DD149896A5 - PESTICIDE MEDIUM - Google Patents

Abstract

The invention relates to pesticidal compositions containing novel phosphorodiamido (di) thioate derivatives as active ingredients. The compositions of the invention exhibit a pronounced activity as pesticides to fight fungi, arthropods and / or nematodes. In this effect, they are superior to known phosphorus derivatives.

Description

- ^ή - 218634

Field of application of the invention **

The invention relates to novel pesticidal compositions containing novel pesticidal phosphoramido (di) thioate derivatives. These agents are particularly useful for controlling pests such as fungi, arthropods and nematodes, especially acarids, insects and nematodes.

Characteristic of the known technical solutions

It is known that certain Phosphoramidothioatderivate have a fungicidal, arthropodizide and / or nematicidal activity (see, DE-OS 26 57 972).

Object of the invention

The aim of the invention is the creation of new pesticidal agents which possess extended biological activities over agents with known active ingredients.

Explanation of the essence of the invention

The invention provides novel pesticidal compositions containing novel phosphorodiamido (di) thioate derivatives that have unexpected biological activities over known phosphoramidothioate derivatives in several respects, particularly with regard to their nematicidal and / or systemic insecticidal properties.

Most of the active ingredients used in the pesticidal compositions of the invention are novel compounds of the formula

NR ³ R ⁴

(D

in which mean:

R is hydrogen, C.-C. _2- alkyl; C.-C. ₂ alkyl substituted with up to three identical or different substituents selected from chlorine, bromine and fluorine; C ₁ -C ₁ -alkyl substituted with a substituent selected from cyano, nitro, C ₁ -C 6 -alkoxy, C ₁ -C 6 -alkylthio, C ₁ -C 6 -alkylsulfinyl, C ₁ -C 8 -alkylsulfonyl, (C ₁ -C 4 ₎ -alkyl C 1-6 -alkyl) carbonyl, (C ₁ -C 6 -alkoxy) carbonyl, (C ₁ -C 6) -alkylcarbonyloxy, mono- or di (C ₁ -C 6) -alkylaminocarbonyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylcarbonyl, phenoxycarbonyl, phenylcarbonyloxy, phenylaminocarbonyl, (C ₃ -C _fi alkenyl) oxy-carbonyl, _(C3 -CG-alkenyl) carbonyloxy, aminocarbonyl, and (C.-Cg-alkyl) carbonylamino; C ^ -C ₁ "alkynyl, preferably Co-C _fi / in particular C ₃ -C _4, C ₃ -C ₁ --Alkenyl, preferably C ₃ -C _6, especially C ₃ -C _4; C ₄ -C ₁ alkadienyl; C ^ -CG-cycloalkyl; (C ₁ -C 9 -alkoxy) -carbonyl, preferably not more than 4 and especially preferably not more than 2 carbon atoms in the alkoxy part; phenyl; Phenyl-C 1 -C 6 -alkyl, preferably phenyl-C 1 -C 4 -alkyl and in particular benzyl; Phenyl or phenyl-C ₁ -C ₃ -alkyl (preferably phenyl-C ₁ -C ₃ -alkyl and especially benzyl), each phenyl or phenylalkyl group having up to three identical or different substituents ring-substituted, selected from cyano, nitro, halogen, C ₁ -C 6 -alkyl, C ₁ -C -alkoxy, C ₁ -C 6 -alkylthio, C ₁ -C 6 -alkylsulfinyl, C ₁ -C 8 -alkylsulfonyl, phenoxy, C ₁ -CG -haloalkyl, trifluoro- ethyl, mono- or di- (C ₁ -C 4 -alkyl) cg-alkylaminocarbonyl,

  -'- 21863

(Cj -CG-alkoxy) carbonyl, (C ₁ -CG-alkyl) -carbonyl, ^(c i ~ Cg-alkyl) -carbonyloxy, phenylthio, phenylsulfinyl, phenylsulfonyl, benzyl, phenylcarbonyl, phenoxycarbonyl, phenylcarbonyloxy, phenylaminocarbonyl, (C - ^ - Cg-alkenyl) oxycarbonyl, (C 1 -C 9 -alkenyl) -carbonyloxy, aminocarbonyl and (C 1 -C 6 -alkyl) -carbonylamino;

R is Cg-Cg-alkyl, preferably C ^ -C. and in particular C ₃ -C ₄ ;

R (if not joined to R) is hydrogen, C 1 -C 4 alkyl, preferably methyl or ethyl (in particular methyl) or C 1 -C 9 alkenyl, preferably propenyl;

ο. "_##'

R is hydrogen, C ₁ -C 10 -alkyl, preferably methyl or ethyl

(especially methyl) or, especially where R and R are not interconnected, C ₃ -C _fi alkenyl, preferably propenyl;

R (if not connected me R) hydrogen, C ₁ -C ~~ alkyl, preferably C ₁ ~ C _fi, in particular C ₁ -C. and most preferably methyl or ethyl; C ₁ ~ C ₁ 2 ~ alkyl _/ substituted with a substituent selected from cyano, nitro, C ₁ -C ₆ -alkoxy, Cj-Cg alkylthio, C ₁ -C ₆ -AIkYlSuIfinyl, .Cj-Cg-alkylsulphonyl, ( C, -C _g alkyl) carbonyl, (C ₁ -C ₆ -alkoxy) carbonyl, _(C1 -CG alkyl) carbonyloxy, mono- or di- (C, -CG-alkyl) aminocarbonyl, Phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylcarbonyl, phenoxycarbonyl, phenylcarbonyloxy, phenylaminocarbonyl, (Co-Cg-alkenyl) -oxycarbonyl, (C ₃ -C 9 -alkenyl) -carbonyloxy, aminocarbonyl and (C ₁ -C 9 -alkylcarbonylamino; C ₃ -C ₁₂ ~ alkynyl (for example ^C 3 ~ ^c q ~ alkynyl), preferably C ₃ -C ₆ and in particular C ₃ -C ^; C ₃ -C ₁ - "alkenyl, preferably C ₃ -C ₆ and in particular C ₃ -C ₄ C 1 -C 8 cycloalkyl, preferably C ₅ -C ₆ phenyl, phenyl-C ₁ -C ₆ -alkyl, preferably phenyl-C ₁ -C 4 -alkyl, phenyl or phenyl-C ₁ -C 4 -alkyl, each ring-substituted with up to three identical or different substituents

Λ.

cyano, nitro, halogen (especially chlorine, bromine and fluorine), C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -alkylthio, C 1 -C 8 -alkylsulfinyl, C 1 -C 8 -alkylsulfonyl, phenoxy, C-Cg-haloalkyl (in particular trifluoromethyl), mono- or di- (C - C _ß alkyl) aminocarbonyl, (C ₁ -C ₆ alkoxy) carbonyl, (C ^ -CG alkyl) - carbonyl, (C 1 -C 8 alkyl) -carbonyloxy, phenylthio, phenylsulfinyl, phenylsulfonyl, benzyl, phenylcarbonyl, phenoxycarbonyl, phenylcarbonyloxy, phenylaminocarbonyl, (C 1 -C 6 -alkenyl) -oxycarbonyl, (C 1 -C 6 -alkenyl) -carbonyloxy, aminocarbonyl or (Ci-Cg-alkyl) -carbonylamino, wherein

R and R (when joined together) form a heterocyclic ring of the formula

(ID

form, in which

-CH ₂ CH ₂ -, - CH ₂ CH ₂ CH ₂ - or -CH ₂ CH ₂ CH ₂ CH ₂ -, preferably - or -CH ₂ CH ₂ CH ^,

X represents oxygen or sulfur, preferably oxygen, and

X represents oxygen or sulfur, preferably oxygen.

R is C -.- Cj ₂ alkyl, it is preferably C ₁ -C _ß alkyl and in particular C ₁ -C ₄ -alkyl and in a particularly preferred manner to methyl or ethyl.

If R is halogen (C ₁ -C ₁₂ ) -alkyl, then it is preferably halo (C ₁ -Cg) -alkyl and in particular trifluoromethyl.

ί- 2 18634

- ν-

R is substituted alkyl, it is preferably Cj-Cg alkyl substituted with a substituent selected from cyano, nitro, C ₁ -C ₄ -alkoxy, C.-C ~ ₄ alkylthio, Cj-C ^ alkylsulfinyl, Cj-C-alkylsulfonyl, acetyl, (Cj-C ₄ -alkoxy) carbonyl, (C - _C4 alkyl) carbonyloxy, mono- or di (C.-C ~ ₄ alkyl) aminocarbonyl, phenoxy , Phenylthio, phenylsulfinyl, phenylsulfonyl, phenylcarbonyl, phenoxycarbonyl, phenylcarbonyloxy, phenylaminocarbonyl, (C ₃ -C ₄ -alkenyl) -oxycarbonyl, (C ₃ -C ₄ -alkenyl) -carbonyloxy, aminocarbonyl and (C ₁ -C ₄ -alkyl) carbonylamino. When the alkyl group contains a substituent with an alkyl moiety, such moiety will typically contain 1 or 2 carbon atoms. When R is substituted alkyl, it is preferably C 1 -C ₄ -alkyl substituted with a substituent selected from cyano, nitro, methoxy, methylthio, methylsulfinyl, methylsulfonyl, acetyl, methoxycarbonyl, ethoxycarbonyl, methylcarbonyloxy, mono- or dimethylaminocarbonyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylcarbonyl, phenoxycarbonyl, Phenylcaronyloxy, phenylaminocarbonyl, (C ₃ -C ₄ alkenyl) oxycarbonyl, (C ₃ ~ C ₄ alkenyl) carbonyloxy, aminocarbonyl and Methylcarbnylamino.

