DE2708863A1 - PHOSPHORAMIDATES, THE PROCESS FOR THEIR MANUFACTURING, AND THE PEST INSPIRATORS CONTAINING THEM - Google Patents

Description

Phosphoramidates, processes for their preparation and pesticides containing them.

The invention relates to agents for controlling arthropods, agents for controlling worms and anthelmintics, which contain phosphoramidates and certain new phosphoramidate compounds, as well as the preparation of these compounds and preparations and their use for controlling arthropod nematodes and worms.

The invention relates to agents for controlling arthropods, nematodes or worms from (A) one for agricultural use Purpose-compatible carrier or a pharmaceutically acceptable carrier and (B) an active ingredient, which from the following

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the components are selected:

1. At least one compound of the formula:

X

R N C N P 't; (A)

¹ 2 '3 R ^ R ^J

where R has the following meanings:

a) a v / ater fabric a torn,

b) a (C.-C ^ ") - alkyl group,

c) a (C ₃ -Cg) cycloalkyl group,

d) an optionally substituted aralkyl group with up to 11 carbon atoms,

e) an optionally substituted (Cg-C ..) -, for example (Cg-C ^ ₀ ) -aryl group,

f) an optionally substituted pyridyl group,

g) an optionally substituted pyridylmethyl or pyridylethyl group or

h) an optionally substituted pyrazinyl group,

2
R stands for the following groups:

a) a hydrogen atom

b) a ( ^c -i ~ ^c io ^ -alkyl group,

c) a (C ₃ -Cg) cycloalkyl group,

d) a (Cp-C-i-J-alkoxyalkyl group,

e) a (C2 ~ C _1Q ) -alkylthioalkyl group,

f) a (C ^ -Cg) cyanoalkyl group,

g) a (C ₃ -Cg) -alkenyl group,

h) an optionally substituted aralkyl group

with up to 11 carbon atoms and i) an optionally substituted (Cg-C _{1 (} J ~

Aryl group,

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1 2
where R and R merge with the nitrogen atom, with

which they are linked, a morpholino or form a piperidino group, which optionally

be substituted with up to 2 (C.-C ₄ ) -alkyl groups

can,

R a) a hydrogen atom,

b) a (C ₃ -C ₃ ) cycloalkyl group,

c) an optionally substituted aralkyl group with up to 11 carbon atoms or

d) is an optionally substituted (C ^ -C ^ ₀ ) - aryl group,

R a) a (C ₁ -Cg) -alkoxy group,

b) a (C ₁ -Cg) -alkylthio group,

c) a di- (C ^ -Cg) -alkylamino group,

d) a (C ^ -Cg) -haloalkoxy group,

e) a phenoxy group or

f) denotes a phenylthio group,

R a) a (C ₁ -Cg) -alkyl group,

b) a (C ₁ -Cg) -alkylthio group,

c) a di- (C ^ -Cg) -alkylamino group,

d) a (C ₁ -Cg) -alkoxy group,

e) a (C ^ -Cg) -haloalkoxy group,

f) a phenyl group,

g) a phenoxy group or

h) represents a phenylthio group and

X is an oxygen or sulfur atom, among which

1 2
A prerequisite that when R and R are each hydrogen and optionally substituted

4 5
Aryl mean, R and R are not each one

(C ₁ -Cg) -alkoxy group or a (C ₁ -Cg) group, and / or

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2. At least for agricultural or pharmaceutical Purposes compatible metal salt or metal salt coraplex a compound of formula (A).

"Optionally substituted" groups, as mentioned above, are to be understood as meaning groups which are substituted with any substituent as it is usually in question as a ring substituent comes.

The invention also relates to new compounds of

Formula:

i X ⁰ R ⁴

1 ^l! Il / ^R

_R ^x N c NP _v (B)

wherein R a) is a hydrogen atom,

b) a (C ₁ -C ₁₂ ) -alkyl group,

c) a (C ^ -Cg) cycloalkyl group,

d) an optionally substituted aralkyl group with up to 11 carbon atoms,

e) an optionally substituted ( ^C 5- ^c -i (0 "~ aryl group,

f) an optionally substituted pyridyl group,

g) an optionally substituted pyridylmethyl or pyridylethyl group or

h) an optionally substituted pyrazinyl group is,

2
R a) a hydrogen atom,

b) a (C ₁ -C ₁₀ ) -alkyl group,

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c) a (C ₃ -Cg) cycloalkyl group,

d) a (Cp-C ₁₀ ) -alkoxyalkyl group,

e) a (C ₂ -C _1Q ) -alkylthioalkyl group,

f) a (C ₁ -Cg) cyanoalkyl group,

g) a (C ₃ -C ₆ ) -alkenyl group,

h) an optionally substituted aralkyl group with up to 11 carbon atoms or

i) represents an optionally substituted ( ^C 6 "~ ^c -in '~ aryl group, provided that

tion that R has a different meaning than

1 2 has hydrogen, R and R together with

the nitrogen atom to which they are linked is a morpholino or piperidino group Form, which are optionally substituted with up to 2 (C ^ -C.) - Alkyl groups can be,

R a) is a hydrogen atom

b) a (C ₃ -Cg) cycloalkyl group,

c) an optionally substituted aralkyl group with up to 11 carbon atoms or

d) an optionally substituted (Cg-C ^ o * " Aryl group symbolized,

R represents a (C ₁ -Cg) -AlkOXy- or a (C ₁ -C ₆ ) -alkylthio group,

R is a (C ₃ -C ₄ ) -alkylthio group and X is an oxygen or sulfur atom, as well as the metal salts and metal salt complexes of the compounds of the formula (B) which are acceptable for agricultural purposes.

Under the terms "alkyl", "alkenyl", "alkoxy", "AIk-

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7 7 08

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oxyalkyl "," alkylthio "," alkylthioalkyl "," alkylsulfinyl ", "Alkylsulfonyl", "cyanoalkyl", "haloalkyl", "hydroxyalkyl", "dialkylamino" and "aralkyl" are intended to be both branched as well as straight-chain groups.

The compounds of the formulas (A) and (B) given above and their metal salts and metal salts can be produced by methods known per se for the production of analogous compounds.

The metal salts according to the invention are preferably alkaline earth metal salts of the compounds of the formula (A) or

2 3 (B), in which at least one of the substituents R and R is a hydrogen atom. The most preferred metal salts are the sodium salts.

The metal salt complexes of the invention are for example Complexes of the following formula, although this formula is for illustrative purposes only:

(C)

. ■ »τ - -
¹¹¹ IM - ■ -
U X "L" O 4th / ^R m M (W) _n R. Il R. Il V X the R ¹ c - - P R ² , R ³ , R ⁵ - in to s - ■ ι « ¹ . R ⁴ , and

the formulas (A) and (B) have given meanings.

M is a metal cation, usually from groups IIA, IIIA, IB, HB, VIIB and VIII of the periodic System of elements is selected, W is an anion,

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such as chloride, bromide, iodide, sulfate, bisulfate, phosphate, Nitrate, perchlorate, carbonate, bicarbonate, hydroxide, acetate,

Oxelate, malate or citrate, m is an integer from 1-2, η is an integer from 1-2 and n ¹ is an integer from 0-4.

Of the compounds of the formula given above (C) those compounds are preferred in which the metal cation is a transition metal, such as Copper, zinc, nickel, cobalt, tin, cadmium or manganese, or an alkaline earth metal such as calcium or magnesium, where the anion is a chloride, promide, nitrate, sulfate or hydroxide. The most preferred salts are those in where the metal cation consists of copper, zinc, nickel, cobalt, tin, cadmium, or manganese, while it is the anion is hydroxide.

The metal salts according to the invention can be prepared in such a way that

1. an alkali or alkaline earth metal hydroxide or hydride of a suspension of the phosphoramidate in a suitable one Solvent is added,

2. the mixture is stirred until a solution forms, and

3. the solution is freeze-dried. Optionally, you can

4. Concentrate the solution in vacuo at room temperature and the residue in a vacuum oven at room temperature dry.

The metal salt complexes according to the invention can be used in the

Way that they are made

1. in an aqueous or alcoholic medium

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phosphoramidate according to the invention with a salt of a Metal, selected from groups IIA, ΙΙΙΛ, IB, HB, VIIB or VIII of the Periodic Table of the Elements is implemented,

2. the precipitate that forms is filtered off and

3. The precipitate is washed and dried to obtain the product.

All for the preparation of the compounds of the invention The starting materials used are known compounds or can be easily prepared by known methods.

Of the new compounds of the formula B, the following compounds may be mentioned, which prove to be arthropodicides and nematodicidal active ingredients are suitable:

X 0 4

R NH G N P / (D);

l3 ^N R ⁵ i

R ^{3 R} I

-1
where R is a (Cg-C ₁₀ ) -aryl group, preferably a phenyl group, which is optionally substituted with up to 5, but preferably with up to 3 identical substituents selected from (C ₁ -C ₄ ) -alkyl groups, (C ₁ -C ₄ ) -alkoxy groups, (C ₁ -C ₄ ) -alkylthio groups, (C ^ C ₄ ) -alkyl sulfinyl groups, (C ₁ -C ₄ ) -alkylsulfonyl groups, di- (C ₁ -C ₄ ) -alkylamino groups, ( C ₁ -C ₄ ) haloalkyl groups, (C ₁ -C ₄ ) -hydroxyalkyl groups, cyano groups, nitro groups, hydroxyl groups and halogen atoms are selected,

3
R a) is a hydrogen atom

b) a (C - Cg) cycloalkyl group, preferably

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a (C ₅ -C ₇ ) cycloalkyl group,

c) an optionally substituted aralkyl group with up to 11 carbon atoms, preferably an unsubstituted benzyl group or

d) is an optionally substituted ^ ^c q ~ ^c aq ^ - aryl group, preferably an unsubstituted phenyl group,

R is a (C ^ -Cg) -alkoxy or (C _-1 -C ₆ ) -alkylthio group, preferably a (C ^ -C.) -Alkoxy or (C ₁ -C ₄ ) -alkylthio group,

R represents a (C ₃ -C ₄ ) -alkylthio group and X symbolizes an oxygen or sulfur atom.

Metal salts and metal salt complexes of the compounds of the formula (D) which are compatible for agricultural purposes also fall within the scope of the invention.

3 In the above formula (D), R is preferable

a hydrogen atom.

The most preferred compounds of the formula (D) have a particularly pronounced nematocidal and arthropodicidal (for example acaricidal and insecticidal) activity. They correspond to the formula:

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;: 7 ο 8 8 β

a *

wherein the substituent A, - the same or different can be, if there is more than one substituent A, can have the following meanings:

a) a (C.-C.) alkyl group, preferably one Methyl group,

b) a (C ^ -C ₄ ) -alkoxy group, preferably a methoxy group,

c) a (C ^ -C.) - Alkylthio group, preferably one Methylthio group,

d) a di- (C ^ -C ₄ ) -alkylamino group, preferably a dimethylamino group,

e) a trihalomethyl group, preferably a trifluoromethyl group or

f) a halogen atom, preferably a chlorine atom.

R is a (C.-C.) Alkylthio group, preferably a propylthio group, or a (C.-C.) alkoxy group, preferably an ethoxy group,

R is a (C3-C ₄ ) -alkylthio group, preferably an n-propylthio group, an isobutylthio group or a sec-butylthio group,

X is an oxygen or sulfur atom, preferably an oxygen atom, and

n "is 0 or an integer from 0-3, preferably 0, 1 or 2.

Of the most preferred compounds of the formula (D), mention may be made of those in which R is an ethoxy group and R for an isobutyl group or a sec-butyl group stands.

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Representative substituents R in Formula D are for example the following:

Phenyl, 2-chlorophenyl, 3,4-dichlorophenyl, 2,4,6-trichlorophenyl, 4-broniphenyl, 4-bromo -? - chlorophenyl, 4-fluorophenyl, 3-trifluoromethylphenyl, 4-chloroethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2-chloro-4-methylphenyl, 2,4-dichloro-3, 5-dimethylphenyl, 2-ethyl-4-mathoxyohecr / l, 4-butylphenyl, 3-methylthiophenyl, 4-methylsulfinylphenyl, 4-methylsulfonylphenyl, 5-methoxyphenyl, 2-athoxyphenyl, 4-dirnethylaminophenyl, 4-mitrophenyl, 2-chloro-4-nitrophenyl, 2-cyanophenyl, 2,4-dihydroxyphenyl, 4-hydroxybutylphenyl, Naphthyl, 4,6-dichloronaphthyl, 2-methylnaphthyl, 3-methyl-5-methoxynaphthyl and 3,5-ditrifluoromethylnaphthyl.

Representative substituents R "in Formula D are for example the following:

Cyclopentyl, cyclohexyl, phenyl, 4-nitrophenyl, 3,5-di- chlorophenyl, benzyl, 3,5-dimebhylbenzyl, 4-chlorobenzyl, Phenethyl, OC-Hofchylbenzyl, Naphthyl, 3-Methylnaphthyl so7ie 3,5-dichloronaphthyl.

Representative R * substituents in Formula D are example sv / iron:

Methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, neopentyl, pentyloxy, hexyloxy, as well as the Thio analogues of these groups.

Examples of compounds of the formula D are as follows:

S- (1-methylpropyl) -N-phenylaminothiocarbonyl-O-propyl phosphoramidothioate

O-Butyl-S ~ (2-methylpropyl) -M-phenyl-N-phenylaminothiocarbonyl phosphoramidothioate

O-ethyl-N- (2-methylphenyl) -aminothiocarbcnyl-S- (l-methyl-

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propyl) phosphoramidothioate,

0-Ethyl-N- (4-methoxyphenyl) aminothiocarbonyl-S-methylethyl-phosphoramidobhioate

O-ethyl S- (1-methylpropyl) -N- (2-methylthiophenyl) arainothiocarbonyl phosphoraniidothioate

O-ethyl S- (2-methylpropyl) -N- (4-methylsulfonylphenyl) aminothiocarbonyl phosphoramidothioate

O-ethyl-S- (2-niethylpropyl) -N- (4-ethy 1 sulfynylphenyl) aminothiocarbonyl phosphoramidothioate O-Ethyl N- (3-methyl-4-methylthiophenyl) aminothiocarbonyl S- (1-methylpropyl) phosphoramidothioate

N- (4-cyanophenyl) aminothiocarbonyl-O-ethyl-S- (1-methylpropyl ) phosphoramidothioate

N- (4-diethylaminophenyl) aminothiocarbonyl-0-ethyl-S- (imethylpropyl) phosphoramidothioate

N- (3,5-dibromophenyl) aminothiocarbonyl-0-ethyl-S-propylphosphoramidothioate , N-iS / S-dichlorophenylJaminotiiiocarbonyl-O-ethyl-N- (4- ^ iEthylbenzyl) -S- (1-methylpropyl) phosphoramidothioate, N— (2 — Bromo-4 — chlorophenyl) aminothiocarbonyl-O-ethyl— S-methylethylphosphoramidothioate

S-butyl-N- (3,5-dichlorophenyl) aminothiocarbonyl-0-ethylphosphoramidothioate

N- (2,4-dichlorophenyl) aminothiocarbonyl-0-methyl-S- (imethylpropyl) phosphoramidothioate

N- (3,4-dichlorophenyl) aminothiocarbonyl-0-hexyl-S- (imethylpropyl) phosphoramidothioate

N- (3,5-dichlorophenyl) aminothiocarbonyl-S, S-dipropyl phosphoramidothioate

O-ethyl S- (1-methylpropyl) -N- (2,4,6-trichlorophenyl) aminothiocarbonyl phosphoramidothioate N- (3,5-Ditrifluoromethylphenyl) aminothiocarbonyl-O-ethyl-S- (2-methylpropyl) phosphoramidothioate

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O-ethyl-N- (2-hydroxyphenyl) aminobhiocarbonyl-S- (1-methylpropyl) phosphoramidothioate

O-Xthyl N- (2-hydroxymethylphenyl) aminothiocarbonyl S- (1-methylpropyl) phosphoramidothioate

O-ethyl-S- (1-methylpropyl) -N- (2-naphthyl) aminothiocarbonyl phosphoramidothioate _

O-ethyl-S-methylethyl-N-jjL- (3-trifluoromethyl) naphthyl] aminothiocarbonyl phosphoramidothioate O-ethyl-S- (2-methylpropyl) -N-phenylaminocarbonyl phosphoramidothioate

N-Benzyl-O-ethyl-S- (1-methylpropyl) -N-phenylaminocarbonyl phosphoramidothioate

S, S-dipropyl-N-phenylaminocarbonyl phosphoramidothioate N- (2,4-Dimethylphenyl) aminocarbonyl-O-ethyl-S- (1-methylpropyl ) phosphoraraidothioate

O-ethyl-S- (1-methylpropyl) -N- (4-propylthiophenyl) aminocarbonyl phosphoramidothioate

N- (2,3,4,5,6-pentachlorophenyl) aminocarbonyl-O-ethyl-S-propylphosphoramidothioate

O-ethyl-N- (4-fluorophenyl) aminocarbonyl-S-propyl-phosphoramidothioate

N- (4-chloro-2-methylphenyl) aminocarbonyl-O-ethyl-S-C1-methylpropyl) phosphoramidothioate N- (4-chloromethylphenyl> aminocarbonyl S- (1-methylpropyl) -O-propyl phosphoramidothioate

N- (4-cyano-2-nitrophenyl) aminocarbonyl-O-ethyl-S- (1-niethylpropyl) phosphoramidothioate

N- (4-Chlorophenyl) aminocarbonyl-N- (4-cyanophenyl) -O-ethyl-S- (1-methylpropyl) phosphoramidothioate O-ethyl-S- (1-methylpropyl) -N- (2-naphthyl) aminocarbonyl phosphoraraidothioate

S, S-dipropyl-N- (1-naphthyl) aminocarbonyl phosphoramidothioate

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N- [1- (5,7-dichloronaphthyl) aminocarbonylj-O-ethyl-S- (2-

methylpropyDphosphoramidothioate

S-Butyl-O-methyl-N- [1- (3-methylnaphthyl) aminocarbonyl-

phosphoramidothioate

N- £ 2- (5,7-Dinitronaphthyl) aminocarbonylj -O-ethyl-S-

propyl phosphoramidothioate.

The metal salts and metal salt complexes of those specified above which are acceptable for agricultural purposes Compounds also fall within the scope of the invention.

The phosphoramidates of formula B can be prepared in this way that a corresponding aromatic amine with an appropriately substituted phosphorus isothiocyanate or phosphorus isocyanate is brought together. This reaction can be expressed by the following equation reproduce:

"4 0 X 0 _R 4

^K ν Il Il HV ^K ■

R ^ NH ₀ + P NCX> R ^1- -NH-C-NH-P /

² _R v \ R ⁵

14 5
in which R, R, R and X have the meanings given in connection with the formula D.

The reaction is generally carried out in the presence of an aprotic solvent such as glyme, acetone, acetonitrile, Ethyl acetate, butyl acetate, diethyl ether or mixtures thereof at a temperature between about 15 and about 120 ° C, preferably at a temperature of about 25 to about 45 ° C. An essentially Equimolar ratio of reactants is preferred, but an excess of the phosphorus isothiocyanate can be used or isocyanate. The wished

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-vs-

Product can be from the reaction mixture according to conventional Methods are separated, for example by fractional crystallization, or chromatography extraction like that.

Another method for the preparation of compounds of the formula D provides a corresponding aromatic amine with an appropriately substituted chloro (thio) carbonyl phosphoramidate bring together. This reaction can be represented by the following equation:

XO _p 4 XO 4

^a + Cl-CNP / ^ R-NH-CN-P. ;

13 4 5
in which R, R, R, R and X have the meanings given in connection with the formula D, with the exception that R cannot be hydrogen.

This latter reaction is carried out generally in the presence of an aprotic solvent such as glyme, acetone, acetonitrile, ethyl acetate, butyl acetate, diethyl ether or mixtures thereof at a temperature between about 15 and about 120 ⁰ C and preferably at about 25 to about 45 ° C . An acid acceptor, such as a tertiary amine, can be used as a scavenger in this preparation method. Representative acid acceptors are, for example, pyridine, trimethylamine, triethylamine or the like. An excess of the amine reactant can also serve as an acid acceptor. In general, an essentially equimolar ratio of the reactants is preferred, but an excess of two or more moles of the amine can be employed if the amine is to serve the dual function of reactant and acid acceptor. The product you want

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can from this reaction mixture according to conventional Methods are separated *.

