CH625209A5 - Process for the preparation of novel aminothiocarbamates and their use as active ingredient in pesticides - Google Patents

Description

The invention relates to a process for the preparation of new aminothiocarbamates and their use as active ingredient in pesticides.

625209

4th

Research is generally being carried out to find chemical pesticides which are effective, more economical to produce and to apply and which are less toxic and more sustainable to insecticides than the desired fauna.

In general, new organic chemicals should also be created that are highly effective in controlling insect pests and preventing insect damage. These new organic chemicals should preferably be more toxic to insects and less toxic to warm-blooded animals than known pesticides.

The process according to the invention for the preparation of new aminothiocarbamates of the formula

0

tr

• CK.

n:

means in which R7 represents an alkyl radical with 1 to 3 carbon atoms or a phenyl radical, Rs stands for an alkyl radical with 1 to 3 carbon atoms and R "represents an alkyl radical with 1 to 3 carbon atoms or a radical -SR10

5 where R10 is an alkyl radical which consists of the same alkyl radical as the alkyl radical R7, and R7 and R10 together with the atoms to which they are attached form a heterocyclic ring containing two sulfur atoms of the formula:

io n:

15

/ \

wherein n represents 2 or 3 and the alkylene part of the ring is optionally substituted by one or two methyl radicals, or in which X and Y together with the carbon atom to which they are attached form a heterocyclic ring of the formula containing two sulfur atoms :

in which mean:

Rt a residue of the formula

25th

(

<ch, k

(a)

in which R4, Rä and Re are the same or different and are hydrogen or halogen atoms, alkyl radicals with 1 to 5 carbon atoms, alkoxy radicals with 1 to 5 carbon atoms, alkylthio radicals with 1 to 5 carbon atoms, dialkylamino radicals with identical or different alkyl parts each with 1 to Can represent 3 carbon atoms or a radical -N = CHN (CH31) 2; or the formula:

11

wherein m is 2 or 3 and the alkylene part of the ring is optionally substituted with one or two methyl radicals, R, and R3, which may be the same or different, an alkyl radical with 1 to 6 carbon atoms, a 35 cycloalkyl radical with 3 to 6 Carbon atoms are a radical of the formula:

40

11

c = n -

(b) in which Q and Rtl are the same or different and can represent 45 hydrogen or chlorine atoms or methyl radicals; or a remainder of the formula:

in which X and Y are the same or different and alkyl radicals with 1 to 5 carbon atoms, alkylthio radicals with 1 to 5 carbon atoms, monocyano-substituted alkylthio radicals with 1 to 5 carbon atoms or phenylthio radicals with an unsubstituted or mono- to trisubstituted phenyl moiety, the substituents being identical or different are and from halogen atoms, alkyl radicals with 1 to

4 carbon atoms, cyano residues, alkoxy residues with 1 to

5 carbon atoms, phenyl radicals or dialkylaminocarbonyl radicals with the same or different alkyl parts each having 1 to 3 carbon atoms, and where in the case that X represents a hydrogen atom, Y represents a radical of the formula

-fCH.4

B "

50

form where D is 1 or 2, or R2 and Ra together with the nitrogen atom to which they are attached form an alkylene ring with 4 or 5 ring carbon atoms, a radical of the formulas:

55

f n

60

V

■ c

0

'12

12

and '

n

V

s

■ 4

12

r,

c - s-

r,

Form 65, in which R12 represents a hydrogen atom or an alkyl radical having 1 to 3 carbon atoms, or a 4-M> thylpiperazinorest, is characterized in that a compound of the formula '

5

625209

(a)

0

fl o r1 ° cn \

^ h with a) ^ N-S-Cl in an organic solvent,

R *

or with R2

b) ^ N-H in sulfur dichloride in an organic

R *

in which R4, R5 and R0 are the same or different and io hydrogen or halogen atoms, alkyl radicals with 1 to 5 carbon atoms, alkoxy radicals with 1 to 5 carbon atoms, alkylthio radicals with 1 to 5 carbon atoms, dialkylamino radicals with the same or different alkyl moieties 1 to a-15 can finally represent 3 carbon atoms or a radical -N = CHN- (CH3) 2; or the formula:

Implement solvent.

The novel aminothio derivatives of N-H-carbamate insecticides which can be prepared according to the invention can be used, for example, as insecticides, mite control agents and and nematocides and have a more sustainable effect under certain environmental conditions, can be processed into a wide variety of formulations which can be applied advantageously and have an improved spectrum of action. The new organic chemicals which can be prepared according to the invention are generally even in low concentrations against a wide variety of insect pests, for example domestic flies, mosquitoes, mosquito larvae, bladder fever, Mexican ladybugs, aphids, worms, alfalfa leaf grain beetles, larvae from the cotton seed damaging bumpers , Salt marsh caterpillars, crickets, cockroaches, lice, ticks, fleas, root tuber nematodes, spider mites, citrus red mites and Colorado potato beetles, effective.

In the following, the term “insect pests” is usually to be understood to mean any harmful insects of any kind. The term "insect" normally corresponds to the meaning of the Federai Insecticide, Fungicide and Rodenticide Act of 1947. In general, the term "insect" stands for organisms belonging to the Arthropoda order. Examples of these are from the “Insects” class, for example the orders Isoptera, Thysanoptera, Mallo-phaga, Hemiptera, Anoplura, Homoptera, Coleoptera, Lepi-doptera, Orthoptera, Diptera and Hymenoptera, and from the Arachnida class, for example the orders Araneae and Acarina.

As already mentioned, the new compounds which can be prepared according to the invention and are active against insects, mites and nematodes are, characteristically, aminothio derivatives of N-H-carbamate insecticides. The parent compounds, namely the N-methyl carbamates, generally belong to a broad class of organic chemicals that have been prepared in a variety of ways.