R may be substituted phenyl or phenylalkyl, but preferably of these two possibilities R is phenyl substituted with up to three substituents selected from cyano, nitro, methyl, methoxy, phenoxy, acetoxy, acetyl, tri-fluorine thy 1, chlorine, fluorine, Bromine, methylthio, methylsulfinyl and methylsulfonyl.

When R is substituted alkyl, it is preferably C ₁ -C 9 -alkyl substituted with one substituent selected from cyano, nitro, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, C ₁ -C ₄ -alkylsulfinyl , C ₁ -C ₄ alkylsulfonyl, acetyl, (C, -C ₄ -alkoxy) carbonyl, (C ₁ -C ₄ alkyl) carbonyloxy, mono- or di- (C ₁ -C ₄ ~ alkyl) - aminocarbonyl, phenoxy, phenylthio, phenyl

sulfinyl, phenylsulfonyl, phenylcarbonyl, phenoxycarbonyl, phenylcarbonyloxy, phenylaminocarbonyl, (C ^ -C.-alkenyl) oxycarbonyl, (C ^ ^- C-alkenyl.) carbonyloxy, aminocarbonyl, and (C.-C.-alkyl) carbonylamino. The alkyl group contains a Subfetituenten having an alkyl moiety, such alkyl dann.enthält a typically 1 or 2 carbon atoms, i When R is substituted alkyl, it is in particular Cj-C alkyl substituted with a substituent selected from cyano , Nitro, methoxy, methylthio, methylsulfinyl, methylsulfonyl, acetyl, methoxycarbonyl, ethoxycarbonyl, methylcarbonyloxy, mono- or dimethylaminocarbonyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylcarbonyl, phenoxycarbonyl, phenylcarbonyloxy, phenylaminocarbonyl, (Co ^- C-alkenyl) -oxycarbonyl, (Co-C ^ -alkenyl) -carbonyloxy, aminocarbonyl and methylcarbonylamino.

R may be substituted phenyl or phenylalkyl, but it is preferable to choose from these two possibilities that R is phenyl substituted with up to three substituents selected from cyano, nitro, methyl, methoxy, phenoxy, acetoxy, acetyl, trifluoromethyl , Chlorine, fluorine, bromine, methylthio, methylsulfinyl, and methylsulfonyl.

When the compounds of the invention contain a phenyl group containing a substituent with an alkyl moiety, such moiety usually contains no more than four carbon atoms, and usually 1 or 2 carbon atoms.

The alkyl, alkenyl and alkynyl moieties in the compounds of this invention may have branched or straight chains. Representative examples of such moieties are methyl, ethyl, propyl, isopropyl, sec-butyl, isobutyl, tert-butyl, pentyl, neo-pentyl, hexyl, allyl, 2-butenyl, 3-methyl-1-pentenyl, 3-hexenyl, Propynyl, 1-pentynyl, 4-methyl-1-pentynyl, hexynyl, nonyl and dodecyl.

-I- 218634

The alkenyl groups, for example allyl, which are present in the compounds according to the invention contain a cis or trans double bond.

Alkynyl groups, for example propargyl, which are present in the compounds according to the invention contain a triple bond. · *

Typical phenylalkyl groups are benzyl, phenethyl and 3-phenyl-i-methylpropyl, wherein the aromatic rings may be substituted in the manner described above.

Alkadienyl groups present in the compounds of the invention, for example 2,4-pentadienyl, may have either cis or trans double bonds, which may be either conjugated or isolated.

If the term "acyl" is used according to the invention, then a group of the formula R ¹ C (X ¹ ) is to be understood, where R ^{1 is} hydrogen or an organic group and X 'is oxygen or sulfur.

Representative N-acyl compounds according to the present invention, the preparation methods of which are given below together with other data, are those of formula I wherein R is C ₁ -C ₉ alkyl, C ₁ -C 4 haloalkyl, methoxycarbonyl, methoxymethyl, (C ₁ -C ₂ -alkoxy) -carbonyl-CjC ^ -alkyl, phenoxymethyl, phenyl optionally substituted with nitro or halogen, phenyl-CJ-C_-alkyl, C 1 -C -cycloalkyl, C-7-alkadienyl or C 1 - Alkenyl is, RC ^ -C ^ alkyl meaning

'3 a

tetra, R is Cj-Cj-alkyl or C ₃ ~ alkenyl, R "is hydrogen or

Methyl is illustrated and R ^{5 is} C ₁ -C ₂ -alkyl or C 1 -alkenyl.

The most preferred compounds according to the invention have a particularly pronounced nematocidal, acaricidal, fungicidal and arthropodicidal, especially nematicidal, acaricidal and insecticidal activity. They can be explained by the formula:

^c " ⁿ / ^HHr , in,

reproduce in what for water! propyl or trifluoromethyl,

R is hydrogen, methyl, ethyl, methoxymethyl, cyclo

R ^{2 is} C ₃ -C ₄ -alkyl, R is methyl,

R is hydrogen, methyl or ethyl, preferably methyl.

Sulfur or oxygen, preferably oxygen, and

Sulfur or oxygen, preferably oxygen.

Particularly preferred compounds correspond to the following formulas:

.4.

10634

HC-N '

CH.

-NHCH.

C I CH

If

H-C-N:

, CH.

.NHCH.

-SCHCH ₂ CH ₃ CH ₃

H-C-N ^

CH ₂ CH ₃

.NHCH.

SCH CH ₂ CH ₃ CH ₃

il CH ₃ -C-NC

.CH.

.NHCH.

GOOD ₂ CH ₃

L ₃

CH.

CF ₃ -C-Ni, NHCH.

'CHOICE ₀ CH-CH ₃

CH ₃ OCH ₂ -CN;

CH-

.NHCH.

-SCHCH ₂ CH ₃ CH ₃

/ JO

.CH.

.NHCH.

CH

If H-C-N '

CH.

NHCH.

GOOD ₃

The compounds of the invention can be prepared by a variety of methods.

One method consists in the acylation of an S-alkylphosphordiamido (di) thioate of the formula IV. For example, the following reaction can be carried out.

2 1 8 <53

R ³ R ⁴ NP-NHR ⁵ (IV)

R ¹ ψ Η

O ¥ H 7 o ι Ι · + R-C ^. I "ι R ¹ ₃₊ R ^J O + AlCl ^L -C-C1 .... - N

3 4

RR-N-P

-R '

2 · SR C-H

Il

3 4 Γ 5

RR-N-P-N-R

SR CR ^X Il O

X ¹

"5

P N-R

I 2 '1 SR C-R

wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ and X ^{1 have} the meanings given in connection with the formula I, with the exception that R ¹ in the above reaction scheme is not hydrogen.

Another method is the hydrolysis of a formamidine. The general reaction can be represented by the following reaction equation:

- TS. -

H-C-N;

, SR

NR ³ R ⁴

NR ³ R ⁴

+ other products

H ₂ O

2 3 4

In the above reaction scheme, R, R, R correspond to the meanings given in connection with the formula I, R ¹ is hydrogen or alkyl (preferably C - C ₁₂ ^υη ^ especially Cj-C, -), while R "hydrogen or one or represents a plurality of ring substituents.

Another method of preparation is that when R is not hydrogen, acyl halides are reacted with substituted or unsubstituted pyridines and the corresponding phosphorodiamidothioate. The reaction proceeds via the formation of an N-acylpyridinium salt. The general procedure, referred to as the "pyridine method", can be represented by the following reaction equation:

J 4 Il 5

R N-P-NHR

xl

(IV)

.NRR

R-C-N-PQ

(VII)

V HY

Ä- 2 1863

12 3 4 5 1 '

R ₁ R,. R, R f R and X have the meanings given in connection with the formula I, with the exception that R is not hydrogen, while

6 7

R and R (if not linked together) are hydrogen,

R and R (when joined together) form the "B" ring of quinoline,

Q · η

R (if not joined to R) is hydrogen, amino, mono- or di- (C 1 -C 4 -alkyl) -amino, or a nitrogen-containing (C ₂ -C _fi ) -heterocyclic ring attached to nitrogen the pyridine ring is linked, such a heterocyclic ring preferably containing ^ or 5 carbon atoms, a nitrogen atom and optionally a heterocyclic oxygen atom,

7 8

R and R (if not connected) the "B" ring

of isoquinoline and Y is chlorine or bromine.

By the aforementioned "B" ring is meant the benzene ring of the fused benzene and pyridine ring system of quinoline or isoquinoline.

The compounds of formula VII are not formed in the presence of amine bases except the pyridines and substituted pyridines of formula V. The compounds of formula V can be used in the presence of acid scavengers and used stoichiometrically or in excess.

