spectra analyses. Compound No. 648 in Table I.

Example 25

1, 3- bis( 2- ethylhexyl)- 1-( succinic anhydride- adduct)- 2- ethyl isothiourea • Et^ N- salt

200 ml of dry CH 2 Cl 2 , 32.8 g of 1,3-(2-ethylhexyl)-2-ethylisothiourea, 11 g of succinic anhydride and 11.1 g of Et₂N were introduced into a 500 ml flask. A slightly exothermic reaction took place with the mixture of these components. The solution stood overnight.

The reaction mixture was then subjected to stripping under reduced pressure. 4 7.3 g of a liquid (89% by weight of theoretical) with an n^° of 1.4899 was recovered. The structure was confirmed as the title compound by IR and NMR spectra analyses. Compound No. 665 in Table I.

Example 26

The reaction product of 2 mol 1,3-di-(2'-ethylhexyl)-2-S-ethylisothiourea + toluene-2,4-diisocyanate

In a 3-necked 200 mL flask fitted with a magnetic stirrer,

3.28 g (0.01 mol) of 1,3-di-(2'-ethylhexyl-2-S-ethyl-isothiourea) was mixed with 20 ml of tetrahydrofuran. To this solution

was added 0.87 g (0.005 mol) toluene-2,4-diisocyanate. The temperature rose from 23°C to 34°C. The mixture was allowed to stand at ambient temperature overnight, after which it was evaporated under vacuum. Infrared analysis showed that the reaction was incomplete, and the mixture was therefore dissolved in 30 ml of methylene chloride, and 1 drop of dibutyltin dilaurate and 2 drops of triethylamine were added. The homogeneous solution was stirred at ambient temperature for 1.5 hours. The mixture was re-evaporated under vacuum to give the product as a viscous yellow liquid with an n^° of 1.5201. The yield was 4.3 g. The product was identified as the title compound by both IR and NMR spectra analyses. Compound No. 85 in Table I.

Example 27

1, 3- di- n- heptyl- l- N- phenylcarbamy1- 2- S- n- propy1- isothiourea

The equipment was as in example 26 above. 6.2 g (0.014 mol) of 1,3-di-n-hepty1-2-S-n-propyl1-isothiouronium hydrogen iodide was dissolved in 35 ml of tetrahydrofuran, and 1.68 g (0.014 mol) of phenyl isocyanate was added, followed of portionwise addition of 1.43 g (0.014 mol) of triethylamine while cooling. A solid precipitate was formed by addition of ^triethylamine. The reaction mixture was stirred at ambient temperature overnight. The reaction mixture was then evaporated in vacuo to remove tetrahydrofuran, and the residue was dissolved in chloroform and washed twice with 150 mL portions of water. The organic phase was then dried over magnesium sulfate, filtered and evaporated in vacuo to remove the chloroform. The product was 5.9 g (96.7% by weight of the theoretical yield) of a yellow liquid with an nj^ of 1.5188. The product was identified as the title compound by IR and NMR spectra analyses. Compound No. 11 in Table I.

Example 28

1, 3- di- n- heptyl- l- N- octadecylcarbamy 3.- 2- S- e ty 1- isothiourins tof f

The equipment was the same as in example 26 above. 4.5 g (0.015 mol) of 1,3-di-n-heptyl-2-S-ethyl isothiourea was mixed with 40 ml of tetrahydrofuran, and 4.43 g (0.015 mol) of N-octadecylisocyanate was added. 3 drops of triethylamine were added and the mixture stood overnight. The mixture was then heated to 40°C for 20 minutes to complete the reaction. A small amount of solid formed on cooling and was filtered off. The reaction mixture was then vacuum evaporated to give

8.9 g (100 percent of theoretical yield) of a pale liquid with an n^° of 1.4750. The product was identified as the title product by IR and NMR spectra analyses. Connection No. 29

in Table I.

Example 29

1, 3- di- n- heptyl- l- N- 4- methylthiophenylcarbamy1- 2- S- ethy1- isothiourea f

The equipment was the same as in Example 26 above. 3.0 g (0.01 mol) of 1,3-di-n-heptyl-2-S-ethyl-isothiourea was mixed with 25 ml of methylene chloride. 2 drops of triethylamine and 1 drop of dibutyltin dilaurate were added, and then 1.65 g (0.01 mol) of 4-methyl-thiophenyl isocyanate was added. The temperature rose from 23° to 33°. The reaction mixture was then vacuum evaporated to remove methylene chloride to give 4.65 g (100 percent of theory) of a yellow liquid with an n^ of 1.5340. The liquid solidified on standing to a semi-solid. The product was identified as the title product by 1R and NMR spectra analyses. Compound No. 47 in Table I.

Example 30

1, 3- di- n-hepty1- 1- N- 2- chloroethylcarbamy1- 2- S- ethy1- isothiourea

The procedure, equipment and reaction components were the same as in Example 29, with the exception that 1.06 g (0.01 mol) of 2-chloroethyl isocyanate was used instead of 4-methylthiolphenyl isocyanate. The reaction gave 4.14 g (102% by weight of theoretical yield) of a clear liquid with an nD of 1.4930. The product was confirmed as the title compound by IR and NMR spectra analyses. Compound No. 48 in Table I.

Example 31

l- sec- heptyl- 3- n- hepty1- 2- S- ety1- isothiourea (intermediate)

■The equipment was the same as in example 26 above. 11.5 g (0.1 mol) of 2-aminoheptane was mixed with 50 ml of ethanol 2B, and 15.7 g (0.1 mol) of N-heptyl isothiocyanate was added, which

resulted in an exothermic reaction during which the temperature rose from 25 to 65°C. The reaction mixture was refluxed on a steam bath for 1.5 hours. 17.16 g (0.11 mol) of ethyl iodide was then added to the thiourea and the mixture was refluxed for 1.5 hours on a steam bath. The product was evaporated in vacuo to give 44.0 g of an isothiouronium salt. The isothiouronium salt was dissolved in 200 ml of toluene and washed with 100 cm 3 of 5 percent sodium hydroxide. The toluene layer was then washed twice with 150 cm 3 portions of water, dried over magnesium sulfate, filtered and vacuum evaporated. The product was then evaporated under high vacuum to give 7.78 g (92.6% by weight of theoretical yield) of a clear yellow liquid with an n^ of' 1.4768. The product was identified as the title product by IR and NMR spectra analyses.

Example 32

1- sec- hepty1- 3- n- hexy1- 2- S- ety1- isothiourea f (intermediate)

The equipment, procedure and reaction components were the same as in Example 31, except that 10.01 g (0.07 mol) n-hexyl isothiocyanate, 8.05 g (0.07 mol) 2-aminoheptane, 35 ml ethanol 2B, 11 .7 g (0.075 µl) of ethyl iodide, 200 ml of toluene and a one percent solution of sodium hydroxide (0.08 mol) were used as reaction components and reagents in the process. The reaction gave 19.6 g (98% by weight of theoretical yield) of a clear liquid with an nj of 1.476 5. The product was identified as the title product by IR and NMR spectra analyses.

Example 3 3

1, 3- di- n- heptyl- 1- N- tert- butylcarbamy1- 2- S- ethyl isothiourea

The equipment was the same as that used in example 26.

3.0 g (0.01 mol) of 1,3-di-n-heptyl-2-S-ethylisothiourea was mixed with 30 ml of methylene chloride. 2 drops of triethylamine and 1 drop of dibutyltin dilaurate were added to the mixture, followed by 1.0 g (0.01 mol) of tert-butyl isocyanate. The temperature rose from 24 to 39°C. The reaction mixture was stirred overnight at ambient temperature and then heated for 1/2 hour at 35 to 40°C to complete the reaction. The reaction mixture was evaporated in vacuo to give 3.83 g (96% by weight of theoretical yield) of a clear liquid with an n^° of 1.4750. The product was identified as the title product by IR and NMR spectra analyses. Compound No. 40 in Table I.

Example 34

1, 3- di- n-hepty1- 1- N- ethylacetate carbamy1- 2- S- ethy1- isothiourea The procedure, equipment and reaction components were the same as in Example 33, except that 1.29 g (0.01 mol) ethyl -isothiocyanatoacetate was used instead of tert-butyl isocyanate. The reaction gave 4.3 g (100% by weight of theory) of a clear liquid with an n^° of 1.4800. The product was identified as the title product by IR and NMR spectra analyses. Compound No. 41 in Table I.

Example 35

1, 3- di- n- heptyl- 3- B- hydroxyethylcarbamy1- methylcarbamy1- 2- S- ethylisothiourea f

The equipment was the same as in Example 26. 9.0 g (0.03 mol) of 1,3-di-n-hepty1-2-S-ethyl1-isothiourea was mixed with 30 ml of methylene chloride to which 3.87 g (0, 03 mol) of ethyl cyanoacetate was added. The temperature rose from 23 to 45°C during the turnover. The mixture was allowed to stand overnight. Then 10 drops of additional isothiourea were added to react with remaining isocyanate. To the reaction mixture was then added 1.83 g (0.03 mol) of 2-aminoethanol, and the reaction mixture was stirred overnight. The reaction mixture was vacuum evaporated to remove the methylene chloride, and 25 ml of ethanol was added to the rest of the reaction mixture. The reaction mixture was then allowed to stand for 3 days. The resulting cloudy mixture was then stirred at ambient temperature overnight and then vacuum evaporated to give 13.7 g of a yellow , cloudy liquid with a

n^p of 1.4800. The product was identified as the title product by IR and NMR spectra analyses. Connection No. 6 4

in Table I. -

Example 36

Reaction product of. 2 mol 1, 3-di-n-sec-hepty1-2-S-ethyl1-isothiourea + pp'-diphenylmethane-diisocyanate

The equipment was the same as in Example 26. 3.0 g (0.01 mol) of 1,3-di-sec-heptyl-2-S-ethylisothiourea was mixed with 30 ml of toluene. 1.25 g (0.005 mol) of pp'-diphenylmethane diisocyanate was added to the mixture, and the reaction mixture was heated and held for 2 hours at 75 to 80°C. IR showed a small isocyanate peak; so that 10 drops of the isothiourea were added, and heating was continued for .30 minutes. The reaction mixture was then stirred at ambient temperature overnight. The reaction mixture was then evaporated in vacuo to give 4.5 g

(104% by weight of theoretical) of an amber liquid with a

nQ of 1.5310. The product was identified as the title product by IR and NMR spectra analyses. Compound No. 127 in Table I.

Example 37

Reaction product of 2 mol 1-N- sec- hepty1- 3- N- n- hexy1- 2- S- methyl1-thiomethyl- isothiourea + toluene- 2, 4- diisocyanate

The procedure and equipment were as in Example 36, but the reagents were 3.8 g (0.01 mol) 1-sec-heptyl-3-N-n-hexyl-2-S-methyl-thiomethyl-isothiourea, 0.87 g (0.005 mol) toluene-2,4-diisocyanate and 25 ml of tetrahydrofuran. After completion of the reaction, 20 drops of the isothiourea were added to react with the rest of the isocyanate at ambient temperature overnight. The reaction mixture was then evaporated in vacuo to yield 4.6 g of a red, viscous liquid with an n^° of 1.5344. The product was identified as the title product by IR and NMR spectra analyses. Compound No. 138 in Table I.