New aminothiocarbamates which can be prepared according to the invention and which are referred to as Group A below correspond to the formula:

4>

vc = n -

(b)

Ri-0

0

X

■ c-

X.

ch *

R =

in which mean:

R, a residue of the formula:

25 in which X and Y are the same or different and are alkyl radicals with 1 to 5 carbon atoms, alkylthio radicals with 1 to 5 carbon atoms, monocyanosubstituted alkylthio radicals with 1 to 5 carbon atoms or phenylthio radicals with a 30 unsubstituted or mono- to trisubstituted phenyl moiety , where the substituents are identical or different and consist of halogen atoms, alkyl radicals with 1 to 4 carbon atoms, cyano radicals, alkoxy radicals with 1 to 5 carbon atoms, phenyl radicals or di-35 alkylaminocarbonyl radicals with the same or different alkyl moieties each with 1 to 3 carbon atoms, , and it is true that in the case that X represents a hydrogen atom, Y represents a radical of the formula:

40

45

• r7

wherein R, represents an alkyl radical with 1 to 3 carbon atoms or a phenyl radical, Rg stands for an alkyl radical with 1 to 3 carbon atoms inclusive and R9 represents an alkyl radical with 1 to 3 carbon atoms inclusive or a -SR10 radical with R10 is an alkyl radical which consists of the same alkyl radical as the alkyl radical R7, and R7 and R10 together with the atoms to which they are attached form a 55 heterocyclic ring containing two sulfur atoms of the formula:

60

wherein n represents 2 or 3 and the alkyl portion of the ring is optionally substituted with one or two methyl radicals; or in which X and Y together with the carbon atom to which they are attached form a heterocyclic ring containing two sulfur atoms of the formula:

625209

6

c-n -

wherein m is 2 or 3 and the alkylene part of the ring is optionally substituted with one or two methyl radicals;

R2 and R3 (which may be the same or different) are an alkyl radical with 1 to 6 carbon atoms,

a cycloalkyl radical having 3 to 6 carbon atoms inclusive, a radical of the formula:

in which Q and R1X are the same or different and can represent hydrogen or chlorine atoms or methyl radicals; or a remainder of the formula:

in which X and Y are the same or different and io from alkyl radicals with 1 to 5 carbon atoms inclusive, alkylthio radicals with 1 to 5 carbon atoms inclusive, monocyano-substituted alkylthio radicals with 1 to 5 carbon atoms inclusive, or phenylthio radicals with an optionally mono- to trisubstituted 15 Can represent phenyl part, the relevant substituents of the phenyl part being the same or different and consisting of halogen atoms, alkyl radicals having 1 to 4 carbon atoms, cyano radicals, alkoxy radicals having 1 to 5 carbon atoms, phenyl radicals or dialkyl-20 aminocarboxyl radicals having the same or different alkyl parts each have 1 to 3 carbon atoms inclusive, and in which, in the case that X represents a hydrogen atom, Y represents a radical of the formula:

4ch24-

<3

wherein D represents 1 or 2, or

R2 and Rs together with the nitrogen atom to which they are attached, an alkylene ring with 4 or 5 ring carbon atoms, a remainder of the formulas:

25th

30th

ra — c s r7

Rs

/ -r1

n '0

'1 2

and

12th

represents in which R7 represents an alkyl radical with 1 to 3 carbon atoms or a phenyl radical, Rs represents an alkyl radical with 1 to 3 carbon atoms including 35 and R0 represents an alkyl radical with 1 to 3 carbon atoms inclusive or a radical -SR10, wherein R10 is an alkyl radical of the same meaning as the alkyl radical R7. And in which R7 and R10 together with the atoms to which they are attached form a heterocyclic ring containing two sulfur atoms of the formula:

wherein R12 represents a hydrogen atom or an alkyl radical having 1 to 3 carbon atoms inclusive, or a 4-methylpiperazinorest

A further group of compounds which can be prepared according to the invention (group B) expediently includes those compounds of group A which correspond to the formula given, in which Rx for a radical of the formula:

x (ch2) s

45

-c / \

rb with n = 2 or 3 and an alkylene part optionally substituted by one or 50 two methyl radicals in the ring; and in which X and Y together with the carbon atom to which they are attached form a heterocyclic ring having two sulfur atoms of the formula:

Re stands in which R4 and R5 represent hydrogen atoms and R "has the meaning given and in which the radicals R2 and R3 have the meaning given.

A further group of compounds which can be prepared according to the invention (group C) preferably includes those compounds of group A which correspond to the formula given in which R! a remainder of the formula:

55

60

r.

with m = 2 and an alkylene part optionally substituted by one or two methyl radical (s) in the ring, and in which R2 and R3 furthermore have the meaning given.

65 Another group of compounds which can be prepared according to the invention (group D) preferably includes those compounds of group C which correspond to the formula given, in which Rj for a radical of the formula:

7

625209

\ ✓

U.N-

in which X and Y together with the carbon atom to which they are attached form a heterocyclic ring having two sulfur atoms of the formula:

c (ch2),

s ^

form m with m = 2 and an alkylene part optionally substituted by one or two methyl radicals in the ring, and in which R2 and Ra also have the meaning given.

A further group of compounds which can be prepared according to the invention (group E) normally includes those compounds of group A which correspond to the formula given, in which Rx for a radical of the formula:

stands, wherein R2, R3, R4, R5 and R6 have the meaning given.

Another group of compounds which can be prepared according to the invention (group F) preferably includes those compounds of group E which correspond to the formula given, in which R4 represents a hydrogen atom or an alkyl radical having 1 to 5 carbon atoms, R5 is an alkyl radical having 1 to 5 inclusive Represents carbon atoms and R0 is a hydrogen or halogen atom or an alkylthio radical having 1 to 5 carbon atoms or a dialkylamino radical having identical or different alkyl moieties each having 1 to 3 carbon atoms and in which R2 and R3 have the meaning given in group A.

Another group of compounds which can be prepared according to the invention (group G) normally includes those compounds of group F which correspond to the formula given in which R2, Rs, R4 and R5 have the meaning given for group I and R0 for a dialkylamino radical having the same or different Alkyl parts with 1 to 3 carbon atoms included.

A further group of compounds which can be prepared according to the invention (group H) expediently includes those compounds of group F which correspond to the formula given in which the radicals R2, R3, R4 and R5 have the meaning given for group A and Rs for an alkylthio radical with 1 up to and including 5 carbon atoms.

Another group of compounds which can be prepared according to the invention (group I) usually includes those compounds of group F which correspond to the formula given, in which R2, R3, R4 and Rs have the meaning given for group F and R0 is a halogen atom.

A further subgroup of the compounds which can be prepared according to the invention (group J) preferably includes those compounds of group F which correspond to the formula given in which R2, Ra, R4 and R5 have the meaning given for group F and R0 represents a hydrogen atom.

5 A further subgroup of compounds which can be prepared according to the invention (group K) generally includes those compounds of group J which correspond to the formula given in which R4 represents a hydrogen atom.

Another group of compounds which can be prepared according to the invention (group L) expediently includes those compounds of group J which correspond to the formula given, in which R4 represents an alkyl radical having 1 to 5 carbon atoms inclusive.

Preferred compounds of groups F, G, H, I, J 15 and L are those in which the alkyl radicals are in the 3- and 5-positions of the phenyl ring.