The pyridine process is carried out by contacting a pyridine of formula V with (1) the acyl halide and (2) a compound of formula IV to form the desired compound of formula VII. The contacting of the pyridine, acyl halide and the phosphorus compound is preferably carried out at a temperature of about -20 to about 100 ^° C, and preferably in the presence of an inert solvent. The N-acylphosphorus

amide product is extracted.

Typical examples of acyl halides suitable for carrying out the pyridine process are as follows:

Acetyl chloride trichloroacetyl chloride

methoxyacetyl

Octadecanoyl chloride 3-Butinoyl chloride Acryloyl chloride Cyclopropylcarboxoyl chloride Cyclohexylcarboxoyl chloride Benzoyl chloride 4-Chlorobenzoyl chloride 4-Nitrobenzoyl chloride 4-Toluyl chloride Phenylacetyl chloride and 5-phenylpentanoyl chloride

Typical pyridines of the formula V which can be used according to the invention are the following:

quinoline

isoquinoline

pyridine

4-Dimethylaminopyridine 4-Pyrrolidinopyridine 4-morpholinopyridine and 4-piperidinopyridine

Preferably, pyridine, 4-dimethylaminopyridine or 4-pyrrolidinopyridine and in particular pyridine are used.

The pyridine process is preferably carried out in the presence of an inert solvent, preferably an aromatic hydrocarbon, such as toluene. Ätherlösungsmit-

218634

Tel and aliphatic hydrocarbons can also be used.

Typical solvents used to carry out the pyridine process are as follows:

Aromatic hydrocarbons, such as toluene, xylene, benzene, chlorobenzene, bromobenzene, nitrobenzene, butylbenzene, diethylbenzene, dichlorobenzenesia and anisole;

Ether, like

Ethyl ether, tetrahydrofuran, dioxane, isoamyl ether, dimethoxyethane;

aliphatic hydrocarbons, such as pentane, hexane,

Cyclohexane or isooctane.

The temperatures are maintained for carrying out the pyridine method, vary from about -20 to about 100 ⁰ C and preferably from about 0 to about 30 ⁰ C and in particular from about 10 to about 25 ° C.

The pyridine process is usually carried out at atmospheric pressure.

The molar ratio of pyridine: acyl halide di-dilnate may vary from about 0.5: 0.5: 1 to about 4: 4: 1, and is preferably about 2: 2: 1.

The general mode of addition is to add the diamidate and the pyridine to a solution of the acyl chloride in a solvent.

The preferred method of the method is to add 1 equivalent of the diamidate and 2 equivalents of the pyridine in toluene to 2 equivalents of the acyl chloride in toluene.

An up to 4-fold excess of one of the reagents can be used, but in most cases a 2-fold excess of pyridine and acyl chloride is preferred.

Of course, the above methods for the preparation of compounds of formula I are not exhaustive. In general, all methods described in the literature can be applied, which relate to the preparation of analogous compounds.

The S-alkyl phosphorodiamidothioate intermediates of formula IV may be prepared in one or two stages by reaction of an S-alkyl phosphorodichloridothioate with monoalkylamines.

If the two amine groups are different, then S-alkyl phosphorodichloridothioate is reacted with one of the amine groups to form a monochloride intermediate. The second Arning group is then added. For example, one can proceed as follows:

218634

O .... O

Cl ₂ -P-SR ₂ + R ³ R ⁴ NH-> R ³ R ⁴ NP-SR ² + HCl

Cl

Ο O

34 '' 2 ς ^ d "ο RR NP-SR ^ + R ⁵ NH _n -> rVn-P-SIT + HCl

Cl NHR ⁵

R and R are the same (Cj-C ₃₎ -Monoalkylgruppen, then the intermediates are formed by the addition of 2 moles of the amine to the S-Alkylphosphordichloridothioat.

Il 5 5 Il c

Cl ^ -P-SR +. 2R ³ NH ₀ - > R NH-P-NHR ³ + 2HCl 2 2 2 I 2

The above reactions are preferably carried out in the presence of an acid-binding agent such as a dialkylaniline, pyridine or trialkylamine. Two more moles of R NH ₂ can serve as an acid binding agent when R NH _{2 is} the reactant.

For the preparation of both the intermediates and the acylphosphordiamido- (di) -thioates, a substantially equimolar ratio of the reactants is generally preferred. Although not required, the reaction may be advantageously carried out in the presence of an inert organic solvent, for example, an ether, aromatic hydrocarbon, halogenated aromatic hydrocarbon, aliphatic hydrocarbon, aliphatic nitrile, nitroalkyl or nitroaryl or the like, or mixtures thereof. Suitable solvents are, for example, ethyl ether, dioxane, methylene chloride, tetrahydrofuran, benzene, toluene, chlorobenzene, heptane, acetonitrile, nitromethane, nitrobenzene or the like. The reaction is generally carried out in a temperature range of about -20 or -10 to 100 ^° C. or above and preferably

1863

in a range of about 0 to about 6O ⁰ C.

All starting materials used to prepare the compounds of the invention are either known compounds, can be readily prepared by adaptation of known methods, or are described below. For example, the formamidine starting materials are prepared by condensation of an aniline with an N-alkylformamide (U.S. Patent 3,502,720).

The following examples illustrate the preparation of compounds of formula I. The temperatures are in ⁰ C.

embodiments example 1

N-formyl-Ν, Ν ¹ -dimethyl-S- (1-methylpropyl) -phosphordiamidothioate

10 ml of formic acid and 20 ml of acetic anhydride are mixed at room temperature and heated to 50 ⁰ C for 15 minutes and then cooled again in ice. A solution of 39.2 g (0.2 mol) of N, N "-dimethyl-S- (1-methylpropyl) -phosphordiamidothioate and 0.5 ml of 85% phosphoric acid in 30 ml of methylene chloride are added The mixture is warmed to room temperature and stirred at room temperature for 6 days, half of the mixture is diluted in 100 ml CH ₂ Cl ₂ and extracted with 3 100 ml portions of water The methylene chloride is dried over 4 Å molecular sieves, filtered and evaporated to give 12 g (50 % yield) of the product als.öl incurred.

The compounds of the following Examples 2 to 12 are prepared in a manner analogous to Example 1:

- 2186 3 4

Example 2 N-Formyl-Ν, Ν ', N ^f -trimethyl-S- (1-methylpropyl) -phosphordiamidothioate

Example 3 N-Formyl-Ν, Ν'-dimethyl-S- (2-methylpropyl) -phosphordiamidothioate

Example 4 N-Formyl-Ν, Ν ¹ -dimethyl-S-propyl-phosphorodiamidothioate

Example 5 N-Formyl-N, N'-di (2-propenyl) -S- (1-methylpropyl) phosphorodiamidothioate

Example 6 Ν, Ν ^1- Diethyl-N-formyl-S- (1-methylpropyl) -phosphordiamidothioate

Example 7 Ν, Ν ^1- Diethyl-N-formyl-S-propylphosphordiamidothioate

Example 8 N-Formyl-Ν, Ν ¹ , N-trimethyl-S-propyl phosphorodiamidothioate

Example 9 N-Formyl-Ν, Ν ¹ -dimethyl-S- (1-methylethyl) -phosphordiamidothioate

Example 10 N-Formyl-Ν, Ν ¹ -dimethyl-S- (3-methylbutyl) -phosphordiamidothioate

Example 11 S-ethyl-N-formyl-Ν, Ν ¹ -dimethyl-phosphorodiamidothioate

Example 12

N-ethyl-N-formyl-N ¹ -methyl-S- (1-methylpropyl) -phosphordiamidothioate

N-ethyl-N'-methyl-N-ί (4-methylphenylimino) methyl ^ S- (1-methylpropyl) -phosphordiamidothioate is added over a period of time

of over 2 weeks as a 5% active ingredient on Celatom MP-78 (granular diatomaceous earth) having a pH of 5 and a water content of 3%. The organic compounds are extracted by stirring 200 g of the 5% Celatom grains in 1200 ml of toluene for 3 minutes. The solvent is filtered through super-Cel (diatomaceous earth) and evaporated to give 6.7 g of an oil. The product is isolated and purified by preparative liquid chromatography using PrePak-500 silica gel columns in series under a mobile phase of 90% ethyl acetate / 10% isooctane (by volume) at a flow rate of 250 ml / min. The product yield is 2.9 g.

Example 13

Ν, Ν'-Dimethyl-N-acetyl-S- (1-methylpropyl) -phosphordiamidothioate

(A) 7.1 g (0.036 mol) of N, ^N-dimethyl-f S- (1-methylpropylphosphordiamidothioat, 7.44 g (0.073 mol) of acetic anhydride

and 0.1 ml of 85% phosphoric acid are heated under reflux in 10 ml of methylene chloride for 9 hours. The mixture is extracted with two 50 ml portions of water, dried with 4 Å molecular sieves and evaporated to give 7 g of an oil. The product is purified by column chromatography on 20 g Biosil A (silica). Elution with toluene (3 x 100 ml portions) and 1/1 by volume, ether / hexane (250 ml) gives 0.7 g (8% yield) of the product as an oil.