A third method of connecting the Formula D provides for bringing together a corresponding phosphoramidate with a corresponding isocyanate or Isothiocyanate. This reaction can be represented by the following equation:

O 4 ^x ° R ⁴ i

NH-P ( + R ¹ NCX> R ^a -NH-CNP '\

I \ 5 ¹ O \ n ⁵

R ^{3 R} * ' ^R

13 4 5
wherein R, R, R, R and X are those in connection with the

Formula D have given meanings.

The reaction is generally carried out in the presence of an aprotic solvent such as Glyrn, acetone, acetonitrile, ethyl acetate, butyl acetate, diethyl ether or mixtures thereof, at a temperature of about 20 to about 60 ⁰ C, but room temperature is preferred. A substantially equimolar ratio of the reactants is preferred. The desired product can be separated from the reaction mixture by conventional methods.

A number of the compounds of the formula D are summarized in Table I below. Illustrative manufacturing methods for some of these Compounds are shown in Examples ID to 9D, "D" being used to denote those prepared according to the Examples Compounds and the corresponding compounds of the formula D given in Table I are to be assigned.

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Example ID - Preparation of O-ethyl S- (1-methylpropyl) -N-phenylaminocarbonyl phosphoramidothioate (Compound ID of Table I).

To a solution of 0.93 g (0.01 mol) of aniline in 5 ml of glyme 2.23 g (0.01 mol) of O-ethyl-S- (1-methylpropyl) phosphorisoqyanate thioate (exothermic reaction) given. The solution is left at room temperature for a period of time stand for 24 hours and then pour them into 250 ml of water. The semi-solid precipitate is isolated and dissolved in 20 ml of ether on slurried. The essential slurry is filtered and dried. This gives 0.35 g (11%) of the product.

Example 2D - Preparation of O-ethyl N- (4-methylphenyl) aminothiocarbonyl S- (1-methylpropyl) phosphoramidothioate (Compound 6D of Table I)

To a solution of 1.07 g (0.01 mol) of 4-methylaniline in 5 ml Glym are 2.39 g (0.01 mol) of O-ethyl-S- (1-methylpropyl) -phosphoroisothiocyanate thioate (exothermic reaction) added. The solution is left at room temperature for a Stand for 6 days and then pour them into excess water (300 ml). The suspension formed is im Vacuum filtered. The filter cake is slurried in 50 ml of hexane, filtered and dried. 1.6 g (47%) of the product are obtained in this way.

Example 3D - Preparation of O-ethyl N- (4-methoxyphenyl) aminothiocarbonyl-S- (1-methylpropyl; phosphoramidothioate (Compound 9D of Table I)

To a solution of 1.23 g (0.01 mol) of 4-methoxyaniline in 5 ml of glyme are 2.39 g (0.01 mol) of O-ethyl-S- (1-methylpropyDphosphorisothiocyanate thioate (exothermic reaction) added. The solution is left at room temperature stand for a period of 18 hours and then pour them

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in an excess of water. The suspension formed is filtered in vacuo. The filter cake is dissolved in 100 ml of hexane slurried, filtered and dried. One obtains 2.4 g (66.5%) of the product.

Example 4D - Preparation of N- (4-Dimethylaminophenyl) ~

aminothiocarbonyl-0-ethyl-S- (1-methylpropyl) phosphoramidothioate (compound IOD of Table I)

To a solution of 1.36 g (0.01 mol) of N, N-dimethyl-4-phenylenediamine in 5 ml of glyme 2.39 g (0.01 mol) of O-ethyl-S- (1-methylpropyl) phosphorus isothiocyanate thioate are added (exothermic reaction) added. The solution is left at room temperature for a period of 24 hours stand and then pour them into excess water. The precipitate formed is slurried in hexane and then filtered in vacuo. The filter cake is slurried again in 15 ml of ethyl acetate and filtered in vacuo and dried. This gives 0.9 g (24.6%) of the product.

Example 5D - Preparation of N- (3,5-dichlorophenyl) -amino-

thiocarbonyl O-ethyl-S-propyl phosphoramidothioate (Compound 14D of Table I)

To a solution of 1.62 g (0.01 mol) of 3,5-dichloroaniline 2.25 g (0.01 mol) of O-ethyl-S-propylphosphoroisothiocyanate thioate are added to 5 ml of glyme given. The product is obtained in such a way that the reaction solution is in excess Water is poured in, whereupon the suspension formed is filtered and the isolated precipitate is taken out Recrystallized methylcyclohexane. The product yield is 1.8 g (47.5%).

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Example 6D - Preparation of N- (3,5-dichlorophenyl) aminothiocarbonyl-0-ethyl-S-methylphenylphosphoramidothioate (Compound 15D of Table I)

To a solution of 2.88 g (0.0178 mol) of 3,5-dichloroaniline in 5 ml of glyme are 4 g (0.0178 mol) of O-ethyl-S-methylethylphosphoroisothiocyanate thioate given. The solution is heated to reflux and kept at room temperature for a Allowed to stand for a period of 2 hours. The suspension formed is filtered in vacuo. The filter cake will washed with 10 ml glyme and 20 ml ether and dried. The product is obtained in a yield of 2 g (29%).

Example 7D - Preparation of N- (3,5-Dichlorophenyl) -

aminothiocarbonyl-0-ethyl-S- (2-methylpropyl) -phosphoramxdothioate (Compound 17D of Table I)

2.39 g (0.01 mol) of O-ethyl-S- (2-methylpropyl) are added to a solution of 1.62 g (0.01 mol) of 3,5-dichloroaniline in 5 ml of glyme phosphorus isothiocyanate thioate given. The solution is heated to reflux and at room temperature for a Allowed to stand for 3 days. The solution is poured into excess water and the semi-solid precipitate formed is isolated. The product comes in 50 ml Slurried hexane and vacuum filtered. The filter cake is dried. This gives 1.8 g (45%) of the product.

Example 8D - Preparation of N- (3,5-Dichlorophenyl) -

aminothiocarbonyl-0-ethyl-S- (1-methylpropyl) -phosphoramxdothioate (Compound 18D of Table I)

4.8 g (0.02 mol) of O-Ethy1-S- (1-methyl-

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3 *

propyl / phosphorus isothiocyanate thioate. The solution is allowed to see at room temperature for a period of 18 hours and then poured into excess viassar. The semisolid precipitate formed is isolated and slurried in 50 ml of hexane. The hexane slurry is filtered. 3.25 g (40.5%) of the product with a melting point of 123 to 125 ° C. are obtained. Recrystallization from methylcyclohexane gives 2.5 g (31%) of the product.

Example 9D - Preparation of N- (3,5-Ditrifluoromethylphenyl) aminocarbonyl-O-ethyl-S- (1-mefchylpropyl) -phosphoramidothioate (Compound 23D of Table I)

To a solution of 1.03 g (0.0045 mol) of 3,5-ditrifluoromethylaniline 1 g (0.0045 mol) of O-ethyl-S- (1-methylpropyl) phosphorus isothiocyanate thioate is added to 5 ml of glyme (exothermic reaction) given. The resulting solution is left at room temperature stand for a period of 1 1/2 hours and then pour them into 200 ml of water. The suspension formed is filtered in vacuo. The filter cake is crystallized from methylcyclohexane. This gives 0.92 g (46%) of the product.

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TABLE I.

Connect
manure
number X R ¹ -2 709 ID 0 ^C 6 ^H 5. -3 OD
GJ
CO 2d S. ^C 6 ^H 5 '065: 3d 0 C ₆ H ₁₊ CH ₃ -k 0 C ₅ H ₁₊ CH ₃ ■ Λ N. 5D 0 C ₆ H ₁₊ CH ₃ 6D S. C ₅ H ₁₊ CH ₃

D 0 C ₅ H ₁₊ CH ₃ - ^ f

R't-NH-C-NH

OC ₂ H ₅ -

OC ₂ H ₅

OC ₂ H ₅

OC ₂ H ₅

OC ₂ H ₅

3D

OC ₂ H ₅ SC ₁₊ H ₉

OC ₂ H ₅ SC ₁₊ H ₉ ³

. F-. ⁰ C,

7 ^ -77 99-101

oil

75-80

130-135

78-80 dec.

120-122

101-10 ¹ *

£ 1 elementary analysis Calculated (found)

^ 9.35 6.69 8.86 9.79 (1 * 9.22) C6.-8 »+) (8.6 ¹ +) (9.60)

+3 5-98 Q.Qh

(! +5.26) (6.03) (8.80)

5O.8 7.0 8.5

(50.5) (6.7J (8.3)

51.O 6.7 8.5

(50.7) (7.1) (8.5)

50.8 7.0 8.5

(50.3) (6.9) (8.1)

Λ2 6.66 7-96 .53) (6.69) (8.09)

50.9 7.0 8.5 (50.6) (6.9) (8.6)

3.3k 19.67 \ _v (9.73) (20.liO $ \

9.12 (8.9 ¹ O

9.7 (9-6)

9.7

(10.0)

9 ·? S (9.9) g

MS.07 6.60 7-57 8.78 17.80 cn W.39) (6Λ1) (7.73) (8.5 ¹ +) (17.69) co

Connection number ώ = &

TABLE I - continued

9D

IOD

OB! 3D

SC ₆ H ₁₊ CCH ₃ -I +

HD 0 C ₆ H ₁₊ NO ₂ -V

^ ₃ 12D SC ₆ H ₁ Cl-V

0 C ₆ H 1 Cl-V

SC ₆ H ₃ Cl ₂ -3.5

15 ^D SC ₆ H Cl -3.5

16 ° SC ₆ H.Cl ₂ -3.5

17 DSC ₆ HCl ₂ -3.5

18D SCH Cl -3.5 ^{6 3 2}

OC ₂ H ₅ SC ₁₊ H ₉ S. 8-83
Zors, OC ₂ H ₅ SC ₁₊ H ₉ S. 99-103
Zers, OC ₂ H ₅ ^Sc vV 108-112 OC ₂ H ₅ SC ₁₊ H ₉ ³ 83-85 OC ₂ H ₅ ^SC V ^H 9 ^S. 89-93
r-9

OC ₂ H ₅ S _C

OC H

OC ₂ H

S3 H

OC ₂ H ₅ S _ClfH 1

OCH. SC, H s
2 5 ^ 9

V6.00 6.23 7Λΐ 8Λ6

(V6.39) (6Λ0) (7.73) (Q.55)

V8.00 7.15 11.20 8.23

(V7.98) (6.98) (11.19) (8.25)

1 + 3.3 5.6 11.6

(V3.1) (5.5) (11.6) - '

V2.7I 5-59 7-3 8.35

V) (5..5Ο) (7.6V) (8.VV)

V3.35 5-7V 7-59

(VV.51) (5.75) (7.99)

122-12V 37.18 V. 5V 7-33

(37.21) (V.V3) (7.23)

3735 3 7 7-98

(37.21) (V.V3) (7.23) (8.00)

38.61 V.8V 6.88

I38.5-IVI 37-35 V.V3 7.10

93-96

_(38f9O)

103-111 '38.90 V.70 6.8V 7.70

(38.90) (ν.77) (6.98) (7.72)

I3O-I31 39.02 V.87 7-08

. _{(38> 9O) 1) (8}

19 ^D 0. C ₆ H.Cl ₂ -3.5 OC ₂ H ₅ se. H _Q s 1VV.5-1V7 VO.18 5.06 6.99 7-93

^{63 2 2} ^ ^{49 2ers} · (^ 0.53) (V.97M7.27) (8.CV

5 99

(^ 0.53) (V.97M7.27) (8.CV)

TABLE ι · - continued

Verb.in- ^

dung X E number

2OD S Cr

21D 22D 23 D

0 p

, -3.5

SC ₆ H ₃ C1 ₂ -2A SC ₆ H ₃ (CF ₃ ) ₂ -3.5

a "a ³

SC ₃ H ₇ SC ₃ H ₇

OC ₂ H ₅

OC ₂ H ₅

OC ₂ H ₅

OC ₂ H ₅

89-91
Decomp.

37.21 ff. 62 6.60

(37Λ1) (if.59) (6.71)

38.99! +. 81 6.75

(38.90) (if.77) (6.9S)

125.5-123.5 38.16 it.15 5.92 (38Λ6) (Italian O9) (5.98)

162-16 ^ .5

183-185
127-128

^ 0.36 if. 52 6.19 (39.82) (I + .23) (6.19)

7Λ2 (7Λ2)

7.79 (7.72)

(6.61) -

38.19 ^ .20 6.33 6.99 7.52

(38.36) (3.92) (6.39) (7.06). (7.31)

37.00 3.86 6. CO '6.7 ¹ + ΐ4 * Λ7

(37.00) (3.78) (6.lit) (6.32Kl ¹ KlI)

i = iso s = .sec.

Of the agents which compounds of the formula A (incl. the metal salts and the metal salt complexes), agents may be mentioned, the arthropodicidal compounds as well metal salts compatible for agricultural purposes and Metal salt complexes of the formula contain:

X ⁰ R ⁴ RNCNP ^ (F)

wherein R a) is a hydrogen atom

b) a (C 1 -C 1) -alkyl group, preferably one (C ^ -Cg) -alkyl group,

c) a (C -C ") - cycloalkyl group, preferably a (C -C ~) -Cycioalkyl group,

d) an optionally substituted aralkyl group with up to 11 carbon atoms, preferably an optionally substituted benzyl or phenethyl group,

e) an optionally substituted (Cg-C ₁₀ ) aryl group, preferably an optionally substituted phenyl group,

f) an optionally substituted pyridyl group,

g) an optionally substituted pyridylmethyl or pyridylethyl group or

h) an optionally substituted pyrazinyl group is,

R a) a hydrogen atom,

b) a (C -, - C ₁ -.) - alkyl group, preferably a (C _a -C ₆ ) -alkyl group,

c) a (C ₃ -Cg) cycloalkyl group, preferably a (C ₅ -C ₇ ) cycloalkyl group,

d) a (Cp-C ₁ _) -alkoxyalkyl group, preferably a (C ₂ -C ₅ ) -alkoxyalkyl group,

- 25 -

709838/0653

e) a (Cp-C _-10 ) -alkylthioalkyl group, preferably a (Cp-C ₆ ) -alkylthioalkyl group,

f) a (C _-3 -C ₆ ) cyanoalkyl group,

g) a (C ^ -Cg) -alkenyl group, preferably a (C ₃ -C ₄ ) -alkenyl group,

h) an optionally substituted aralkyl group with up to 11 carbon atoms, preferably an unsubstituted benzyl or phenethyl group, or

i) an optionally substituted (Cg-C ₁₀ ) aryl group, preferably an unsubstituted one

Phenyl group,

2
R and R together with the nitrogen atom to which they are linked form a morpholino or piperidino group which is optionally _{substituted with up to 2 (C 1} -C ₄ ) -alkyl groups, preferably methyl groups,

R a) a hydrogen atom,

b) a (C ₃ -Cg) -cycloalkyl group, preferably a (Cc-C ^) - cycloalkyl group,

c) an optionally substituted aralkyl group with up to 11 carbon atoms, preferably an unsubstituted benzyl or phenethyl group, and

d) represents an optionally substituted (Cg-C ^ ₀ ) -aryl group, preferably an unsubstituted phenyl group,

R a) a (C ₁ -Cg) -AIkOXYgJTUpPe, preferably one

(C ₁ -C ₄ ) -alkoxy group,

b) a (C - C _ß ) -alkylthio group, preferably a (Cj-C ₄ ) -alkylthio group, or

c) a di- (C, -C, -) - alkylamino group, preferably a di- (C ..- C ₄ ) -alkylamino group, symbolized,

- 26 709838/0653

- 26 -

R a) a (C _> .-Cg) -alkyl group, preferably a (C -C ₄ ) -alkyl group,

b) a (C, -C,) -alkylthio group, preferably a (C ₁ -C ₄ ) -alkylthio group, or

c) a di- (C ₁ -Cg) -alkylamino group, preferably

represents a di- (C -C.) - alkylamino group,

12 provided that then, v / enn R and R are each hydrogen or optionally substituted (Cc-C ₁₀ ) _

Aryl, R and R are not each (C ₁ -C ₆ ) -alkoxy (or (C 1 -C 6) -alkylthio) or (C ₃ -C ₄ ) -alkylthio and X is an oxygen or sulfur atom .

Preferred compounds of the formula F, specifically those with of the highest acaricides, especially miticides, as well as insecticides Activity, can be expressed by the following formula:

1 »H /

_R ^x N c: NH P \ (G)

I ₂ V

wherein R a) is a hydrogen atom,

b) a (C ^ -Cg) -alkyl group, preferably a (C ₁ -C ₄ ) -alkyl group,

c) a (Cg-C ^) cycloalkyl group, preferably a cyclohexyl group,

d) a phenyl group, benzyl group or phenethyl group, preferably a benzyl or phenethyl group,

e) a phenyl, benzyl or phenethyl group, preferably a phenyl group, which has up to 3, preferably up to 2, (C ₁ -C ₄ ) -alkyl groups, preferably methyl groups, (C ₁ -C ₄ ) -alkoxy groups, preferably Methoxy groups, (C, -C ₄ ) -alkylthio groups, preferably methylthio groups, di- (C ₁ -C ₄ ) -alkylamino groups, preferably methyl

709-83 ^ 06 5 3

/ 708863

amino groups, halogen, preferably chlorine atoms, or nitro groups are substituted,

f) a pyridyl group which is optionally substituted by up to 2, but preferably 1, (C ₁ -C ₄ ) -alkyl groups, preferably methyl groups, and

g) is a pyrazinyl group,

2 1

R is a hydrogen atom, where R has a different meaning as a substituted or unsubstituted one

2 has a phenyl group, or R is a benzyl

1 2

represents a group, R and R together with the nitrogen atom, with which these substituents are linked, form a piperidino group,

R is an n-propylthio group, an n-butylthio group, an isobutylthio group or a sec-butylthio group means and

X is an oxygen or sulfur atom.

Metal salts and metal salt complexes of compounds of the formula G which are compatible for agricultural purposes are also said to be mentioned.

Of the most preferred compounds of the formula G, mention may be made of those in which R stands for a sec-butyl group.

In connection with the formula F it should be pointed out that the term "substituted", if it is used to modify aralkyl groups, aryl groups, pyridyl groups, pyridylmethyl groups, pyridylethyl groups or pyrazinyl groups, mainly indicates that such groups are substituted with one or more substituents are selected from (C ^ -C.) - alkyl, (C ₁ -C ₄₎ alkoxy, (C ^ -C ₄₎ alkylthio, (C ₁ -C ₄₎ alkylsulfinyl groups, (C ₁ -C ₄ ) -

- 28 -

709838/0653

/ '708863

MC

Alkylsulfonyl groups, di- (Q.-C.) - alkylamino groups, (C 1 -C ₄ ) -hydroxyalkyl groups, (C -C-Hcilogenalkyl groups, cyano, nitro, hydroxy and halogen are selected. In the pyridyl and pyrazinyl rings are selected to preferred to 2 substituents, while up to 3 substituents are preferred in the aralkyl and aryl groups, although up to 2 substituents are more preferred.

Representative examples of substituents R in the formula F are, for example, the following:

Viasserstoff, methyl, propyl, tert _r butyl, dodecyl, Cyclopro-Pyl> cyclohexyl, cyclooctyl, phenyl, 3,5-dichlorophenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 2,4,6-trichlorophenyl, 2,3, 4,5,6-pentachlorophenyl, 4-bromophenyl, 4-bromo-2-chlorophenyl, 4-fluorophenyl, 3,5-ditrifluoromethylphonyl, 2-methylphenyl, 4-methylphenyl, 2,5-dimethylphenyl, 2-chloro-4- methylphenyl, 2,4-dichloro-3,5-dimethylphenyl, 2-ethyl-4-methoxyphenyl, 4-butylphenyl, 4-methylthiophenyl, 3-methylsulfinylphenyl, 4-methylsulfonylphenyl, 5-methoxyphenyl, 2-ethoxyphenyl, 4-hydroxyphenyl, 4-chloro-2-hydroxyphenyl, 2-hydroxybutylphenyl, 4-dimethylaminophenyl, 4-nitrophenyl, 2-cyanophenyl, benzyl, 3,5-dichlorobenzyl, 4-methylbenzyl, phenethyl, methylbenzyl, 4-chlorophenylpropyl, naphthyl, 4,6- Dichloronaphthyl, 2-pyridyl, 3-pyridyl, 2- (5-chloropyridyl) 2- (3,5-dimethylpyridyl), 3-pyridylmethyl, 3-pyridylethyl, pyrazinyl, 2- (5-chloropyrazinyl) and 2- (5- Methylpyrazinyl).