Preferred group K compounds are those in which the alkyl radical is in the 3-position of the phenyl ring.

Another group of compounds which can be prepared according to the invention (group O) generally includes those compounds of group C which correspond to the formula given, in which X and Y are identical or different and consist of alkyl radicals having 1 to 5 carbon-25 inclusive Substitute atoms, alkylthio radicals with 1 to 5 carbon atoms inclusive, monoeyano-substituted alkylthio radicals with 1 to 5 carbon atoms inclusive or phenythio radicals with an optionally mono- to trisubstituted phenyl part, where the substituents 30 are the same or different and consist of halogen atoms, alkyl radicals with 1 up to and including 4 carbon atoms, cyano radicals, alkoxy radicals with 1 to 5 carbon atoms, phenyl radicals or dialkylaminocarbonyl radicals with the same or different alkyl moieties each with 1 to 35 including 3 carbon atoms, and R2 and R3 have the meaning given for group C. n.

Another group of compounds which can be prepared according to the invention (group N) usually includes those compounds of group M which correspond to the formula given, in which X represents an alkyl radical having 1 to 5 carbon atoms inclusive, Y has the meaning given for group M and R2 and Rg have the meaning given for group C.

45 Another group of compounds which can be prepared according to the invention (group O) generally includes those compounds of group N which correspond to the formula given, in which Y represents an alkylthio radical having 1 to 5 carbon atoms inclusive or a phenylthio radical with an optionally one to one triple substituted phenyl part, the substituents being the same or different and consisting of halogen atoms, alkyl radicals having 1 to 4 carbon atoms, cyano radicals or alkoxy radicals having 1 to 5 carbon atoms, 55 and Ro and R3 have the meaning given for group C.

A further group of compounds which can be prepared according to the invention (group P) generally includes those compounds of group N which correspond to the 60 formula given, in which Y represents a monoeyano-substituted alkylthio radical having 1 to 5 carbon atoms inclusive and R2 and R which are in group C have the specified meaning.

Another group of compounds which can be prepared according to the invention (group Q) expediently includes those compounds of group N which correspond to the formula given, in which Y is a dialkylaminocarbonyl radical having the same or different alkyl moieties

625209

8th

• each has 1 to 3 carbon atoms and R2 and R3 have the meaning given for group C.

A further group of compounds which can be prepared according to the invention (group R) normally includes those compounds of group O which correspond to the formula given in which Y represents a phenylthio radical with an optionally mono- to trisubstituted phenyl part, the substituents being identical or different and may consist of halogen atoms, alkyl radicals having 1 to 4 carbon atoms, cyano radicals or alkoxy radicals having 1 to 5 carbon atoms, and R2 and R3 have the meaning given for group C.

A further group of compounds which can be prepared according to the invention (group S) generally includes those compounds of group O which correspond to the formula given, in which Y represents an alkylthio radical having 1 to 5 carbon atoms inclusive and R2 and R3 have the meaning given for group C. have.

A further group of compounds which can be prepared according to the invention (group T) generally includes those compounds of group C which correspond to the formula given, in which the radical R, the formula:

. x /

in which X and Y together with the carbon atom to which they are attached form a heterocyclic ring containing two sulfur atoms of the formula:

f * i \

S S.

II

form with m - 2 or 3 and an alkylene part optionally substituted with one or two methyl radicals in the ring, and R2 and R3 have the meaning given for group C.

Another group of compounds which can be prepared according to the invention (group U) usually includes those compounds of group C which correspond to the formula given in which R! of the formula:

X

\

C = N

/

Y

in which X represents a hydrogen atom and Y represents a radical of the formula:

i r8 — c —s — r7

I.

r9

represents in which R7 represents an alkyl radical with 1 to 3 carbon atoms or a phenyl radical, Rg represents an alkyl radical with 1 to 3 carbon atoms and R "represents an alkyl radical with 1 to 3 carbon atoms or a radical of the formula -SRi, n,

in which R10 represents an alkyl radical of the same meaning as the alkyl radical R7, and R7 and R10 together with the atoms to which they are attached form a heterocyclic ring containing two sulfur atoms of the formula:

5

with n = 2 or 3 and an alkyl part in the ring which is optionally substituted by one or two methyl radicals, form 15 and furthermore R2 and R3 have the meaning given for group C.

A further group of compounds which can be prepared according to the invention (group V) normally includes those compounds of group U which correspond to the formula given in which R7 is an alkyl radical having 1 to 3 carbon atoms or a phenyl radical, Rg is an alkyl radical having 1 to or including Represents 3 carbon atoms and R8 is an alkyl radical having 1 to 3 carbon atoms inclusive, and furthermore R2 25 and Rj have the meaning given for group C. Another group of compounds which can be prepared according to the invention (group W) usually includes those compounds of group U which correspond to the formula given in which R7 is an alkyl radical having 1 to 30 including 3 carbon atoms or a phenyl radical, Rg is an alkyl radical having 1 to including 3 carbon atoms and R9 represents a radical -SR10, in which R10 represents an alkyl radical of the same meaning as the alkyl radical R7 and R7 and R10 together with the atoms 35 to which they are attached form a heterocyclic ring containing two sulfur atoms of the formula:

45 with n = 2 or 3 and an alkylene part optionally substituted by one or two methyl radicals in the ring, and furthermore R2 and R3 have the meaning given for group C.

A further group of compounds which can be prepared according to the invention (group X) expediently include those compounds of group U which correspond to the formula given in which R7 is an alkyl radical having 1 to 3 carbon atoms or a phenyl radical, Rs is an alkyl radical with 1 up to and including 3 carbon-55 atoms and R9 is a radical of the formula -SR10, where R7 and R10 together with the carbon atoms to which they are attached form a heterocyclic ring containing two sulfur atoms of the formula:

with n = 2 or 3 and an alkylene part optionally substituted by one or two methyl radicals in the ring,

9

625209

and furthermore R2 and R3 have the meaning given for group C.

The term “alkyl radicals having 1 to 6 carbon atoms inclusive” includes, for example, methyl, ethyl, propyl, butyl, pentyl or hexyl radicals or their isomers. Alkyl residues with a lower carbon atom content usually stand for corresponding residues of corresponding carbon content. The term “alkylthio radicals” is usually understood to mean a unit of the formula: alkyl-S-, in which the rest of the molecule is bonded to the sulfur atom. The term "phenylthio residue" can generally be defined in a similar way. "Dialkylamino residues" usually include units of the formula:

alkyl ^

"tn -

alkyl ^

to understand where the rest of the molecule is attached to the nitrogen atom. Halogen atoms are usually to be understood as fluorine, chlorine, bromine and iodine atoms.