Example 38

l- N- sec- heptyl- 3- N- n- octy1- n- octadecylcarbamy1- 2- S- ally1- isothiourea

The procedure and equipment were the same as in example 26. 1.9 g (0.006 mol) of 1-sec-heptyl-3-n-octyl-2-S-allyl-isothiourea was mixed with 25 ml of tetrahydrofuran to which was added 1 .77 g (0.006 mol) of n-octadecylocyanate. The reaction mixture was then stirred at ambient temperature overnight and then evaporated in vacuo to give 3.79 g (100% by weight of theory) of a clear liquid with an n^° of 1.4769. The product was identified as the title product by IR and NMR spectra analyses. Compound No. 144 in Table I.

Example 39

Reaction product of 2 mol 1-phenyl-3-n-hepty1-2-S-ethylisothiourea + toluene-2,4-diisocyanate

The equipment was the same as that used in example 26.

2.78 g (0.01 mol) of 1-phenyl-3-n-heptyl-2-S-ethylisothiourea in 35 ml of tetrahydrofuran was mixed with 0.87 g (0.005 mol) of toluene-2,4-diisocyanate. The reaction mixture was then refluxed on a steam bath for 1 hour, then 15 drops of the isothiourea were added, and the reaction mixture was refluxed for an additional 1 hour to convert all of the isocyanate. The reaction mixture was evaporated in vacuo to give 4.1 g of a viscous yellow liquid with an n^ of 1.5737. The product was identified as the title product by IR and NMR spectra analyses. Compound No. 151 in Table I.

Example 40

N-(5-sila-5,5-dimethyl-1-heptyl)-N'-n-hepty1-n-octadecylcarbamyl-2-S-ethy1- isothiourea

The equipment was the same as in example 26. 2.4 g

(0.007 mol) 1-(5'-sila-5',51-dimethyl-N-heptyl)-3-n-heptyl-2-S-ethyl-isothiourea in 25 ml of tetrahydrofuran was mixed with 2.06 g (0.007 mol) of N-octadecylocyanate and stirred at ambient temperature for 2 hours. The reaction mixture was vacuum evaporated to give 4.51 g (100% by weight of theoretical yield) of a clear liquid with an nj^ of 1.4765. The product was identified as the title product by IR and NMR spectra analyses. Compound No. 184 in Table I.

Example 41

N- dichloroacety1, N, N'- di- n- heptyl, S- ety1- isothiourea

3.0 g (0.01 mol) of 1,3-di-n-hepty1-2-S-ethylisothiourea dissolved in 25 ml of methylene chloride was introduced into a 3-necked 200 ml

flask equipped with a magnetic stirrer. 1.1 g of triethylamine was added to the mixture. Then 1.5 g (0.01 mol) of dichloroacetyl chloride in 10 ml of methylene chloride was added slowly while the reaction mixture was cooled in an ice bath. The reaction mixture was heated to and then held at 40°C for 1/2 hour. The reaction product was washed with water, and the organic layer was dried with magnesium sulfate, filtered and subjected to vacuum stripping to give 4.1 g of a liquid with an n^ of 1.4723. The product was identified as the title compound by NMR spectra analyses. Compound No. 332 in Table I.

Example 4 2

Adduct of 1 mol 1,3-di-n-hepty1-2-S-ethyl- isothiourea and

1 mole of diglycolic anhydride

The equipment was the same as in Example 41. 3.0 g (0.01 mol) of 1,3-di-n-hepty1-2-S-ethyl1-isothiourea was dissolved in 15 ml of glycol, and 1.2 g (0 .01 mol) of diglycolic anhydride dissolved in 10 ml of glycol was added. The reaction mixture was heated to reflux for 10 minutes and evaporated under vacuum to give 4.1 g of a liquid with an n^ of 1.4608. The product was identified as the title product by IR and NMR spectra analyses. Compound No. 321 in Table I.

Example 4 3

Adduct of 1 mol 1, 3-di-n-hepty1-2-S-ethyl1- isothiourea and

1 mole of succinic anhydride

The equipment, procedure and reaction components were the same as in Example 42, except that 1.0 g (0.01 mol) of succinic anhydride was used instead of the diglycolic anhydride. The reaction yield was 4.1 g of a semi-solid. The product was identified as the title product by NMR spectra analyses. Compound No. 331 in Table I.

Example 4 4

Adduct of 1 mol 1, 3-di-n-hepty1-2-S-ethyl1- isothiourea and

1 mole of formaldehyde

The procedure, equipment and reaction components were the same as in Example 42, except that 1.2 g of formaldehyde as a 37% solution in water (0.01 mol plus about 20% excess) was used instead of diglycolic anhydride. The reaction yield was 3.3 g of a semi-solid which was identified as the "title product by NMR spectra analysis. Compound No. 323 in Table I.

Example 45

Adduct of 1 mol 1, 3-di-n-hepty1-2-S-ethyl1- isothiourea and

1 mol p-anisaldehyde

The equipment, procedure and reaction components were the same as in Example 42, except that 1.4 g (0.01 mol) of anisaldehyde was used instead of the diglycolic anhydride. The reaction yield was 4.3 g of a liquid with an nj^ of 1.4825. The product was identified as the title product by NMR spectra analysis. Compound No. 328 in Table I.

LEPIDOPTERICIDE ASSESSMENT

Lepidoptericidal activity of the above compounds •was evaluated for effectiveness on different lepidopterous species as follows:

I. Marsh butterfly larva [Estigmene acrea (Drury)]

A test solution is prepared by dissolving the test compound in a 50-50 acetone-water solution. Part of a mugwort (Rumex crispus) leaf, approx. 2.5 cm wide and 4 cm long, immersed in the sample solution for 2-3 seconds and then placed on a wire cloth to dry. The dried leaf is placed in a Petri dish containing a moistened piece of filter paper and infected with 5 second-stage marsh butterfly larvae. The mortality of the larvae is recorded 48 hours later. If surviving larvae are still present, a piece of synthetic medium is added to the dish and the larvae are observed for an additional 5 days to detect delayed effects of the test compound. The primary test concentration for this sample is 0.05% by weight of the test compound in the solution.

II. Cabbage scale [Trichoplusia ni (Hubner)]

The procedure for cabbage measurer larvae is the same as that used for marsh butterfly larvae, except that a hyzini pumpkin (Calabacita abobrinha) seed leaf of approximately the same size as the mugwort leaf part is used instead of the latter. The primary test concentration for this sample is 0.05% by weight of the test compound in the solution.

III. Tobacco budworm [Heliothis virescens (F.)]

Tobacco budworm larvae are used in this experiment by a method identical to that used for the marsh butterfly larvae, except that a piece of romaine lettuce (Latuca sativa) leaf of approximately the same size as the piece of mugwort leaf is used instead of the latter . The primary test concentration for this sample is 0.1% by weight of the test compound in the solution.

Table II summarizes the results of the lepidoptericidal studies carried out on the compounds in Table I. These test results are expressed as LD^^ values, which represent

the dose of the test compound which was lethal to 50 per cent of the insect population at the test. The values in Table II were obtained as follows: For a particular lepidoptera, each compound was first examined at the primary test concentration. The compounds which showed less than 50 percent eradication at this concentration are indicated in the table at the primary test concentration with a "greater than" sign (>) in front. Those compounds showing approximately 50 percent eradication are indicated with the primary test concentration alone.

Those compounds showing more than 50 percent eradication were subjected to further investigation at successively lower concentrations, until the concentration which gave approximately 50 percent eradication was found. The latter concentration is indicated as LD^^ for this group.

Phytotoxicity tests

Phytotoxicity tests are carried out on cotton (Gossaypium hirsutum) and hyzini pumpkin (Calabacita abobrinha) seedlings. The plants are grown and treated in Kaiser No. 1059 15 cm x 22.5 cm x 7.5 cm flat aluminum planters. Each planter contains a row of cotton and a row of pumpkins, with 6-8 plants

per row. The plants are grown in greenhouses and treated when they are approx. 8 days old and 5 cm tall.

Technical test compounds are diluted in a 50-50 acetone-water solution, and prepared compounds are diluted in water. These sample solutions are then sprayed onto the plant trays

in a Ducon-Savko Model 3400 linear sprayer at rates of 1/2, 1, 2 and 4 Ibs active ingredient/80 gallons/acre. The treated plants are then placed in the greenhouse and watered in such a way that the foliage is not wet.

One week later, the treated plants are inspected, and the degree of: phytotoxicity is subjectively assessed from 0 to 5 as follows:

0 = no damage

1 = slight damage = slight to moderate damage

•3 = moderate damage

4 = moderate to severe damage

5 = serious injury or death

Table II also summarizes the results of the phytotoxicity tests carried out with the compounds in Table I.

The primary test concentration for each of the tests described above was chosen only for practical reasons, and none of the figures in the table should be understood to represent the highest concentration at which a feasible test for lepidoptericidal activity can be performed.

Biocide samples

In vitro ampoule samples

Tubes of sterilized nutrient and malt extract liquid were prepared. Portions of the toxin, dissolved in a suitable solvent, were injected through the cork into the liquid to give concentrations ranging from 50 ppm downwards. The test organisms consisted of a fungus, Botrytus cinerea, and a bacterium, Staphylococcus aureus (S.a.) Roseenbach.

Three drops of a spore suspension of each of the fungi were injected into the tubes containing malt liquor, and three drops of the bacterium were injected into the nutrient liquor. One week later, the growth of each organism was observed, and the effectiveness of the chemical was recorded as the lowest concentration in ppm that produced 100 percent inhibition of growth compared to untreated, inoculated tubes. The results are shown in Table III.

Fungicide samples

Leaf protection spray

Bean meal dew - The chemicals were dissolved in a suitable solvent and diluted with water containing several drops of a wetting agent. Sample concentrations, ranging from 1000 ppm and below, were sprayed until runoff on the primary leaves of pinto beans (Phaseolus vulgaris L.).

After the plants were dry, the plants were dusted with powdery mildew (Erysiphe polygoni de Dancolle) spores, and the plants were kept in greenhouses until fungal growth appeared on the leaf surface. The efficiency was recorded as the lowest concentration,

in ppm, which produces a 75 percent or greater reduction of mycelial growth on the leaf surface compared to untreated, inoculated plants. The results are shown in Table III.

The primary test concentration for each of the above-described samples was chosen for practical reasons only, and none of the numbers in the table should be understood to represent the highest concentration at which a feasible test for lepidoptericidal activity can be performed.

The compounds according to the invention are usually used in preparations which are suitable for practical use. Usually such preparations will contain inert or other active ingredients or diluents in addition to the active compound. Examples of such components or carriers are organic solvents, such as sesame oil, xylene solvents and heavy oil; water; emulsifiers; surfactants; talc; pyrophyllite; diatomite; plaster; camps; and propellants, such as dichlorodifluoromethane.