Representative substituents R in the formula F are for example the following:

Hydrogen, methyl, butyl, tert-octyl, nonyl, cyclobutyl, Cyclohexyl, 2-ethoxyethyl, 4-butoxybutyl, 2-cyanoethyl, 4-cyanobutyl, 3-ethylthiopropyl, 2-butylthioethyl, allyl, 2-butenyl, phenyl, 3,5-dichlorophenyl, 4-methylphenyl,

- 29/30 -

7 09838/0653

/ • 708863

2-chloro-4-methylphenyl, 4-nitrophenyl, benzyl, 4-cyanobenzyl, 3,5-dichlorobenzyl, phenethyl, 4-fluorophenethyl, 2-methylbenzyl, 3-phenylpropyl, naphthyl, 1- (3-methylnaphthyl) as well as 2- (5,7-ditrifluoromethylnaphthyl).

Representative substituents R in the formula F are for example the following:

Cyclopentyl, cyclohexyl, phenyl, 4-methoxyphenyl, 2,4-dichlorophenyl, Benzyl, 4-nitrobenayl, 3,5-dimethylbenzyl, Phenethyl, naphthyl and 3-methylnaphthyl.

Representative substituents R in the formula F are, for example:

Methoxy, ethoxy, butoxy, isobutoxy, pentoxy, methylthio, Propylthio, sec-butylthio, hexylthio, dime'chylarnino, diethylamino, Diisopropylamino, dibutylamino and dihexylamino.

Representative substituents R in the formula F are, for example:

Methyl, ethyl, isopropyl, propyl, isobutyl, butyl, sec-butyl, Pentyl, hexyl, methylthio, ethylthio, isopropylthio, Propylthio, butylthio, neopentylthio, hexylthio, dimethyl amino, Diethylamino, Diisopropylamino, Dipropylamino and D ih exylamino.

Examples of compounds of the formula F are as follows:

Amxnothiocarbonyl-0-ethyl-S- (2-methylpropyl) phosphoramidothioate

O-butyl-S-d-methylpropyaminothiocarbonyl phosphoramidothioate

N- (N'-Allyl, N '-äthyDaminothiocarbonyl-O-ethyl-S-d-methyl propyl) phosphoramidothioate

- 31 709838/0653

/ 708863 -

Ml

N- (N'-2-ethoxyethyl, N'-hexyl) aminothiocarbonyl-O-ethyl-S- (1-methylpropyl) phosphoramidothioate

N-Cyclohexylaminothiocarbonyl-O-ethyl-S-12-methylpropyl) phosphoramidodithioate

N- [N '- (3,5-dichlorophenyl), N'-2-cyanoethyl jaminothiocarbonyl-S, S-dipropyl phosphoramidodithioate

O-Ethyl-N-fN '- (3-methyl-4-methylthiophenyl), N'-cyclohexylJ aminothiocarbonyl S- (1-methylpropyl) phosphoramidothioate O-Afchyl-N- [N '- (4-methylsulfonylphenyl), N'-methyl] aminothiocarbonyl S- (2-methylpropyl) phosphoramidothioate N-benzylaminothiocarbonyl-S, S-dipropyl phosphoramidodithioate O-ethyl-N- (4-methylbenzyl) -S- (1-methylpropyl) -N-phenethylamino thiocarbonyl phosphoramido thioate

O-ethyl-S- (2-methylpropyl) -N-phenethylaminothiocarbonyl-N-phenylphosphoramidothioate

N- (N ', N' -dibenzyl) aminothiocarbonyl-0-ethyl-S- (2-methylpropyl) phosphoramidothioate

N- (2,4-dichlorophenyl) aminothiocarbonyl-0-ethyl-S-ethylphosphoramidothioate

N'-Dimethyl-O ~ ethyl-N- (4-methylthiophenyl) aminothiocarbonyl phosphorodiamidate

N- (3,5-dichlorophenyl) aminothiocarbonyl-N · -dimethyl-O-propyl- phosphorodiamidate

Ethyl-O-ethyl-N- (4-methylphenyl) aminothiocarbonylphosphoramidate

O-ethyl-N- (2-hydroxyphenyl) aminothiocarbonyl-S- (1-methylpropyl ) phosphoramidothioate

O-ethyl N- (2-hydroxymethyl) aminothiocarbonyl S- (1-methylpropyl) phosphoramidothioate

O-ethyl S- (2-methylpropyl) -N- (2-pyridyl) aminothiocarbonyl phosphoramidothioate

O-ethyl-S- (1-methylpropyl) -N- (3-pyridylmethyl) aminothiocarbonyl phosphoramidothioate

O-ethyl-S- (1-methylpropyl) -N-JjL- (3-pyridyl) ethyl aminothiocarbonyl phosphoramidothioate

- 32 -

709838/0653

27080R3

λ HS

N-J2- (5-chloropyridyl) | aminothiocarbonyl-O-ethyl-S-C1 ~ methylpropyl) phosphoramidothioate

N- | 2- (6-chloropyrazinyl) | aminothiocarbonyl-O-ethyl-S-propyl-

phosphoramidothioate

S- (1-methylpropyl) -O-propyl-N-pyrazinylaminothiocarbonyl-

phosphoramidothioate

Aminocarbonyl-O-ethyl-S-C2-methylpropyl) phosphoramidothioate O-ethyl-N-methylaminocarbonyl-S-C1-methylpropyl) phosphorami-

dothioah

0-ethyl-S- (l-methylpropyl) -N-ocfcylaminocarbonylphosphorami-

dothioate

N-Cyclopentylaminocarbonyl-O-ethyl-S-C 1-niethylpropyl) -

phosphoramidothioate

N-Jn - (2-Bubenyl), N'-phenyl | aminocarbonyl-O-methyl-S- (1-methylpropyl) phosphorainido thioate

N-JN'-butyl, N '- (3,5-ditrifluoromehylphenyl)! aminocarbonyl O-ethyl-S-propyl phosphoramidothioate

Ν — Bi'-Benzyl, N ^f - (4-cyano-2-nitrophenyl) | aminocarbonyl-O-ethyl-S- (1-methylpropyl) phosphoramidothioate

N-Jn · - (3,5-dichloronaphthyl), N'ethyljaminocarbonyl-0-ethyl-S- (2-methylpropyl) phosphoramidothioate N-Cydohexylaminocarbonyl-N-C 3,5-d.ichlorophenyl) -O-ethyl-S-propylphosphoramidothioate

N-fN '- (3,5-dichlorophenyl), N' - (4-methylphenyl) j aminocarbonyl-O-ethyl-S- (1-methylpropyl) phosphoramidothioate N- (3,5-dichlorophenyl) aminocarbonyl-S-ethyl-0-methylphosphorus

amidothioate

O-ethyl-N-phenylaminocarbonylpropyl phosphoramidate N-Benzylaminocarbonyl-N ', N "-bis-dimethylphoGphortriamidat N-Benzylaminocarbonyl-N-cyclohexyl-O-methylethyl-S- (1-methylpropyl) phosphoramidothioate

N-Benzyl-O-ethyl-S- (2-methylpropyl) -N- (2-phenethyl) aminocarbonyl phosphoramidothioate

N- (N ', N'-dibenzyl) aminocarbonyl-0-ethyl-S- (2-methylpropyl) -

phosphoramidothioate

O-ethyl-S- (1-methylpropyl) -N- (2-pyridyl) aminocarbonyl-phosph-

phoramidothioate

70 "98 ³ 38/0653

? 7088R3

0-ethyl-S- (2-methylpropyl) N- (3-pyridylmethyl) aminocarbonyl-

phosphoramidothioate

N- (5-bromo-2-pyrazinyl) aminocarbonyl-O-ethyl-S-d-methylpropyl)

phosphoranidothioate

0-ethyl-S- (2-rr.ethylpropyl) -N-morpholincarbonylphosphorarai-

dothioate.

The metal salts acceptable for agricultural purposes and metal salt complexes of the above-mentioned compounds are also possible.

The compounds cer formula F can be prepared by methods which are analogous to the methods as described above for the preparation of the compounds of the formula D. are.

One method provides the following reaction:

_R 4 0 X 0 4 j

λ \ H ι »» / ι

R-NH +, P-NCX> -R-N-C-NH-P- I

12 4 5
wherein R, R, R, R and X are those related to the formula

F have given meanings.

Another method is to do the following:

! X 0 4 ■ 1

ι I! II /

R-NH + Cl-C-N-P '

I ₂ I ₃

X 0 4

! ti II /

R ² R

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709838/0653

ν 7 O 8 S B

wherein R, R, R, R ₁ R and X have the meanings given in connection with the formula F, with the exception

3
that R must not be hydrogen

A third method consists in the following reaction: 0 4 ^X ° R ⁴

NH J { ₊ R ¹ NCX- ^ R ^ NH-CNP (j

I ₃ V J3 V i

^K i

13 4 5
wherein R, R, R, R and X are those in connection with the

Formula F have given meanings.

In Table II below, a number of compounds of the formula F are summarized, namely together with methods for the preparation of these compounds (examples IF-8F, where the letter F is used to prepare the compounds according to the examples, as well as the compounds summarized in Table 2 to be assigned to the formula F).

Example IF - Preparation of N-Cyclohexylaminocarbonyl-

O-ethyl-S- (1-methylpropyl) phosphoramidothioate (Compound 10F in Table II)

To a solution of 0.99 g (0.01 mol) of cyclohexylamine in 5 ml of glyme are 2.23 g (0.01 mol) of O-ethyl-S- (1-methylpropyl) phosphorus isocyanate thioate (exothermic reaction) given. the The resulting suspension is allowed to stand at room temperature for a period of 1 hour and then poured in 20 ml of ether. The suspension is filtered in vacuo. The filtrate is left at room temperature for a Stand for 18 hours after which it is concentrated under a stream of nitrogen. The semi-solid residue is slurried in 50 ml of hexane, filtered and dried. This gives 0.4 g (12.5%) of the product.

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7098 3 8/0653

/ '7088R3 - ys -

Example 2F - Preparation of N- (3,5-dichlorophenyl) aminothiocarbonyl-O, S-diethyl phosphoramidothioate (Compound 11F in Table II)

To a solution of 1.9 g (0.0118 mol) of 3,5-dichloroaniline 2.5 g (0.0118 mol) of OjS diethylphosphoroisothiocyanate thioate are contained in 7 ml of glyme given. The product is obtained in such a way that the reaction solution is in an excess V / water is poured, whereupon the suspension formed is filtered in vacuo and the isolated precipitate from methylcyclohexane is recrystallized. The product yield is 1.2 g (27.3%).

Example 3F - Preparation of N- (3,5-dichlorophenyl) -amino-

thiocarbonyl-N ', N "-bis-dimethylphosphorus triamidate (Compound 14F in Table II)

To a solution of 3.24 g (0.02 mol) of 3,5-dichloroaniline in 10 ml of glyme are 3.86 g (0.02 mol) of N, N'-bis-dimethylphosphorus

isothiocyanate given.

The desired product precipitates from the glyme solution and is isolated by vacuum filtration. The yield is 3.2 g (45.6%).

Example 4F - Preparation of N- (3,5-dichlorophenyl) aminothiocarbonyl-N'-dimethyl-O-ethylphosphorodiamidate (Compound 15F in Table II)

Add 1.62 g (0.01 mol) of 3,5-dichloroaniline in 10 ml of glyme 1.94 g (0.01 mol) of N'-dimethyl-O-ethylphosphorus isothiocyanate given. The glyme solution is allowed to stand at room temperature for a period of 4 days. After this The product has precipitated out of solution and is isolated by vacuum filtration. The product is obtained in a yield of 1.5 g (43%).

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709838/0653

r / 08863 -

Example 5F - Preparation of N- (N ', N'-dibenzyl) aminocarbonyl-O-ethyl-S »- ( 1-methylpropyl) phosphoramidothioate (Compound 16F in Table II)

1.12 g (0.005 mol) of O-ethyl-S- (1-methylpropyl) are added to a solution of 0.99 g (0.005 mol) of dibenzylamine in 5 ml of glyme phosphorus isocyanate thioate (exothermic reaction) given. The solution is left to stand at room temperature overnight. the fine suspension formed is filtered in vacuo. The filtrate is dissolved in 50 ml of ether, washed with water, dried over magnesium sulfate and concentrated under a stream of nitrogen. This gives 1.5 g (50%) of a colorless Oil.

Example 6F - Preparation of N-Benzylaminocarbonyl-O-ethyl-S- (1-methylpropyl) phosphoramidothioate (Compound 19F in Table II)

2.23 g (0.01 mol) of O-ethyl-S- (1-methylpropyl) phosphorus isocyanate thioate are added to a solution of 1.07 g (0.01 mol) of benzylamine in 5 ml of glyme v / earth (exothermic reaction). The resulting suspension is allowed to stand at room temperature for a period of 2 hours, after which it is filtered in vacuo. The filter cake is washed with ether and dried. This gives 1.5 g (46%) of product with an F · 117-120 ⁰ C. Recrystallization from methylcyclohexane gives 0.7 g (23%) of product.

Example 7F - Preparation of O-Ethyl-S- (1-methylpropyl) -N-

Q? - (5-methylpyridyriamino thiocarbony l-phosphoramidothioate (Compound 23F in Table II)

To a solution of 1.08 g (0.01 mol) of 2-amino-5-methylpyridine in 5 ml of glyme , 2.39 g (0.01 mol) of O-ethyl-S- (1-methylpropyl) phosphorus isothiocyanate thioate (exothermic Reaction) given. The solution is allowed to stand at room temperature for a period of 2 hours and then poured into a

- 37 -

709838/0653

_ "7708883

- yn -

Excess water. The suspension formed is filtered in vacuo. The filter cake is slurried in 50 ml of hexane. The slurry is vacuum filtered, whereupon the filter cake is dried. This gives 2.2 g (65%) of the product.

Example 8F - Preparation of O-Ethyl-S-propyl-N-pyrazinyl-

aminothiocarbonyl phosphoramidothioate (compound 24F in Table II)

2.25 g (0.01 mol) of O-ethyl-S-propylphosphoroisothiocyanate thioate are added to a fine suspension of 0.95 g (0.01 mol) of aminopyrazine in 5 ml of acetonitrile given. The resulting solution is left at room temperature for a period of time stand for 5 days and then pour them into an excess of water. This suspension is filtered in vacuo. Of the Filter cake is washed with ether and dried. This gives 0.5 g (15%) of the product.

- 38 -

709838/0653

* t IO

Λ / »

O = O /.

«Μ-

s = 3 αί

C Φ Xl

• η ¹

ι ι

OO

• ·

CMCVi t- \ r- \

OCJN

r-id

I I

vO vO

vOCJN

COvO

• ·

VOvO

J-O

ιΗ γΗ

CMO <"Ο« -Ι ΟΝΟ ON ON

CMO-νθ CJN

<MrO

COCO

CO ON co J- vO CM

COCO

C ^ -CO

HO

COCO

VO CO O-CM

VO O-O O *

CMCM roro

J-J-roro

ο- O- CMr-I ro ro CMCM

O O- O η ι VO O O OO U.N. O- H "H Φ UNCO CM I. I.
O· N ro ro O- Cu O O- r-ii-i r-l f-I

i-H

:O

CM H I. I. H τ-Λ O-CJn O-νθ • · • · ONCJN CJN ON

VC On

Cv-vO

CO co

rH OJ νθ J "

co ON ~

V- ^ CO CO

vOJ- O ro

• · vO J-

J-CO · ·

J-J-O-CO

^ J-J-

J-. O ω • Η U

8 ™

ι ι

J-VO vcco,

• · J "CM ι

ONON · ·;

• Η UN

• ·

COCO

vOH

νθ OO

ro CO

J-O

• ·

coco

CO ONrH

J "VO \ O

:O

) ON η ON Vl V) ON Vl ON Vl ON approx ON approx ON approx: J- JJN J-- "j- ¹ ^ J- J- J- C? \ Ι O ϋ -J- O O O O J- < co co O approx co co co approx CJ! co CO

CM

I. Xl C. •H 'β Λ c ε Φ ■ Ο2

CO

CM

el CJN I ' νθ approx ON νθ Ο- · CJN O
ι O τ \ J " I.
Ö -T I.
O ro O J- rH CJ rH ro O CJ CJ U O (J υ

do

co

CO

CTN

709838/0653

TABLE II ~ continued

Connection -: _χ - _R 1

Number - -

1OF 0

R_-

^S V9

C.

. Elemental analysis: Calculated (found )

8Λν 8.69 9.61

(P.56; (8.76) (9.71)

ob 12F SC ₆ H ₃ Cl ₂ -3.5

SCH ₃

SO ₂ HY

Decomp.

133-135

33.65 3.7 ¹ + 7.73 8.62

(33Λ3) (3.65) (7-80) (8.62)

35.67 ¹ KlI 7-58 8 ·. 03

(35.39) (»f.05) (7.5D (8.30)

co 13F S C ₆ H ₃ Cl ₂ -3.5

14P SC ₆ H ₃ Cl ₂ -3.5 15F SC ₆ H ₃ CI ₂ -3.5

N (CH ₃ J ₂

191.5-19 ¹ + ho. 3 ¹ +> +. 92 6.52 dec. . (1 + 0Λ8) (5.10) (6.75)

, 5 37Λ2 k. 72 15.73

(37.19) O * .83) (15.77)

37. 2h h. 51 11.96

(37.09) (^ .53) (11.80)

7Λ2 (7Λ6)

8.67 (8.72)

8.86 (8.70)

TABLE II - Cont

co cn co

Connect
manure
Niiinmiay * / · 0 Rl R ² a- ⁵ F ⁰ C Elemental Analysis Calculated (Found) 6.95
(6.98) 6.66
(6Λ5) % P : I. ■ ---_— 16F S. C ₆ H ₅ CH ₂ C ₆ K ₅ CH ₂ SC ₁ ^ H ₉ ³ oil 6.70
(6.73) 6.52
(6.67) 7.37 _x
(7.17) - I. - 17F S. C ₆ H ₅ CH ₂ C ₆ H ₅ CH ₂ SCj ₊ Hq oil 59.98
(58.65) 6.87
(6.69) 7.29
(8.02) 7.10
(7.12) - 18F 0 C ₆ H ₅ CH ₂ H sc ^ h / oil. 57.77
(57.53) 7.0V
(7.02) 8.6?
(8.V3) 9.Ο3
(8.9V) - _ 0
OO 19F S. C ₆ K ₅ CK ₂ H SO,,"/ 120-122 (V8! 53) 7.15
(6.99) 7.38
i7.77) 9.53
(9.33) Tcher "" K a ~ uiraethyl- "q ^
OJ 2OF 0 C ₆ K ₅ CH ₂ CH ₂ H oil 50.9V
(50.89) 7-27
(7-32) 7.96
(8.1V) - 2 IF 0 C ₅ K ₅ CKjOHj, H 95 _z -98 _r 50.75
(V9.96) 5.17
(5.30) 5.96
(5-89) 9.00
(8.99) 22F • s C ₆ VJl ₂ -J, 5 C ₆ H ₅ CH ₂ SC ₁ ^ H ₉ S 118-120 52.07
(52.3D 6.08
(6.38) 07/12
(12.09) 6.51
(6.52) 23F S. H 118-120 50.39
(50.53) 5.35
(5-38) 17-9.
(17.31) 8.83
(8.92) '24F 0 H 106-107
Decomp. VV. 78
(VV.9V) 8.2
(8.5) 9.1
(9-2) 9.67
(9.66) 25F R ¹ , R ² = -4Cl .X T SC ₁ ^ H ₉ ⁵ 69-71 37.V9
(37Λ ¹ +) - R ⁴ = means an ethoxy group
represents amino group. with the exception
s = sec. V6.8
(V7.1) in connection with I4r

Sf

Of the new compounds of the formula B are compounds of the following formula:

X 0 4

HM K Ii /

R ^x NCNP \ (H)

R ² R ^{3 R} ι

wherein R a) is a hydrogen atom,

b) a (C ₁ -C ₁₂ ) -alkyl group, preferably a C ₁ -C ₉ ) -alkyl group,

c) a (C ~-Cn) cycloalkyl group, preferably a (Cg-C ^ cycloalkyl group,

d) an optionally substituted aralkyl group With up to 11 carbon atoms, preferably an. Optionally substituted benzyl or Phenethyl group,

e) an optionally substituted (Cg-C ₁ -) - aryl group, preferably an optionally substituted phenyl group,

f) an optionally substituted pyridyl group,

g) an optionally substituted pyridyl methyl group or Pyrxdylethylgruppe, or

h) an optionally substituted pyrazinyl

group is

R a) is a hydrogen atom, provided that R has a meaning other than an optionally substituted (C, -C ..) aryl group,

b) a (C ₁ -C ₁ Q) -AIkYIgJTUpPe, preferably a (C ₁ -Cg) -alkyl group,

c) a (C ^ -Cg) cycloalkyl group, preferably a (C ₅ -C ₇ ) cycloalkyl group,

d) a (Cp-C ₁₀ ) -alkoxyalkyl group, preferably a (C ₂ -Cg) -alkoxyalkyl group,

e) a (Cp-C ₁ Q) -alkylthioalkyl group, preferably a (C ₂ ~ Cg) -alkylthioalkyl group,

f) a (C ₁ -Cg) cyanoalkyl group,

- 42 -

709838/0653

/ 708863

q) a (C_-C, -) - alkenyl group, preferably one (C - C.) - alkenyl group,

h) an optionally substituted aralkyl group with up to 11 carbon atoms, preferably an unsubstituted benzyl or phenyl group, as

i) an optionally substituted (Cg-C ..) - aryl group, provided that R has a meaning other than hydrogen, preferably an unsubstituted phenyl

group, is,

1 2

R and R together with the nitrogen atom with which they

are linked, a morpholino or piperidino group form, optionally with up to 2 (C.-C.) - alkyl groups, preferably methyl groups, is substituted,

R a) a hydrogen atom,

b) a (C ₃ -Cg) cycloalkyl group, preferably a (C ₅ -C ₇ ) cycloalkyl group,

c) an optionally substituted aralkyl group with up to 11 carbon atoms, preferably an unsubstituted benzyl or phenethyl group, or

d) is an optionally substituted (C ₆ -C ^ ₀ ) aryl group, preferably an unsubstituted phenyl group,

R ^{4 is} a (C ₁ -Cg) -AIkOXy- or (C ^ C ^ alkylthio-

group, preferably a (C ₁ -C.) - alkoxy or a (C.-C _/ .) - alkylthio group,

R symbolizes a (C ₃ -C ₄ ) -alkylthio group and

X is an oxygen or sulfur atom.