The new organic compounds which can be prepared according to the invention are obtained from N-methylcarbamate precursors by two different, generally known processes. In one process, the desired amount of the respective N-methylcarbamate is preferably dissolved in tetrahydrofuran together with an equivalent or, if appropriate, an excess of an acid acceptor, such as trialkylamine, for example triethylamine. The mixture obtained is then expediently heated to a temperature of cooled about 10 ° C and with stirring with an equivalent of an aminosulfenyl chloride of the formula:

. r2

nn - s — ci offset. The reaction mixture is then usually stirred until the reaction has ended. The stirring can take 5 to 8 days. After the reaction has ended, the reaction mixture is filtered, whereupon the solvent is evaporated off under reduced pressure from the filtrate. The evaporation residue is purified by chromatography, advantageously by means of adsorption chromatography on silica gel.

In the other method, a solution of a secondary amine, e.g. a dialkylamine, such as dimethylamine, dissolved in a suitable organic solvent, for example n-hexane, whereupon the solution obtained is slowly added dropwise to a solution of sulfur dichloride in a similar solvent, for example cooled to -5 ° C.

The cooled reaction mixture is then stirred for a period of time, for example 30 minutes, to allow the reaction to proceed to completion. Then the reaction mixture is usually filtered in order to separate out precipitated salts. The separated salts are washed with, for example, diethyl ether. The desired secondary aminosulfenyl chloride is normally obtained in the concentrate after removal of the excess solvent by evaporation. The evaporation residue obtained in this way can then slowly, for example dropwise, into a solution of the desired N-methyl carbamate in a suitable organic solvent, for example dimethylformamide, which is an acid acceptor; suitably a tertiary amine, e.g. contains a trialkylamine such as triethylamine. The reaction mixture obtained in this way is preferably quenched with water, whereupon the desired disubstituted aminothioalkylcarbamate is separated off and purified in a conventional manner, for example by solvent extraction, washing to remove traces of salt, drying and removal of the extraction solvent.

The following table contains examples of aminothiocarbamates which can be prepared according to the invention:

35

ri v> d £

r *

r «

r,

r,

H

H

H

CH3 CiL,

H

2-CH3

4-C, H7

O CH »

3-CA

4-iso-CgHj

5-CA

CjH, iso-CßH ^

2-C, Hold

H

6-iso-CsHn

.c2h5

-i \

2-C3H7 '

4-iso-C3H7

6-GjH7

0 0

625209

10th

Ri

Rs

R,

R,

R *

3-C2H5

2-C1

3-C1 H

2-1

2-OCH3

3-oc2hg

4-OCsH ^

2-C4H9

3-SCH3

3-SCH3 H

3-SC2H5 H

2-N (CaH7) 2H

2-N (C2H5) 2

H H

4-tert-C4H "

H

5-C1 4-F

4-Br 3-OCH3

5-0-tert.-C4H9 • H

5-C4H9

H

4-S-tert-C4Hn

H

5-SC2H5 H

H

3-N; H

H H

CH ^ CA

6-CH3

4-Br

6-C1 H

6-F

4-OCH3 H

ö-O-iso-CjH,

6-C4H9

6-SC4H9

5-SC2H5

4-SCsHn

6-SCÄ

3-N (CHa) 2

5-N (C3H7) 2

4-N (CH3) 2

6-N (C2H5) 2

3-N = CHN (CH3) 2 3-N = CHN (CH3) 2

CH3 iso-C3H7

cttfö -O-cî

tert-C4'H9

v

CHg C6H1S

-a

CHS -CH.CH ^

o iso-C4H,

CM

ç?

-Gkh>

cä

q - <h * c c2h5 c2h5

-CH.-Q CH ^

cp d "

iso-C3H7 -CH2CH2

ÇHj

-q

CH3

V

CH,

4th

cä

CH,

cv

11

625209

r4

R «

Rß

R *

R,

3-N = CHN (CH0) 2 H

3-C4H9

2-iso-C0H7

3-OC4H9

2-br

3-CHa 2-SC »Hb h

2-CM,

Zn5

5-Br

4-SCH3

5-sc

4-iso-C3H7

5-C2Hs 4-SQH,

H

4-C1

6-OC2H5

c2h5

5-n:

V

0. □

iso-QH,

CH,

6-N = CHN (CH3) 2

6-n (cha) 2

6-1

Î-NCT,

- n ch3

^ 2

^ ci iso-OjjHj!

- n

\

C4H9

O

c2h5

iso-C3H7

chs o

x

^ c = n—

y

x y

r2

R *

chs c2h5

C4Ho c2hï

ch3

QH7 C.H "

tert-C4H9

CH, CHa tert-C4H9 C2H5

□

□

iso-C3H7

SCH,

SC2H5

chg sc <hi

SC2H5

/ \ - N N-CH,

-o <$

c3 c2H5

a

625 209

12

x y

r2

SCjjH7

sc4h9

iso-QH,

O-*

S-tert-C4H9

scho ch3

-CHr-0

sch2cn sc2h3 (cn) c2h5

-c

)

sc2h4cn schg

iso-C4Hg scghg sqh5

c2h5

sch3

scä

iso-C5Hu iso-chshn sc0h5

sc ^ g

0

en,

sc0h5

CEt cä

c2H5

SQHg both substituents

2-CN

4-C, H5

4-C6H5

5-CkH5

2-CH.

4-C1

5-CN

-N S

w

CHj

CHa

2-CN

3-cl

3-OC4H9

2-F

5-C3Ht Y

iso-CaHT S-C4H9

s-0

a

-CH2CH2- (3 -CH2CH2-Q

o ch3

C.H ,.

Cl ch3

ch3

• -ö

-chj r ~ \

- n 0

CH3

ch3 c3h7

-O

13

625209

X

Y

r2

Ra

4-oca

ìso-C ^ Ht iso-C4Hg o

X = H

I.

Y = R8-C-SR7

R? R-8 ^ -9 ^ 2 ^ 3

______

CH3 C3H7 CA - n 0

C2H, C2H5 iso-C3H7 C "H13 CA.

cA chg ch3 v; c2h:

c3h7

o iso-c3H7 CA CA. N 0

- (

c, h7

C6H5 iso-C3H7 C3H7 C4H9 iso-C3; H7

CHa iso-C3H7 S-CHs \ - / CAi

CT ^

C2H5 CA S-CA tert-C4H9 tert-C4H9

CA CH3 S-CA -CH2- ^ J) -CH2 ^ 3

/ ~ \

iso-QA C3H7 S-iso-C3H7 - tf -CH,

625209

14

P!