(B) 7.0 g (0.052 mol) of aluminum chloride are dissolved in 30 ml of nitro-methane, which has been dried over 4 Å molecular sieves. The reaction temperature exotherms to 35 ° C. It is cooled to room temperature. 3.8 ml (0,052 mol) of acetyl chloride are added and the reaction mixture

i4 _Λ

- »- 2 1863

tion mixture is stirred for 10 minutes at room temperature. A solution of 5 g (0.026 mol) of N, N'-dimethyl-S- (1-methylpropyl) -phosphordiamidothioate in 20 ml of nitromethane is added, followed by stirring for 8 hours at room temperature. After allowing to stand overnight, the reaction mixture is diluted with 100 ml of ether, extracted with 50 ml of water and then with a 5% sodium bicarbonate solution. The ether layer is dried over 4 Å molecular sieves, filtered and evaporated to give 2.6 g (40% of theory) of the product as a yellow oil. '

Example 14

N, N ¹ -dimethyl-S- (1-methylpropyl) -N-trifluoromethylcarbonylphosphordiamidothioate

15 g (0.08 mol) of N, N ¹ -dimethyl-S- (1-methylpropyl) -phosphordiamidothioate, 25.2 g (0.12 mol) of trifluoroacetic acid, 0.2 ml of an 85% Η-, ΡΟ. and 20 ml of methylene chloride are refluxed for 7 hours. The reaction mixture is extracted with 100 ml of water, dried over 4 Å molecular sieves, heated and evaporated to give 19.2 g of an oil. Purification of 10 g of the material by preparative high pressure liquid chromatography using two PrePak 500 silica gel columns in series and a mobile phase of 70 ethyl acetate / 30 isooctane (by volume) gives 2 g of the product.

Example 15 . , ,

N, N'-dimethyl-S- (1-methylpropyl) -N-nonylcarbonylphosphordiamidothioat

.. <A) A solution of 10.6 g (0.054 mol) of N, N ¹ -dimethyl-S- (1-methylpropyl) -phosphordiamidothioate and 4.3 g (0.054 mol) of pyridine in 4 0 ml of toluene is an ice-cooled Solution of 10.3 g (0.054 mol) of decanolyl chloride in 50 ml of toluene was added. A white solid forms after a few minutes.

SX

The suspension is stirred for 4 days at ambient temperature. It is extracted successively with 250 ml of a 5% sodium bicarbonate solution and 2% hydrochloric acid. The organic layer is dried with 4 A molecular sieves and evaporated to give 15 g of a yellow oil. Chromatography on 60 g Biosil A (elution with 10% ether in toluene) gives 3 g (17% yield) of product.

(B) A solution of 5.3 g (0.026 mol) of N, N'-dimethyl-S- (1)

Methylpropyl phosphorothiamidothioate and 3.80 g (0.026 mol) of 4-pyrrolodinopyridine in 20 ml of toluene are added dropwise over 10 minutes to an ice-cooled solution of 5.13 g (0.026 mol) of decanoyl chloride in 25 ml of toluene at a temperature of 10 to 13 ° C half an hour after completion of the addition is maintained. The reaction mixture is stirred for 24 hours, diluted with 100 ml of ether, filtered and evaporated to give 8.4 g of a crude product. The spectral values (NMR and IR) are similar to those obtained in the case of the compound prepared by Method A of this example.

The following Examples 16 to 27 are carried out analogously to Example 15, Part A.

Example 16 N, N ¹ -dimethyl-S- (1-methylpropyl) -N- (4-nitrophenylcarbonyl) -phosphordiamxdothioate

Example 17 N- (2-Methoxycarbonyl) -ethylcarbonyljN, N'-

dimethyl-S- (1-methylpropyl) -phosphordiamxdothioat

Example 18 N-Methoxymethylcarbonyl-Ν, Ν ¹ -dimethyl-S- (1-methylpropyl) -phosphordiamxdothioate

Example 19 N-Dichloromethylcarbonyl-t, N'-dimethyl-S- (1-methylpropyl) -phosphordiamxdothioate

JLI

1 863

Example 20

Example 21

N I (1-bromoethyl) carb-Nyl-N ^f , N ¹ -dimethyl-S - {1-methylpropyl) -phosphordiamidothioate

N- [{ 1-chloroethyl) carbonyl} N, N · -dimethyl-S- (i-methylpropyl) -phosphordiamidothiate

Example 22 N ₇ N ¹ -Dirnethyl-S- (1-methylpropyl) -N-phenylcarbonyl phosphorodiamidothioate

Example 23 Ν, Ν ^1- Dimethyl-S- (1-methylpropyl) -N- (2-phenethylcarbonyD-phosphorodiamidothiate

Example 24 N-Chloromethylcarbonyl-NjN ¹ -dimethyl-S- (1-methylpropyl) -phosphordiamidothioate

Example 25 N-Broitunethylcarbonyl-Ν, Ν'-dimethyl-1-S- (1-methylpropyl) -phosphordiamidothioate

Example 26 N - ^ (Ethoxycarbonylmethyl) carbonyl-N, N'-dimethyl-S- (1-methylpropyl) -phosphordiamidothioate

Example 27

N-cyclopropylcarbonyl-N'-dimethyl-S- (1-methylpropyl) -phosphordiamidothioate

Example 28

N- (methoxycarbonyl) -carbony1-N, N'-dimethyl-S- (1-methylpropyl) -phosphordiamidothioate

A solution of 10 g (0.051 mol) of N, N ¹ -dimethyl-S- (1-methylpropyl) -phosphordiamidothioate and 8.1 g (0.102 mol) of pyridine in 50 mL of toluene is added dropwise to an ice-cooled solution of 12.5 g ( 0.102 mol) of methoxalyl chloride in 50 ml of toluene. The mixture is stirred for 4 hours at room temperature, filtered to remove the pyridine hydrochloride and evaporated. The remaining oil is diluted with 200 ml of ether, whereby further pyridine hydrochloride is precipitated,

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filtered and evaporated to give 11 g of an oil. Purification by preparative high pressure liquid chromatography using a PrePak 500 silica gel column and a mobile phase of ethyl acetate gives 2.0 g (14% of theory) of the product.

The compounds of the following Examples 29 to 37 are prepared in a manner analogous to Example 28.

Example 29

N- (3-chloropropyl) carbonyl-Ν, Ν'-dimethyl-S- (1-methylpropyl) -phosphordiamidothioate

Example 30

N- (8,11-heptadecadienyl) carbonyl-Ν, Ν'-dimethyl-S- (1-methylpropyl) -phosphordiamidothioate,

Example 31

Ν, Ν'-dimethyl-N- -phosphordiamidothioat (1-propencarbonyl) -S- (1-methylpropyl)

Example 32

Ν, Ν'-dimethyl-N- -phosphordiamidothioat (phenylmethyl) carbonyl-S- (1-methylpropyl)

Example 33

N- (4-chlorophenyl) carbonyl-Ν, Ν ^1- dimethyl-S- (1-methylpropyl) -phosphordiamidothioate

Example 34

N- (2,4-dichlorophenyl) carbonyl-Ν, Ν ^1- dimethyl-S- (1-methylpropyl) -phosphordiamidothioate

Example 35

N-cyclohexylcarbonyl-Ν, Ν ^1- dimethyl-S- (1-methylpropyl) -phosphordiamidothioate

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Example 36

Ν, Ν'-dimethyl-S- (1-methylpropyI) -N- (phenoxymethyl) -carbonylphosphordiamidothioat

Example 37

N- (2-bromoethylcarbonyl) -N, N'-dimethyl-S- (1-methylpropyl) -

phosphorothiamidothioate,.

Example 38

N-Thioformy1-N, N'-dimethyl-S- {1-methylpropyl) -phosphordiamidothioat

17.8 g (0.08 mol) of phosphorus pentasulfide are added to a solution of 14 g (0.063 Mdl) of N-formyl-N, N'-di-butyl-S- ( - ( - methylpropyl) -phosphordiamidothioate in 2 00 ml of pyridine. The reaction temperature exotherms to 55 ° C. After stirring for 24 hours at room temperature, the mixture is diluted with 300 ml of ether and filtered through 5 g Biosil A (silica). Evaporation of the solvent gives 3.1 g of an oil. Purification by high pressure liquid chromatography using a PrePak 500 silica gel column and a mobile phase of 70/30 ethyl acetate / isooctane (by volume) gives 3 g of the product (25% of theory).

Example 39

N-Formyl-N, N ¹ -dimethyl-S- {1-methylpropyl) -phosphordiamidothioate

1.76 g (0.017 mol) of acetic anhydride are added to a solution of 3.0 g (0.014 mol) of N, N'-dimethyl-S- (1-methylpropyl) phosphorodiimidothiate and 0.69 g (0.015 mol) of formic acid in 20 ml of methylene chloride. After 7 days at room temperature, 1.76 g of acetic anhydride and 0.69 g of formic acid are added. After a further 3 days at room temperature, the reaction mixture is concentrated, diluted with 50 ml of chloroform, extracted with three 20 ral portions of 5% sodium bicarbonate, dried over 4 Å molecular sieves, filtered.

triert and evaporated, whereby 2.8 g (83% of theory) of the product are obtained. The compound of the following example is prepared in an analogous manner.