Metal salts and metal salt complexes of the compounds of the formula H which are compatible for agricultural purposes

- 43 -

709838/0653

OK

also fall within the scope of the invention.

2 In the formula H given above, R is preferably represents a hydrogen atom or a benzyl group, or along with R and the nitrogen atom, with soften the sub substituents are linked, a piperidino group, while R represents a hydrogen atom.

A preferred class of compounds of the formula H corresponds to the formula:

R- ¹ __ _{N c NH} - p (I)

wherein R a) is a hydrogen atom,

b) a (C -Cg) -alkyl group,

c) a (Cg-C ₇ ) cycloalkyl group,

d) a phenyl · - »benzyl or phenethyl group, preferably a benzyl or phenethyl group,

e) a phenyl group, benzyl group or phenethyl group, preferably a phenyl group containing up to 3 and preferably up to 2 methyl groups , Methoxy groups, methylthio groups, Dimethylamine groups, cyano groups, halogen atoms, in particular chlorine atoms or trifluoromethyl groups is substituted,

f) a pyridyl group which is optionally _{substituted with up to 2 (C ^ -C 4} ) -alkyl groups, preferably methyl groups, or

g) is a pyrazinyl group,

represents a hydrogen atom or a benzyl group, provided that if

2 1

R is a hydrogen atom, R has another meaning as a substituted or not sub-

- 44 -

909838/0653

;: 7 O 8 S 6

has substituted phenyl group, ammen mit dem.Stickstoffatom, m are linked, form a piperidino group,

2
R and R together with the nitrogen atom with which they

R is an n-propylthio group, an isobutylthio group

or represents a sec, -3utylthio group and X is an oxygen or sulfur atom.

Furthermore, the metal salts and metal salt complexes of the compounds are acceptable for agricultural purposes of formula I mentioned.

Of the preferred compounds of Formula I are those Most preferred compounds in which R a) is a hydrogen atom,

b) a (C ^ -C ^ -alkyl group,

c) a cyclohexyl group,

d) a benzyl or phenethyl group,

e) a phenyl group substituted with up to 2 halogen atoms, preferably chlorine atoms is,

f) a pyridil group which is linked to a (C ..- C-) - alkyl group, preferably methyl group, is substituted, or

g) represents a pyrazinyl group, 2

R represents a hydrogen atom or a benzyl group

is, provided that if

2 1

R is a hydrogen atom, R is another

Has meaning as a substituted phenyl group,
R and R together with the nitrogen atom with which they

are linked, form a piperidino group, R is an n-propylthio group or a sec-butylthio-

group and
X is an oxygen or sulfur atom.

- 45 -

709838/0653

In connection with the formula H, "substituted", if this term is used to modify aralkyl, aryl, pyridyl, pyridylmethyl, pyridylethyl or pyrazinyl groups, usually means that such groups are substituted by one or more substituents, those from (C ₁ -C ₄ ) -alkyl, (C ₁ -C ₄ ) -alkoxy, (C ₁ -C ₄ ) -alkylthio, (C ₁ -C ₄ ) -alkylsulfinyl, (C ₁ -C ₄ ) - Alkylsulfonyl, di (C ₁ -C ₄ ) alkylamino, (C ₁ -C ₄ ) haloalkyl, (C.-C.) hydroxyalkyl, cyano, nitro, hydroxy and halogen. The preferred substituents are methyl, methoxy, methylthio, diethylamino, cyano, nitro, trifluoromethyl, and halogen, especially chlorine.

Up to 2 substituents are preferred in the pyridyl and pyrazinyl rings, while in the aralkyl and aryl groups up to 3 substituents are preferred, but in particular up to 2 substituents are provided.

Representative substituents R in the formula H are for example the following:

Hydrogen, methyl, propyl, tert-butyl, dodecyl, cyclopropyl, Cyclohexyl, cyclooctyl, phenyl, 3,5-dichlorophenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 2,4-dichlorophenyl, 2,4,6-trichlorophenyl, 4-bromophenyl, 4-bromo-2-chlorophenyl, 4-fluorophenyl, 3,5-ditrifluoromebhylphenyl, 2-chloro-4-methylphenyl, 2,4-dichloro-3,5-dimethylphenyl, 2-ethyl-4-methoxyphenyl, 4-butylphenyl, 4-methylthiophenyl, 3-methylsulfinylphenyl, 4-methylsulfonylphenyl, 5-methoxyphenyl, 2-ethoxyphenyl, 4-dimethylaminophenyl, 4-nitrophenyl, 2-cyanophenyl, 2-hydroxyphenyl, 2-hydroxymethylphenyl, benzyl, 3,5-dichlorobenzyl, 4-methylbenzyl, phenethyl, 4-methylthiophenethyl, Ct-methylbenzyl, Naphthyl, 3,5-dichloronaphthyl, 3-trifluoromethylnaphthyl, 3-methylnaphthyl, 2-pyridyl, 3-pyridyl, 2- (5-chloropyridyl), 2- (3,5-dimethylpyridyl), 3-pyridylmethyl,

- 46 -

709838/0653

3-Pyridyläthy1, Pyrazinyl, 2- (5-Chlorpyrazinyl) and 2- (5-methylpyrasinyl).

Representative substituents R in the formula H are for example the following:

Hydrogen, methyl, butyl, tert-butyl _r, nonyl, cyclobutyl, cyclohexyl, 2-ethoxyethyl, 4-butoxybutyl, 2-Cyanoäbhyl, 4-cyanobutyl, 3-Äthylthiopropyl, 2-Butylthioäthyl, allyl, phenyl, 3,5-dichlorophenyl, 2-methylphenyl, 4-cyanophenyl, 4-nitrophenyl, 4-methoxy-2-methylphenyl, benzyl, 3,5-ditrifluoromethylbenzyl, phenethyl, flf-methylbenzyl, 3-phenylpropyl, 3,5-dichlorophenyl, naphthyl and 4,6- Dimethylnaphthyl.

Representative substituents R in the formula H are, for example:

Cyclopentyl, cyclohexyl, phenyl, 2-methylphenyl, 3,5-dichlorophenyl, Benzyl, 4-methylbenzyl, phenethyl, naphthyl and 3-methylnaphthyl.

Representative substituents R are, for example: methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, Isobutoxy, pentyloxy and hexyloxy as well as the thio analog of these groups.

Examples of compounds of the formula H are as follows: aminothiocarbonyl-0-ethyl-S- (2-methylpropyl) phosphoramidothioate

O-butyl-S- (1-methylpropyl) aminothiocarbonylphsophoramidothioate

N- (N'-allyl, N'-ethyl) aminothiocarbonyl-0-ethyl-S- (1-methylpropyl) phosphoramidothioate

N- (N · -2-ethoxyethyl, N · -hexyl) aminothiocarbonyl-O-ethyl-S- (1-methylpropyl) phosphoramidothioate N-Cyclohexylaminothiocarbonyl-O-ethyl-S-12-methylpropyl) phosphoramidothioate

- 47 -

909838/0653

27G88S3

N- [ΐ · Ι '- (3,5-dichlorophenyl) -N' -2-cyanoethyl / aminothiocarbonyl S, S-dipropyl phosphoramidotliioate

N- [N '-Cyclohexyl-N' - (3-methyl-4-methylthiophenyl) l aminothio carbonyl-O-ethyl-S- (l-methylpropyl) phosphoramidothioate O-ethyl-N-fn '-methyl-N ^l - (4-methylsulfonylphenyl) J aminothiocarbonyl-S- (2-mebhylpropyl) phosphoramidothioate 0-ethyl-iI- (4-methylbenzyl) -S- (l-methylpropyl) -N-phenethylaminothiocarbonylphosphorarnidothioate N -benzylaminothiocarbonyl-O- methylpropyl) -N-phenyl-phosphoramidothioate

O-ethyl S- (2-methylpropyl) -N- (2,3,4,5,6-pentachlorobenzyl) aminothiocarbonyl phosphoramidothioate N- (N *, N'-DibensyDaminothiocarbonyl-O-ethyl-S-i2-methylpropyl ) phosphoramidothioate

O-ethyl S- (1-methylpropyl) -N- (3-pyridylmethyl) aminothiocarbonyl phosphoramidothioate

O-ethyl-S- (1-methylpropyl) -N- [3- (pyridyl) -1-ethyl / aminothiocarboryl phosphoramidothioate

Ν-Γ2- (5-chloropyridyl) | amxnothiocarbonyl-0-ethyl-S- (1-methyl propyl) phosphoramidothioate

N-j_2- (6-chloropyrazinyl) J aminothiocarbonyl-O-ethyl-S-propylphosphoramidothioate

Aminocarbonyl-O-ethyl-S-C2-methylpropyl) phosphoramidothioate O-ethyl-N-methylaminocarbonyl-S-d-methylpropyl) phosphoramidothioate

N-Cyclopentylaxninocarbonyl-O-ethyl-S-d-methylpropyl) phosphoramidothioate

N- | n • - (2-butenyl), N'-phenyl ^ aminocarbonyl-0-methyl-S- (imethylpropyl) phosphoramidothioate

N- [n • -butyl, N '- (3,5-ditrifluoromethylphenyl) J aminocarbonyl-O-ethyl-S-propylphosphoramidothioate

N- [n'-Benzyl, N · - (4-cyano-2-nitrophenyl) J aminocarbonyl-O-ethyl-S- (1-methylpropyl) phosphoramidothioate N- {n · -jl- (3,5-dichloronaphthyl), N'ethy ^ j aminocarbonyl-O-ethyl-S- (2-methylpropyl) phosphoramidothioate

- 48 -

709838/0653

N-Cydohexylaminocarbonyl-N-S, 5-dichlorophenyl-O-ethyl-S-propyl phosphoramidothioate

N-jN '- (3,5-dichlorophenyl), N' - (4-methylphenyl)! aminocarbonyl-O-ethyl-S- ( l-mathylpropyl) phosphoramidothioate O-ethyl-N- (2-hydroxyphenyl) aminocarbonyl-5- (1-mebhylpropyl) -phosphoramidofchioate

O-ethyl N- (2-hydroxymethyl) aminocarbonyl S- (1-inefchylpropyl) phosphoramidothioate

N-Benzylaminocarbonyl-N-cyclohexyl-O-methylethyl-S-C1-methylpropyl) phosphoramido bhioat

N-Benzyl-O-ethyl-S- (2-methylpropyl) -N- (2-phenethyl) aminocarbonyl phosphoramidothioate

N- (N ·, N '-dibensydaminocarbonyl-O-ethyl-S-i 2-methylpropyl) phosphoramidothioate

O-ethyl ~ S- (1-methylpropyl) -N- (2-pyridyl) aminocarbonyl phosphoramidothioate

O-Ethyl S- (2-aethylpropyl) -N- (3-pyridylmethyl) aminocart) onyl phosphoraniidothioate

N- (5-bromo-2-pyrazinyl) arainocarbanyl-0-ethyl-S- (1-methylpropyl ) phosphoramidothioate

O-ethyl-S- (2-methylpropyl) -N-morpholinocarbonyl phosphoramidothioate .

The metal salts and metal salt complexes of the above-mentioned compounds which are acceptable for pharmaceutical purposes are also possible.

The phosphoramidates of the formula H can be prepared by methods which are analogous to the methods used for the preparation of the compounds of the formula D.

One method provides the following reaction:

4 0 X 0 4

1 \ H ν 1 ^{| f! F} / R-NH + ^X P-NCX>RNC-NH-P;

- 49 -

709838/0653

in which R, R, R, R and X have the meanings given in connection with the formula H.

Another method provides the following reaction:

NH

· Cl

Il c

Ii C

⁰ / R ⁴

R

wherein R, R, R, R ", K and X have the meanings given in connection with the formula H, with the exception.

3
that R must not be hydrogen.

A third method provides the following reaction:

⁰ / R ⁴

Il / ^R

NH-P '

R ¹ NCX

R -NH-C-N-P

13 4 5
in which R, R, R, R and X have the meanings given in connection with the formula H.

In Table III below, a number of compounds of the formula H are listed together with illustrative methods of preparation for these compounds, specifically as Examples IH-6H, the letter H being used to denote the compounds prepared according to the examples as well as those in FIG Table III to be assigned to compounds of the formula H summarized.

- 50 -

709838/0653

/ ^ 08863

-ys -

Example IH - Preparation of N-Cyclohexylaminocarbonyl-

0-ethyl-S- (l-tinethylpropyl) phosphoramidothioate (Compound 7H from Table III)

To a solution of 0.99 g (0.01 mol) of cyclohexylamine in 5 ml Glym v / earth 2.23 g (0.01 mole) O-ethyl-S- (1-methylpropyl) -phosphoroisocyanate thioate (exothermic reaction) given. The suspension formed is left at room temperature stand for 1 hour and then pour them into 20 ml of ether. The suspension is filtered in vacuo. Man the filtrate is allowed to stand at room temperature for a period of 18 hours, after which it is placed under nitrogen electricity is concentrated. The semi-solid residue is slurried in 50 ml of hexane, filtered and dried. This gives 0.4 g (12.5%) of the product.

Example 2H - Preparation of N (N ¹ , N '-DibenzyDaminothiocarbonyl-0-ethyl-S- (1-methylpropyl) phosphoramidothioate (Compound HH in Table III)

1.12 g (0.005 mol) of O-ethyl-S- (1-methylpropyl) -phosphoroisocyanate thioate are added to a solution of 0.99 g (0.005 mol) of dibenzylamine in 5 ml of glyme (exothermic reaction) given. The solution is left to stand at room temperature overnight. the fine suspension formed is filtered in vacuo. The piltrate is dissolved in 50 ml of ether, washed with water, dried over magnesium sulfate and under a stream of nitrogen concentrated. This gives 1.5 g (71%) of a colorless oil.

Example 3H - Preparation of N-Benzylaminocarbonyl-O-

ethyl S- (l-methylpropyl) phosphoramidothioate (Compound 13H in Table III)

2.23 g (0.01 mol) of O-ethyl-S- (1-methylpropyl) -phosphoroisocyanate thioate are added to a solution of 1.07 g (0.01 mol) of benzylamine in 5 ml of glyme (exothermic reaction) given. the

709838/0653

- fr *

The resulting suspension is allowed to stand at room temperature for a period of 2 hours, after which it is filtered in vacuo. The filter cake is washed with ether and dried. In this case, 1.5 g (46%) of the product (mp 117-120 ⁰ C). Recrystallization from methylcyclohexane gives 0.7 g (23%) of the product.

Example 4H - Preparation of N- | n'-Benzyl, N '- (3,5-dichlorophenyl Y) -aminocarbonyl-O-ethyl-Si 1-methylpropyl) phosphoramidothioate (Compound 16H of Table III)

To a solution of 1.26 g (0.005 mol) of N-benzyl-3,5-dichloroaniline 1.12 g (0.005 mol) of O-ethyl-S- (1-methylpropyDphosphoroisocyanate thioate are found in 50 ml of glyme) given. The solution is allowed to stand at room temperature for a period of 3 days. The suspension formed is filtered. Of the The filter cake is washed with hexane and dried, 0.3 g (13%) of the product being obtained.

Example 5H - Preparation of O-Ethyl-S- (l-methylpropyl) -N- [2- ( 5-methylpyridyl) ^ laminothiocarbonyl phosphoramidothioate (Compound 17H in Table III)

To a solution of 1.08 g (0.01 mol) of 2-amino-5-methylpyridine in 50 ml of glyme 2.39 g (0.01 mol) of O-ethyl-S- (1-methylpropyl) phosphorus isothiocyanate thioate (exothermic reaction) given. The solution is allowed to stand at room temperature for a period of 2 hours and is poured then in an excess of water. The suspension formed is filtered in vacuo. The filter cake is in 50 ml Slurried hexane. The slurry is filtered in vacuo. The filter cake is dried. One obtains 2.2 g (65%) of the product.

- 52 -

709838/0653

/ 708863

Example 6H - Preparation of O-ethyl-S-propyl-N-pyrar.inylarainothiocarbonyl phosphoramidothioate
(Compound 18H in Table III)

2.25 g (0.01 mol) of O-ethyl-S-propylphosphorisothiocyanate thioate are added to a fine suspension of 0.95 g (0.01 mol) of aminopyrazine in 5 ral acetonitrile. The educated
Solution is allowed to stand at room temperature for a period of 5 days and then poured into excess water. The suspension is filtered in vacuo. Dar
Filter cake is washed with ether and dried. This gives 0.5 g (15%) of the product.

909838/0653

Connection number χ · R

IH

2H OH-3 H 0 CH, 0 Cl

5h 6 η 7H 8 H 9 HS CyClO-C ₆ H _n

TABLE E III

X ~ 0

1 Il! I

R -.Ν — C —NH-P

SC ,, K

V'9

SCl ₊ H ₉

SCi ₁ Kq

»C.

ΙΟ5-ΙΟ7

177-180 decomp.

135.5-138

72-76

oil _

oil

100-104 decs.

83-86 oil

Elemental analysis calculated (found)

3 ^L. 8 ¹ +

37.8
(37.4)

42.6

(41.2)

(42.28)

(43 Λ)

(48 Λ3)

. 6th

^ f. 1)

32.3 ¹ ^ 6.86 (32.80) (6.69)

7-32 (7.13)

7.5 (7.3)

8.2 (8.3)

8.17 (8.08)

8.1 (9.2)

8.56

8.1 (8.5)

1 + 6.98 8Λ (46.13)

Λ3 .04

ι ¹ .03 (10.93)

11.58 (11.66)

11.0 (11.0)

9.9 (9.0)

8.62 (8.97)

10.6 (10.7)

8.76 (8.69)

9Λ (9.6)

7.46 (8.28)

05/12 (08/12)

9.72 (9.91)

9-71 (9.61)

_ OO OO

. Connection γ · ■ number—

1OH

15H
16H

17th

S 0 0 S

₆ K ₅ CH ₂

SC ₆ K ₅ CH ₂

12H SC ₆ H ₅ CH ₂ 13H 0 C ₆ K ₅ CH ₂

C ₆ K ₅ CH ₂ CH ₂

C ₅ H ₅ CK ₂ CH

C ₆ H ₃ CI ₂ -3.5

C ₆ H ₅ CH ₂

C ₆ H ₅ CH ₂

■ Η

H H H

C ₆ H ₅ CH ₂

TABLE III - continued Elemental analysis

⁰ C.

oil

oil

oil

118-120

Mt. 78

59.93 6.95

(58.65) (6.93)

57.77 6.70

(57-53) (6.73)

^ 9.52 6.S7

(^ 8.53) (6.69)

120-122 50.9 ¹ ^ 7.0V

(50.89) (7.02)

öi 50.75 7.15.