'(CH2V

/ Y

R.

Rs n

p r2

Rs ch3

2nd

h o

c2h5

3rd

H •

-ch2ch2- <Q

ch3

c3h7

2nd

H

0

te en approx

, x iso-

/ \

"c3h7

iso-C3H7

3rd

H

- N S

^ iso-

• C3H7

ch,

2nd

1-ch3

-0

c4h3

c2h5

2nd

2-CHg

CaH7

V

QSÌHT

3rd

I-CH3

iso-CgH ^

-CH 2-Q

iso-CäH7

3rd

2,2- (ch3) 2

CHa tert.-C4Hj,

f m

P

c i!

r,

m

45

50

2nd

h ch3

ch3

3rd

h c)

1

ch3

2nd

1-ch3

O

0

3rd

2-ch3

-ch2ch2 ^ Q

c2h5

55 3

1,1- (CH3) 2

1,3- (CH3) 2

r,

r,

Q

2,2- (CH3) 2 C3H7

iso-C4H9

0

The following examples are intended to illustrate the invention in more detail.

example 1

Preparation of 3-isopropylphenyl-N - [(dimethylamino) thio] -N-methylcarbamate:

65 A solution of 1.93 g (0.01 mol) of meta-isopropylphenyl-N-methylcarbamate in 25 ml of tetrahydrofuran is mixed with 1.01 g (0.01 mol) of triethylamine. The solution obtained is then cooled to 10 ° C. and added dropwise at 1.115 j

15

625209

(0.01 mol) of dimethylaminosulfenyl chloride were added. The amount of triethylamine hydrochloride precipitated does not appear to be quantitative, so the reaction mixture is left to stand at a temperature of 25 ° C. for 8 days. The precipitate formed is then filtered off and the filtrate is processed further. For this purpose, the tetrahydrofuran is first removed from the filtrate by evaporation under reduced pressure. The evaporation residue is applied to a column of 100 g silica gel for chromatographic purification. The chromatogram is developed with a solvent system consisting of 5% ethyl acetate in benzene. After the solvents had been removed from the collected eluate by evaporation under reduced pressure, 0.53 g of 3-isopropylphenyl-N - [(dimethylamino) thio] -N-methyl-carbamate was obtained in the form of an oil.

An elementary analysis of the compound C13H20N2O2S gives the following values:

calculated: C 58.18 H 7.51 N 10.44 found: C 58.00 H 7.91 N 10.09

Example 2

Preparation of methyl N- <{[methyl (4-morpholinylthio.) - amino] carbonyl} oxy> athanimidothi'óat:

A solution of 7.8 g (0.090 mol) of morpholine in 100 ml of hexane is added dropwise over 30 minutes to a solution of 4.93 g (0.047 mol) of sulfur dichloride in 100 ml of hexane, cooled to -5 ° C. The resulting reaction mixture is stirred at a temperature of -5 ° C for 30 minutes and then filtered. The filtrate obtained is concentrated by evaporation of the hexane under reduced pressure. The concentrate obtained in the form of an orange liquid is added dropwise within 15 min to a solution of 4.87 g (0.03 mol) of methyl-N- {[(methylamino) carbony 1] which has been cooled to a temperature of -5 ° C. oxy} -äthanimidothioat in 15 ml of dimethylformamide containing 5.6 ml (0.04 mol) of triethylamine entered. When the addition is complete, the reaction mixture is stirred at a temperature of 0 ° C. for 2 hours and then diluted with cold water, a precipitate being formed. The precipitate is filtered off, whereupon the filter cake is washed with water and dried. This gives 8.35 g (99% yield) of the desired compound. Recrystallization from ethyl acetate gives pure methyl N - <{[methyl (4-morpholinylthio) amino] carbonyl} oxy> ethane imidothioate in the form of a white solid, mp of 128 ° to 129 ° C.

An elementary analysis of the compound CgH ^ NjOjSj gives the following values:

calculated: C 38.69 H 6.14 N 15.04 S 22.95 found: C 38.91 H 6.18 N 15.25 S 22.86 According to Examples 1 and 2, various aminothiocarbamates are prepared according to the invention and compared to the N-monosubstituted mother carbamates in terms of their effectiveness against a wide variety of insect pests. The pests in the tests are southern armyworm larvae (Spodoptera eridania) (SAW), house crickets in the nymph stage (Acheta domesti-cus) (HC), adult house flies (Musca domestica) (HF), adult seed beetles (Anthonomus grandis) (BW), yellow fever mosquito larvae (Aedes aegypti) (YFM) and coal lathe larvae (Trichoplusia ni) (CL) are used.

Example 3 The details of the test are as follows:

Preparation of the test chemicals: analytically pure samples of the individual chemicals are dissolved in acetone. The Ace

Clay solutions are applied as such or in dilution with a "network water" containing 0.132% by volume of a commercial polyoxyethylene sorbitan monolaurate or a "network water" containing 10% sucrose.

The southern armyworm and cabbage wrapper tests are performed on Henderson bushlima bean leaves with two primary leaves per replicate. The leaves are immersed in a "network water" emulsion of the chemical to be tested, then left to dry and finally placed on a moistened filter disc with a diameter of 9 cm in a plastic Petri dish. Five larvae of the respective test insects are then placed on the leaves, whereupon the Petri dish is covered and set aside for further evaluation. The test is carried out three times for each quantity of chemicals.

The test with the house crickets is carried out in such a way that 5 ml portions of the acetone solution are pipetted into petri dishes with a diameter of 9 cm, whereupon the acetone is allowed to evaporate. Finally, nine house crickets in the nymph stage are placed in the Retri dishes treated in this way, after which the Petri dishes are covered. The test is carried out three times for each quantity of chemicals.

The test with the house flies and seed beetles is carried out in such a way that a golf ball-sized cotton ball is first saturated with 10 ml of a «network water» preparation of the chemical to be tested containing 10% cane sugar, after which the saturated ball is placed in a portion cup becomes. The portion cup hangs on the inner wall of a 142 g wax paper cup. Then ten full-blown house flies or seed beetles are placed in the 142 g cup, after which it is covered with a plastic cap for further attention. The experiment is repeated twice for each quantity of chemicals.