The active compounds can also be mixed with dust carriers for application as dust, with granular carriers for application by means of fertilizer spreaders or in ground state or with aerial seeders. They can also be prepared as a wettable powder or a liquid preparation for use as an aqueous suspension, or with solvents and surfactants for use as sprays, aerosols or emulsions. The compounds or their prepared mixtures can be applied to any area where the pests reside. . Examples of such habitats are insect habitats, clothing, plant surfaces and soil. Optionally, however, the active preparations can be applied directly to organic material, seeds or precursors in general, which the pests eat, or directly to the pests themselves. When they are used in such a way, it will be advantageous to use a preparation that is not volatile.

Particularly preferred preparations are those which contain an insecticidally effective amount of the active compound together with an inert, insoluble, solid carrier. Examples of such preparations are wettable powders, dust and preparations that can • flow, where the solid carrier is in finely divided form; and granular preparations where the solid carrier is a pre-formed granule.

These isothioureas can also be prepared to contain compounds that induce feeding reactions in the lepidopteran larvae, resulting in early ingestion of the lepidoptericidal isothioureas. Effective agents include cottonseed meal, cottonseed oil, mature cottonseed extract, sucrose, invert sugar, citrus molasses, soybean oil, soybean meal, corn oil, corn kernel extract, corn wool extract, corn kernel extract and mixtures thereof, together with suitable emulsifiers and wetting agents.

The amount of active compound or preparation considered to be insecticidally effective is that amount which, when applied to the pest habitat or food, will kill, or substantially injure, a significant proportion living or feeding there. The active compounds according to the invention can be used either as the only pesticidal component in the preparations or as one of a mixture of compounds in the preparation with a similar beneficial effect. Furthermore, it is not necessary that the pesticide preparations specified here are active as such. The purpose of the compound will be fully served by means of a preparation which is made active by means of external influences, such as light, or physiological action which takes place when the preparation is ingested or penetrates the pest's body.

The precise way in which the pesticide compounds according to the invention are used in any single case will be easily understood by a person skilled in the art. In general, the active, pesticidal compound will be used as a component in a liquid preparation, e.g. an emulsion, suspension or aerosol spray. Although the concentration of the active pesticide compound in the present preparation can vary within fairly wide limits, the pesticide mixture will normally comprise no more than approx. 50.0 percent by weight of the preparation.

Claims (1)