Example 40 N-Formyl-N, N'-dimethyl-S-propyl phosphorodiamidodithioate

In the following Table I the calculated and found elemental analysis values for the compounds of the above Examples 1 to 40 are summarized.

Table I

formula Elemental analysis (38.21) , calculated (found) H 12:50 N C ₇ H ₁₇ N ₂ O ₂ HP Elemental analysis, (40.98) (7.93) 11.76 (12:52) At play empirical C ₈ H ₁₉ N ₂ O ₂ PS (37.30) (8.65) 12:50 (5.10) No. ^C 7 ^H 17 ^N 2 ° 2 ^HP C (34.83) 7:58 (7.94) 13:33 (12:50) 1 ^C 6 ^H 15 ^N 2 ° 2 ^HP 37.50 (46.11) 7.98 (7:51) 10:14 (13:53) 2 40.33 (41.81) 7:58 (7.63) 11:11 (8.10) 3 ^C 9 ^H 21 ^N 2 ° 2 ^HP 37.50 (39.66) 7.19 (8:41) 11.76 (11.92) 4 ^C 8 ^H 19 ^N 2 ^OPS 34.28 (35.55) 7.60 (8.25) 12:50 (10.82) 5 C ₇ H ₁₇ N ₂ O ₃ HP 47.82 (35.05) 8:33 (7.60) 13:33 (12.89) 6 C H N 0 PS 42.85 (40.79) 7.98 (7.19) 11.76 (14:55) 7 C ₈ H ₁₉ N ₂ OPS 40.33 (31.04) 7:58 (8:50) 14:35 (11.94) 8th C ₅ H ₁₃ N ₂ O ₂ PS 37.50 (40.38) 7.19 (6.65) 11.76 (8.14) 9 C ₈ H ₁₉ N ₂ O ₂ PS 34.28 (39.52) 7.98 (8.12) 11.76 (11.94) 10 ^C 8 ^H 19 ^N 2 ° 2 ^HP 40.33 (31.98) 6.66 (8.61) 9:58 (11.98) 11 ^C 8 ^H 16 ^F 3 ^N 2 ° 2 ^HP 30.76 (55.44) 7.98 (5:34) 8.23 (9.60) 12 ^C 16 ^H 25 ^N 2 ° 2 ^HP 40.33 (45.34) 7.98 (7.97) 12:17 (10:42) 13 JL Vl ^. -J £ * ** ^C 13 ^H 20 ^N 3 ° 4 ^HP 40.33 (38.43) 5:47 (5.94) 8.23 (12.19) 14 ^C 11 ^H 23 ^N 2 ° 4 ^HP 32.87 (40.59) 7:35 (6:08) 10:44 (10.81) 15 C ₉ H ₂₁ N ₂ O ₃ HP 56.47 (32.10) 5.79 (7.90) 9.12 (9.84) 16 C ₈ H NCl ₂ PS 45.21 6.80 (5:40) (8:40) 17 39.05 7.83 18 40.29 5:58 19 31.27

Table I (continued) Elemental analysis

At-. , , Elementary analysis, calculated (found)

play empirical Χ formula

_N r-, formula ' -Q-- H "' · " N

20 C ₉ H ₂₀ N ₂ BrO ₂ HP 32.62 (36.00) 6.04 (6.98) 8.46 (8.97)

21 C ₉ H ₂₀ N ₂ ClO ₂ PS 37.69 (40.27) 6.98 (7.33) 9.77 (11.44)

22 C ₁₃ H ₂₁ N ₂ O ₂ HP 52.00 (56.58) 7.05 (7.23) 9.32 (9.74)

23 C ₁₅ H ₂₃ N ₂ O ₂ HP 55.21 (55.42) 7.10 (7.64) 8.58 (8.41)

^{24 C} 8 ^H 18 ^N 2 ^C1O 2 ^HP 35.33 (35.21) 6.65 (6.85) 10.28 (9.81)

25 CgH ₁₈ BrN ₂ O ₂ HP 30.29 (30.54) 5.71 (6.17) 8.83 (8.79)

26 C ₁₁ H ₂₃ N ₂ O ₄ HP 42.58 (42.35) 7.47 (7.64) 9.03 (9.21)

27 C _n H ₀ , N ₀ O ₀ PS 45.45 (45.27) 8.01 (8.15) 10.59 (10.49)

₁₀₂₁₂₃

28 C ₉ H ₁₉ N ₂ O ₄ HP 38.09 (33.15) 6.78 (6.21) 9.92 (10.72)

29 C ₁₀ H ₂₂ ClN ₂ O ₂ HP 39.93 (39.92) 7.37 (7.74) 9.31 (9.63)

30 C ₂₄ H ₄₇ N ₂ O ₂ HP 62.88C62.32) 10.26 (10.79) 6.10 (6.31)

31 ^c ₁₀ ^H 21 ^N 2 ° 2 ^HP 45.45 (46.18) 8.01 (8.10) 10.60 (10.40)

32 C ₁₉ H ₂₃ N ₂ O ₂ HP 53.50 (53.79) 7.37 (7.59) 8.91 (8.77)

33 C ₁₃ H ₂₀ N ₂ ClO ₂ HP 46.59 (45.78) 6.02 (5.94) 8.37 (7.87)

34 C ₁₃ H ₁₉ Cl ₂ N ₂ O ₂ PS 42.28 (42.65) 5.19 (7.79 ^) 7.59 (10.48)

35 C ₁₃ H ₂₇ N ₂ O ₂ HP 50.98 (50.24) 8.88 (9.27) 9.14 (9.09)

36 C ₁₄ H ₂₃ N ₂ O ₃ HP 50.91 (50.83) 7.00 (7.29) 8.50 (8.25)

37 C H BR O O PS 32.62 (36.00) 6.10 (6.98) 8.40 (8.97)

38 C ₇ H ₁₇ N ₂ OPS ₂ 35.00 (35.25) 7.08 (7.55) 11.70 (12.22)

39 C ₇ H ₁₇ N ₂ OPS ₂ 35.00 (35.30) 7.08 (7.22) 11.70 (11.47)

40 C ^ H ,, N ₀ OPS ₀ 31.80 (31.57) 6.68 (6.90) 12.38 (12.01)

6 15 2 2

Assays were performed using the following mites, insects and nematodes:

Code symbol conventional designation Latin designation · Tion

TSM two-leaved leaf spider mite Tetranychus urticae

SAW Southern Army worm Spcdoptera eridania

Nema Southern wort Iknot nematode Meloidogyne incognita

A test solution containing 600 ppm of the test compound is prepared by dissolving the test compound in a solvent (acetone: methanol, 1: 1) followed by a surfactant and then water to adjust an acetone-methanol: water system of 10:10:80 by volume. A 1% by weight mixture of an alkylaryl polyether alcohol (commercially available under the trademark Triton X-155) and a modified phthalic acid / glycerine alkyd resin (commercially available under the trademark Triton B-1956 ') is considered to be the equivalent of 28 g per 380 liters of test, solution and surfactant used.

To perform the mite assay, infected 3.2 cm diameter Phaseuminous Bean Leaves (Phaseolus limeanus) containing about 50 mites are placed in a Petri dish lid on a moistened cotton piece. The leaves are then sprayed with the test solution using a rotating turntable and stored for 24 hours, after which the percentage of kill is determined.

To carry out the armyworm tests detached bean leaves are sprayed on pieces of moistened filter paper in ^s in the manner described above in connection with the mite test in similar dishes and allowed to dry. The dishes are infected with 10 Southern Army worm larvae in the third appearance. The cups are covered. After 48 hours, the percentage of kill is determined.

To perform the nematode test, soil is inoculated homogeneously with a kneaded mixture of tomato roots that have been heavily infested by the root-knot nematodes. 10 ml of the test solution is added to 200 ml of the inoculated soil in a vessel to set a volume concentration of about 30 ppm. The jar is then shaken to ensure thorough mixing, opened immediately.

218634

net and exposed to the action of air for 24 hours. The soil is then transferred to a 7.5 cm plastic pot, whereupon three cucumber seedlings (Cucumis sativus) are planted. About 2-3 days later, the cucumber plants are removed from the soil and the root system examined for the presence of nodules. A total of 15 knots or less is considered an acceptable level of control.

In the following Table II, the results of the above biological studies are summarized for most of the compounds of Examples 1 to 40 above.

table II NEMA ^C - Screen Results ,% Combat + Example no. 'TSM ^a '' SAW ^a , + 1 100 100 + 2 100 100 + . 3 100 100 + 4 100 100 5 100 100 +. 6 100 100 i 100 100 + 8th. 100 100 + . 9 100 , Ϊ00 +. 10 , 100 100 - 11 100 , 100 + 12 , 100 100 13 .100 100 +. 14 100 100 + 15 100 100   + 16 , 100 100 +. 17 , 100 40 +. 18 100 100 +. 19 100 100 20 ; loo 100 21 100 100

Table ΐχ. (Continuation)

Example no. TSM 22 100 23 100 24 100 25 100 27 100 29   100 30 100 31 100 32 100 33 '100 34 100 35 100 36 100 37 .100 38 , 100 39 . ' 100 40 , 100

SAW

100 100 100 100 100 100 0

100 100 100 100 100 100 100 100 100

NEMA

a) TSM = two-leaved leaf spider mite; SAW = Southern Army Worm; NEMA = nematode

b)% control at 600 ppm

c) + means fighting down to 15 knots or less (at 30 ppm in the soil).