The test with the yellow fever mosquito larvae is carried out in such a way that a suitable amount of wetting water and acetone solution of the chemical to be tested are first introduced into 100 ml of distilled water in a 142 g wax paper beaker. Then ten mosquito larvae are used. After 24 hours, dried yeast is added. The .Test is repeated twice for each quantity of chemicals.

The tests with the southern armyworm, the house crickets, the beetles, the house flies and the cabbage wrappers are carried out at 22 ° C, the test with the yellow fever mosquito larvae is carried out at a temperature of 27 ° C.

The test results are based on how many insects are killed or dying after 24 h, 48 h and in some cases 72 h.

Examples of new aminothiocarbamates according to the invention are:

0 - {[(Dimethylaminothio) methylamino] carbonyl} oxime of 2-methyl-2- (methylthio) propanal, mp 50 ° to 51 ° C.

An elementary analysis of the compound CaH18N302S2 gives the following values:

calculated: C 40.73 H 7.22 N 15.83 S 24.16 found: C 40.53 H 7.73 N 15.35 S 24.51 0 - ([methyl (l-pyrrolidinylthio) amino] carbonyl} oxime of 2-methyl-2- (methylthio) propanal, mp. 73 ° to 74 ° C.

An elementary analysis of the compound CuH2IN302S2 gives the following values:

calculated: C 45.33 H 7.26 N 14.42 S 22.00 found: C 45.23 H 7.77 N 14.22 S 22.01 0 - {[methyl (l-piperidinylthio) amino] carbonyl} oxime of 2-methyl-2- (methylthio) propanal, mp. 51 ° to 53 ° C.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

625209

16

An elementary analysis of the compound C ^ H ^ N ^ O-jS. Gives the following values:

calculated: C 47.18 H 7.59 N 13.76 S 21.00 found: C 47.38 H 8.14 N 13.81 S 21.35 0 - {[methyl (4-morpholinylthio) amino] carbonyl} oxime of 2-methyl-2- (methylthio) propanal, mp. 75 ° to 76 ° C.

An elementary analysis of the compound C ^ H ^ NsC) ^ gives the following values:

calculated: C 42.97 H 6.89 N 13.69 S 20.86 found: C 43.38 H 6.92 N 13.55 S 21.13 O- {[(2,6-dimethyl-4-morpholinylthio ) methylamino] -carbonylj-oxime of 2-methyl-2- (methylthio) propanal. Mp 61 ° to 62 ° C.

An elementary analysis of the connection gives the following values:

calculated: C 46.54 H 7.51 N 12.53 S 19.12 found: C 46.97 H 8.16 N 12.52 S 19.11 If the latter compound is tested in the manner described in Example 3, one obtains following results:

insect

Amount of chemicals

Mortality in%

SAW

60 ppm

100

HC

30 ng / plate

63

HF

30 ppm

95

BW

30 ppm

95

CL

180 ppm

93

insect

Amount of chemicals

Mortality in%

HC

10p.g / plate

100

HF

30 ppm

90

BW

10 [ig / plate

100

Example 4

Starting from the known compound methyl-N - {[(methylamino) carbonyl] oxy} ethaneimidothioate, the following new aminothiocarbamate derivatives according to the invention are obtained by appropriate processes, as described in Examples 1 and 2:

Methyl N - <({[(dimethylamino) thio] methylamino} carbo-nyl) oxy> -ethaneimidothioate, mp. 68 ° to 70 ° C.

An elementary analysis of the compound C7Hlr> N302S2 gives the following values:

calculated: C 35.42 H 6.37 N 17.70 found: C 35.73 H 6.45 N 17.60 methyl N - <({f (diisopropylamino) thio] methylamino} car-bonyl) oxy> ethanimidothioate , Mp 81 ° to 82 ° C.

An elementary analysis of the compound CuH ^ NaPaSa gives the following values:

calculated: C 45.02 H 7.90 N 14.31 S 21.85 found: C 45.26 H 8.34 N 14.08 - S 22.17 methyl-N- <{[methyl (l-piperidinyithio) amino] carbonyl} -oxy> ethanimidothioate, mp. 53 ° to 54 ° C.

An elementary analysis of the compound C10H10N3O2S2. gives the following values:

calculated: C 43.39 H 6.90 N 15.15 S 23.12 found: C 43.20 H 6.88 N 15.25 S 23.56 methyl-N - <{[methyl (4-morpholinylthio) amino ] carbonyl} -oxy> äthanimidothioat, mp. 128 ° to 129 ° C.

An elementary analysis of the compound C9H17N3v03S2 gives the following values:

calculated: C 38.69 H 6.13 N 15.04 S 22.95 found: C 38.91 H 6.18 N 15.25 S 22.86 If the latter compound is tested in the manner described in Example 3, the following are carried out Get results:

Methyl-N - <{[(di-n-butylaminothio) methylamino] carbo-nyl} oxy> ethane imidothioate as an oil.

15 An elementary analysis of the compound C13H27NaO „S2 gives the following values:

calculated: C 48.56 H 8.47 N 13.07 S 19.95 found: C 48.26 H 9.06 N 12.95 S 19.93 methyl-N - <{[(2,6-dimethyl- 4-morpholinylthio) methyl-20 amino] carbonyl} oxy> ethane imidothioate, mp. 65 ° to 67 ° C. An elementary analysis of the compound C11H21NaOBS2 gives the following values:

calculated: C 42.97 H 6.89 N 13.67 S 20.85 found: C 42.92 H 6.85 N 13.45 S 20.91

25th

Example 5

Starting from the known compound 3,5-diisopropylphenyl-N-methylcarbamate, the following new aminothiocarbamate derivatives according to the invention are obtained according to the processes described in Examples 1 and 2:

3,5-DiisopropyIphenyI-N-methyI-N- (dimethyIamino) carbamate as an oil.

35 An elementary analysis of the compound ClßH20N2O2S gives the following values:

calculated: C 61.90 H 8.44 N 9.03 S 10.33 found: C 61.68 H 8.81 N 8.91 S 10.27 If the latter compound is tested in the manner described in Example 3 you get the following results:

45

insect

Amount of chemicals

Mortality in%

HC

30 ng / plate

! 97

HF

90 ppm

95

YFM

0.6 ppm

100

50

3,5-Diisopropylphenyl-N-methyl-N- (l-piperidinylthio) carbamate as an oil.

An elementary analysis of the compound C19H30N2O2S gives the following values:

55 calculated: C 65.10 H 8.63 N 7.99 S 9.15 found: C 64.94 H 8.80 N 7.66 S 10.05 3,5-diisopropylphenyl-N-methyl-N- ( 4-morpholinylthio) carbamate as an oil.