-1. * New connection, characterized by that the .• ha r the formula where R and R^ are independently selected from the group consisting of: C2~ C10 alkY 1' C2~ C10 alkoxyalkyl, and phenyl, and R and R^ together contain from 12 to 22 carbon atoms; where R^ is selected from the group consisting of: Cl" C14 alkY 1' c3~ cio aikenyi' C3 -C4 alkynyl, ^ 2~ c^ hydroxyalkyl, C„-C, alkylthioalkyl,- 2 b C2 -C8 alkyloxyalkyl1, (CH_) [X(CH„) ] y where n = 1 or 2, X is 0 or S 2 n 2 n and y = 1-4, where n = 1-10, phenyl, and phenethyl; where R^ is selected from the group consisting of: carboalkoxyalky1 where the alkyl part is C^ -C^ alkyl, alkylketoalkyl1 where the alkyl part is C^-C^ alkyl, hydroxyalkeny 1 where the alkenyl part is C-j-C^ alkyl, hydroxyalkyl where the alkyl part is C^-C^ alkyl, formylhydroxymethyl, hydroxyhalogenety1 where the halogen atom is chlorine, bromine or iodine, substituted phenoxyalkyl where the alkyl part is <^ y~ <^ 2 a^ Y^-' and the substituents are p-methoxy, Cl, NO^ or CN,. where R"*" is selected from the group consisting of: -OH, -NH2 or -C-L" C4 alkoxy, where R, R1 and R2 are as indicated above, where R, R 1 and R 2 are as indicated above, or where B is a base; C1~ C22 alkY 1' hydroxyethyl, naphthyl, phenyl, substituted phenyl where the substituents independent of each other is selected from the group consisting of halogen, C^-C^ alkyl, C1~C5 alkoxy, nitro, cyano and~ CF-, where R, R 1 and R 2 are as indicated above, where R, R 1 and R 2 are as indicated above, where R, R 1 and R 2 are as stated above, where R, R 1 and R 2 are as indicated above, where R, Rj, and R2 are as stated above, where x is .1 to 8, and R, R, and R 2 are as indicated above, where m is 2 or 3 and R, R 1 and R 2 are as stated above, where R, R 1 and R 2 are as indicated above, where R, R 1 and R 2 are as indicated above, where X is selected from the group consisting of: 0, S, NH and NRU, Y is hydrogen or methyl; and R1Q is selected from the group consisting of: H, C1~ CJ8 alky1' C₁ -C₁ alkenyl, C3-C4 alkynyl, C2~ C6 nal°9ena-'-ky ' ■ <:> C_-CQ cycloalkyl, Yes c7~ c2o p° 1ycycloalkY 1'C2~ ci6 p° 1yalkol' :' syaiky1' C-p-Cg hydroxyalkyl, C3~C^0 alkoxyalkyl, C-,-C0 nrboalkoxyalky1, Yes C4 -C8 cycloalkylalkyl, C 1 -C 6 alkylcycloalkyl, HO C^-C-j cycloalkylimino, C.^ -C^ q alkylimino, C 1 -C 1 alkylamino, C4~C^2 dialkylaminoalkyl, Cg-C^Q cycloalkeny1, phenyl, alkylphenyl where the alkyl part is C^ -C^ , p-chloroalkylphenyl where the alkyl part is ci~ c^ > naphthyl, anthracenyl, benzamidocycloalkyl1 where the alkyl moiety is CrC2' pyranyIme tulle, tetrahydrofurfuryl, thiophenemctyl, benzhydry1, h.a loge nbenzhy dry 1, polycyclic alcohol and substituted,phenyl where the substituents is selected from the group consisting of: C 1 -C 4 alkyl, lia the lodge, nitrous, tri fluormcty 1, formyl, chloracety1, C 1 -C 4 alkoxy, hydrogen, benzyl, chlorobenzyl, phenethyl and substituted phenethyl where the substituents are selected from the group consisting of: Cx-C4 alkyl and halogen, and R11 is the group consisting of: C1-C4 alkyl, C₁-C₆ alkoxyalkyl, and C₁-C₆ alkenyl; R10°9 R11 ta*-t together form heterocyclic compounds; provided that when X = 0 or S, then R^O is different from hydrogen; and substituted phenyl wherein the substituents are selected from the group consisting of: halogen, C1~ C4 Alkoxy, phenoxy, trifluoromethyl, C 1 -C 8 thioalkyl, nitrous, isocyanato, C2~ C4P° lyalcoxY' C3~ C7 cycloalkyl, G3~C'24 carboalkoxyalky 1, Ci -C8 nal° genalky1' <C> 3~ <C>12 alkeneY 1' C2~ Cg dialkylamino, phenylamino, C1 -C24 alkyl, C3~ ci2 nydroxyaikyiamidoaikyi, C5~ CIQ Nf N-hydroxyalkylureido- alky1, isocyanatoalky1, where the alkyl part is C1~ C5 , C3~ C^2 alkylamidoalkyl, polyalkoxyamidoalkyl where the polyalkyl part contains from 3-6 repeating C 1 -C 2 - alkoxy units and the amidoalkyl part contains from 4-12 carbon atoms, -so2 ci, -S02 polyalkoxyamidoalkyl where the polyalkoxy part contains from 3-6 repeated C2~C3 alkoxy units and the amidoalkyl part contains from 4-12 carbon atoms, Rj. is selected from the group consisting of: hydrogen, C1 -C4 alkyl, C 1 -C 8 alkoxyalkyl, C₁ -C₁ alkenyl, hydroxyethyl and phenyl; R 4 and R 1 , taken together form heterocyclic compounds; where X is 0 or S, n is 0 or 1, Rg is selected from the group consisting of: C1~ C18 alkY 1' C2~Cg haloalkyl1, phenyl, and substituted phenyl wherein, when n = 1, the substituents are selected from the group consisting of: nitrous, chlorine, C1-C2 alkyl, C₁ -C₂ polyalkoxyalky1, C3 -C8 cycloalkyl, C3 -C4 alkenyl, C3" C8 Alkoxyalkyl, C2~ C8 hydroxyalkyl, C 1 -C 3 carboxyalkyl, and C 1 -C 8 trialkylammonium alkyl salts, and when n = 0, the substituents are selected from the group consisting of: chlorine, thiopotassium, Cl" C18 alky1' benzyl, Ci-C2 neteroa-'-ky-'-' C^- C^ chlorocarboxyalky1, C 1 -C 8 polyalkyloxyalkyl, and acetyl; where R- is selected from the group consisting of: -(CH„-) where n = 0 to 8, 2 . n-CH=CH-, where M is H or Cl, -CC1=CC1-, -CH2 OCH2 -, and -OCH 2 CH 2 0-; d = 0 or 1, and when d = 1, Y is selected from the group consisting of: -0, -S, and -NH; Z is selected from the group consisting of: "Cl" C18 alkv1' hydrogen, C 1 -C 2 g polyalkyloxyalkyl, C 1 -C 2 dialkylaminoalkyl, C3~C5 alkynyl, phenyl, substituted phenyl, organic salts, inorganic salts, and when d = 0 Z is Cl or where R, R 1 and R 2 are as defined above; where Rg is selected from the group consisting of: <ci> ~ <c> io alkoxy' amino, C^-C-^Q Alkoxyamino, hydroxy, and organic base; -SOw Rg, where w = 0-2, and Rg is selected from the group consisting of: amino, C1 -C10 alkyl, C-^ -C^ haloalkyl, phenyl, C 1 -C 10 dialkylamino, C^ -C^ q alkylamino, C₁ -C₂ 0 alkoxy, substituted phenyl, wherein the substituents are selected from the group consisting of: nitrous, chlorine, C1~ C4 alkylJL,. and methoxy. 2. Compound as stated in claim 1, characterized in that R and R are independently selected from the group consisting of: C5-C8 alkyl, C₁-C₆ alkoxyalkyl, and phenyl, and R and R^ together contain from 12 to 22 carbon atoms; and R2 is selected from the group consisting of: C1~C6 alkyl, . C-j-Cj-alkenyl, C3 -C4 alkynyl, C2~ C3 hydroxyalkyl, C2~C4 alkylthioalkyl, C2~C4 alkYloxyalkyl1, (CH2) [X(CH2) ] y where n = 1 or 2, X is 0 or S and y = 1-2, where n = 1-5, f phenyl and phenethyl. 3. Compound as stated in claim 1, characterized in that R and R are independently selected from the group consisting of: Cg-Cg alkyl and C 8 -C 8 alkoxyalkyl, and phenyl and R and R 1 together contain from 12 to 22 carbon atoms; and R2 is selected from the group consisting of: C1~ C13 alkY 1' C2~C3 alkenyl, C3 -C4 alkynyl, C2~ C3 hydroxyalkyl, C2~C4 alkylthioalkyl C2~C4 alkyloxyalkyl (CH2 )n[ X(CH2 )n ] y where n = 1 or 2, X is 0 or S and y = 1-2, where n = 1-3, phenyl and phenethyl. 4. Compound as stated in claim 1, 2 or 3, characterized in that it is selected from the group consisting of: carboalkoxyalkyl where the alkyl part is C^-C2 alkyl, alkylketoalkyl where the alkyl part is C^-C2 alkyl, hydroxyalkenyl where the alkenyl part is C^-C^ alkyl, .hydroxyalkyl where the alkyl part is C-^-Cg alkyl, formylhydroxymethyl, hydroxyhaloethyl where the halogen atom is chlorine or bromine, substituted phenoxyalkyl where the alkyl part is C1 alkyl and the substituents are p-methoxy, Cl, NO 3 or CN, ' where R"*" is selected from the group consisting of: -OH, -NH2 or methoxy, where R, R 1 and R 2 are as indicated above, where R, R 1 and R 2 are as indicated above, or where D is an organic base; v where R^ is selected from the group consisting of:-H crci2 alk^' hydroxy ty1, naphthyl, phenyl, substituted phenyl where the substituents independent of each other is selected from the group consisting of chlorine, C1-C2 alkyl, £^~^ 2 alkoxys' nitrob, cyano and -CF^ , where R, and R are as indicated above, where R, R 1 and R 2 are as indicated above, where R, R 1 and R 2 are as indicated above, R2 is as stated above, where R, R 1 and R 2 are as stated, above, where x is .1 to 8, and R, 1^ and R 2 are as anqitt above, where m is 2 or 3 and R, R1 and R2 are as indicated above, where R, R^ and -R are as indicated above, where R, R 1 and R 2 are as indicated above, where X is selected from the group consisting of: 6/ S , NOW, NRU, Y is hydrogen or methyl; and R^Q is selected from the group consisting of: 11 C 1 -C 8 alkyl, C₁ -C₁ alkenyl, C3 -C4 alkynyl, C2 -C3 haloalky1, C -CQ cycloalkyl, Yes C7 _C20 p°1ycy'<-loa-'-ky 1' C2 _ci6 p°iyaikoksyaiky 1' C2 _Cg hydroxyalkyl, <C> ^ <-C> ^q Alkoxyalkyl, C 1 -C 8 carboalkoxyalkyl/ C 1 -C 8 cycloalkylalkyl, Cg-Cg alkylcycloalkyl, C^-Cy cycloalkylimino, C2~^io alkylimino, C 1 -C 4 alkylamino, C 1 -C 12 dialkylaminoalkyl, Cg-C^Q cycloalkenyl, phenyl, alkylphenyl where the alkyl part is C^ -C^ , p-chloroalkylphenyl where the alkyl part is c^~^^ > naphthyl, an traceny 1, benzamidocycloalkyl1 where the alkyl moiety is <c> r <c>2' pyranyyl, tetrahydrofurfuryl, thiophenmctyl, benzhydry1, ■halobenzhydry1, polycyclic alcohol and substituted . feny1 where the substituents is selected from the group consisting of: C1-C/} alkyl, halogen, nine faiths, trifluoromethyl 1, formyl, chloracety1, C-^-C^j Alkoxy, hydrogen, benzy1, chlorobenzyl, phenethyl and substituted phenethyl where the substituents are selected from the group consisting of: C1 -C1} alkyl and halogen, and R11 is optionally selected from the group consisting of: C1-C4 alkyl, C-C, alkoxyalkyl, and. C 1 -C 4 alkenyl; R-^q and R^^ taken together form heterocyclic compounds selected from the group consisting of: azepiny1, morpholinyl, piperidinyl, C 1 - C 3 alkyl-succin;'-substituted piperidinyl; provided that when X = 0 or S, then R^ q is different from hydrogen, and substituted phenyl wherein the substituents are selected from the group consisting of: halogen, C 1 -C 4 alkoxy, phenoxy, trifluoromethyl, C1~ C6 thioalkyl1' nitrous, isocyanato, <"2~G4 p° iyaicoxy' C3~ C7 cycloalkyl, C-j-C^ q carboalkoxyalky 1, Ci -C4 haloalkyl1, C3 -C4 alkenyl, C2~ Cg dialkylamino, phenylamino, C1 -C4 alkyl, C3~C12 hydroxyalkylamidoalkyl, C^ -C^0 N,N-hydroxyalkylureidoalkyl, isocyanatoalkyl1 where the alkyl part ef C1~ C5 , C3-<~12 α-*-alkylamidoalkyl, polyalkoxyamidoalkyl where the polyalkyl part contains from 3-6 repeated