Some of the S-alkyl phosphorodiamidothioate intermediates of formula (IV) (wherein X is oxygen) are novel compounds. These new compounds, which also have an arthropozide and / or nematocidal activity, correspond to the following formula VIII

»- 218634

Ir ⁹

wherein R is Co-C-alkyl, for example C, or C ,,

10 y 4

R is hydrogen or methyl,

11

RC ₁ -C ₃ -Al] means CyI or allyl and

R ^{12 is} C ₁ -C ₃ -alkyl or allyl.

A particularly preferred subclass of compounds of the

Formula VIII are those in which R is C _o -C, -alkyl,

10 -ίο

preferably C ₀ -C -alkyl, R is hydrogen,

1112 R is methyl and R is methyl. The preparation of the intermediates of the formula VIII has hitherto been generally described, but the following preparative examples 1 to 9 illustrate specific embodiments.

Production Example 1

N, N'-dimethy1-S- (1-methylpropyl) -phosphordiamidothioat

Excess methylamine is bubbled into an ice-cooled solution of 11 g (0.054 mol) of S- (1-methylpropyl) -phosphordichloridothioate in 50 ml of tetrahydrofuran (THF). The reaction mixture is stirred at room temperature for half an hour, diluted with 200 ml of ether, filtered to remove methyl thy-amine hydrochloride and evaporated to give 10 g (94% of theory) of the product as an orange oil.

Production Example 2

N, N'-dimethy1-S- (2-methylpropyl) -phosphordiamidothioat

Excess methylamine is bubbled into a solution of 50 g (0.24 mol) of S- (2-methylpropyl) -phosphordichloridothioate in 300 ml of ether. The reaction mixture is stirred for 2.5 hours at room temperature and filtered. The ether solution is washed with 100 ml of water, dried over 4 Ä molecular sieves and evaporated to an oil. The washings are saturated with sodium chloride and extracted with ether. The ether solution is dried over 4 Ä molecular sieves and eingedanpft to an oil. The two oils are combined to give 41 g (85% of theory).

The following intermediates are prepared in an analogous manner as in the case of Preparation Example 2.

Production Example 3

N, N'-diethyl-S-propyl-phosphordiamidothioat

Production Example 4

N, N'-diethyl-S- (1-methylpropyl) -phosphordiamidothioat

Production Example 5

S- (1-methylpropyl) -N, N '.- (2-propenyl) -phosphordiamidothioate

Production Example 6

S- (1-methylpropyl) -N, N'-dipropylphosphordiamidothioat

Preparation 7 Ν, Ν'-dimethyl-Sd-methylpropyl) -phosphordiamidothioate

Production Example 8

N, N ¹ , N'-trimethyl-S- (1-methylpropyl) -phosphordiamidothioate

A solution of 5.8 g (0.13 mol) of dimethylamine and 13.0 g (0.13 mol) of triethylamine in 100 ml of THF is added dropwise to an ice-cooled solution of 27 g (0.13 mol) of S- (1-methylpropyl ) phosphorodichloridothioate in 200 ml of THF. The reaction mixture is at room temperature for 1 hour

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touched. A solution of 3.96 g (0.13 mol) of methylamine and 13.0 g (0.13 mol) of triethylamine is added at ice bath temperature. The reaction mixture is stirred for 2 hours at room temperature and allowed to stand overnight. The triethylamine hydrochloride is filtered off and the THF evaporated. 150 ml of ether and 100 ml of hexane are added, whereupon further triethylamine hydrochloride precipitates. The suspension is filtered through super-Cel (diatomaceous earth) and the solvents are evaporated off. This gives 2 6 g (95% of theory) of an oil.

The following intermediate is prepared in an analogous manner as in the case of Preparation Example 8.

Production Example 9

N, N ', N'-trimethyl-S-propylphosphordiamidothioat

The elemental analysis values, calculated and found, are given in the following Table III for most of the compounds of Preparation Examples 1 to 9.

empirical C ₆ H ₁₇ N ₂ OPS table III (36.43) H (9:02) (found) (09.14) tion formula no. C _c H__N _o 0PS (36.32) 8.67 (8.83) N (14.4) manufacturing 1 C ₇ H ₁₉ N ₂ OPS Elemental analysis (39.41) 8.67 (9.35) 14:28 (12.77) 2 C ₅ H ₁₅ N ₂ OPS Elemental analysis, calculated (32.61) 9.10 (8.23) 14:28 (15:40) 3 CHN ₂ OPS C (41.00) 8.24 (8.65) 13:32 (10.10) 7 36.73 8:55 15:38 8th 36.73 12.61 39.98 32.96 43.24

3 '

Most compounds of Preparation Examples 1 and 9 are tested for their biological activity in the manner described above in connection with Examples 1 to 40 for compounds of Formula (I). The results are shown in the following Table IV, wherein the symbols a, b and c have the meanings given in connection with Table II.

Table IV Screen Results,% Control

Herstellungsb sisp.Nr. TSM ^a SAW ^a NEMA ^C 1 100 100   + · 2 100 100 + 3 100 100 + 7 100 0

The compounds according to the invention, namely the compounds of the formulas (I) and (VIII) are suitable for protecting plants against attack by pests. The compounds are particularly effective against arthropods (at various stages of development) as well as members of the class Arachnoidea, which includes the order Acarina, mentioning as mites and ticks, as well as the class Insecta, which include the insects. Of the arthropods which can be effectively controlled by the compounds of the present invention, mention may be made of chewing insects such as the southern army worm (Spodoptera eridania), mites (for example, the two-leaved leaf spider mite (Tetranychus urticae) or the like.

The compounds of the invention further develop an activity as fungicides, in particular for controlling phytopathogenic fungi.

18634

As can be seen from Tables II and IV, the compounds of the invention have a nematicidal activity. Of the nematodes that can be effectively controlled by the compounds of the invention, mention may be made of ground nematodes such as the Southern Root Node Nematode (Meloidogyne incognita).

In general, the control of pests according to the invention is achieved in that the compounds are applied in pesticidal amounts (for example, arthropodizid effective amounts) either directly on the pests to be controlled or on the sites to be freed from such pests or protected against pests , Of particular importance is the use of the compounds of the invention for protecting plants, in particular live plants, which represent or provide economic crops. The plant protection sites may be airborne sites as well as subterranean plant sites, as well as reproductive subunits and their immediate or future environments. For example, wood, fibers, leaves, forests and ornamental plants and stored products to be protected places. The compounds may be placed on or in the soil to which plants, insects, structures or other substrates are deposited as deposits, coatings, etc. The compounds of the invention are useful as essential agents of pesticidal agents used for agricultural as well as sanitary purposes.

The term "combat" used according to the invention means all methods by which the presence or growth of a living organism is adversely affected. For example, a completely killing effect, an eradication, a stoppage of growth, an inhibition, a reduction of the number or a combination thereof are to be understood.

When used as pesticides, one or more of the compounds of the invention, ie, the compounds of formulas (1) and (VIII), are used in conjunction with an agriculturally acceptable carrier or diluent, so that a pesticidal agent is used, generally , 1 to 9 9.9 wt .-%, in particular 1 to 99 wt .-% and most preferably 1 to 88 wt .-% of the active pesticidal component of one or more compounds according to the present invention is used. These pesticidal agents may be in the form of ready-to-use dusts, solutions, emulsions, suspensions, granules or pellets. Optionally, they may be employed in the form of concentrated solutions, wettable powders, emulsifiable concentrates, flowable emulsion concentrates, pastes or dust concentrates, which may each be supplemented with additional liquid (usually water) or finely divided solids as required to dilute solutions, suspensions To obtain emulsions or dusts which are then directly usable as pesticidal agents.

By "agriculturally acceptable carrier or diluent" is meant any substance which is capable of dissolving, dispersing, diffusing or otherwise diluting the active ingredient without affecting the efficacy of the active ingredient without permanently the treated areas, such as the soil, the devices used and the crops are damaged.

When the compounds of the invention are formulated as wettable powders, emulsifiable concentrates, dusts, granular formulations or flowable emulsion concentrates, one or more of the compounds is formulated with a liquid compatible with agricultural use or with

3 *

a solid diluent or carrier acceptable for agricultural purposes, optionally also including suitable surfactants. Surfactants conventionally used are listed in the publication "Detergents and Emulsifiers Annual" by John W. McCiitcheon, Inc. ,

The compounds according to the invention can be taken up in or mixed with a finely divided solid carrier, for example with clays, inorganic silicates, carbonates and silicas. Organic carriers can also be used. Dust concentrates are conventionally prepared with the active ingredient present in an amount of from about 10% to about 20% by weight, however, dust concentrates containing from 10% to 80%, for example, 20% to 80%, of the active ingredient can be prepared %, by weight. For end-use purposes, these concentrates are normally drawn with further finely divided solid to adjust an active ingredient content of from about 1 to about 20% by weight.