An elementary analysis of the compound C18H28N203S er-60 gives the following values:

calculated: C 61.33 H 8.01 N 7.95 S 9.10 found: C 61.04 H 8.30 N 7.83 S 9.25 3,5-diisopropylphenyl-N- (dibutylaminothio) -N- methyl carbamate as an oil.

65 An elementary analysis of the compound C22H3, gN202S gives the following values:

calculated: C 66.96 H 9.71 N 7.10 S 8.13 found: C 66.86 H 10.06 N 7.07 S 9.85

17th

625209

3,5-Diisopropylphenyl-N- (diisopropylaminothio) -N-methyl carbamate as an oil.

An elementary analysis of the compound C20H34N2O2S gives the following values:

calculated: C 65.53 H 9.35 N 7.64 S 8.75 found: C 65.29 H 9.07 N 7.36 S 13.40

Example 6

Using the known compound meta-iso-propylphenyl-N-methylcarbamate, the following aminothiocarbamate derivatives according to the invention are obtained by appropriate processes, as described in Examples 1 and 2:

3-Isopropylphenyl-N-methyl-N- (l-piperidinylthio) carbamate as an oil.

An elementary analysis of the compound C16H24N202S gives the following values:

calculated: C 62.30 H 7.84 N 9.08 S 10.40 found: C 62.33 H 8.05 N 8.94 S 10.31 3-isopropylphenyl-N-methyl-N- (4-morpholinylthio ) carbamate as an oil.

An elementary analysis of the compound C15H22N203S gives the following values:

calculated: C 58.03 H 7.15 N 9.03 S 10.33 found: C 57.96 H 6.95 N 9.15 S 10.18 3-isopropylphenyl-N- (dibutylaminothio) -N-methyIcarba- mat as oil.

An elementary analysis of the compound C19H32N202S gives the following values:

calculated: C 64.73 H 9.15 N 7.95 S 9.10 found: C 64.45 H 8.81 N 7.71 S 9.29 3-isopropylphenyl-N- (diisopropylaminothio) -N-methyI- carbamate as an oil.

An elementary analysis of the compound C17H28N202S gives the following values:

calculated: C 62.92 H 8.70 N 8.64 S 9.88 found: C 62.79 H 8.67 N 8.33 S 11.61 If the latter compound is tested in the manner described in Example 3, one obtains following results:

o-Isopropoxyphenyl-N-methyl-N- (l-piperidinylthio) carbamate as an oil.

An elementary analysis of the compound C10H24N2O3S gives the following values:

5 calculated: C 59.22 H 7.46 N 8.64 S 9.88 found: C 59.81 H 7.51 N 8.52 S 9.58 o-isopropoxyphenyl-N- (ethyl-n-butylaminothio) -N-methyl-carbamate as an oil.

An elementary analysis of the compound C17H28N203S er-io gives the following values:

calculated: C 59.97 H 8.79 N 8.23 S 9.42 found: C 59.88 H 8.09 N 7.92 S 9.19 If the latter compound is tested in the manner described in Example 3, one obtains following results:

15

20th

25th

insect

Amount of chemicals

Mortality in%

HC

30 (ig / plate

100

HF

90 ppm

85

BW

30 ppm

80

YFM

0.067 ppm

100

insect

Amount of chemicals

Mortality in%

SAW

300 ppm

100

HC

3.3 (ig / plate

100

BW

30 ppm

95

YFM

0.067 ppm

100

3-Isopropylphenyl- (dimethylaminothio) -N-methylcarbamate as an oil.

An elementary analysis of the compound C ^ HaoNaCLS gives the following values:

calculated: C 58.18 H 7.51 N 10.44 found: C 58.00 H 7.91 N 10.09

Example 7

Starting from the known compound o-isopropoxy-phenyl-N-methylcarbamate, the following aminothio derivatives according to the invention are obtained by appropriate processes, as described in Examples 1 and 2:

o-Isopropoxyphenyl-N- (diethylaminothio) -N-methyl-carbamate as an oil.

An elementary analysis of the compound Cir) H24N203S gives the following values:

calculated: C 57.66 H 7.74 N 8.97 found: C 57.91 H 7.57 N 9.05

o-Isopropoxyphenyl-N- (diisobutylaminothio) -N-methyl-carbamate as an oil.

An elementary analysis of the compound C10H32N2O3S gives the following values:

30 calculated: C 61.92 H 8.75 N 7.60 S 8.70 found: C 61.76 H 9.08 N 7.53 S 8.18 o-isopropoxyphenyI-N- (dimethylaminothio) -N-methyl carbamate as an oil.

An elementary analysis of the compound C13H20N.O3S er-35 gives the following values:

calculated: C 54.90 H 7.09 N 9.85 S 11.28 found: C 54.71 H 7.08 N 9.61 S 11.11 o-isopropoxyphenyl-N-methyl-N- (o-morpholinyithio ) carbamate as an oil.

40 An elemental analysis of the compound C15H22N204S gives the following values:

calculated: C 55.19 H 6.79 N 8.58 S 9.82 found: C 55.10 H 6.93 N 8.55 S 9.62 o-isopropoxyphenyl-N- (di-n-butylaminothio) - N-methyl-45 carbamate as an oil.

An elementary analysis of the compound C10Ha2N2O3S gives the following values:

calculated: C 61.92 H 8.75 N 7.60 S 8.70 found: C 62.26 H 8.67 N 7.37 S 8.65 50 o-isopropoxyphenyl-N- (diisopropylaminothio) -N-methyl -carbamate, mp. 32 ° to 34 ° C.

An elementary analysis of the compound C17H28N203S gives the following values:

calculated: C 59.97 H 8.29 N 8.23 S 9.42 55 found: C 60.24 H 8.30 N 8.04 S 9.42

Example 8

Using the known compound 0 - {[methylamino] carbonyl} oxime of 1,3-dithiolan-2-one, the following aminothio derivatives according to the invention are obtained in 60 by corresponding processes, as described in Examples 1 and 2:

0 - {[(Dimethyiaminothio) methylamino] carbonyl} oxime of 1,3-dithiolan-2-one, mp 85-86.5 ° C.

65 An elementary analysis of the compound CTH13Na02 & 3 gives the following values:

calculated: C 31.44 H 4.90 N 15.71 S 35.98 found: C 31.74 H 5.00 N 15.54 S 35.91

625209

18th

0 - {[Methyl (l-piperidinylthio) amino] carbonyI} oxime of 1,3-dithiolan-2-one, mp 99 ° to 99.5 ° C.