C^-C^ alkoxy units and the amidoalkyl part contains from 4-12 carbon atoms, -so2 ci, -SC₁ -polyalkoxyamidoalkyl where the polyalkoxy part contains from 3-6 repeated C₁-C₁ alkoxy units and the amidoalkyl part contains from 4-12 carbon atoms; R,, is selected from the group consisting of: hydrogen, C1 -C4 alkyl, C 1 -C 8 alkoxyalkyl, C₁ -C₁ alkenyl, hydroxyethyl, and phenyl; R. and R. - taken together form heterocyclic compounds selected from the group consisting of: azepiny1, morpholinyl, piperidinyl, and C1~C3 alkyl-substituted piperidinyl; where X is 0 or S, n is 0 or 1, Rg is selected from the group consisting of: C1~ C12 alkv1' C2_C8 haloalkyl, phenyl, and substituted phenyl wherein, when n = 1, the substituents are selected from the group consisting of: nitrous, chlorine, C1~ C2 alkv1' C3 -C8 polyalkoxyalkyl, C3 -C8 cycloalkyl, C₁-C₁ alkenyl, C 1 -C 8 alkoxyalkyl, C2~ C8 hydroxyalkyl, C1~ C3 carcoxvalcY 1' C5 _C8 tria-1-kylanimonium alkyl salts, and when n = 0, the substituents are selected from the group consisting of; chlorine, thiopotassium, C1~ C12 alky1' benzyl, C1~C2 heteroalkyl' C2~C4 chlorocarboxyalkyl, C 1 -C 8 polyalkyloxyalkyl, and acetyl; where R_ is selected from the group consisting of: -(CH2 -)n where n = 0 to 8, -CH=CH-, where M is H or Cl, v -CC1=CC1-, -CH-2 OCH2 -, -OCH2 CH2 0- and d = 0 or 1, when d = 1, is Y selected from the group consisting of: -oh, -S, and -NH, and Z is selected from the group consisting of C1~ C12 alky1' hydrogen, C4~C16 polyalkoxyalkyl, C^ -Cg dialkylaminoalkyl, C3~C5 alkynyl, phenyl, substituted phenyl, organic salts, inorganic salts, and when d = o is Z Cl or where R, R 1 and R 2 are as defined above; where Ro0 is selected from the group consisting of: Cl -C5 alk° ksy, amino, C₁ -C₁ Alkoxyamino, hydroxy, and organic base; -SO^Rg where w = 0-2 and Rg is selected from the group consisting of: amino, C1~C5 alkyl, C-^ -C^ haloalky 1, phenyl, C^ -C^ q dialkylamino, C 1 -C 4 alkylamino, C1~ C5 aikoxy' substituted phenyl wherein the substituents are selected from the group consisting of: nine faiths, chlorine, C^-C^j alkyl and methoxy. 5. Compound as specified in claim 1, 2 or 3, characterized in that R. is selected from the group consisting of: carboalkoxyalkyl 1 \ jwhere the alkyl moiety is C 1 -C 2 alkyl, alkylketoalky1 where the alkyl part is C^-C2 alkyl, hydroxyalkeny1 where the alkenyl moiety is C^ -C^ alkyl, 'hydroxyalkyl where the alkyl part is C^ -C^ alkyl, formylhydroxymethyl, hydroxyhalogenety1 where the halogen atom is chlorine, substituted phenoxyalkyl where the alkyl portion is C 1 alkyl and the substituents are p-methoxy, Cl, NO3 or CN where R"*" is -OH, -NH^ or methoxy, OH OH SR„ I I I 2 -CH-CHN-C=NR, R where R, R 1 and R 2 are as above, . where R, R^ and R^ are as indicated above, OH-PO3' B, -PO2' B or -SO^^ B where B is an organic base selected from the group consisting of: and where R^ is selected from the group consisting of: -H C 1 -C 8 alkyl, hydroxyethyl1, naphthyl, phenyl, substituted phenyl wherein the substituents independently of each other are selected from the group consisting of chlorine, ci~C2 alkY 1' ci~C2 alkoxy/nitro, cyano and -CF , where R, R 1 and R 2 are as indicated above, where R, R 1 and R 2 are as indicated above, where R, R-^ and R 2 are as indicated above, R2 is as stated above, where R, R 1 and R 2 are as stated above, where x is 1 to 8, and- R, R-j^ and R 2 are as indicated above, where m is 2 or 3 and R, R 1 and R 2 are as indicated above, where R, R^ and R~ are as indicated above, where R, R^ and R^ are as indicated above, where X is selected from the group consisting of: 6/ S , NOW NRn, and Y is hydrogen or methyl; R-^0 is selected from the group consisting of: II, C1~C2 alkyl, C3-C4 alkenyl, C'3-C4 alkynyl, C"2~C3 haloalky 1, C -C„ cycloalkyl, ^7 _C20 P°lycy'<loalky 1, ^ 2~ <~ l( jP° lyalkoxyalkyl1, C2~C(. hydroxyalkyl, C3~cl0 Alkoxyalkyl, C--C0 carboalkoxyalkyl, in o C 1 -C 8 cycloalkylalkyl, Cg-Cg alkylcycloalkyl, C^-C-j cycloalkylimino, C2~C10 alkylimino, ('1 _C3 alkylamino, C4~C^2 dialkylaminoalkyl, Cg-C^Q cycloalkeny1, phenyl, alkylphenyl where the alkyl part is C^~ C4' p-chloroalkylphenyl where the alkyl part is ci~ c^ > naphthyl, anthraceny1, benzamidocycloalkyl1 where the alkyl moiety is CrC2' pyranyIme tulle, tetrahydrofurfuryl, thiophenemethyl, benzhydry1, halobenzhydry1, polycyclic alcohol and substituted phenyl where the substituents is selected from the group consisting of: C}-C4 alkyl, halogen, nitrous, tri fluormc ty 1, formy1, chloroacetyl, C₁-C₁₆ alkoxy, hydrogen, benzyl, chlorbcn'zy.1, phenethyl and substituted phenethyl where the substituents are selected from the group consisting of: , C1~C4 alkyl halogen, and R11 is va 1CJt ^ra the group consisting of: C 1 -C 4 alkyl, C₁ -C₆ alkoxyalkyl, and C3~C4 alkenyl; R^^ and R.| taken together form heterocyclic compounds, preferably heterocyclic. compounds selected from the group consisting of azepinyl, morpholiny 1, piperidiny1, C 1 -C 4 alkyl-substituted piperidinyl; provided that when X = 0 or S, then R^0 is different from hydrogen, and substituted phenyl wherein the substituents are selected from the group consisting of: halogen, C₁-C₁ alkoxy, phenoxy, trifluoromethyl, C1-C6 thioalkyl, nitrous, isocyanato, C2_C4 P^yalkoxy > C-1-C3 cycloalkyl, C₁-C₁ carboalkoxyalkyl, C^-C^ haloalkyl1, C3~C4 alkenyl, Q.^'^-^ dialkylamino, phenylamino, C1-C4 alkyl, C3" C12 hydroxyalkylamidoalky1, ■C,-- C| q N, N-hydroxyalkyl lureidoalkyl, isocyanatoalky1 where the alkyl part is -cr c5 , C 3_C 2 alkyl lamidoalkyl 1, polyalkoxyamidoalkyl where the polyalkylene part contains from 3-6 repeated C2~C3 alkoxy units and the amidoalkylene part contains from 4-12 carbon atoms, -so2 ci, -SO 2 -polyalkoxyamidoalkyl where the polyalkyl part contains from 3-6 repeated C 1 -C 6 alkoxy units and the amidoalkyl part contains from 4 to 12 carbon atoms; R,- is selected from the group consisting of: hydrogen, C1 -C4 alkyl, C 1 -C 8 alkoxyalkyl, C₁ -C₁ alkenyl, hydroxyety1, and phenyl; R^ and Rj. taken together form heterocyclic compounds selected from the group consisting of: azepinyl, morpholinyl, piperidinyl, oq C1-C3 alkyl-substituted piperidinyl; where X is 0 or S, n is 0 or 1, Rg is selected from the group consisting of: C 1 -C 4 alkyl, C₁-C₂ halogenoalky1, phenyl, and substituted phenyl where, when n = 1, the substituents is selected from the group consisting of: nitrous, chlorine, C1 -C2 alkyl, C4~ C6P° lyalkoxyalkyl, C3 -C8 cycloalkyl, C₁ -C₁ alkenyl, C 1 -C 8 alkoxyalkyl, G2~ Cg hydroxyalkyl, C1~ C3 carboxyalkyl, C -CQ trialkylammonium alkyl salts, and when n = 0, the substituents are selected from the group consisting of: chlorine, thiopotassium, C1~C4 alkyl, benzyl, C1 _C2 hetGroa-l-ky i, C2~ C4 chlorocarboxyalkyl, C 1 -C 8 polyalkyloxyalkyl, and acetyl; where Ry is selected from the group consisting of: -(CH2-) where n = 0 to 8, -CH=CH-, where M is II or Cl, -CC1=CC1-, -CH2 OCH2 -, -OCH2CII20- and d = 0 or .1, when d = 1, is Y selected from the group consisting of: -0, -S , and -Nile, and Z is selected from the group consisting of ■ Cl" C4 alkyl» hydrogen, C 1 -C 2 g polyalkoxyalkyl, C 2 -C 8 dialkylaminoalkyl, C 2 -C 1 . alkynyl, pheny1, substituted phenyl, pp organic salts, inorganic salts, and when d = 0 is Z Cl or where R, Rj and are as indicated above; where Rg is selected from the group consisting of: C₁-C₂. Alkoxy, amino, C^-C,. alkoxyamino, hydroxy, and organic base; -SOw Rg where w = 0-2 andR g is chosen from the group consisting of: amino, C1~C5 alkyl, C₁ -C₁ haloalky1, phenyl, C^-C^q dialkylamino, C^ -C^ q alkylamino, C -j —Cj. Alkoxy, substituted phenyl wherein the substituents are selected from the group consisting of: nine faiths, k lor , C.^ -C(j alkyl and mc took sy .'6. Compound as stated in claim 1, characterized in that R is -secC-H,,., R. is -C^H , R is -C^ H ,.and R3 is 7. Compound as stated in claim 1, characterized in that R is -secC7H15, R^^ is -CgH17, R2 is -C-^r^ and R3 is 8. Compound as stated in claim 1, characterized in that R is -secC7 H15 , R1 is -CgH17, R2 is ~ C1 H3 and R3 is 9. Compound as stated in claim 1, characterized in that R is -CgH^, R1 is -CgH^, R2 is ~ C2H5 and R3 is 10. Compound as set forth in claim 1, characterized in that R is _-secC7H15 > is -CgH^, R2 is ~C 2H and R3 is 11/ Compound as stated in claim 1, characterized in that R is 2-ethylhexyl, R1 is 2-ethylhexyl, R is "C2H and R3 is 12. Compound as stated in claim 1, characterized in that R is -secC_H15, R1 is -CgH^, R2 is ""C2H5 °9 R3 is' r 13. Compound as stated in claim 1, characterized in that R is -secCyH.^ , R.j^ is -2-ethylhexyl, R.sub.2 is - C^ H^ and R3 is 14. Compound as stated in claim 1, characterized in that R is -secC-H,_, R, is -CR H,_, R„ is -CH2CH=CH„ and R3 is 15. Compound as stated in claim 1, characterized in that R is -secC7 H15 , R1 is <-C> 8H17' R2 is _CH2 CH=CH2 and R3 is 16. Compound as stated in claim 1, characterized in that R is -secC7Hiq, R, is -CR<H,>7 , R- is -CH„C H=CH:? and R3 is 17. Compound as stated in claim 1, characterized in that R is -secC7H15, R1 is -C<g>H^ , R2 is -C3H7 and R3^ is 18. Compound as stated in claim 1, characterized in that R is -CgH17 , R^ is -secCyH^, R2 is -C2 H^ and R3 is 19. Compound as stated in claim 1, characterized in that R is -2-ethylhexyl, R^ is -secCyH^,., <R>2 is -C2Hj- and R3 is 20. Compound as stated in claim 1, characterized in that R is secC7H15, R1 is -CR H17, R2 is -C2H5 and R3 is 21. Compound as stated in claim 1, characterized in that R is -secC7H15, R^ is -CRH17, R2 is -C^^ and R3 is 22. Compound as stated in claim 1, characterized in that R is -secC7 H15 , R^ is - <C>8 H17' R2 is -C2 H5 and R3 is 23. Compound as stated in claim 1, characterized in that R is -secC7 H15 , R1 is -CgH17, R2 is -C2H5 and <R> 3 <:er> 24. Compound as stated in claim 1, characterized in that R is -secC^H^j. , R^ is -CRH^7, R^ is - C^ H^°9 R3 is 25. Compound as stated in claim 1, characterized in that R is -C-H,.., Rn is -C-H...-, R_ is -Cn Hc and / lb 1 / lb 2 Z b R3 is 26. Lepidoptericidal preparation containing the compound according to claim 1 and an inert carrier. 27. Lepidoptericidal preparation containing the compound according to claim 2 and an inert carrier. 