Granular formulations are prepared using a granular or pelletized form of a carrier, for example using granular clay, vermiculite, activated carbon or maize waste, these formulations usually containing the active ingredient in an amount of from about 0.1 to about 25% by weight and especially 5 to 15 wt .-% included. Granules, which typically have an average diameter of about 0.5 to 2 mm or comparable sieve sizes, can be prepared by mixing the active pesticidal active ingredient with finely divided inert solids, if necessary with the addition of a binder, whereupon the mixture becomes granules in a granulation device is deformed. Optionally, preformed granules of an inert solid may be treated with the active pesticidal active ingredient.

be layered or impregnated.

Wettable powder formulations may be prepared by incorporating the active ingredient in an inert finely divided solid carrier (e.g., kaolin) together with a surfactant, which surfactant may be an emulsifier, wetting agent, dispersant or spreading agent, or a mixture of these agents , In such formulations, the active ingredient content is usually about 1 to about 35, and more preferably 10 to 35 weight percent. Surface active agents are usually present in an amount of from about 0.5 to about 10 weight percent. Typical surfactants are sodium lauryl sulfate and sodium lignosulfonate.

A convenient method of preparing a solid formulation is to impregnate the active ingredient onto the solid support by means of a volatile solvent such as acetone. In this way, adjuvants such as activators, adhesives, plant nutrients, synergists and various surfactants can also be applied.

Emulsifiable concentrate formulations can be prepared by dissolving the active ingredient in an agriculturally acceptable organic solvent and adding a solvent-soluble emulsifier. Suitable solvents are usually immiscible with water. Mention may be made of hydrocarbons, ketones, esters, alcohols and amides, which are regarded as organic solvents. Solvent mixtures are used in a conventional manner. The surfactants useful as emulsifying agents may be from about 0.5 to about 10% by weight of the emulsifiable concentrate and may be anionic, cationic or nonionic. The concentration of the drug varies between about 1 and about 50 and

-S-218634

in particular between 20 and 50% by weight.

Flowable emulsion concentrates usually contain the active ingredient in an amount of from 1 to 50% by weight, and more preferably from 20 to 40% by weight.

The compounds according to the invention can be applied as pesticides by known methods. Usually, a preparation containing the active ingredient and an agriculturally acceptable carrier is used. In certain cases, however, it may be advantageous and advantageous to apply the compounds directly to the point to be protected against pests or from the pests to be liberated site, without causing a significant amount of carrier is used. This is a particularly effective method when the physical nature of the active ingredients is such that low volume application is possible, i. h., That this method is particularly suitable when it comes to compounds in liquid form or compounds that are very soluble in higher boiling solvents.

The amount applied of course varies depending on the purpose of such application, the active ingredient used, the frequency of application or the like.

For use as insecticides and acaricides, dilute sprays may be applied at a level of from about 5.4 grams to about 11 kilograms of the phosphorodiamido) thioate component per 380 liters of the spray. Usually, an application is made in an amount of about 54 g to 11 kg per 380 l. In the case of more concentrated sprays, the active ingredient is increased by a factor of about 2 to about 12. In the case of diluted sprays, the applications are applied to the plants until runoff is detected, while in the case of more concentrated low volume sprays, the materials are applied as a mist.

For use as a fungicide, the compounds of the invention may be applied as fungicidal sprays by conventional methods, for example in the form of large volume hydraulic sprays, low volume sprays, air blown sprays, air sprays and dusts. The dilution, as well as the amount applied, will depend on the type of device used, the method of application, and the diseases to be controlled, but the preferred effective amount is usually between about 54 g and about 27 kg of active ingredient per 0.4 hectare.

In the case of a fungicidal seed-protecting agent, the amount of seed-coated active ingredient is usually about 2.8 g to about 570 g per 54 kg of the seed. In the case of a soil fungicide, the active ingredient may be incorporated into the soil or applied to the soil surface, usually in an amount of from about 54 g to about 27 kg per 0.4 hectare. In the case of a foliar fungicide, the active ingredient is usually applied to the growing plants in an amount of about 140 g to about 5 kg per 0.4 hectare.

When used as a nematocidal systemic insecticide or as a soil insecticide, the compounds of the present invention may be employed as a solid formulation, preferably as a granular formulation, or as a dilute liquid preparation by littering, side by side fertilization or by seed treatment.

The pesticidal compositions may further be added to a water used for irrigation purposes or to a transplanting water or units used for breeding, such as seeds, tubers, roots, seedlings, etc., for disinfection and / or protection against nematodes, soil insects (and mites). There is also a systemic intake for controlling leaf pests

-w- 2 Ig ^ ₃ 4

possible. The amount used may be about 270 g to about 27 kg per 0.4 hectares, but larger amounts may also be used. The preferred amount is between about 54 g and about 13.5 kg per 0.4 hectares. For incorporation into the soil, the compounds of the invention may be mixed with the soil or other plant growth medium in an amount of from about 1 to about 100 ppm of the active ingredient.

The compounds of the present invention may be used as the sole pesticidal agents, but they may also be used in conjunction with other pesticides, for example, bactericides, fungicides, herbicides, insecticides, acaricides, and nematicides and comparable pesticides.

The following formulation examples illustrate the invention. The percentages are by weight.

Wettable powder

a) 1% iq

1.0% active ingredient

0.5% sodium lauryl sulfate

3.0% sodium lignosulfonate

95.5% kaolin (particle size 10 to 50 microns)

b) 35%

35.0% active ingredient

0.5% sodium lauryl sulfate

3.0% sodium lignosulfonate

20.0% precipitated silica, particle size 1 micron

41.5% kaolin, particle size 10.50 microns

granules

a) 0.1%

0.1% active ingredient

99.9% Celatom MP78 (diatomaceous earth) grains (average diameter -1.5 mm)

b) 25%

% Active ingredient% attapulgite granules (average diameter 1.5 mm or such particle size as to allow passage through a sieve with a mesh size of 1.68 mm (U.S. Standard Sieve Series))% fumed silica, particle size 1 micron.

A solution of the active ingredient is sprinkled on the attapulgite granules, whereupon the fumed silica is added

c) 10%

% ^: Drug% Agsorb MB (montmorrilonite clay, Mississippi Brown)

d) 10%

% Active ingredient% corn reclaimed granules (average diameter 1.5 mm or particle size that allows passage through a sieve with a mesh size of 1.68 mm (US Standard Sieve Series))

e) · 5%

% Active ingredient% walnut shell granules (average diameter 1.5 mm or such that it is possible to pass through a sieve with a mesh size of 1.68 mm (US standard sieve series))

Ο

d 1 8634

If not indicated, the above-mentioned granular formulations are prepared by dissolving the active ingredient in three parts by weight of xylene, whereupon this solution is sprayed onto the granular material and the xylene

is then evaporated. Optionally, the above granular formulations can be prepared by dissolving the active ingredient in four parts by weight toluene and applying this solution to the granular material in a rotating vessel. The toluene is then evaporated off.

Flowable emulsion concentrate

a) 1%

1% active ingredient 41% cyclohexane 57.6% xylene

0.4% mixture of calcium dodecylbenzenesulfonate and octylphenol ethoxylate

b) 50%

50% active ingredient 15% xylene '25% cyclohexanone

10% mixture of calcium dodecylbenzenesulfonate and octylphenol ethoxylate

dust concentrate

a) 10%

10% active ingredient 80% montomorrilonite

b) 20%

20% active ingredient 75% montomorrilonite

5% precipitated silica with a particle size of 1 micron

In the above formulations, the active ingredient consists of a compound of any of Examples 1 to 40 above and Preparation Examples 1 to 9. The active ingredient in the case of each of the above formulations is preferably the compound of Example 1.

A preferred lower class of compounds of formula (I) are those compounds in which R is hydrogen or a substituent defined in connection with formula (I), with the exception of alkadienyl and alkoxycarbornyl, while X is preferably oxygen and one the

3 4

Substituents R and R is hydrogen or Cj-Cj-alkyl, while the other substituent is Cj-Co-alkyl or C ₃ -Cg -alkenyl (especially C ₃ , such as 2-propenyl), and RC, -Cg-alkyl or CU -Cg alkenyl, (especially C ,, such as 2-propenyl). A notable subclass includes links

3 4

in which one of the substituents R and R is hydrogen or C ₁ -C ₅ -alkyl, while the other substituent

5 is C ₁ -C ₃ alkyl, and R is C ₁ -C 6 alkyl.

All of the compounds of this invention are preferably purified to be substantially free from impurities due to their production to a significant extent, especially impurities in the form of unreacted precursors and by-products. The compounds usually contain <0.1%, <0.5%, <1%, <5%, <10% and <15%, by weight, of such impurities, based on the total weight of the compound in question or compounds and the impurities. The above statements refer in particular to the compounds of formula I (wherein R x is H) prepared by hydrolysis of said precursors or analogs of such precursors. In the case of a compound of formula (I) (wherein R is H) obtained by direct hydrolysis of a precursor. and thus having one or more by-products due to such hydrolysis, the compound is preferably less

21 8634

as 20% (more preferably less than 15%, and most preferably less than 5%, and at most less than 20%) by weight of (a), if any, of the precursor plus (b) the or By-products, wherein the amount of (a) plus (b) refers to the total weight of compound, precursor and by-products.