(4-9-96) (6.99)

95-9S 52.07 7.27

Decomp. C5i.il) C7.M)

118-120 50.39
(50.53)

6.08 (6.33)

Calculated (found)

(7.17)

7th IO (7.12)

9.Ο3 (8.9 ¹ O

6.66 (6Λ5)

6.52 (6.67)

7.29 (p.02)

3.65 (8Λ8)

7.38 (7.77)

7-96.

07/12 (09/12)

9-53 (9.38)

9. co

5. 17 ' 5. 96 6th 51 (5. 30) (5. 89) (6. 52)

8.83

(P.92)

18th
19th

S 0

R x ¹ , R ² = -4CH ₂ ^ ₅

SC ₃ H ₇

s a sec-butyl ·

t = tert-butyl 106-107
Decomp. .

69-71

37 ^ 9
¹ ^

1 + 6.8

5.35 (5.33)

8.2 (8.5)

17Λ9 (17.31)

9 Ί (9.2)

9.67 (9.66)

Of the means, which compounds of the formula A (incl. the metal salts and the metal salt complexes thereof), anthelmintics should be mentioned, which compounds of the following Formula as well as its pharmaceutically acceptable metal salts and metal salt complexes contain:

SO _D 4

! H H /

_R ^x _{K C N} ρ (J)

^! 2 I ₃ V i

rr r ^{j K} !

wherein R 'a) a (C ^ -C _fi ) -cycloalkyl group, preferably a (Cc-C ₇ ) -cycloalkyl group,

b) an optionally substituted aralkyl group with up to 11 carbon atoms, preferably an optionally substituted benzyl or phenethyl group,

c) an optionally substituted (C, .- C _1Λ ) - aryl group,

d) an optionally substituted 2-pyridyl group, or

e) an optionally substituted pyrazinyl group is

R a) a hydrogen atom,

b) a (C ₁ -C ₁₀ ) -alkyl group, preferably a (C ₁ -C ₆ ) -alkyl group,

c) a (C_-C _fl ) cycloalkyl group, preferably a (C ₅ -C ₇ ) cycloalkyl group,

d) a (Cp-C. _n ) -alkoxyalkyl group, preferably a (C ₂ -Cg) -alkoxyalkyl group,

e) a (Cp-C .-) - alkylthioalkyl group, preferably a (Cp-Cg) -alkylthioalkyl group,

f) a (C ₁ ~ Cg) cyanoalkyl group,

g) a (C ₃ -Cg) -alkenyl group, preferably a (C ^ -C.) - alkenyl group,

h) an optionally substituted aralkyl group with up to 11 carbon atoms, preferably an unsubstituted benzyl or phenethyl group, or

709838/0653

7708863

i) is an optionally substituted ^ ^C a ~ ^c - \ Q ^ ~ aryl group, preferably an unsubstituted phenyl group,

1 2

R and R together with the nitrogen atom with which they

are linked, form a morpholine) - or piperidino group, is optionally _{substituted with up to 2 (C ^ -C 4} ) -alkyl groups, preferably methyl groups, R a) is a hydrogen atom,

b) a (C ₃ -Co) cycloalkyl group, preferably a (C ₅ -C ₇ ) cycloalkyl group,

c) an optionally substituted aralkyl group with up to 11 carbon atoms, preferably an unsubstituted benzyl or unsubstituted phenethyl group, or

d) an optionally substituted (C ^ -C) -aryl group, is preferably an unsubstituted phenyl group,

R a) a (C ^ -C, -) alkoxy group, preferably a (C ₁ -C ₄ ) alkoxy group,

b) a (C ₁ -C ₆ ) haloalkoxy group, preferably a (C ₁ -C ₄ ) haloalkoxy group,

c) a di- (C ₁ -Cg) -alkylamino group, preferably a di- (C ₁ -C ₄ ) -alkylamino group,

d) a (C ₁ -Cg) -alkylthio group, preferably a (C ^ -C ₄ ) -alkylthio group,

e) a phenoxy group, or

f) is a phenylthio group,

R a) a (C _-1 -C -) - alkyl group, preferably a (C ₁ -C ₄ ) -alkyl group,

b) a (C ₁ -Cg) alkoxy group, preferably a (C ₁ -C.) alkoxy group,

c) a (C ₁ -Cg) -haloalkoxy group, preferably a (C ₁ -C ₄ ) -haloalkoxy group,

d) a di- (C ^ -Cg) -alkylamino group, preferably a di- (C ₁ -C ₄ ) -alkylamino group,

e) a (C ₁ -Cg) -alkylthio group, preferably a (C ₁ -C ₄ ) -alkylthio group,

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7708883

V \

f) a phenyl group,

g) a phenoxy group, or

h) denotes a phenylthio group.

2 In the above formula J, R is preferred is a hydrogen atom or a benzyl group and R is preferably a water peat atom.

Preferred compounds of the formula J can be represented by the following formula:

SO.

1 ti (IR ⁴ i

R —II C — NH-P '· (K)

1 ₂ V

R-

wherein R * a) is a (CV-C ₇ ) cycloalkyl group, preferably a cyclohexyl group,

b) a benzyl or phenethyl group,

c) a phenyl, benzyl or phenethyl group, preferably a phenyl group, is substituted with up to 3, preferably with up to 2,

(C.-C.) - alkyl groups, preferably methyl groups, (C ^ -C.) - alkoxy groups, preferably methoxy groups, di- (C _y) -C ₄ ) -alkylamino groups, preferably dimethylamino groups, (C ₁ -C ₄ ) - Hydroxylalkyl group, halogen atoms, preferably chlorine atoms, halomethyl groups, preferably trifluoromethyl groups, hydroxyl groups or cyano groups,

d) a fruorenyl group,

e) a 2-pyridyl group, optionally substituted or with up to 2, preferably 1, (C 1 -C ₄ ) -alkyl groups, preferably methyl groups or halogen atoms, preferably chlorine atoms

f) represents a pyrazinyl group, 2

R is a hydrogen atom or a benzyl group means,

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IS

R a) a (C ^ -C ^) alkoxy group, preferably

an ethoxy group,

b) a (C 1 -C 4 haloalkoxy group, preferably a trichloroethoxy group,

c) a di- (C ^ -C ₄ ) -alkylamino group, preferably a dimethylamino group, or

d) a (C _- JC ₄ ) -alkyl thio group, preferably a propylthio group, and

R a) a (C ^ -C _/ ,) - alkyl group, preferably an ethyl group,

b) a (C ^ -C.) alkoxy group, preferably one Ethoxy group,

c) a (C, - C.) haloalkoxy group, preferably a trichloroethoxy group,

d) a di- (C ₁ -C ₄ ) -alkylamino group, preferably a dimethylamino group, or

e) a (C.-C ^) alkylthio group, preferably represents a (C 1 -C 4) alkylthio group.

Pharmaceutically acceptable metal salts and metal salt complexes of compounds of the formula K are also suitable.

The most preferred compounds of the formula K are those

4 5

mentioned in which R is an ethoxy group and R is an ethoxy group, an isobutylthio group or a sec-butylthio group represents.

In connection with the formula J, when the term "substituted" to modify aralkyl, aryl, pyridyl or pyrazinyl groups are used to mean that such groups have one or more substituents are substituted, which are selected from the following substituents:

(C ₁ -C ₄ ) -alkyl, (C ₁ -C ₄ ) -alkoxy, (C ₁ -C ₄ ) -alkylthio, (C ₁ -C ₄ ) -alkylsulphinyl, (C ₁ -C ₄ ) -alkylsulphonyl, Di- (C ₁ -C ₄ ) -alkylamino, (C ₁ -C ₄ ) -haloalkyl, (C ₁ -C ₄ ) -Hy-

- 59 -709838/0653

27088R3 -

lh

hydroxyalkyl, cyano, nitro, hydroxy and halogen. In the pyridyl and pyrazinyl rings are preferred up to 2 substituents, while in the aralkyl and aryl groups up to 3 substituents are preferred, but up to 2 substituents are even more preferred.

Representative substituents R in the formula J are for example the following:

Cyclopropyl, cyclohexyl, cycloheptyl, phenyl, 3,5-dichlorophenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 2,4-dichlorophenyl, 2,4,6-trichlorophenyl, 2,3,4,5, ß-penta ^ chlorophenyl, 4-bromophenyl, 2-chloro-4-bromophenyl, 4-fluorophenyl, 3,5-ditrifluoromethylphenyl, 2-methylphenyl, 4-methylphenyl, 2,5-dimethylphenyl, 2-chloro-4-methylphenyl, 2,4-dichloro-3,5-dimethylphenyl, 2-ethyl-4-methoxyphenyl, 4-butylphenyl, 4-methyithiophenyl, 3-methylsulfinylphenyl, 4-methylsulfonylphenyl, 5-methoxyphenyl, 2-ethoxyphenyl, 4-dimethylaminophenyl, 4-mitrophenyl, 3-cyanophenyl, benzyl, 3,5-dimethylben3yl, 3,5-D! Hydroxyphenyl, 4-hydroxybutylphenyl, 4-3rom-3,5-dichlorobenzyl, phenethyl, et-methylbenzyl, 4-methylphenethyl, 4-methoxyphenethyl, maphthyl, 4,6-dichloronaphthyl, anthryl, 5,6-dichloroanthryl, phenanthryl, 4-fluorenyl, 4-chloro-9-fluorenyl, 4,5-dimethyl-9-fluorenyl, 2-pyridyl, 2- (5-chloropyridyl), 2- (3,5-dimethylpyridyl), Pyrazinyl, 2- (5-chloropyrazinyl) and 2- (5-methylpyrazinyl).

Representative substituents R in the formula J are, for example, the following:

Hydrogen, methyl, butyl, tert-butyl, nonyl, cyclobutyl, cyclohexyl, 2-ethoxyethyl, 4-butoxybutyl, 2-cyanoethyl, 4-cyanobutyl, 3-ethylthiopropyl, 2-butylthioethyl, allyl, phenyl, 3,5-dichlorophenyl, 2-methylphenyl, 4-cyanophenyl, 4-nitrophenyl, 4-methoxy-2-methylphenyl, benzyl, 3,5-ditrifluoromethylbenzyl _s phenethyl, ° ^ -methylbenzyl, 3-phenylpropyl, 3,5-dichlorophenyl, naphthyl, 4,6-dimethylnaphthyl.

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709838/0653

Representative substituents R in the formula J are for example the following:

Cyclopentyl, cyclohexyl, phenyl, 2-methylphenyl, 3,5-dichlorophenyl, Bensyl, 4-methylbenzyl, phenethyl, naphthyl as well 3-methylnaphthyl.

Representative substituents R in the formula J are for example the following:

Methoxy, ethoxy, sec-butoxy, pentoxy, trichloroethoxy, Chloropropoxy, trifluoroethoxy, dimethylamino, dipropylamino, Methylthio, propylthio, isobutylthio, kexylthio, phenoxy as well as phenylthio.

Representative substituents R in the formula J are for example the following:

Methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, pentyl, Hexyl, ethoxy, propoxy, isopropoxy, butoxy, pentoxy, chlorobutoxy, Trifluoroethoxy, bromopentoxy, dimethylamino, dihexylamino, ethylthio, propylthio, isobutylthio, sec-butylthio, Pentylthio, phenyl, phenoxy and phenylthio.

The following are examples of compounds of the formula J mentioned:

N- (N'-Butyl-N'-cyclohexyl) aminothiocarbonyl-0, O-diethyl phosphoramidate

O, O-D. diethyl piperidinothiocarbonyl phosphoramidate N- (2-Cyanophenyl) aminothiocarbonyl-0,0-diethyl phosphoramidate, N- (N'-3,4-dichlorophenyl-N'-ethoxymethyl) aminothiocarbonyl-O, O-diethyl phosphoramidate

N- (N'-3,5-dichlorophenyl N'-2-ethylthioethyl) aminothiocarbonyl-0 , O-diethyl phosphoramidate

N- (N - (4-cyanoethyl) -N '- (3,5-dichlorophenyl)] aminothiocarbonyl-O, O-diethyl phosphoramidate

N-Benzyl-N- (3,5-dichlorophenyl) aminothiocarbonyl-0, O-diethyl phosphoramidate

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r / 08063

O, O-dibutyl-N- (N'-2,4-dichlorophenyl-M-phenyl) aminothiocar-

bonyl phosphoramidate

0, O-diethyl-N- (2-naphthyl) aminothiocarbonyl phosphoramidate

N-Benzylaminothiocarbonyl-O-ethyl-O-propyl phosphoramidate

N- (N ', N'-DibensylJaminothiocarbonyl-OjO-diethyl phosphoramidate O, O-dimethyl-N- (3-phenylpropyl) aminothiocarbonylphosphorate iidate N- (3, S-dichlorophenylJaminothiocarbonyl-OjO-diphenylphosphor-

amidate

O-ethyl N- (4-hydroxybutyl) aminothiocarbonyl S- (1-methylpropyl phosphoramidothioate

N- (3,5-Ditrifluoromethylphenyl) aminothiocarbonyl-0-ethyl-O-phenylphosphoramidate

O, O-diethyl-N- (2-fliaorenyl) aminothiocarbonyl phosphoramidate O, O-diethyl-N- <3,5-dimethyl-2-pyridyl) aminothiocarbonyl phosphoramidate

N- (4-chloro-2-pyridyl) aminothiocarbonyl-0, O-diethyl phosphoramidate

0, O-diethyl-N- (5-ethyl-2-pyridyl) aminothiocarbonyl phosphoramidate

N-Cyclohexylaminothiocarbonyl-O-ethyl-S-12-methylpropyl) phosphoramidothioate

O-ethyl S- (2-methylpropyl) -N-morpholinothiocarbonyl phosphoramidothioate

N-Benzylaminothioxarbonyl-S, S-dipropylphosphoramidodithioate N- (4-Cyanobenzyl) aminothiocarbonyl-0, S-diethyl phosphoramidothioate

O-ethyl-S- (2-methylpropyl) -N-phenethylaminothiocarbonyl phosphoramidothioate

N- (3,5-Ditrifluoromethylphenyl) aminothiocarbonyl-0-ethyl -.-S- (2-methylpropyl) phosphoramidothioate

S-butyl N- (4-methoxyphenyl) aminothiocarbonyl S-propyl phosphoramidodithioate

N- (4-Ethylsulfonylphenyl) aminothiocarbonyl-0-ethyl-S-methylethylphosphoramidothioate

N-Q ^ '- (4-Dimethylaminophenyl) -N' -methyl] aminothiocarbonyl-O-ethyl-N-methyl-S-pentylphosphoramidothioate

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709838/0653

; ■ ν ο 8 η s

N- [ν '- (3, 5-dichlorophenyl) -N' ~ (4 ~ me!: Hylphenyl) J aminothiocarbonyl -O-ethyl-S-propyl phosphoramidothioate S- (1-methylpropyl) -M- (4-nitrophenyl) aminothiocarbonyl O-phenyl phosphoramidothioate

O-ethyl-N-i 3-methyl-4-methylthiophenyl) aminothiocarbonyl-S-propyl phosphoramidothioate

O-ethyl-S- (2-methylpropyl) -N- (2-pyridyl) aminothiocarbonylphosphoratenidothioa t

N- (2,4-dichlorophenyl) aminothiocarbonyl-0, S-diethyl phosphoramidothioate

N- (2,4-dichlorophenyl) aminothiocarbonyl-O-ethyl-S-methylethylphosphoramidothioate

S-Butyl-Nii- (3, 5-DichlorophGnyl) aminothiocarbonyl ~ 0-ynethylphosphoramidobhioate

N- (3-Broni-5-chlorophenyl) aminothiocarbonyl-0-ethyl-S- (2-raethylpropyl) phosphoramidothioate

O-ethyl-N- (4-fluorophenyl) aminothiocarbonyl-N- (4-methoxyphenethyl) -S- (1-methylpropyl) phosphorarnidothioate N- (2,5-dichlorophenyl) aminothiocarbonyl-O-ethyl-S-C1-methylpropyl ) phosphoramidothioate

N- (3,5-dichlorophenyl) aminothiocarbonyl-N'-dimethyl-0-propylphosphorodiamidate

Ethyl O-ethyl-N- (4-methylphenyl) aminothiocarbonylphosphonamidate

N- (4-chlorophenyl) aminothiocarbonyl-S, S-dipropyl phosphoramidodithioate

S, S-bis (1-methylpropyl) -N-phenethylaminothiocarbonyl phosphoramidothioate

S- (1-methylpropyl) -O-propyl-N- (3,5-bis-trifluoromethylphenyl) -aminothiocarbonyl phosphoramidothioate N- (2,4-Dimethylphenyl) aminothiocarbonyl-O-ethyl-S- (1-methylpropyl ) phosphoramidothioate

O-Ethyl-M-CS-methoxyphenyDaminothiocarbonyl-S-pentylphosphoramidothioate

N- (4-diethylaminophenyl) aminothiocarbonyl-0-ethyl-S- (lraefchylpropyl) phosphoramidothioate

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709838/0653

S- (1-Iiethylpropyl) -O-propyl-N-pyra ^ inylaminothiocarbonyl-

phosphoramidothioate N- (4-chlorophenyl) aminotliiocarbonyl-0-ethyl-3-phenylphosphoramidothioate

O-ethyl-M- (N'-4-fluorenyl) aminothiocarbonyl-S- (2-methyl-

propyl) phosphoramidothioate

N- {n '- [9- (3, 6-dichlorofluorenyl) J aminothiocarbonylj -O-ethyl-

S- (1-methylpropylphosphoramidothioate

N- (2-Anthryl) aminothiocarbonyl-O-ethyl-S-n-propyl-phosphorus-

amidothioafc

N- [1- (3-methylanthryl) aminothiocarbonyl] -O-ethyl-S- (1-methylpropyDphosphoramidothioate.

The pharmaceutically acceptable metal salts and metal complexes of the compounds given above also come in question.

Compounds of the formula J can be prepared by methods which are analogous to the methods used to prepare them of the compounds of the formula D have been given.

One method is to do the following:

'40

R ¹ NH + 'P NCS

n ⁵ /

S Ο

₁ II II / ^R

R- ¹ _N c NH P ^;

wherein R, R, R and R have the meanings given in connection with the formula J.

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709838/0653

7.708G63

Another method is to do the following:

^S ° R ⁴

R ¹ - NH + Cl - C - N - P, ± i

R ² Yes « ⁵ ^^

S 0 _n 4 1 Π H /

R ^x _{N C N} p /

I ₂ I ₃ V

where R, R, R, T? and R those related to the Formula J have given meanings, with the expression

3
assume that R cannot be a hydrogen atom.

A third method consists in the following reaction: O 4

NII P _n ^ + R ^- TICS) ■

R ^{3 rS}

S 0 _4

R NH C N P ^ j

V!

13 4 5
wherein R, R, R and R are those in connection with the formula J

have given meanings.

In Table IV below, there are a number of compounds of Formula J along with illustrative methods of preparation for some of them Compounds summarized as examples IJ to 20J. Of the The letter J is used to denote the compounds that are prepared according to the examples, as well as the compounds which are summarized in Table IV, to be assigned to the formula J.

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Sl

Example IJ - Preparation of 0,0-Diethyl-N- (4-nitrophenyi) ~ aminothiocarbonyl phosphoramidate (Compound 3J of Table IV)

To a solution of 3.46 g (0.025 mol) of 4-mitroaniline in 50 ml of Glyni are 4.87 g (0.025 mol) of 0,0-diethylphosphorisothiocyanatoab given. The solution is left to stand at room temperature for a period of 18 hours, whereupon it is refluxed for a period of 3 hours. The product falls out of the glyme solution in an amount of 1.5g (18%).

Example 2J - Preparation of O, O-diethyl-N- (3,5-bis-trifluoromethylphenyl) aminothiocarbonyl phosphoramidate (Compound 4J in Table IV)

To a solution of 8.23 g (0.0359 mol) of 3,5-bis-trifluoromethylaniline 7 g (0.0359 mol) of 0,0-diethylphosphoroisothiocyanatoate are contained in 100 ml of glyme given. The solution is left at room temperature for a period of 24 hours Stand for hours, after which it is concentrated in vacuo. The precipitate is crystallized from hexane and from methylcyclohexane recrystallized. The product yield is 10 g (67X).

Example 3J - Preparation of M- (3,5-dichlorophenyl) aminothiocarbonyl-OjO-diethylphosphoramidate (Compound 5J in Table IV)

To a solution of 5.98 g (0.0359 mol) of 3,5-dichloroaniline 7 g (0.0359 mol) of 0,0-diethylphosphoroisothiocyanatoate are contained in 100 ml of glyme given. The solution is left to stand at room temperature for a period of 24 hours, whereupon it is concentrated in vacuo. The precipitate is recrystallized from methylcyclohexane. 8.5 g are obtained (56%) of the product.