28. Lepidoptericidal preparation containing the compound according to claim 3 and an inert carrier. 29. Lepidoptericidal preparation as stated in claim 26, 27 or 28, characterized in that it is: carboalkoxyalky 1 where the alkyl part is C^-C,, alkyl, alkylketoalkyl where the alkyl part is C-^-C^ alkyl, hydroxyalkeny1 where the alkenyl part is C^-C^ alkyl, hydroxyalkyl where the alkyl part is C, -C, alkyl, lb formylhydroxymethyl, hydroxyhalogenety1 where the halogen atom is chlorine or bromine, substituted phenoxyalkyl where the alkyl moiety is alkyl and the substituents are p-methoxy, Cl, NO 3 or CN, wherein R 1 is -OH, -NII 2 or methoxy, where R, R-^ and R 2 are as defined above, where R, R-j^ and R 2 are as indicated above, e lier where D is an organic base; where R^ is selected from the group consisting of: -H C1~ C12 alk;y1' hydroxyethyl, naphthyl, phenyl, substituted phenyl where the substituents independent of each other is selected from the group consisting of halogen, C1~C5 alkyl, C1-C8 alkoxy, nitro, cyano and -CF.., where R, Rj and R2 are as indicated above, where R, R-1°9 R2 are as indicated above, where R, R1 and R2 are as stated above, where R, R1 and R2 are as indicated above, where R, Rx and R2 are as stated_above, where x is 1 to 8, and R, R] _ and R 2 are as above, where m is 2 or 3 and R, Rx and R2 are as indicated above, where R, R^ and R^ are as indicated above, where R, R 1 and R 2 are as indicated above, where X is selected from the group consisting of: b; S, NH, NRU, Y is hydrogen or methyl; and R^ q is selected from the group consisting of: M , C 1 -C 8 alkyl, C₁-C₁ alkenyl, C3-C4 alkynyl, C2 -C3 haloalkyl, C -CQ cycloalkyl, Yes <C> 7 <_C> 20 P°lycycloalkyl1, <C> 2~ <C> 16 Polyalkoxyalkyl, C2-Cg hydroxyalkyl, C^-C^Q alkoxyalkyl, C j -CtQ s nirboalkoxyalkyl, C^-Cg cycloalkylalkyl, Cg-Cg alkylcycloalkyl, C^-C-j cycloalkylimino, C^-C^O alkylimino, C 1 -C 4 alkylamino, C 1 -C 2 dialkylaminoalkyl, Cg-C^Q cycloalkeny1, phenyl, alkylphenyl where the alkyl part is C^ -C^/ p-chloroalkylphenyl where the alkyl part is C^ -C^ , naphthyl, an tr a co ny .1, benzamidocycloalkyl where the alkyl moiety is <c>1 - <c>2 , pyranyIme tulle, tetrahydrofurfuryl, ten five twenty 1, benzhydry1, halobenzhydry1, polycyclic alcohol and substituted phenyl where the substituents is selected from the group consisting of: C1-C4 alkyl, halogen, nine faiths, trifluoromethyl 1, formyl, chloroacetyl, C₁-C₁ alkoxy, hydrogen, benzyl, chlorbeh zyl, phenethyl and substituted phenethyl where the substituents are selected from the group consisting of: ... C1 -C4 alkyl, halogen, and R11 Gr vnl9 t from the group consisting of: C1-C4 alkyl, C-C,, alkoxyalkyl, and in b C3-C4 alkenyl; R^ q and R^j taken together form heterocyclic compounds selected from the group consisting of: azepinyl, morphology new 1, piperidinyl, C 1 -C 1 alkyl-substituted piperidinyl; provided that when X = 0 or S, then R^ q is different from hydrogen, and substituted phenyl wherein the substituents are selected from the group consisting of: halogen, C₁-C₁ alkoxy, phenoxy, trifluoromethyl, C 1 -C 8 thioalkyl, nitrous, isocyanato, C^-Cq polyalkoxy, C3~C7 cycloalkyl, G3~ C10 CarboAlkoxyalkyl, C^-C^ haloalky1, C3~C4 alkenyl, C₁-C₁ dialkylamino, fcnylamino, C1-C4 alkyl, C^-C-j 2 hydroxyalkylamidoalky 1, C5~ CIQ N'N-hydroxyalkylureidoalkyl, isocyanatoalky1 where the alkyl part eir C]_-C5f C3~C22 alkylamidoalkyl, polyalkoxyamidoalkyl wherein the polyalkyl part contains from 3-6 repeated C2~C3 alkoxy units and the amidoalkyl part contains from 4-12 carbon atoms, -so2 ci, -SO 2 -polyalkoxyamidoalkyl where the polyalkoxy part contains from 3-6 repeated C^~C^ aIkpxy units and the amidoalkyl part contains from 4-12 carbon atoms; R,- is selected from the group consisting of: hydrogen, C1 -C4 alkyl, C 1 -C 8 alkoxyalkyl, C₁ -C₁ alkenyl, hydroxyety1, and phenyl; R^ and Rj. taken together form heterocyclic compounds selected from the group consisting of: azepinyl, morpholiny1, piperidinyl, and C 1 -C 1 alkyl 1-substituted piperidinyl; where X is 0 or S, n is 0 or 1, Rg is selected from the group consisting of: C1 -C12 alkyl, C2 -Cgh alo <g> enalky.1 , phenyl, and substituted phenyl wherein, when n = 1, the substituents are selected from the group consisting of: nitrous, chlorine, Cl"" C'2 alkyl, C₁ -C₆ polyalkyloxyalkyl, C -CQ cycloalkyl1, YES C3 -C4 alkenyl, C 1 -C 8 alkoxyalkyl, C2~C6 hydroxyalkyl, C₁ -C₁ carboxyalkyl, C5 c -C80 trialkylammonium alkyl salts, and when n = 0, the substituents are selected from the group consisting of; chlorine, thiopotassium, C1_C12 alkvl' benzyl, C1~ C2 neteroalkv1, C2 -C4 chlorocarboxyalkyl, C 1 -C , polyalkoxyalkyl, and 4 D acetyl; where R7 is selected from the group consisting of: -(CIU-) where n = 0 to 8, 2 n -CH=CH-, where M is II or Cl, -CC1=CC1-, -CH2 OCH2 -, -OCH2CH20- and d = 0 or 1, when d = 1, is Y selected from the group consisting of: -0, -S, and -Nile, and Z is selected from the group consisting of ci~ ci2 al^ y1, hydrogen, C4~C.l 6 PolynJ-coxva-1-ky ' C4 .-Co0 dialkylaminoIkyl, C^ -C, alkynyl, phenyl, substituted phenyl, organic salts, inorganic salts, and when d = 0 is Z Cl or where R, R^ and R^ are as indicated above; where RR is selected from the group consisting of: C₁-C₂. Alkoxy, amino, C^-C,. alkoxyamino, hydroxy, and organic base; -SOw Rg where w = 0-2 and Rg is selected from the group consisting of: amino, C1~C5 alkyl, C₁ -C₁ haloalky1, phenyl, C^ -C^ q dialkylami.no, C₁ -C₄ alkylamino, Cl~ ^5 Alkoxy, substituted phenyl wherein the substituents are selected from the group consisting of: nitrous, chlorine, C1~ C4 alkyl and methoxy. 30. Lepidoptericidal preparation as stated in claim 26, 27 or 28, characterized in that it is in carboalkoxyalky1 where the alkyl part is C^ _C2 alkyl, alkylketoalky1 where the alkyl part is C^_C2 alkyl, hydroxyalkeny1 where the alkenyl part is C^ -C^ alkyl, hydroxyalkyl where the alkyl part is C^-C^ alkyl, formylhydroxymethyl 1, hydroxyhalogenety1 where the halogen thorn is chlorine, substituted phenoxyalkyl where the alkyl portion is C 1 alkyl and the substituents are p-mctoxy, Cl, NO3 or CN where R<1> is -Oll, -NU or mctoxy, where R, R^ and R^ are as indicated above, where R, R^ and R^ are as indicated above, or where B is an organic base selected from the group consisting of: and where R^ is selected from the group bcs. designed by:-H C 1 -C 8 alkyl, hydroxycty1, naphthyl, phenyl, substituted phenyl wherein the substituents are independently selected from the group consisting of chlorine, C1 _C2 alkyl, c^ -c2 alkoxy, nitro, cyano and -CF3 , li vor R, R^ and R^ are as stated above, where R, R1 and R2 are as indicated above, where R, R1 and R2 are as stated above, where R, R-j^ and R 2 are as indicated above, where R, R-^ and. R2 is like angiti-.above or , • where x is 1 to . 8, and R, R1 and R2 are as above. where m is 2 or 3 and R, Rx and R2 are as indicated above, where R, R-^ and R 2 are as indicated above, where R, R 1 and R 2 are as indicated above, where X is selected from the group consisting of: 0, S , Nile, NR-q/ and Y are hydrogen or methyl; Ri0 is selected from the group consisting of: II, C1 -C2 alkyl, C₁ -C₁ alkenyl, C3 -C4 alkynyl, C2~C^ haloalky1, C -CD cycloalkyl," ' C7~ <C> 20P oiycycloalky1' * • <C> 2~ <c> i6 p° 1yalkol<sya-1-ky- 1-' C2 -C8 hydroxyalkyl, C3-C]q alkoxyalkyl, C-.-C0 carboalkoxyalkyl, YES C 1 -C 8 cycloalkylalkyl, Cg-Cg alkylcycloalkyl, C 1 -C 7 cycloalkylimino, C2~C10 alkylimino, C 1 -C 4 alkylamino, C 1 -C 2 dialkylaminoalkyl, C<g-C> 1Q cycloalkeny1, phenyl, alkylphenyl where the alkyl part is C-^-C^j, p-chloroalkylphenyl where the alkyl part is C^-C^ , naphthyl, anthracenyl, benzamidocycloalkyl where the alkyl moiety is CrC2' pyranyImethyl, tetrahydrofurfuryl, thiophenemcty 1, benzhydry1, v halobenzhydry1, polycyclic alcohol and substituted phenyl where the substituents is selected from the group consisting of: C1 -C3 alkyl, halogen, nine faiths, trifluoromethyl 1, formyl, chloractyl, C₁ -C₁ alkoxy, hydrogen, benzyl, k lorbenzy1, phenethyl and substituted phenethyl where the substituents are selected from the group consisting of: ... C 1 -C 4 alkyl, halogen, and R 11 is selected from the group consisting of: C1 -C4 alkyl, C₁ -C₆ alkoxyalkyl, and. C 1 -C 4 alkenyl; R, and taken together form heterocyclic compounds selected from the group consisting of: azepiny1, morpholinyl, piperidinyl, Cl~('3 alkyl 1-substituted piperidinyl; provided that when X = 0 or S, then R^ q is different from hydrogen, and substituted phenyl wherein the substituents are selected from the group consisting of: halogen, C-^-C^ alkoxy, phenoxy, trifluoromethyl1, C 1 -C 8 thioalkyl, nitrous, isocyana two, C2~C4P oleoalkyl, C3~C7 cycloalkyl!, C-j-Cj0 carboalkoxyalkyl, C^-C^ haloalkyl1, C3-C4 alkenyl, C'2_Cg dia lky lamino , phenyllainino, C 1 -C 4 alkyl, C^-C-j 2 hydroxyalkylamidoalky 1, C^-C-j0 N, N-hydroxyalkylureidoalkyl, isocyanatoalkyl where the alkyl part G rCi" C5' C3 -C12 alkyllamidoalkyl, polyalkoxyamidoalkyl wherein the polyalkyloxy part contains from 3-6 repeated C^-Cj alkoxy units and the amidoalkyl part contains from 4-12 carbon atoms, -so2 ci, -SC₁ -polyalkoxyamidoalkyl where the polyalkoxy part contains from 3-6 repeating C₁ -C₁ alkoxy units and the amidoalkyl part contains from 4-12 carbon atoms; R,- is selected from the group consisting of: hydrogen, C1 -C4 alkyl, G₁ -C₃ alkoxyalkyl, C3 -C4 alkenyl, hydroxyety1, and phenyl; R4 and Rj. taken together form heterocyclic compounds selected from the group consisting of: azepinyl, morpholinyl, piperidinyl, and C 1 -C 1 alkyl-substituted piperidinyl; where X is 0 or S, n is 0 or 1, Rg is selected from the group consisting of: C1 -C4 alkyl, C2 -C6 uaiOCJenalkyl, phenyl, and substituted phenyl wherein, when n = 1, the substituents are selected from the group consisting of: nitrous, chlorine, C-L-C2 alkyl, C4~C8 polyalkyloxyalkyl, C -C0 cycloalkyl, Yes C 1 -C 4 alkenyl, C 1 -C 8 alkoxyalkyl, C 2 -C 8 hydroxyalkyl, C 1 -C 6 carboxyalkyl, C 1 -C 8 trialkylammonium alkyl salts, and when n = 0, the substituents are selected from. the group consisting of: chlorine, thiopotassium, C1 -C4 alkyl, benzyl, C1_C2 leteroa1' C2~C4 chlorocarboxyalkyl, C4~C6 Polyalkoxyalky1, and acetyl; where R7 is selected from the group consisting of: — (CII2~) n where n = 0 to 8, -CH=CH-, where M is II or Cl, -CC1=CC1-, -CH2O CII2- , -OCH2 CH2 0- and d = 0 or .1, when d = 1, is Y selected from the group consisting of: -oh, -S , and — NOW, and Z is selected from the group consisting of C1~C4 alkyl, hydrogen, C4 -c-L(5 polyalkyloxyalkyl, C 1 -C 0 dialkylaminoalkyl, C^ -C^ . alkynyl, phenyl, substituted phenyl, organic salts, inorganic salts, and when d = 0 is Z Cl or where R, R^ and R^ are as indicated above; where RR is selected from the group consisting of: C^ -Cj - alkoxy, amino, C₁ -C₁ alkoxyamino, hydroxy, and organic base; -SOw Rg where w = 0-2 and Rg is selected from the group consisting of: amino, C.