Claims (10)

Invention s claim A pesticidal composition, characterized in that it contains one or more pesticidal active substances as well as an agriculturally acceptable vehicle or an agriculturally acceptable diluent, the active substance being selected from a compound of the formula , 5 NR ³ R ⁴ exists, in which mean: R is hydrogen (especially when X is for Is oxygen, one of the substituents R ³ and R ^{4 is} hydrogen or C ₁ -C ₃ -alkyl and the other substituent is Cj-C ₃ -alkyl or C ₃ -Cg -alkenyl, and R ^{5 is} Cj-Cg-alkyl or C ^ Cg - «- 2 18634 C ₁ -C ₁₂ alkyl substituted with up to three identical or different substituents selected from chlorine, bromine and fluorine; C ₁ -C ₂ -alkyl substituted with a substituent selected from cyano, nitro, C ₁ -C 6 -alkoxy, C ₁ -C 6 -alkylthio, C ₁ -C 6 -alkylsulfinyl, C ₁ -C 8 -alkylsulfonyl, (C ₁ -Cg -ARyI) carbonyl, (C ₁ -C 9 alkoxy) carbonyl, (C ₁ -C 9 alkyl) carbonyloxy, mono- or di (C ₁ -C 6 alkyl) aminocarbonyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl , Phenyl carbonyl, phenoxycarbonyl, phenylcarbonyloxy, phenylaminocarbonyl, ( ^C 3 -C 9 -alkenyl) -oxycarbonyl, (C 1 -C 6 -alkenyl) -carbonyloxy, aminocarbonyl and (C ₁ -C 9 -alkyl) -carbonylamino; C ₃ -C -alkynyl, C ₂ -C -alkenyl, C 1 -C ₁₇ -alkadienyl, C 1 -C 6 -cycloalkyl, (C 1 -C 6 -alkoxy) -carbonyl, phenyl, phenyl-C, C 1 -C 4 -alkyl; phenyl or phenyl-C 1 -C 4 -alkyl, each ring-substituted with up to three identical or different substituents selected from cyano, nitro, halogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 4 -alkyl, C ₁ -C 4 -alkylthio, C ₁ -C 6 -alkylsulfinyl, C ₁ -C 4 -alkylsulfonyl, phenoxy, C ₁ -C 6 -halogenoalkyl, trifluoromethyl, mono- or di- (C ₁ -CG) -alkylaminocarbonyl, (C ₁ -C 6 -alkoxy) - carbonyl, (C ₁ -C 9 -alkyl) carbonyl, (C ₁ -C 6 -alkyl) -carbonyloxy, phenylthio, phenylsulfinyl, phenylsulfonyl, benzyl, phenylcarbonyl, phenoxycarbonyl, phenylcarbonyloxy, phenylaminocarbonyl, (C ₃ -C 6 -alkenyl) -oxycarbonyl, (C ₃ -C 9 -alkenyl) -carbonyloxy, aminocarbonyl and (C ₁ -C 8 -alkyl) -carbonylamino, R ^{2 is} C ₂ -Cg -alkyl; R (if not connected to R) is hydrogen, _Cj-C3 alkyl or _C3 -CG-alkenyl; 4
R is hydrogen, C ₁ -C ₃ -alkyl or Cj-Cg-alkenyl; R (if not attached to R) hydrogen; C ₁ -C ₁₂ "alkyl; C - C _{1 2} alkyl substituted with a substituent selected from cyano, nitro, C ₁ -Cg, C ₁ -C 6 -alkylthio, C ₁ -C 6 -alkylsulfinyl, C ₁ -C 5 -sulfonyl , (C ₁ -C 9 -alkyl) carbonyl, (C ₁ -C 9 -alkoxy) carbonyl, (C ₁ -C 9 -alkyl) carbonyloxy, mono- or di- (C 1 -C 4 -alkyl) -aminocarbonyl, phenoxy, phenylthio, phenylsulfinyl ₇ phenylsulfonyl, phenylcarbonyl, phenoxycarbonyl, phenylcarbonyloxy, phenylaminocarbonyl, (C ₃ -C _fi alkenyl) oxycarbonyl, (C ₃ -C, - Alkeriyl) carbonyloxy, aminocarbonyl, and (Cj-Cg-alkyl) carbonylamino C ₃ -C ₁₂ -alkynyl; C ₃ -C ₁₂ -alkenyl; C ₃ -Cg -cycloalkyl; phenyl; phenyl-C ₁ -C ₄ -alkyl; phenyl or phenyl-C ₁ -C ₁ -alkyl, each ring-substituted with up to three identical or different substituents selected from cyano, nitro, halo, C ₁ -Cg -alkyl, C ₁ -Cg -alkoxy, C ₁ -Cg -alkylthio, Cj-Cg-alkylsulfinyl, Cj-Cg-alkylsulfonyl , phenoxy, C.-Cg haloalkyl, mono- or di- (C ₁ -CG alkyl) aminocarbonyl, (C ₁ -CG -alkoxy) carbonyl, (C.-Cg-alkyl) -Carbon yl, (C ₁ -C 9 -alkyl) -carbonyloxy, phenylthio, phenylsulfinyl, phenylsulfonyl, benzyl, phenylcarbonyl, phenoxycarbonyl, phenylcarbonyloxy, phenylaminocarbonyl, (C ₁ -C 6 -alkenyl) -oxycarbonyZ, (C ₃ -C 6 -alkenyl) -carbonyloxy, Aminocarbonyl and (C 1 -C 8 -alkyl) carbonylamino; in which R and R (when joined together) together form a heterocyclic ring of the formula can form, in which a -CH ₃ CH ₂ -group, -CH ₂ CH ₀ CH ₀ group or -CH _O CH _O CH _O CH _O -group, .X oxygen or sulfur Z Z Z - | Z is Fei and X ^{1 is} oxygen or sulfur. 2. Composition according to item 1, characterized in that R is hydrogen or a substituent other than alkadienyl and alkoxycarbonyl (in particular CH ₃ , ^c o ^H 5 ', cyclopropyl or CF ₇ ), X is oxygen, one of 3 4
Substituents R and R are hydrogen or C ₁ -Co ~ alkyl and 5 is the other C 1-13 -j-alkyl or 2-propenyl; and R is Cj-Cg-alkyl or 2-propenyl. 3. A composition according to item 1, characterized in that R is hydrogen, Cj-C ^ alkyl, halogen (C ₁ -Cg) alkyl, (C ₁ -C. alkoxy) carbonyl (C ₁ -Cg -alkyl), (C ₁ -C ₄ -alkoxy) -C ₁ -C 6 -alkyl, phenoxy-C ₁ -C ₆ -alkyl, phenyl optionally substituted by nitro or halogen, phenyl- (C ₁ -C 6) -alkyl, 3 is C ₃ -Cg -cycloalkyl or C ₃ -Cg -alkenyl, R is C ₁ -C or C ₃ -C 9 -alkenyl, R is hydrogen or C ₁ -C ₃ -alkyl, and R C is -C -alkyl or C ₃ -Cg alkenyl. 4. Means according to item 1, characterized in that R is Cj-Cg-alkoxycarbonyl or C ₄ -C. _7- alkadienyl. 5. Means according to item 1, characterized in that R is hydrogen, methyl, ethyl, methoxymethyl, cyclopropyl or trifluoromethyl, RC ₃ -C ₄ -A ^ yI, RC ₁ -C ₃ alkyl or Co alkenyl, R is hydrogen or methyl, and R is hydrogen, methyl or Represents ethyl. 6. A composition according to item 1, characterized in that (1) R is hydrogen, R ^{2 is} 1-methylethyl or 1-methylpropyl, R is methyl, R is hydrogen, R is methyl, X is oxygen and X is oxygen. 1 "> (2) R is hydrogen, R 'is 1-methylpropyl, R ^{3 is} methyl, R ^{4 is} hydrogen, R ^{5 is} methyl, X is sulfur and X is oxygen, (3) R is hydrogen, R ² 1- Methylpropyl, R ^{3 is} methyl, R is hydrogen, R is ethyl, X is oxygen and X ^{1 is} oxygen, or (4) R ¹ .for. "Methyl, tri- 2 is fluoromethyl, methoxymethyl or cyclopropyl, R O A ί-methylpropyl, R is methyl, R is hydrogen, X is oxygen and X is oxygen. 7. Composition according to item 1, characterized in that the active ingredient consists of a compound of formula R ¹² HN - ρ "- exists in which R ^{9 is} C 3 -C 12 -alkyl, 10 ^{3 6} R is hydrogen or methyl, R ^{11 is} C ₁ -C 4 -alkyl or allyl and R ^{12 is} C ₁ -C ₃ -alkyl or allyl. 8. Composition according to item 7, characterized in that R is C ₃ -C -alkyl, R is hydrogen, R 12 Methyl is and R is methyl. 9. Composition according to items 1 to 8, characterized in that the active ingredient is present in an amount of 0.1 to 99 and preferably 1 to 99 wt .-% and the agent preferably consists of a granules, the 0.1 to 25 Wt .-% of one or more of the active ingredients. 10. A method for protecting living plants against the attack of pests in the form of phytopathogenic fungi, acarids, insects and / or nematodes, characterized in that directly on the pests or on the pests to be protected against a means, according to one of Points 1 to 8 is applied.