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_ 27088S3

Example 4J - Preparation of N- (3,5-dichlorophenyl) arcinothiocarbonyl-O-ethyi-S-methylphosphoramidothioate (Compound 6J in Table IV)

To a solution of 1.62 g (0.01 Hol) 3,5-Dichlorani.lin in 5 ml of glyme 1.97 g (0.01 mol) of O-ethyl-S-methylphosphoroisothiocyanate thioate earths given. The reaction solution is left at room temperature for a period of 13 months Stand for hours. The product is obtained in the manner that the reaction solution is poured into excess water, whereupon the precipitate is isolated by vacuum filtration. The product yield is 2.55 g (71%).

Example 5J - Preparation of H- (3,5-dichlorophenyl) aminoth.iocarbonyl-0, S-diethylphosphoramido thioate (Compound 7J in Table XV)

To a solution of 1.92 g (0.0018 mol) of 3,5-dichloroaniline in 7 ml glyme v / earth 2.5 g (0.0118 hol) OjS diethylphosphoricothiocyanate thioate given. The product is obtained in such a way that the reaction solution is dissolved in an excess of water is poured, whereupon the suspension formed is filtered and the isolated precipitate is recrystallized from methylcyclohexane will. The product yield is 1.2 g (27.3%).

Example 6J - Preparation of N- (3,5-dichlorophenyl) aminothiocarbonyl-O-ethyl-S-propylphosphoramidothioate (Compound 8J in Table IV)

To a solution of 1.62 g (0.01 mol) of 3,5-dichloroaniline in 5 ml of glyme 2.25 g (0.01 KoI) of O-ethyl-S-propylphosphoroisothiocyanate thioate are added given. The product is obtained in such a way that the reaction solution is in excess V / water is poured, whereupon the suspension formed is vacuum filtered and the isolated precipitate from methylcyclohexane is recrystallized. The product yield is 1.8 g (47.5%).

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Example 7J - Preparation of M- (3,5-dichlorophenyl) aminothiocarbonyl-O-ethyl-S-methylethylphosphoramidothioate (Compound 10J in Table IV)

To a solution of 2.88 g (0.0178 hol) of 3,5-dichloroaniline in 5 ml of glyme v / earth 0.4 g (0.0178 mol) of 0-ethyl-S-methylethylphosphorisothiocyanate thioate was added. The solution is heated to reflux and allowed to stand at room temperature for a period of 2 hours. The suspension formed is vacuum filtered, before the filter cake is washed with 10 ml of glyme and 20 ml of ether and dried. This gives 2 g (29%) of the product.

Example 8J - Preparation of N- (3,5-dichlorophenyl) aminothiocarbonyl-0-ethyl-S- (2-methylpropyl) -phosphoramidothioate (Connection 13J in Table IV)

To a solution of 1.62 g (0.01 mol) of 3,5-dichloroaniline in 5 ml of glyme become 2.39 g (0.01 mol) of O-ethyl-S- (2-methylpropyl) phosphorisothiocyanate thioate given. The solution is heated to reflux and at room temperature for a Allowed to stand for 3 days. The solution is poured into excess water and the semi-solid precipitate formed is isolated. The product comes in 50 ml Slurried hexane and vacuum filtered. The filter cake is dried. This gives 1.8 g (45%) of the product.

Example 9J - Preparation of N- (3,5-dichlorophenyl) aminothiocarbonyl-0-ethyl-S- (1-methylpropyl) -phosphoramidothioate (Compound 14J in Table IV)

To a solution of 3.24 g (0.02 mol) of 3,5-dichloroaniline in 15 ml of glyme are 4.8 g (0.02 mol) of O-ethyl-S- (1-methylpropyl ) phosphorisothiocyanate thioate given. The solution is left at room temperature for a period of 18 months Stand for hours and then pour them into excess water.

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it

The semisolid precipitate formed is isolated and slurried in 50 ml of hexane. "The hexane slurry is filtered. This gives 3.25 g (40.5%) of the product with a melting point of 123-125 ° C. The product is made from ethylcyclohexane recrystallized. This gives 2.5 g (31%) of the product.

Example 1OJ - Preparation of O-ethyl-N- (4-methylphenyl) -aminothiocarbonyl-S- (l-methylpropyl) phosphoramidothioate (compound 18J in Table IV)

To a solution of 1.07 g (0.01 Hol) 4-methylaniline in 5 ml of glyme are 2.39 g (0.01 mol) of O-ethyl-S- (1-methylpropyl ) Phosphorus isothiocyanate thioate (exothermic reaction) given. The solution is left at room temperature for a period of time stand for 6 days and then pour them into an excess (300 ml) of water. The suspension formed is im Vacuum filtered, whereupon the filter cake is slurried in 50 ml of hexane, filtered and dried. Receives 1.6 g (47%) of the product.

Example IU - Preparation of 0-Ethyl-N- (4-methoxyphenyl) -aminothiocarbonyl-S- (1-methylpropyl) - phosphoramidothioate (Compound 19J in Table IV)

To a solution of 1.23 g (0.01 mol) of 4-methoxyaniline in 5 ml Glym are 2.39 g (0.01 mol) of O-ethyl-S- (1-methylpropyl) phosphorisothiocyanate thioate (exothermic reaction) given. The solution is left at room temperature for a period of time Stand for 18 hours and then pour them into excess water. The suspension formed is in vacuo filtered, whereupon the filter cake slurried in 100 ml of hexane, is filtered and dried. This gives 2.4 g (66.5%) of the product.

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Example 12J - Preparation of N- (4-Dimethylaminophenyl) -

aminothiocarbonyl-O-ethyl-S-C1-methylpropyl) phosphoramidothioate (compound 2OJ in Table IV)

To a solution of 1.36 g (0.01 mol) of N, M-dimethyl-4-phenylenediamine in 5 ml of glyme, 2.3 g (0.01 mol) of O-ethyl-S- (1-methylpropyl) phosphorus isothiocyanate thioate (exothermic reaction) given. The solution is left at room temperature stand for 24 hours and then pour them into excess water. The black tarry one Precipitate is slurried in Kexan and then vacuum filtered. The filter cake is slurried again in 15 ml of ethyl acetate, vacuum filtered and dried, whereby one 0.9g (24.6%) of the product is obtained.

Example 13J - Preparation of N- (3,5-dichlorophenyl) aminothiocarbonyl-O, O-bis- (2-tricblorafchyl) phos- phoramidate (compound 22J in Table IV)

To a solution of 32.4 g (0.02 mol) of 3,5-dichloroaniline in 10 ml glyme v / earth 8 g (0.02 mol) O, O-bis- (2-trichloroethyD-phosphorisothiocyanatoate given. The product is obtained in such a way that the reaction solution is in excess Water is poured, whereupon the suspension formed is vacuum filtered and the isolated precipitate is recrystallized from isopropanol will. The product yield is 0.5 g (4.5%),

Example 14J - Preparation of N- (3,5 ~ dichlorophenyl) aminothiocarbonyl-N ', N "- (bis-dimethyl) phosphorus triamidate (Compound 23J in Table IV)

To a solution of 3.24 g (0.02 mol) of 3,5-dichloroaniline in 10 ml of glyme are 3.86 g (0.02 mol) of Ν, Ν-bis-dimethylphosphorus isothiocyanate given. The desired product precipitates from the glyme solution and is isolated by vacuum filtration. This gives 3.2 g (45.6%) of the product.

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_ / 708863

Example 15J - Preparation of N- (3,5-DichlorophGnyl) aminothiocarbonyl-N'-dimethyl-O-ethylphosphorodiamidate (Compound 24J in Table IV)

To 1.62 g (0.01 mol) of 3,5-dichloroaniline in 10 ml of Glym v / ground 1.94 g (0.01 mol) of N-dimethyl-O-ethylphosphorus isothiocyanate given. The glyme solution is allowed to stand at room temperature for a period of 4 days, after which time the product has precipitated out of solution and is isolated by vacuum filtration. Dabai you get 1.5 g (43%) of the product.

Example 16J - Preparation of O, O-Diethyl-N- (2-pyridyl) -aminothiocarbonyl phosphoramidate (Compound 31 J in Table IV)

To 1.88 g (0.02 mol) of a solution of 2-aminopyridine in 8 ml of glyme, 3.9 g (0.02 mol) of 0,0-diethylphosphoroisothiocyanatoate are added given. The reaction solution is left at room temperature for a period of 1 hour stand. The product is obtained in such a way that the reaction solution is poured into an excess of water, whereupon the precipitate is isolated by vacuum filtration. The product yield is 2.9 g (50%).

Example 17J - Preparation of O, O-Diethyl-N- [2- (5-methylpyridyl ) J aminothiocarbonyl phosphoramidate (Compound 32 J in Table IV)

To a solution of 2.16 g (0.02 mol) of 2-amino-5-methylpyridine in 8 ml of glyme 3.9 g (0.02 mol) of 0,0-diethylphosphoroisothiocyanatoate are added given. The reaction solution is left at room temperature for a period of Stand for 1 hour. The product is obtained in such a way that the reaction solution is poured into an excess of water whereupon the precipitate is isolated by vacuum filtration will. The product yield is 3.6 g (60%).

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ft

Example 1OJ - Preparation of O-Ethyl-S- (1-methylpropyl) -N- [2- (5-methylpyridyl Y \ aminothiocarbonyl phosphoramidothioate (Compound 35J in Table IV)

To a solution of 1.03 g (0.01 mol) of 2-amino-5-methylpyridine in 5 ml Glym v / earth 2.39 g (0.01 mol) O-ethyl-S- (1-methylpropyl) phosphorisothiocyanate thioate (exothermic reaction) given. The solution is allowed to stand at room temperature for a period of 2 hours and is given then into an excess of water. The suspension formed is vacuum filtered, followed by the filter cake in 50 ml of hexane is slurried. The slurry is vacuum filtered and the filter cake dried. This gives 2.2 g (65%) of the product.

Example 19J - Preparation of N- [2- (5-chloropyridyl)]] aminothiocarbonyl-0 , O-diethyl phosphoramidate (compound 36J in Table IV)

To a solution of 2.57 g (0.02 mol) of 2-amino-5-chloropyridine in 8 ml of glyme v / earth 3.9 g (0.02 mol) of 0,0-diethylphosphoroisothiocyanatoate given. The reaction solution is allowed to stand at room temperature for a period of 18 hours. The product is obtained by pouring the reaction solution into an excess of water, whereupon the precipitate is isolated by vacuum filtration. the Product yield is 3.56 g (55.5%).

Example 20J - Preparation of O-Ethyl-S-propyl-N-pyrazinyl-

aminothiocarbonyl phosphoramidothioate (Compound 39 J in Table IV)

2.25 g (0.01 mol) of O-ethyl-S-propylphosphoroisothiocyanate thioate are added to a fine suspension of 0.95 g (0.01 mol) of aminopyrazine in 5 ml of acetonitrile given. The resulting solution is left at room temperature for a period of 5 Stand for days and then pour them into excess water.

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The suspension is vacuum filtered, whereupon the filter cake washed with ether and dried. This gives 0.5 g (15%) of the product.

709838/0653

Connection number

IJ

1 R · ■

R ¹ - TABLE IV Y. 4
/ ι?. ·
-P ^
V ύ: S.
Il
-Ν — C-KH- F. ⁰ C. a! OC ₂ HY ι 109-110 H OC ₂ H ₅

Elemental analysis Calculated (found)

5.9 ¹ + 9.72 (9 5δ)

CD IF CO CO

CT) CTl CJ

2Y 3Y 4Y 5Y 6Y • 7Y 8Y

0 0 0

0 0

C _Α Hi. NO ₀ - ^

-H ₃ (CF ₃ _) ₂ -3.5 H; K, Cl ₉ -3.5 K

OC ₂ H ₅

OC ₂ H ₅

OC ₂ H ₅

OC ₂ H ₅

H ₃ Cl ₂ -3.5 H OC ₂ H ₅

K ₃ c; ₂ -3.5 η Oc ₂ H ₅

OC ₂ H ₅ 1U0-1V2

^c 6 ^H 3 ^cl 2-3 ₅ 5 η OC ₂ H ₅ 'SCII3

151-153 139-1 ^ 0 I28-I3O

138-1 ^ 0 2 s.

133-135

SCK "n 122-

^ 5.67
^ 5.99:

39.6 '+

5.12 13.20 9-oü

(5.16) (13 mi, (9.88)

^ .3U 12.61 9.29

(^ 7.2) (12.5O) (9.O3)

36.80 .3.56 6.60

(37.07) (3.53) (6.53) -

36.99 ± .2k 7. ^

(37.19) ( ^L .O9) (7.01)

33.65 '3.7V 7.73. 8.62

(33Λ3) (3.65) (7.8O) (p.62)

35.67 & 11 7.5s 0.03

(35-39) C ¹ * .05) (7.51; (p.30)

10.

(10.2

37.13
(37.21)

7o3 (7.23)

OO OO • CD

Connection · ' Nu m mer Σ ώ—

TABLE 'IV - continued

² -Elemental Analysis p. tartar Vm α Ι- (

5s «

/ I? O

9Y O 1OJ 0

IU °

0 0

12y

13Y
14y

15Y 0

16Y 0

17Y 0

18 J- O

19Y 0

-S, 5

C ₆ HCCF ₃ ) ₂ -3.5H

₆ H ₃ Cl ₂ -3.5

C ₆ H ₃ Cl ₂ -3.5 H.

OC ₂ H ₅

OC ₂ H ₅ OC ₂ K ₅

H. OC ₂ H ₅

C ₆ H ₁₊ CH ₃ - ^ H OC ₂ H ₅

C ₆ H ₁₊ OCH ₃ -H. H OC ₂ H ₅

SCJL iso 3

OC ₂ H ₅ SC ₃ H ₇ ISO

SC ^ H ₀ iso

OC ₂ H- · SCrH ₀ SSS.

OC ₂ H ₅ SC ₁₊ H ₉ SeC.

99-101 ^ ₂₆ -)

37.35 (37.21)

37.00 (37.00)

3P.61 (33.90)

38.90 (38.90)

39.02 (3 ^ .90)

127-128

93-96

108-111

126-128

83-85

S2-8H-

122.5-I23.5

73-80
Decomp.

80-83
Decomp.

5.93 (6.03)

3.86 (i-78)

H. Bk (^ .77)

1 + .70 C ^ .77)

^ .87 (^ .77)

5-59 (5. 50)

38.99 (38.90)

38.16. (38 Λ6)

i + S. ^ 2 . 53)

8.3h 9.9V- _19i

(5.80) (9-73) (20.

7.10 7.93 -

(7.23) (8.00) -

6.00 6.7h- I ¹ +,

(6.Ih-) (6.82) (IW-.

6.88

(6.93) -

6.8 ^ 7.70 -

(6.93) (7.72) -

7.08

(6.93) -

.7Λ3. P.35 -

6.75 7-79 (6.93) (7.72) -

^ 6.00 (^ 6.39)

H-.15 5.92 6.5h -

(^ .09) (5.96) (6.61) -

6.66 7.96 9.12 -

(6.69) (έ.09) (3.9-) -

6.23 7- ¹ H 8Λ6 -

(6Λ0) (7.73) (8.55) -.

TABLE TV - Continuation

V erb in - elemental analysis ■ - ■ "

j _Iinfl - .. ο 'λ c Berec HNET (Found)

Y. R ¹ '.. έ. R ⁴ R · ⁵ -. F. «Ο. Ic £ h ^ -

22y 0 O OD 00 23Y O· 00 • * · »
O 24Y 0 OO cn ω -

2OJ 0 C, H, N (CH -) -! + H OC ₂ H ₅ SChHgSeC 99-103 W8.C0 7.15 11.20 8.23 -

21J 0 C ₆ H, Clp-3,5 H OC ₂ K. SC-H ₁₁ H 191-5- ¹ ^ O.3 ¹ + ^ .92 6.52 7Λ2 -

• ^ ^ ⁵ 19 ^ dec. (^ 0Λ8) (5..10) (6.75) (7 ^ 6) -

Oil 3 ^ .35 ^ .18 - 7-26 -

(33.93) (3-88) - (7.96) -

H N (CH) N (CH) lVi.5-37Λ2 Jf.72 15.73 * 8.67 - ^,

5 (37.19) (if.83L) (15.77) (8.72) - '

C, H, Cl ₅ -3.5 H. OC ₂ H. N (CH.) _? 1 ^ 3-1 ^ 7 37-2 ^ ^ .51 11-96 8.86 -

^{ό ά ?} . . (37.09) (^ .53) (11th SO) (p.70) -

25Y 0 ^ ¹ * 5 ¹ 2- 3, 26Y 0 I ₅ C H ₂ - 27Y 0 ^C 6> H ₂ C H ₂

H SC, H ₇ n SC.H ₇ n -89-91 37-21 ^ .62 6.60 7Λ2 -

^J '■ ^J ' decomp. (37Λ1) (it. 59) (6.71) (7Λ2) - _iNJ

H OC ₉ H, - SC _u H _o sec _ö ■ '^ 9-52 6.87 7.29 9-03 - ο

* '' ^{y 01} . (W.53) (6.69) (8.02) (3.9 ¹ ^) 00

H OCpH ₁ - SC ^ H ₀ SeC oil 50.75 7.15 7.38 -. - cn

⁰ '' (^ 9.96) (6.99) (7.77) - - °°

Connect Y.. • ^C 6 ^K 11 ^ ^£ · - TABLE IV 2 OC ₂ H ₅ - Continuation F. ⁰ C. manure .. .0.;. C ₆ HjCH ₂ ' OC ₂ H ₅ 5 oil number 0 6 ρ 2 0. H. OC ₂ H ₅ IO3-IO5
Zers, . 28Y. 0 C ₆ H ₅ CH ₂ 103-106 29Y C ₆ H ₅ CH ₂ OC ₂ H ₅ OC ₂ K ₅ Decomp. * 3OJ 0 ^CH> a OC ₂ HY 137-2A0 0 ' H 3 U ^CH 3'Y ^ H OC ₂ HY OC ₂ H ₅ 7098 32J 0 OC ₂ H ₅ 118-120 H co 33J Cl SC), HoSec O OC ₂ H ₅ 0 OC ₂ H ₅ 122-125
Decomp. do 0 H OC ₂ H ₅ 175-176 34J 0 · Cr H OC ₂ H ₅ OC ₂ K ₅ 133-135 35Y 0 H. OC ₂ K ₅ . 106-107
Decomp. 36 y H DP w 37J SC ₃ H ₇ -,

Elemental analysis calculated (found)

^ 6.98 8Λ3 7Λ6

(W6.13) (8.O »+) (8.23)

58.37 6.22 7.06 '

(5δ.1 ^) (6Λ2) (7.1 ^)

7.77 (7.89)

57.77 6.70 6Λ2 7.10

C57.53X6.73) (6.67) (7.12)

^ 1.70 5-62 1 ^ .58 10.51

^ S) C ^ .53) (10.71)

^ ■ 3.96 6.12 13. S 5 10.31 ^ 56) (5.93) (13.S5) (10.21)

UU.78 6.03 12.07 3.83 (UU.9U) (6.38) (12.09) (8.92)

37.31 +.55 I3.23 9.36 (37.1O) (U.67) (12.9Ö) (9O7)

57.56 5-53 7.38 δ.30 8.55

(57.U3) (5.62) (7.UU) (8.23) (3.52)

58.33 5-67 7.Uo

(57.U3) (5.62) (7.Vm)

1-7.U9 5.35 Γ7Λ9 9.67 (37.WC5.37) (17.31) (9-66

7th 72 - NJ (3. 23) _ - ^ J CD CO q. 67 - CO

Connection number

st

TABLE rv - "continued

. ⁰ C

Elemental analysis
Calculated (found)

38J 0 'C _0. \ 0H-2

^ 3Λ1 5.63 9.21 10.IS

(^ 3.16) (5.62) (9.36) (9.85)

39Y

OC ₂ HY

^OC 2 ^H

101-10 ¹ - * ^ 5.27 6.02 8.80 9.73 (-5.33) (6.10) (p.9S) (9.69)

σ> cn u>

OD CO CO

The compounds of the formulas B, D, F and H and their metal salts and metal salt complexes (summarized below known as pesticide phosphoramidates) are suitable for the protection of plants and animals, including Humans, against the influences of harmful and annoying vermin. The compounds of formula D are especially against nematodes and arthropods in different Stages of development effective. Some compounds of the formula D can be used as anthelmintics. the Compounds of formula F can be used as arthropodicides will. Some of these compounds can be used as nematocides as well as anthelmintics. The connections can be used as arthropodicides and / or anthelmintics, in particular as nematocides.