-C,. alkyl, lb C^-C^j haloalky 1, phenyl, C^ -Cj q dialkylamino, .C^ -C^Q alkylamino, C-^-C,. a] kok sy, substituted phenyl where the substituents are selected' from the group consisting of: nine faiths, chlorine, C^-C^ alkyl and me took sy . 31. Lepidoptericidal preparation as stated in claim 26, characterized in that R is -secC7 H^ ,.,• R^ is - <c> gH^3' R2 is -C2 H5 and R3 is 32. Lepidoptericidal preparation as stated in claim 26, characterized in that R is -secC7H^, R1 is - <C> gH17 , R2 is"" C-^ and R3 is 33. Lepidoptericidal preparation as stated in claim 26, characterized in that R is -secC7 H^ ,-, R^ is -CgH17 , R2 is "C-^ and R_ is 34. Lepidoptericidal preparation as stated in claim 26, characterized in that R is -Co 0H1 ._/,R^ is ~C3H;l7' r2 is~ C2 H5 and R3 is 35. Lepidoptericidal preparation as stated in claim 26, characterized in that R is -secC7H^,-,. R^ is -cqh17' R2 is~ C2 H5 and R3 is 36. Lepidoptericidal preparation as stated in claim 26, characterized in that R is -2-ethylhexy1,' Rj. is -2-ethylhexyl, R 2 is ~C 2 H 5 and R 3 is 37. Lepidoptericidal preparation as specified in claim 26, characterized in that R is -secC_,H. r , / lb R1 is -CgH17 , R2 is ~C2H and R3 is 38. Lepidoptericidal preparation as stated in claim 26, characterized in that R is -secC7<H> 15, R1 is -2-ethylhexyl, R2 is -C3 H7 and R3 is 39. Lepidoptericidal preparation as stated in claim 26, characterized in that R is -secC7 Hlc, / lb R, is -CgH , R is -CH CH=CH„ and R is 40. Lepidoptericidal preparation as stated in claim 26, characterized in that R is -secC7<H> 1 <5,> R1 is -CgH17 , R2 is -CH2 CH=CH2 and R3 is 41. Lepidoptericidal preparation as stated in claim 26, characterized in that R is -secC7H^^,•R^ is -CgH17, R2 is -CH2CH=CH2 and R3 is 42. Lepidoptericidal preparation as stated in claim 26, characterized in that R is -secC7H^^, R^ is -CgH17, R is -C^ H- and R_ is 43. Lepidoptericidal preparation as stated in claim 26, characterized in that R is -CQ H._, o LI R, is -secC_H,c , R» is -C_Hr and R-, is 1 7 15 2 25^3 44. Lepidoptericidal preparation as stated in claim 26, characterized in that R is -2-ethylhexyl, R^ is -secC7H^5, R2 is -C2H5 and R^ is 45. Leipdoptericidal preparation as stated in claim 26, characterized in that R is -secC_,H, c , / ID R, ;is -CRH, _, R_ is -C-H- and R., is 46. Lepidoptericidal preparation as stated in claim 26, characterized in that R is -sekC_H.r , / ib• R^- is - <C>R H17 , R2 is -C2 H5 and R^ is 47.. Lepidoptericidal preparation as specified in claim 26, characterized in that R is secC7 H^^ , R.^ is -CgH17 , R2 is -C2 H5°9 R3 is 48. Lepidoptericidal preparation as stated in claim 26, characterized in that R is -secC7H^^ , R 1 is -CgH 17 , R 2 is _C 2 H 1 - and R 2 is 49. Lepidoptericidal preparation as stated in claim 26, characterized in that R is -secC^H^j. , R 1 is -CgH 17 , R 2 is -C 2 H 5 and R 3 is 50. Lepidoptericidal preparation as stated in claim 26, characterized in that R is -C7 H^5' is -C7 H15 , R2 is -C2 H5 and R_ is 51. Method for combating lepidoptera, characterized in that the aforementioned ' lepi*doptera or on their habitat or food is applied a lepidoptericidally effective amount of the compound as claimed. 1. 52. Method for combating lepidoptera, characterized in that a lepidoptericidally effective amount of the compound as stated in claim 2 is applied to said lepidoptera or to their place of residence or food. 53. Method for combating lepidoptera, characterized in that a lepidoptericidally effective amount of the compound as stated in claim 3 is applied to said lepidoptera or to their place of residence or food. 54. Method as stated in claims 51, 52 and 53, characterized in that R^ is carboalkoxyalky1 where the alkyl part is C^ -C2 alkyl, alkylketoalky 1 where the alkyl part is C-^ -C^ alkyl, hydroxyalkenyl where the alkenyl part is C^~ C^ alkyl, hydroxyalkyl where the alkyl part is C^ -C^ alkyl, formylhydroxymethyl1, hydroxyhalogenety1 where the halogen atom is chlorine or bromine, substituted phenoxyalkyl where the alkyl part is C, alkyl and the substituents are p-methoxy, Cl, NO^ or CN, wherein R1 is -OH, —NH2 or methoxy, wherein R, R^ and R^ are as indicated above, where R, R^ and R^ are as indicated above, or where D is an organic base; where R^ is selected from the group consisting of:-H C1~ C12 alkv1' hydroxyoctyl, naphthyl, feny1, substituted phenyl where the substituents independent of each other is selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 1 - alkoxy, nitro, cyano and" CF_, where R, Rj and R^ are as indicated above, where R, R-^ and are as indicated above, where R, R 1 and R 2 are as stated above, where R, R^ and R_ are as indicated above, where R, R^ and R^ are as stated-above, where x is 1 to 8, and R, R 1 and R 2 are as defined above, where m is 2 or 3 and R, R-^ and R 2 are as indicated above, where R, R1 and R2 are as indicated above, where R, and R2 are as indicated above, where 7. is chosen from the group consisting of: 0, NOW, NRn , Y is hydrogen or methyl; and R is selected from the group consisting of: H, Cl -Cg alkyl, C3 -C4 alkenyl, C3~C4 alkynyl, C2~ C3 fialoc,Gnalky 1 1 C -C0 cycloalkyl, Yes C7~ <C> 20 p°1 ycycloalk <y> 1' C2 -Ci6 poiyaikoxyaikyi < C2 -Cg hydroxyalkyl, c3 -c]o nlkoxyalkyl1' C-.-C0 carboalkoxyalkyl 1, C 1 -C 8 cycloalkylalkyl, Cg-Cg alkylcycloalkyl, Cq-C-j cycloalkylimino, ("2~<"10 alkylimino, C-^ -C^ alkylamino, C4~C12 dialkylaminoalky1, Cg-C-^Q cycloalkeny 1, phenyl, alkylphenyl where the alkyl part is C^-C^, p-chloroalkylphenyl where the alkyl part is Ci~ c^ > naphthyl, anthracenyl, benzamidocycloalkyl1 where the alkyl moiety is <c> r <c>2' pyranyIme ty1, tetrahydrofurfuryl, thiophenemethyl, benzhydryl, halocnbenzhydry1, polycyclic alcohol and substituted .phenyl where the substituents is selected from the group consisting of: C 1 -C 4 alkyl, have the lodge, nine faiths, trifluoromethyl1, formy1, chloracety1, C₁ -C₁ alkoxy, hydrogen, benzy1, chlorobenzyl, phenethyl and substituted phenethyl where the substituents are selected from the group consisting of: C1 -C4 alkyl, halogen, and is selected from the group consisting of: C 1 -C 4 alkyl, C-C, alkoxyalkyl, and in b C 1 -C 4 alkenyl; Rjq and R^^ taken together form heterocyclic compounds selected from the group consisting of: azepinyl, mother foliny1, piper idiny1, C1-C3 alkylsulfonated piperidinyl; provided that when X = 0 or S, then Rj0 is different from hydrogen, and substituted phenyl wherein the substituents are selected from the group consisting of: halogen, C-^-C^ alkoxy, phenoxy, trifluoromethyl 1, C 1 -C 8 thioalkyl, , . nine faiths, isocyanato, C"2_<~'4 polyalkyloxy, C3-C7 cycloalkyl, C-j-CjQ carboalkoxyalky 1, Cj -C^ have loqenalky1, C₁-C₁ alkenyl, C 1 -C 8 dialkylamino, phenylamine no, C 1 -C 4 alkyl, C3 _C12 hydroxyalkylamidoalkyl, C5~C.l 0 N 'N-nydroxyalkyl lureidoalkyl, isocyanatoalky1 where the alkyl part is Cr C5 , C1 -C12 alkylamidoalkyl1, polyalkoxyamidoalkyl wherein the polyalkoxy part contains from 3-6 repeated C-C, alkoxy units and the amidoalkyl part contains from 4-12 carbon atoms, -SOCl, -SO2 -polyalkoxyamidoalkyl where the polyalkoxy part contains from 3-6 repeated C2~C3 alkoxy units and the amidoalkyl part contains from 4-12 carbon atoms; R,- is selected from the group consisting of: hydrogen, C 1 -C 4 alkyl, C 1 -C 8 alkoxyalkyl, C₁ -C₁ alkenyl, hydroxyety1, and phenyl; R4 and R<- taken together form heterocyclic compounds selected from the group consisting of: azepinyl, morpholinyl, piperidinyl, and C 1 -C 1 alkyl 1-substitutes t piperidinyl; where X is 0 or S, n is 0 or 1, Rg is selected from the group consisting of: C 1 -C 12 alkyl, G2 _("6 ^haloalkyl, phenyl, and substituted phenyl wherein, when n = 1, the substituents are selected from the group consisting of: nitrous, chlorine, C1 -C2 alkyl, C₁ -C₆ polyalkyloxyalkyl, C..-C0 cycloalkyl, Yes C₁ -C₁ alkenyl, C3 -C8 Alkoxyalkyl, C2" C8 hydroxyalkyl, Cj-C^ carboxyalkyl1, C 5 -C 8 D trialkylammonium alkyl salts, and when n = 0, the substituents are selected from the group consisting of: chlorine, . thiopotassium, C1~ C12 alkv1' benzyl, C1-C4 chlorocarboxyalkyl, C 1 -C , polyalkoxyalkyl, and 4 b acetyl; where R- is selected from the group consisting of: -(CH2-)n where n = 0 to 8, -CH=CH-, where M is H or Cl, -CC1=CC1-, -CH2 OCH2 -, -OCH2CH20- and d = 0 or 1, when d = 1, is Y selected from the group consisting of: -0, -S , and -Nile, and Z is selected from the group consisting of C1 -C12 alkyl, hydrogen, C.-C., polyalkyloxyalkyl, 4 ib C^ -Cg dialkylaminoalkyl, C3~ C5 alkynyl, phenyl, substituted phenyl, organic salts, inorganic salts, and when d = 0 is Z Cl or where R, R^ and R^ are as indicated above; where Rfl is selected from the group consisting of: Cj - Cj. Alkoxy, amino, C₂ -C₂ . alkoxyamino, hydroxy, and organic base; -SOw Rg where w'= 0-2 and Rg is chosen Era group consisting of: amino, C1~C5 alkyl, C₁ -C₁ haloalky1, phenyl, C^ -C^ q dialkylcknino, C^ -C^ q alkylamino, C-j-C,- alkoxy, substituted phenyl wherein the substituents are selected from the group consisting of: nine faiths, chlorine, C^ -C^j alkyl and ■ mc toxic. 