As arthropodicides, the pesticidal phosphoramidates are particularly effective against members of the arachnoid class, which includes the genus Acarina, such as bugs and ticks, as well as the class of Insecta, such as the Insects. Of the arthropods and nematodes that can be effectively controlled by the pesticidal phosphoramidates, are chewing insects, for example the cotton caterpillar (Spodoptera eridania), the sucking insects, for example the green peach aphid (Myzus persicae), the terrestrial insects, for example the corn rootworm (Diabrotica undecimpunctata howardi), houseflies and mites, for example the double-spotted leaf spider mite (Tetranychus urticae) and the southern root-knot nematode (Meloidogyne incognita).

In general, a control is carried out by applying the pesticidal vermin in phosphoramidates'

in pesticidally effective amounts (e.g. arthropodicidally or nematodicidally effective amounts) either directly on the vermin to be controlled or on the

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Bodies facing an attack by such a thing Vermin are to be protected. For example, wood, fibers, fodder, forests and ornamental plants or stored Products represent places to be protected. Treatment of pets, people and their immediate surroundings with the phosphoramidates is used in a similar way to protect against various annoying ectoparasitic or endoparasitic acarina (acari) and insects carried out. Pesticide phosphoramidates are used as essential active ingredients used by pesticidal agents used for agricultural and sanitary purposes.

The term "control" is to be understood as any method by which the existence or growth is disadvantageous the living organisms in question is affected. Such methods can turn out to be completely killing Effect, an eradication, a sustained growth, a rejection, an inhibition, a degradation the number or any combination thereof.

For use as pesticides, the pesticidal phosphoramidates can be used as solutions, suspensions or mixtures be used in organic solvents or formulations. For example, they can be used as a wettable powder, Emulsifiable concentrates, dusts, granular formulations or flowable emulsifiable concentrates can be formulated. In such formulations, the pesticidal phosphoramidates can be used at a concentration of from about 0.00001 to about 99% and preferably at a concentration of about 1 to about 95% by weight. you will be diluted with an agriculturally acceptable liquid or solid carrier. Possibly suitable surfactants can be incorporated. Surfactants as used in conventional

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Wise used can be found in the publication of John VI. McCutcheon, Inc. "Detergents and Emulsifiers Annual ".

"Agricultural carrier" is to be understood as meaning any substance which is used for this purpose can dissolve, dispose or distribute the concentrated pesticide phosphoramidate in the agent without doing so the effectiveness of the toxic agent is lost, with no permanent damage to the environment, for example the soil, the devices used and useful plants.

The pesticide phosphoramidate can with a finely divided solid carrier, for example with a clay, an inorganic Silicate, a carbonate or with a silica, mixed or incorporated in such a material will.

Organic carriers can also be used. Usually dust concentrates are made in which the pesticides Phosphoramidates are present in an amount of from about 20 to about 80 percent by weight. For the end uses these concentrates are normally diluted with an additional solid to achieve an active ingredient content of 1 to to set about 20% by weight. Granular formulations can be made using a granular or pelletized Produce carrier, for example using granular clays, vermiculite, activated charcoal or corn waste. They can contain the active ingredient in an amount of approximately 1 to 25% by weight.

Wettable powder formulations are prepared in such a way that the pesticidal phosphoramidates in an inert finely divided solid carrier together with an interfacial

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active agents are mixed, consisting of one or more emulsifying, wetting, dispersing or spreading agents Means or a mixture of such means may consist. The pesticidal phosphoramidates are usually in an amount of from about 10 to about 80% by weight and the surfactants in an amount of about 0.5 up to about 10% by weight. Conventionally used emulsifying and wetting agents are, for example, polyoxyethylated Derivatives of alkylphenols, fatty alcohols, fatty acids, Alkylamines, alkylarenesulfonates and dialkylsulfosuccinates. . Spreading agents are, for example, glycerine, mannitan laurate or a condensate of a polyglycerine and Oleic acid modified with phthalic anhydride. Dispersants are for example the sodium salt of the copolymer from maleic anhydride and an olefin, such as diisobutylene, sodium lignin sulfonate and sodium formaldehyde naphthalene sulfonate.

A convenient method of making a solid formulation is to apply the pesticide phosphoramidate to the impregnate solid carrier with a volatile solvent such as acetone In this way, auxiliaries, such as activators, adhesives, plant nutrients, synergistic agents, and various surfactants Mix in funds as well.

Emulsifiable concentrate formulations are produced in the orphan that the pesticidal phosphoramidates in one organic solvents acceptable for agricultural purposes are dissolved, after which a solvent- soluble emulsifier is added. Suitable solvents are usually immiscible with water. Mentioned let the hydrocarbon, chlorinated hydrocarbon, ketone, Ester, alcohol and amide classes of organic solvents. Solvent mixtures can also generally

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mine to be used. The surfactants useful as emulsifying agents can range from about 0.5 to represent approximately 10% by weight of the emulsifiable concentrates. They can be anionic, cationic or non-ionic. The concentration of the active ingredients can range from about 10 to about 80%, and preferably from about 25 to about 50% by weight.

When used as a pesticidal agent, the pesticidal Phosphoraiaidate should in a manner known per se in a Amount applied sufficient to develop the desired pesticidal activity. In certain cases However, it can be expedient and advantageous to apply the pesticide phosphoramidate: directly to the to be protected or from to apply the vermin to be freed without a to use substantial inertia. This is a particularly effective method if the physical nature the active ingredient is such that a "low volume" application is possible, d. H. that the compounds are in liquid form or very well in higher-boiling solvents are soluble.

The amount applied depends, of course, on various factors, for example the purpose of application and the one used pesticides phosphoramidate, the frequency of application and the type and spread of the substance to be controlled Vermin.

Many of the formulations given above can be used on animals to control parasites.

When used as an arthropodicide, for example Acaricide and Insecticide, can be diluted sprays in concentrations from about 4.5 g to about 9.0 kg (0.01 to 20 pounds) of the material per 380th liter of spray liquid

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upset. Usually an amount of from about 45 grams to about 2.25 kg per 380 liters (0.1 to 5 pounds per 100 gallons) is applied. In more concentrated sprays, the content of the material is increased by a factor of 2 to 40. When using dilute sprays, applications are usually made until runoff is detected from the plants, while in the case of more concentrated or lower volume sprays, the materials are applied in the form of mist.

In the case of use as soil insecticides or as nematocides, the pesticidal phosphoramidates can be used in liquid Form, but they are preferably applied in the form of a granular formulation by sprinkling, side fertilization, Introduced into the seed furrow or inserted into the soil by piling it up. The pesticidal phosphoramidates can also be used for transplanting purposes Water added or dipping or soaking liquids added for plant parts that are necessary for propagation can be used, for example seeds, tubers, roots, seedlings, etc., in order to carry out disinfection and / or to achieve permanent protection against nematodes.

The amount applied can be between approximately 450 g and

2
22.5 kg per 4050 m (1 to 50 pounds per acre). However, higher amounts can also be used. The preferred one

2 Amount is between approximately 450 grams and 11.2 kg per 4050 m (1 to 25 pounds per acre). For introduction into the earth may add the pesticidal phosphoramidates to the soil in an amount of from about 2 to about 100 ppm of the active ingredient be mixed.

The invention generally provides a method of adding value to a contaminated commercial product or a product that is susceptible to attack by vermin in the form of arthropods or nematodes,

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where the vermin is fought in the way that on the product and / or on a site in the vicinity thereof a pesticidally effective amount of one or more of the pesticides Phosphoramidate is applied. The commercial product can be (a) a salable plant product in a growth state or in another condition such as food for humans and pets, furthermore it can be ornamental plants or timber, (b) soil or other medium that is suitable for the Growth of the plant material is prepared.

The pesticidal phosphoramidates can be used as the sole pesticidal agent, they can also be used together with other bactericides, fungicides, herbicides, insecticides, acaricides and comparable pesticides used "

The compounds of the formula J and their metal salts and their metal salt complexes (hereinafter collectively referred to as anthelmintic compounds) are so / ohl therapeutic as well as prophylactically active as anthelmintics. They are particularly effective against pinworms and tapeworms.

Using the following worms, anthelmintic compounds are examined for their effectiveness:

Common name Latin name

Mouse hookworm Nematospiropdes dubius

Dwarf tapeworm Hymenolypis nana

Pinworm Syphacia oblevata

Maggot Aspicularis tetraptera

Leech Schistosomara mansoni

Pork nematode Ascaris suum.

A pre-test to determine the anthelmintic activity can be carried out in such a way that animals are used

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be either natural or experimental with different Worms have become infected. For example, mice with pinworms (Syphacia oblevata and Aspicularis tetraptera) infect the animals naturally with worms one week before the test infected v / earth. Mice can get tapeworms (hymenolypsis nana) by oral administration through a tube into the esophagus. After the infection a test food from the test compound or compounds can be added to the feed vessels, the test compounds being homogeneous are mixed into ground flour. One such food is commercially available under the trademark Lab-Blox available. The mice are fed ad libitum for a 13 day period. On the 10th, 11th and 12th day after Administration of the test food to the mice can be by force-feeding a mixture of the test compound or the Administer test compounds in 1/2% methyl cellulose once daily for a period of 3 days. On the 13th day of the administration of the test diet, the test can be stopped and the mice subjected to a necropsy. The effectiveness of the test compounds, recorded as the percentage reduction, can be determined from results based on the removal and counting of the worms.

The anthelmintic compounds easily become one Formulate a variety of suitable pharmaceutical dosage forms, e.g. into large pills, tablets, Pills, powders, capsules, liquids and suspensions. The dosage forms are pharmaceutical in use compatible carrier and known formulation and manufacturing methods manufactured. In the veterinary field, such formulations can be administered in animal feed.

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The anthelmintic compounds become more expedient Administered as medicaments in unit dosage form. Drugs in unit dosage form usually contain a pharmaceutically acceptable carrier. These are drugs in the form of discrete portions, each one contains a unit dose or a multiple dose or a fraction of a unit dose of the active ingredients. Such Portions can, for example, in a single cohesive form are administered, for example in the form of tablets, pills or dragees, they can also in oiled or enclosed form suitable for oral administration, for example in the form of soluble capsules.

Representative solid carriers that are conventionally available and for pharmaceutically acceptable unit dosage formulations are satisfactory are, for example, corn starch, powdered lactose, powdered Cane sugar, talc, stearic acid, magnesium stearate and finely divided bentonite. The active ingredient can be with a carrier in varying amounts from, for example, about 0.001% by weight in animal feed to about 90 to 95% by weight or more in into a pill or capsule. In the latter form one does not need to use a larger amount of support than it is necessary to bind the particles of the active ingredient together.

Will the anthelmintic connections with animal feed mixed, then this should be done in such a way that the connection in question is avoided will. Therefore, administration to animals via their feed requires certain information, expertise as well Preliminary tests.

In general, the anthelmintic compounds can be made into stable powders or granules for mixing into a

- 87 709838/0653

certain amount of food for a single feeding or in a sufficient amount of food for one day, whereby the therapeutic effect achieved without difficulty can be formulated. In the case of a prepared and stored Feed or in the case of feed premixes, it is recommended to coat a granular formulation to protect and preserve the active ingredient.

A solid, diluting carrier does not have to be a homogeneous unit; it can also be a mixture of different ones act diluting carriers. Formulations with a solid Small amounts of excipients such as water, alcohols, protein solutions and suspensions, edible oils, and sugar solutions can be used as carriers as well as organic auxiliaries such as propylene glycols, sorbitol, glycerine or diethyl carbonate.

Liquid formulations can also be used. Representative liquid formulations are, for example, aqueous Suspensions (including isotonic saline solutions), oil solutions and suspensions, and oil-in-water emulsions. Aqueous suspensions are obtained in such a way that the anthelmintic compound is dispersed in water, preferably a .suitable surface-active dispersant, such as a cationic, anionic or nonionic surfactant is added.

Representative suitable surfactants are Polyoxyalkylene derivatives of fatty alcohols and sorbitan esters, also glycerol and sorbitan esters of fatty acids. Various dispersing and suspending agents can also be used be added. Representative examples of dispersing or suspending agents are synthetic and natural Gums, tragacanth, acacia, alginates, dextran, gelatin, sodium carboxymethyl cellulose and methyl cellulose and polyvinyl pyrrolidone. The amount of anthelmintic compound in

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708863

v / other suspensions can range from about 1 to about 20% by weight or more. Oil solutions are used in the Way made that the anthelmintic connection with an oil, for example an edible oil v / ie tree whole seed oil, Peanut oil, coconut oil, modified soybean oil, or sesame oil, mixed together. Solubility is common limited in oil. Oil suspensions can be prepared in the form of a finely divided anthelmintic Compound is mixed into the oil.

Oil-in-water emulsions are produced in such a way that an oil solution or suspension of the anthelmintic Compound is mixed or dispersed in water, preferably surface-active agents and dispersants or suspending agents as mentioned above can also be used.

In general, the anthelmintic formulations are administered to animals in such amounts that a therapeutic or prophylactic effect of the active ingredient is achieved. The exact concentration of the administered compounds can depend on various factors, for example the type of animal treated, its age, its weight and tolerability, as well as the administration time and the type and number of worms present. The dosage levels can vary from about 1 mg to about 800 mg per kg of body weight. A preferred dosage range varies between about 5 mg and about 400 mg per kg of body weight. When used against species of both pinworm and tapeworm, a compound in an amount between about 12 mg and about 100 mg / kg will be administered in the worst possible manner. When used against tapeworms only, the effective dose can be somewhat lower, for example from about 3 to about 50 mg / kg.

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The concentration of the anthelmintic compound in the for the administration of the selected formulation is in many cases not critical. One can use a large amount of a formulation Administer at a relatively low concentration and the same therapeutic or prophylactic Dosage as in the case of a relatively small amount of a relatively more concentrated formulation. More often Similarly, small doses give results comparable to a large dose. Unit dosage forms can vary from less than 1 rag to 500 mg of active ingredient per unit.

Optionally, the solid unit dosage forms can be used the anthelmintic compounds, such as pellets and granules, are coated to provide sustained release in the digestive system of animals to achieve. Such coated or enteric coated molds are manufactured in such a way that that in corresponding Weice on a pill or a large pill oine polymeric acid or a mixture of one polymeric acid with shellac or cetyl alcohol, cellulose acetate or a styrene / maleic acid copolymer is applied.

The following formulations I and II explain tablets and chewable tablets, respectively.

Formulation I.

A tablet is formulated with the following composition:

Anthelmintic Compound 220 mg

Lactose 53.23 mg

Magnesium Aluminum Silicate Gel 2.24 mg

Strength 13.13 mg

Calcium stearate 0.65 mg

Macrocrystalline Cellulose 35.75 mg

A total of 325 mg
- 90 -

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- B6 -

401

A granulation practice that water through the use of magnesium aluminosilicate and starch in the form of Containing pastes will form flattened, double or quadruple scored, uncoated tablets of S.C.A. hardness from 6 to 9 tabletted. The appropriate number (and fraction of the tablets) are administered to the host animals.

Formulation II

Another formulation is made into a tasty chewable tablet · Each chewable tablet contains the following Components:

Anthelmintic Compound 110 mg

Dried fish meal 1027 mg

Dried liver powder, pork 1027 mg soybean oil meal 97 mg

Cane sugar 239 mg

a total of 2500 mg

The exact concentration of the anthslmintic compounds to be used in the remedies may vary, but it is Prerequisite that a sufficient amount of the agent is ingested by the animal, so that the required dosage of the active ingredient is available. The anthelmintic connections are suitable for killing and controlling parasitic worms in humans, sheep, horses, pigs, Birds, dogs, cats and fish.

The anthelmintic compounds can be used to treat animals that are killed for food to manufacture for human consumption. The treatment is carried out by incorporating the anthelmintics into the feed for the animals in question. This gives you food with increased value, for example better quality, which are harmless to people due to the fact

- 91 709838/0653

27088 (33- $ n -AOt

that they have been freed from infestation or damage that go back to a worm attack.

The anthelmintic compounds are the only ones that can be anthelmintic Agents can be used, but they can also be used together with other anthelmintics. Appropriate Dosage forms containing a variety of anthelmintic compounds are also included in US Pat Scope of the invention.

Various manufacturing methods according to the invention have been made already mentioned, however, a method is to be emphasized, which in compliance with known chemical measures used for the preparation of analogous compounds v / ird for the preparation of compounds of the formula

* °, R ⁴ ■ i

R ¹ NC N p '(L) 1

where R a) a VJass er substance atom,

b) a (C ^ -C. ^^ - alkyl group,

c) a (C_-Cg) cycloalkyl group,

d) an optionally substituted aralkyl group with up to 11 carbon atoms,

e) an optionally substituted (Cg-C ^ ₄ ) -aryl group,

f) an optionally substituted pyridyl group,

g) an optionally substituted pyridylmethyl or pyridylethyl group, or

h) an optionally substituted pyrazinyl group

pe is
2
R a) a hydrogen atom,

b) a (C ₁ -C ^ ₀ ) -alkyl group,

c) a (C, -C _R ) -cycloalkyl group,

d) a (Cp-C ^ ₀ ) -alkoxyalkyl group,

- 92 -

709838/0653

e) a (C ₂ -C ^ -) - alkylthioalkyl group, ■ f) a (C ^ -Cg) cyanoalkyl group, g) a (C ₃ -Cg) -alkenyl group, h) an optionally substituted aralkyl group

with up to 11 carbon atoms, or i) an optionally substituted i ^c g- ^c io ^ ~

Arylyruppe, with the proviso that

-1
R o has a meaning other than hydrogen,

1 2
R and R together with the nitrogen atom to which they are linked form a morpho, lino or piperidino group, which can optionally be mixed with up to 2

(C.-C.) alkyl groups are substituted,

R a) a hydrogen atom,

b) a (C ₃ -C ₃ ) cycloalkyl group,

c) an optionally substituted aralkyl group with up to 11 carbon atoms, or

d) an optionally substituted (Cg-C ..) aryl group is,

R a) a (C. ~ Cg) -Alko>: y group,

b) a (C _-5 -C) -haloalkoxy group,

c) a di (C ₁ -Cg) -alkylamino group,

d) a (C ^ -C,.) - alkylthio group,

e) a phenoxy group, or

f) represents a phenylthio group and R ' a) a (C - Cg) -alkyl group,

b) a (C ^ -Cg) -alkoxy group,

c) a (C ^ -C) -haloalkoxy group,

d) a di (C ^ -Cg) -alkylamino group,

e) a (C ^ -Cg) -alkylthio group,

f) a phenyl group,

g) a phenoxy group, or

h) denotes a phenylthio group or of for pharmaceutical or agricultural purposes compatible metal salts or metal salt complexes of a compound of the formula L, the compound of the formula L or a metal salt or a metal salt

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709838/0653

N - S. ι I ₂ fl R —— R. - C

complex thereof is prepared by a method that is known per se for the preparation of analogous compounds is.

An analogy procedure as mentioned above is particularly applicable to the preparation of anthelmintic compounds of the above formulas J and K (as well as their Metal salts and metal salt complexes), in particular on the production of anthelmintic compounds (as well as their Metal salts and metal salt complexes) of the formula

ι 0 _R 4!

n / ^R

-NH P '(M)

wherein R ^x a) is a (C ₃ -Cp) cycloalkyl group,

b) an optionally substituted aralkyl group with up to 11 carbon atoms,

c) an optionally substituted (Cg-C ..) - aryl group,

d) an optionally substituted pyridyl group, or

e) an optionally substituted pyrazinyl

group is
2
R a) a hydrogen atom, or

b) an optionally substituted aralkyl group

with up to 11 carbon atoms means

R a) a (C.-Cg) alkoxy group,

b) a (C ^ -Cg) -haloalkoxy group,

c) a di (C.-Cg) -alkylamino group, or

d) is a (C ₁ -Cg) -alkylthio group and R a) is a (C.-C,) -alkyl group,

b) a (C ^ -Cg) -alkoxy group,

c) a (C - Cg) haloalkoxy group,

d) a di (C 1 -C 6) -alkylamino group, or

e) symbolizes a (C ^ -Cg) -alkylthio group.