55. Method as stated in claim 51, 52 or 53, characterized in that R^ is carboalkoxyalkyl where the alkyl part is C1 -C2 alkyl, ": alkylketoalkyl 1 where the alkyl part is C^-C^ alkyl, ; hydroxyalkeny1 where the alkenyl part is C^-C^ alkyl, hydroxyalkyl where the alkyl part is C^-C^ alkyl, formylhydroxyrnety 1, hydroxyhalogenety1 where the halogen thorn is chlorine, substituted phenoxyalkyl where the alkyl part is C-j alkyl and the substituents are p-methoxy, Cl, NO3 or CN where R"^ is -Oll, -N112 or methoxy, where R, R^ and R^ are as indicated above, where R, R-^ and R^ are as indicated above, or where D is an organic base selected from the group consisting of: and where R^ is selected from the group consisting of:-II C 1 -C 8 alkyl, hydroxyc ty .1, naphthyl, phenyl, substituted phenyl wherein the substituents are independently selected from the group consisting of chlorine, C2_C2 alkyl, C1 ~ C2 a-lkoxy, nitro, cyano and -CF3 , where R, R^ and R are as indicated above, NR1 where R, R1 and R2 are as indicated above, where R, R1 and R2 are as stated above, where R, R 1 and R 2 are as indicated above, where R, R1 and R2 are as stated- above, where x is 1 to 8, and R, Rx and R2 are as above, where m is 2 or 3 and R, R± and R2 are as indicated above, where R, R1 and R2 are as defined above, where R, R1 and R2 are as defined above, where ^X is selected from the group consisting of: 0, S, NH, NR1.1'° g Y is hydrogen or methyl; R^ q is selected from the group consisting of: H, C1 -C2 alkyl, C₁ -C₁ alkenyl, C3~ C4 alkynyl, C2~ C3 haloalky1, '■' C -CQ cycloalkyl, JO C_,-C2q polycycloalkyl 1, C 2 -C 3 g polyalkoxyalkyl, C 2 -C 8 hydroxyalkyl, C3"~ C10 Alkoxyalkyl, C_,-C0 Carboalkoxyalkyl, 3 o C4-Cg cycloalkylalkyl, CC-CQ alkylcycloalkyl, -C^-C-, cycloalkylimino, C2~C10 alkylimino' C1~C3 alkylamino' C4~ ci2 dialkylaminoalky1/ C,-C,~ cycloalkenyl, 6 10 phenyl, alkylphenyl where the alkyl part is ^ L~ c^' p-chloroalkylphenyl where the alkyl part is C^ C^, naphthyl, anthraceny1, benzamidocycloalkyl where the alkyl moiety is <C>l " <C>2' pyranyIme ethyl, tetrahydrofurfuryl, thiophenemethyl, benzhydry1, *halobenzhydry1, polycyclic alcohol and substituted' phenyl where the substituents is selected from the group consisting of: C 1 -C 4 alkyl, halogen, nine faiths, tri f luormety ]., formyl, chloroacetyl, C 1 -C 4 alkoxy, hydrogen, benzy1, chlorobenzy1, phenethyl and substituted phenethyl where the substituents are selected from the group consisting of: ... C1 -C4 alkyl, halogen, and R11 is selected from the group consisting of: C1 -C4 alkyl, C₁-C₆ alkoxyalkyl, and. C3-C4 alkenyl; and R.| taken together form heterocyclic compounds, preferably heterocyclic compounds selected from the group consisting of: azcpinyl, morpholinyl, piperidinyl, C 1 -C 1 alkyl-substituted piperidinyl; provided that when X = 0 or S, then Rj q is different from hydrogen, and substituted phenyl wherein the substituents are selected from the group consisting of: halogen, C 1 -C 4 alkoxy, phenoxy, trifluoromethyl, C1-C6 thioalkyl, ,,.. . nine faiths, isocyana two, C2~C4 polyalkyloxy, C3-C7 cycloalkyl, C3~ C^0 carbo alkoxyalkyl, C^-C'4 haloalky 1, C3~C4 alkenyl, G2_<"G ^ialkylamino, phenylamine no, Cl -C4 alkyl, C3~ C]2 hydroxyalkylamidoalky1,. C5 -Cj0 N' N_hydroxyalkylureidoalkyl, isocyanatoalky1 where the alkyl part is C^ -Cj/ C3~ C12 cl 1 alkylamidoalkyl, polyalkoxyamidoalkyl wherein the polyalkylene part contains from 3-6 repeated C₁-C₄ alkoxy units and the amidoalkyl part contains from 4-12 carbon atoms, -so2 ci, -SG^ -polyalkoxyamidoalkyl where the polyalkoxy part contains four 3-6 repeated C^~C^ alkoxy units and the amidoalkyl part contains from 4-12 carbon atoms; R,- is selected from the group consisting of: hydrogen, C1 -C4 alkyl, C 1 -C 8 alkoxyalkyl, C₁ -C₁ alkenyl, hydroxyety1, and phenyl; and Rj. taken together form heterocyclic compounds selected from the group consisting of: azepinyl, morpholinyl, piperidinyl, and C 1 -C 1 alkyl-substituted piperidinyl; where X is 0 or S, n is O or 1, Rg is selected from the group consisting of: C-|-C4 alkyl, C₁ -C₂ halogen alkyl, phenyl, and substituted phenyl wherein, when n = 1, the substituents are selected from the group consisting of: nitrous, chlorine, C1 -C2 alkyl, C4~C8 polyalkyloxyalkyl, C3 -C8 cycloalkyl, C3~C'4 alkenyl, C3 -C8 Alkoxyalkyl, C2~ Cg hydroxyalkyl, C1~ C3 carboxyalkyl1, Cc -C0 trialkylammonium alkyl salts, and when n = 0, the substituents are selected from the group consisting of: chlorine, thiopotassium, C 1 -C 4 alkyl, benzyl, C1~C2 beteroalkyl, C2~ C4 chlorocarboxyalkyl, C 1 -C , polyalkoxyalkyl, and 4 b acetyl; where R7 is selected from the group consisting of: -(CIU-) where n = 0 to 8, 2 n -CH=CH-, where M is H or Cl, -CC1=CC1-, -CH2OCH2-, -OCH2 CII2 0- and d = 0 or 1, when d = 1, is Y selected from the group consisting of: -oh, -S, and -Nile, and Z is selected from the group consisting of C1 -C4 alkyl, hydrogen, C4~ C16 PolyalkoxyYa-1 kY1' C^-Cg dialkylaminoalky1, C3~ C5 alkynyl, phenyl, substituted phenyl, organic salts, inorganic salts, and when d = 0 is Z Cl or where R, R1 and R2 are as defined above; where R8Q is selected from the group consisting of: C 1 -C 1 - alkoxy, amino, C₁ -C₁ alkoxyamino, hydroxy, and organic base; -SO w R 9 where w = 0-2 and Rn y is selected from the group consisting of: amino, C1-C5 alkyl, C1-C6 haloalkyl, phenyl, C1 -C1Q dialkylamino, C1~C10 alkylamino' C-^- C^ alkoxy, substituted phenyl where the substituents are selected from the group consisting of: nine faiths, chlorine, Cj-C^ alkyl and me took sy . 56. Method as stated in claim 51, characterized in that Rer -secC7H15,•R^ -is -C6H13, R2 is -C2H5 and R3 is 57. Method as stated in claim 51, characterized in that R is -secC7 H15 , R1 is -CgH17 , R2 is -C^ 11^ and R3 is 58. Method as stated in claim 51, characterized in that R is -secC7H15, is -C8H17' R2 is ~ciH3 and R3 Gr 59. Process as stated in claim 51, characterized - 'in that R is _C8 H17' R1 is -CgH17 , R2 is ~C2H5 and R3 is 60. Method as stated in claim 51, characterized in that Rer -secC7 H15 , R. is -CRH , R is -C2H5 and R, is 61. Process as set forth in claim 51, characterized in that Rer -2-ethylhexyl, 'Ry is -2-ethylhexyl, R2 is -C2I!5 and R^ is 62. Process as stated in claim 51, characterized in that R is -secC7H^, R1 is -C8 H17' R2 is _C2H5° gR3 is 63. Process as set forth in claim 51, characterized in that R is -secC7 H15 , R1 is -2-ethylhexyl, R2 is -C1H, and R1 is 64. Method as stated in claim 51, characterized in that Rer -secC^H^, Rx is -CgH17 , R2 or -CH 2CH=CII 2 and R3 is 65. Procedure which. stated in claim 51, characterized in that R is -secC-,!!.^ , Rx is~ C8 H2.7' R2 cr -clI2C" = cn2 oc' H3 cr 66. Method as stated in claim 51, characterized in that R is -secC7 H^ ,-, TRj. is -CgH17, R2 is -CH2CH=CH2 and R3 is 67. Process as stated in claim 51, characterized in that R is -secC^H^^, R, is ~C3Hi7> R2 is~ C3 H7 and R3 cr 68. Method as stated in claim 51, characterized in that R is -CRH^7, R, is -secCJI,.-/ R-, is -C_Hc .and R-, is 1 / ib Z Z b 3 69. Method as stated in claim 51, characterized in that R is -2-ethylhexy1, R. is -secC.,H,r, Rn is -C~Hr and R., is 1 715 2 25 3 70. Method as stated in claim 51, characterized in that R is -sckC_Hlc ., / ib: R1: is~c<g>H 17»R 2 Gr ~C2H5 OCJ R3 is 71. Process as stated in claim 51, characterized in that R is C 7H^^ , is _C3 H17' R2 is ~C2H5° and R3 is 72. Procedure as stated in claim 51, r; characterized in that R is secCyll^ ,-,R^ is -C8 H17' R2 is ~C2H5 and R3 is 73. Process as stated in claim 51, characterized in that Rer -secC^H^,R^ is -CgMj7, R2 is -C2 H5 and R^ is 74. Procedure which. stated in claim 51, characterized in that R is -secCyH^,-, Ry is -CgH17 , R2 is - C2[ lS OCJR3 or 75. Process as stated in claim 51, characterized in that R is "C-yH^^, R^ is rrCjH^tj, R2 is —Cog and R-^ is 76. Compound as stated in claim 1, characterized in that said R, R^ , R2 °9 R3 groups are chosen so that said 'f fortfindings are approximately non-phytotoxic and entail an LD,-^ -effect on said lepidoptera when said lepidoptera's food or place of residence is brought into contact with up to a 0.05% by weight solution of said compound. 77. Preparation as stated in claim 26, characterized in that said R, R^, R^ and R^ groups are chosen so that said compounds are virtually non-phytotoxic and cause an LDj -Q effect on said lepidoptera when said lepidoptera' s food or place of residence is brought into contact with up to a 0.05% by weight solution of said compound. 78. Method as set forth in claim 51, characterized in that said R, R^ , R2 °9 R3 groups are chosen so that said compounds are virtually non-phytotoxic and cause eh LD^^ effect on said lepidoptera when said lepidoptera's food or place of residence is brought into contact with up to a 0.05% by weight solution of said compound. 79. Connection with the formula wherein R and R^ are independently selected from the group consisting of C2-C10 alkyl, c2~ cio aikosyaikyi'°9 phenyl and R and Ry together contain from 12 to 22 carbon atoms; where R2 is selected from the group consisting of cl -c14 alkyl, C^ -C^ q alkenyl, C3 -C4 alkynyl, C2~C4 hydroxyalkyl, C 2 -C 8 alkylthioalkyl, C2~ C8 alkyloxyalkyl, (CH„) [X(CH0) ] y where n = 1 or 2, 2 n 2 . n X is 0 or S and y = 1-4, where n = 1-10, phenyl, and phenethyl; and where R is an organic group or a group containing phosphorus and oxygen or sulfur and oxygen; wherein said R, R^ , R2 and R^ groups are chosen so that said compound is virtually non-phytotoxic and produces an LD^ effect on said lepidoptera when said lepidoptera <1>'s food or op <p> hold place is brought into contact with up to a 0, 05% by weight solution of said compound. 80. Lepidoptericidal preparation containing the compound according to claim 79 and an inert carrier. 81. Procedure for combating lepidoptera, comprehensive that a lepidoptericidally effective amount of the compound according to requirement 79.82. Method for combating lepidoptera, comprising applying to said lepidoptera or their habitat or food a lepidoptericidally effective amount of a compound of the formula wherein R, Ry and R^ are organic groups which may be the same or different, and R and R^ together contain from 12 to 22 carbon atoms; and where R 1 is an organic group or a group containing phosphorus and oxygen or sulfur and oxygen; wherein said R, Ry, R2 and R^ groups are chosen so that said compound is virtually non-phytotoxic and produces an LD5Q effect on said lepidoptera when said lepidoptera's food or habitat is brought into contact with up to a 0.05% by weight solution of said compound.