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709838/0653

The compounds of the formulas L and H are preferably used produced by a method which consists in (1) an appropriate amine with an appropriately substituted one (a) phosphonic or phosphorus isothiocyanate or (b) halogen thiocarbonylphosphonamidate or to implement phosphoramidate or (2) a corresponding phosphonamidate or phosphoramidate to react with an appropriate isothiocyanate

The metal salts and metal salt complexes of a compound of the formulas A to M can each be prepared in that a Compound (a) with a corresponding metal compound, for example with an alkali or alkaline earth metal hydroxide or hydride and (b) with a corresponding metal salt, usually in an aqueous or alcoholic medium, is reacted

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709838/0653

Claims (19)

7708863 Expectations Arthropodicides, nematocides or anthelmintic Means, characterized by (A) a carrier or a compatible for agricultural purposes for pharmaceutical purposes acceptable carrier and (B) as active ingredient (1) at least one compound of the formula X O. P- {c (A) where R a) is a hydrogen atom, b) an a (C ₁ ~ C _1? ) -alkyl group, c) a (C ₃ -Cg) cycloalkyl group, d) an optionally substituted aralkyl group with up to 11 carbon atoms, e) an optionally substituted (Cg-C, ^) - aryl group, f) an optionally substituted pyridyl group, g) an optionally substituted pyridylmethyl or pyridylethyl group, or h) an optionally substituted pyrazinyl group stands,
R a) a hydrogen atom, b) a (C ₁ -C ₁₀ ) -alkyl group, c) a (C ₃ -Cg) cycloalkyl group, d) a (C ₂ -C ₁₀ ) -alkoxyalkyl group, e) a (C ₂ -C ₁₀ ) -alkylthioalkyl group, f) a (C ₁ -Cg) cyanoalkyl group, g) a (C ₃ -Cg) -alkenyl group, h) an optionally substituted aralkyl group with up to 11 carbon atoms, or i) is an optionally substituted ^ ^c g- ^c ^ o) -aryl group,
- 97 - 709838/0653 ORIGINAL INSPECTED "1 2 R and R together with the nitrogen atom to which they are linked form a morpholino or piparidino group, which is optionally _{substituted by up to 2 (C 1} -C ₄ ) -alkyl groups, R a) is a hydrogen atom, b) a (C ₃ -C _ß ) cycloalkyl group, c) an optionally substituted aralkyl group with up to 11 carbon atoms, or d) an optionally substituted ^ ■ ^c q ~ ^c iq ^ ~ aryl group, R a) a (C ₁ -Cg) alkoxy group, b) a (C ^ Cg) -alkylthio group, c) a di- (C ₁ -Cg) -alkylamino group, d) a (C.-Cg) -haloalkoxy group, e) a phenoxy group, or f) represents a phenylthio group, R a) a (C ₁ -Cg) -alkyl group, b) a (C ₁ -Cg) -alkylthio group, c) a di- (C ₁ -Cg) -alkylamino group, d) a (C ₁ -Cg) -alkoxy group, e) a (C ₁ -Cg) -haloalkoxy group, f) a phenyl group, g) a phenoxy group, or h) symbolizes a phenylthio group and X is an oxygen or Schwafel atom, among which 1 2 prerequisite that if R and R are each hydrogen and optionally substituted aryl, then R and R are not (C ₁ -Cg) alkoxy and (C ₁ -Cg) alkYl, and / or (2) at least a metal salt which is acceptable for agricultural or pharmaceutical purposes or a metal salt complex of a compound of the formula A which is acceptable for agricultural or pharmaceutical purposes. 2. Composition according to claim 1 for oral administration, characterized by one for pharmaceutical purposes - 98 -709838/0653 -ι- compatible carrier and an anthelmintically effective one Amount (1) of at least one compound of the formula S O R- MC _N p / (j) U ι ^x5 2 3 R R wherein R a) is a (C ₃ -Cg) cycloalkyl group, b) an optionally substituted aralkyl group with up to 11 carbon atoms, c) an optionally substituted ^ ^c g ~ ^c i4 ^ ~ aryl group, d) an optionally substituted 2-pyridyl group, or e) an optionally substituted pyrazinyl group is
2 R a) a hydrogen atom, b) a (C ^ -C ^^ - alkyl group, c) a (C ₃ -Cg) cycloalkyl group, d) a (C ₂ -C ^ ₀ ) -alkoxyalkyl group, e) a (C ₂ -C ^ ₀ ) -alkylthioalkyl group, f) a (C ^ -Cg) cyanoalkyl group, g) a (C ₃ -Cg) -alkenyl group, h) an optionally substituted aralkyl group with up to 11 carbon atoms, or i) an optionally substituted ^ g ^ in ^ " Is aryl group, 1 2 R and R together with the nitrogen atom with which they are linked, form a morpholino or piperidino group which is optionally _{substituted by up to 2 (C 1} -C ₄ ) -alkyl groups, R a) is a hydrogen atom, b) a (C ₃ -C ₈ ) cycloalkyl group, c) an optionally substituted aralkyl group with up to 11 carbon atoms, d) an optionally substituted ^ g-C ^ o ^ - Aryl group means - 99 709838/0653 _? 7 Π 8 8 β 3 R a) a (C ₁ -C ₆ ) -alkoxy group, b) a (C ₁ -Cg) - ^ haloalkoxy group, c) a Di- (C ₁ -Cg) - d) a (C ₁ -Cg) e) a phenoxy group, or f) a phenyltio group and R "a) a (C ₁ -Cg) -AIlCyIgJTUpPe, b) a (C ₁ -Cg) alkoxy group, c) a (C ₁ -Cg) -haloalkoxy group, d) a di- (C ₁ -Cg) -alkylamino group, e) a (C ^ -Cg) -alkylthio group, f) a phanyl group, g) a phenoxy group, or h) symbolizes a phenylthio group and / or (2) a pharmaceutically acceptable metal salt or metal salt complex a compound of the formula J. 3. Composition according to claim 2, characterized in that the compound of the formula J also corresponds to the following formula S O. ! HH y ι R ^x NC -NH P \ c (K) I ^R j wherein R a) is a (C ₅ -C ₇ ) cycloalkyl group, b) a benzyl or phenethyl group, c) a phenyl, benzyl or phenethyl group, substituted with up to 3 (C ^ -C -) - alkyl groups, (Cj-C -) - alkoxy groups, di (C ₁ -C ₄ ) -alkylamino groups, (C ₁ - C ₄ ) -hydroxyalkyl groups, halogen atoms, halomethyl groups, hydroxyl groups or cyano groups, d) a fluorenyl group, e) a 2-pyridyl group optionally substituted by up to 2 (C ₁ -C ₄ ) -alkyl groups or halogen atoms or - 100 - 909838/0663 - Ιββ is a pyrazinyl group, / 708863 R is a hydrogen atom or a bansyl group ^ is, R a) a (C ₁ -C ₄ ) -alkoxy group, b) a (C ₁ -C ₄ ) haloalkoxy group, c) a di- (C ₁ -C ₄ ) -alkylamino group or d) is a (C ₁ -C ₄ ) -alkylthio group and R a) is a (C ₁ ~ C ₄ ) -alkyl group, b) a (C ₁ -C ") alkoxy group, c) a (C ₁ -C ₄ ) haloalkoxy group, d) a di (C ₁ -C ₄ ) alkylamino group or e) represents a (C.-C ^ arylthio group. 4. Composition according to claim 2, characterized in that the compound of formula J Cl I Cl
the Porrael MH Il C MH OC .H, - or OC ₂ H ₅ OC "H _r or II / ^{2 5} • ^XoC 2 ^H 5 the formula -C-NH S. / ^OC 2 ^H 5 P ^ ^IIX 0C H 0 ^OC 2 ^H 5 odej - 101 - 709838/0653 the formula NH S. > 6 ^cl v- ζ y- the formal CH ₂ C _n C ₆ H ₅ CH is equivalent to. > 2 ~ 7 " / ²⁵ 5. Agent according to one of claims 2 to 4, characterized in that that it is in a unit dosage form, preferably in the form of a tablet. 6. Arthropodicides or nematocides agent according to claim 1, characterized by one for agricultural purposes compatible carrier and (1) at least one compound of the formal X 0 4
R ¹ MCN P { (F) wherein R a) is a hydrogen atom, b) a (C ^ -C ₂₃ ) -alkyl group, c) a (C ₃ -Cg) cycloalkyl group, d) an optionally substituted aralkyl group with up to 11 carbon atoms, e) an optionally substituted (Cg-C-i_) - aryl group, f) an optionally substituted pyridyl group, - 102 - 709838/0653 g) an optionally substituted pyridyl methyl or pyridyl group or h) an optionally substituted pyrazinyl group is
2
R a) a hydrogen atom, b) a (C ₁ -C ₁₀ ) -alkyl group, c) a (C - Cq) cycloalkyl group, d) a (C ₂ -C ₁₀ ) -alkoxyalkyl group, e) a (Cp-C ^ ₀ ) -alkylthioalkyl group, f) a (C ₁ -Cg) cyanoalkyl group, g) a (C ₃ -Cg) -alkenyl group, h) an optionally substituted aralkyl group with up to 11 carbon atoms or i) an optionally substituted ^ g-C ^ o ^ " Represents aryl group, 1 2 R and R together with the nitrogen atom to which they are linked form a morpholino or piperidino group which is optionally _{substituted by up to 2 (C 1} -C.) -Alkyl groups, R a) is a hydrogen atom, b) a (C ₃ -Cg) cycloalkyl group, c) an optionally substituted aralkyl group with up to 11 carbon atoms, d) an optionally substituted ( ^c c- ^c ^ o ^ "aryl group. is, R a) a (C ₁ -Cg) -AIkOXYgJTUpPe, b) a (C ₁ -Cg) -alkylthio group or c) denotes a di- (C ^ -Cg) -alkylamino group, R a) a (C ₁ -Cg) -alkyl group, b) a (C ^ -Cg) -alkylthio group or c) represents a di- (C ₁ -C,) - alkylamino group, 1 ? with the proviso that when R and R are each hydrogen and optionally substituted (Cg-C ₁₀ ) -aryl, R ⁴ and R ⁵ do not correspond to (C ₁ -Cg) -AIkOXy (or (C ₁ -Cg) - Alkylthio) and (C ₃ -C ₄ ) -alkylthio, and X is an oxygen - 103 - 70 9838/0653 or represents a sulfur atom, and / or (2) at least one which is acceptable for agricultural purposes Metal salt or an agriculturally acceptable metal salt complex a compound of the formula F. 7. Composition according to claim 6, characterized in that the compound of the formula F also corresponds to the following formula: X O - N - C - NH - P R ^{2 R} wherein R a) is a hydrogen atom, b) a (C ^ -C _Q ) -alkyl group, c) a (C ₅ -C ₇ ) cycloalkyl group, d) a phenyl, benzyl or phenethyl group, e) a phenyl, benzyl or phenethyl group, substituted with up to 3 methyl groups, Methoxy groups, methylthio groups, dimethylamino groups, Cyano groups, nitro groups, halogen atoms or trifluoromethyl groups, f) a pyridyl group, optionally substituted with up to 2 (C ^ -C -) - alkyl groups or halogen atoms or g) is a pyrazinyl group, 2 R represents a hydrogen atom or a benzyl group 2 represents, provided that when R is hydrogen, R has a different meaning as an optionally substituted phenyl group owns, 2
R and R together with the nitrogen atom to which they are linked form a piperidino group, 5
R is an n-propylthio group, an n-butylthio group, an isobutylthio group or a sec, -butylthio group and X is an oxygen or sulfur atom. - 104 - 709838/0653 8. Composition according to claim 6, characterized in that the compound of the formula F of the formula Cl Cl ' H-C-NH-P I Y ciu or the formula ⁰ " NH-C ° OC H NH-P or the formula S. NH-P or the formula Il «/ ^OC 2 ^H 5 _N H - C - NH-P / "He" u. or : the formula NH-C -. NH-P / ■ corresponds to « - 105 - 709838/0653 9. Compound of Formula ΛΟ Il ° R ⁴ N P ^ (B) wherein R a) is a hydrogen atom, b) a (C ₁ -C ₁₂ ) -alkyl group, c) a (C ₃ -Cg) cycloalkyl group, d) an optionally substituted aralkyl group with up to 11 carbon atoms, e) an optionally substituted ^ g- ^ io ^ " Aryl group, f) an optionally substituted pyridyl group, g) an optionally substituted pyridyl methyl group or pyridylethyl group or h) an optionally substituted pyrazinyl group means
R a) a hydrogen atom, b) a (C ₁ -C ₁ Q) -alkyl group, c) a (C ₃ -C ₈ ) cycloalkyl group, d) a (C ₃ -C ₁₀ ) -alkoxyalkyl group, e) a (C ^ -C ₁₀ ) -alkylthioalkyl group, f) a (C ₁ -Cg) cyanoalkyl group, g) a (C ₃ -Cg) -alkenyl group, h) an optionally substituted aralkyl group with up to 11 carbon atoms or i) an optionally substituted ( ^c g "" ^c io ^ "" aryl group, with the proviso that R has a meaning other than hydrogen owns, 2 R and R together with the nitrogen atom with which they are are linked, form a morpholino or piperidino group which is optionally _{substituted by up to 2 (C 1} -C ₄ ) -alkyl groups, R a) is a hydrogen atom, - 106 709838/0653 ΑΛ b) a (C ₃ -C ₈ ) cycloalkyl group, c) an optionally substituted aralkyl group with up to 11 carbon atoms or d) is an optionally substituted i ^c g ~ ^C 10 ^ ~ aryl group, R ^{4 is} a (C ₁ -Cg) -AIkOXy- or (C ₁ -C ₅ ) -alkylthio- group means R represents a (C ₃ -C ₄ ) -alkylthio group and X is an oxygen or sulfur atom, or a compound which is an agriculturally acceptable metal salt or an agriculturally acceptable metal salt complex of a compound of the formula B, 10. Composition according to claim 9, characterized in that the compound of formula B also corresponds to the following formula : X O 4 Il «I, R ¹ -NH-CNP ^/ '(13) wherein R a) a (Cg-C ₁₀ ) -aryl group, optionally substituted by up to 5 identical or different substituents, selected from (C ₁ -C ₄ ) -alkyl groups, ( ^C ₁ ~ ^C 4 * -alkoxy groups, (C ₁ -C ₄ ) -alkylthio groups, (C ₁ -C ₄ ) -alkylsulfinyl groups, (C ₁ -C ₄ ) -alkylsulfonyl groups, di- (C ₁ -C ₄ ) -alkylamino groups, (C ₁ -C ₄ ) -hydroxyalkyl groups, ( C ₁ -C ₄ ) haloalkyl groups, cyano groups, nitro groups, hydroxyl groups or halogen atoms,
R a) a hydrogen atom, b) a (C ₃ -C ₈ ) cycloalkyl group, - 107 - 709838/0653 c) an optionally substituted aralkyl group with up to 11 carbon atoms, d) an optionally substituted ( ^C fi ~ ^c -io ^ "~ aryl group, R ^{4 represents} a (C ₁ -Cg) -AIkOXy- or (C ₁ -Cg) -alkylthio group, R symbolizes a (C ₃ -C ₄ ) -alkylthio group and X is an oxygen or sulfur atom. 11. A compound according to claim 10, characterized in that it also corresponds to the following formula: x 0 11 it / ^K NII-C-MH-P wherein the substituent A, which can be the same or different if more than one substituent A is present, a) a (C ₁ -C ₄ ) -alkyl group, b) a (C ₁ -C ₄ ) alkoxy group, c) a (C ₁ -C ₄ ) -alkylthio group, d) a di- (C ₁ -C ₄ ) -alkylamino group, e) a trihalomethyl group or f) is a halogen atom, R a) is a hydrogen atom, b) a (C ₅ -C ") - cycloalkyl group, c) an unsubstituted benzyl group or d) represents an unsubstituted phenyl group, R is a (C ₁ -C ₄ ) -alkylthio group or a (C ₁ -C ₄ ) - Alkoxy group means R represents a (C3-C4) -alkylthio group, X is an oxygen or sulfur atom and η "Ο or an integer from 1 to 3. - 108 - 709838/0653 '/' 708863 12. A compound according to claim 11, characterized in that A a) is a methyl group, b) a methoxy group, c) a methylthio group, d) a dimethylaraino group, e) a trifluoromethyl group or £) is a chlorine atom, R is a propylthio group or an ethoxy group, R is an n-propylthio, isobutylthio or sec-butylthio group symbolized, X is an oxygen or sulfur atom and n "is 0, 1 or 2. 13. A compound according to claim 10, characterized in that the compound of formula B of formula the formula Cl ^ 0 0 _or . ο ο ¹¹ NH-C-HH-P - 109 - 709838/0653 the formula the formula ,, / OC ₂ H ₅ NH-C-NH-P or is equivalent to, 14. A compound according to claim 9, characterized in that the compound of formula B also of the following formula is equivalent to: R ' X Il C Il N P '.3 (H) wherein R a) is a hydrogen atom, ■ b) a (C ^ -C ₁₂ ) -alkyl group, c) a (C ₃ -C ₃ ) cycloalkyl group, d) an optionally substituted aralkyl group with up to 11 carbon atoms, e) an optionally substituted ( ^c g- ^c -i0 ^ "~ aryl group, f) an optionally substituted pyridyl group, g) an optionally substituted pyridylmethyl group or pyridylethyl group or h) an optionally substituted pyrazinyl group is
2
R a) a hydrogen atom, provided that that R has a meaning other than an optionally substituted (Cg-C.-J-aryl group owns, - 110 - 709838/0653 b) a (C ₁ -C ₁₀ ) -alkyl group, c) a (C ₃ -Cg) cycloalkyl group, d) a (C ₂ -C ₁₀ ) - alkoxyalkyl group, e) a (C ₂ -C ₁₀ ) -alkylthioalkyl group, f) a (C ₁ -Cg) cyanoalkyl group, g) a (C ₃ -Cg) -alkenyl group, h) an optionally substituted aralkyl group with up to 11 carbon atoms or i) an optionally substituted ^ g ^ -jo ^ " Aryl group, with the proviso that •1
R has a different meaning than hydrogen owns, is, 2
R and R together with the nitrogen atom with which they are linked, form a morpholino or piperidino group which is optionally _{substituted by up to 2 (C 1} -C) -alkyl groups, 3
R a) a hydrogen atom, b) a (C ₃ -Cg) cycloalkyl group, c) an optionally substituted aralkyl group with up to 11 carbon atoms or d) an optionally substituted (Cg-CiQ ^ " Is aryl group, R ^{4 is} a (C ₁ -Cg) -AIkOXy- or (C ₁ -Cg) -alkylthio- group means R ^{5 is} a (C ₃ -C ₄ ) -alkylthio group and X is an oxygen or sulfur atom. 15. Compound according to claim 14, characterized in that it corresponds to the following formula: _t η __h / ^0C 2 ^h 5; wherein R a) is a hydrogen atom, b) a (C ^ C ^ c) a (C ₅ -C ₇ ) cycloalkyl group, d) a phenyl, benzyl or phenethyl group - 111 - 709838/0653 :, '7 O 8 8 β 3 e) a phenyl group, banzyl group or phenethyl group, substituted with up to 3 methyl groups, methoxy groups, methylthio groups, Dimethylamino groups, cyano groups, halogen atoms or trifluoromethyl groups, f) a pyridyl group, optionally substituted with up to 2 (C ^ -C ^ -alkyl groups, or g) is a pyrasinyl group, 2 R is a hydrogen atom or a benzyl group, 2 with the proviso that when R is a Is hydrogen, R has another meaning as a substituted or unsubstituted one Has phenyl group, 2
R and R together with the nitrogen atom with which they are are linked, form a piperidino group which is optionally _{substituted by up to 2 (C 1} -C ₄ ) -alkyl groups,
R a) a hydrogen atom, b) a (C ₅ -C ₇ ) cycloalkyl group, c) an unsubstituted benzyl or phenethyl group or d) is an unsubstituted phenyl group, R is a (C ₁ -C.) Alkoxy group, x ^ *
R is an n-propylthio group, an isobutylthio group or a sec-butylthio group and
X represents an oxygen or sulfur atom. 16. A compound according to claim 14, characterized in that the compound of formula H of formula 0 ^; ρ / or - - 112 - 709838/0663 the formula - 1 * 2 - Il I / ^oc ? S or of the formula r.oc O O Il C - - P - CH - 2 "5 ^or the formula C NH the formula 49- ti NH P { or is equivalent to. 17. Arthropodicides or nematocides agents, characterized in that they contain a compound according to one of the Claims 9 to 16 and a carrier compatible for agricultural purposes. 18. Means according to claim 17, characterized in that it in the form of (a) a dust, (b) a granulate or (c) an emulsifiable concentrate, a flowable one Emulsion concentrate or a wettable powder, each containing a surfactant, is present " - 113 - 7 09838/0653 At 19. Method of combating vermin in the form of Arthropods or Nematodan, characterized in that they hit the vermin or the areas that should be free from the vermin or from an attack
the vermin are to be kept free, a pesticidally effective amount of a compound according to any one of claims 6 to 16 is applied. 709838/0653