An elementary analysis of the compound C10H17Nl3lO2S3 gives the following values:

calculated: C 39.06 H 5.57 N 13.67 S 31.29 found: C 39.13 H 5.91 N 13.57 S 31.05 If the latter compound is tested in the manner described in Example 3, one obtains following results:

insect

Amount of chemicals

Mortality in%

SAW

100 ppm

100

HF

3.3 ppm

95

BW

10 ppm

100

CL

300 ppm

93

YFM

0.6 ppm

100

0 - {[Methyl (4-morpholinylthio) amino] carbonyl} oxime of 1,3-dithiolan-2-one, mp 124 ° to 126 ° C.

An elementary analysis of the compound C9H15N303Sk gives the following values:

calculated: - C 34.93 H 4.89 N 13.58 S 31.09 found: C 35.08 H 5.15 N 13.39 S 30.81 0 - {[(di-n-butylaminothio) methylamino] carbonyl} oxime of l, 3-dithiolan-2-one, mp. 39 ° to 41 ° C.

An elementary analysis of the compound QaHj.gNjOj.Sü gives the following values:

calculated: C 44.41 H 7.17 N 11.95 S 27.36 found: C 44.42 H 7.29 N 12.05 S 27.55 0 - {[(2,6-dimethyl-4-morpholinylthio ) methylamino] carbo-nyljoxim of 1,3-dithiolan-2-one, mp. 81 ° to 83 ° C.

An elemental analysis of compound C,

gives the following values:

calculated: C 39.15 H 5.67 N 12.45 S 28.51 found: C 39.42 H 5.86 N 12.17 S 28.62

> Na03Ss

Example 9 /

Starting from the known compound 3-tert-butyl-phenyl-N-methylcarbamate, the following aminothio derivatives according to the invention are obtained by appropriate processes, as described in Examples 1 and 2:

3-tert-ButylphenyI-N-methyl-N- (dimethylaminothio) carbamate as an oil.

An elementary analysis of compound C, 4H22N202S gives the following values:

calculated: C 59.54 H 7.85 N 9.92 found: C 59.77 H 7.57 N 9.73 If this compound is tested in the manner described in Example 3, the following results are obtained:

3-tert-Butylphenyl-N-methyl-N- (4-morpholinylthio) carbamate as an oil.

An elementary analysis of the compound C10H24N2O3S gives the following values:

5 calculated: C 59.23 H 7.46 N 8.64 S 9.88 found: C 59.00 H 7.08 N 8.56 S 9.82 3-tert-butylphenyI-N- (di-n -butylaminothio) -N-methyl-carbamate as an oil.

An elementary analysis of the compound CsoH ^ NjOjS erto gives the following values:

calculated: C 65.53 H 9.35 N 7.64 S 8.75 found: C 65.89 H 9.47 N 7.47 S 9.08 3-tert-butylphenyl-Nl (diisopropylaminothio) -N- methyl carbamate as an oil.

ij An elementary analysis of the compound C18HG0N2O2S gives the following values:

calculated: C 63.86 H 8.93 N 8.28 S 9.47 found: C 63.50 H 9.32 N 8.18 S 9.72

2o i Example 10

Starting from the known compound 3,5-dimethyl-4-dimethylaminophenyl-N-methylcarbamate, the following aminothio derivatives according to the 2s invention are obtained by corresponding processes as described in Examples 1 and 2:

3,5-Dimethyl-4-dimethylaminophenyl-N- (diisobutylphe-ny! Thio) -N-methyl carbamate as an oil.

An elementary analysis of the compound C20H35N3O2S gives the following values:

30 calculated: C 62.95 H 9.25 N 11.01 S 8.40 found: C 62.61 H 9.60 N 10.75 S 8.58 3,5-dimethyl-4-dimethylaminophenyl-N- ( diethylamino-thio) -N-methylcarbamate as an oil.

An elementary analysis of the compound C16H27N302S er-35 gives the following values:

calculated: C 59.04 H 8.36 N 12.91 S 9.85 found: C 59.03 H 8.43 N 12.81 S 10.10 3,5-dimethyl-4-dimethylaminophenyl-N- (2nd , 6-dimethyl-4-morpholinylthio) -N-methyl carbamate as an oil.

40 An elementary analysis of the compound C18H29Nb, 03S gives the following values:

calculated: C 58.82 H 7.95 N 11.43 S 8.73 found: C 58.58 H 7.82 N 11.34 S 8.96 The latter compound is tested in the manner described in Example 3 , you get the following results:

insect

Amount of chemicals

Mortality in%

HC

30 [ig / plate

100

YFM

0.6 ppm

100

50

55

insect

Amount of chemicals

Mortality in%

SAW

100 ppm

100

BW

30 ppm

95

YFM

0.6 ppm

75

CL

100 ppm

80

3-tert-Butylphenyl-N-methyl-N- (l-piperidinylthio) carbamate as an oil.

An elementary analysis of the compound C17H2 (iN20, S gives the following values:

calculated: C 63.33 H 8.13 N 8.69 S 9.95 found: C 63.33 H 8.09 N 8.57 S 10.33

3,5-Dimethyl-4-dimethylaminophenyl-N- (dimethylamino-thio) -N-methylcarbamate as an oil.

An elementary analysis of the compound C ^ H ^ NgO-jS er-60 gives the following values:

calculated: C 56.53 H 7.70 N 14.13 S 10.78 found: C 56.48 H 8.01 N 14.28 3,5-dimethyl-4-dimethylaminophenyl-N-methyl-N- (l --piperidinylthio) carbamate as an oil.

65 An Elemental Analysis of Compound C17H27 '

gives the following values:

calculated: C 60.50 H 8.07 N 12.45 S 9.50 found: C 60.51 H 8.25 N 12.56 S 9.89

N302S

19th

625209

3,5-Dimethyl-4-dimethylaminophenyl-N-methyl-N- (4-raorpholinylthio) carbamate, mp 74-75 ° C.

An elementary analysis of the compound ClßH26N, 30aS gives the following values:

calculated: C 56.61 H 7.42 N 12.38 S 9.45 found: C 56.30 H 7.54 N 12.12 S 9.20 3,5-dimethyl-4-dimethylaminophenyl-N- (di -n-butyl-aminothio) -N-methylcarbamate as an oil.

An elementary analysis of the compound C2oH3SNfl, 02S gives the following values:

calculated: C 62.95 H 9.25 N 11.01 S 8.40 found: C 62.84 H 9.51 N 10.75 S 8.73 3,5-dimethyl-4-dimethylaminophenyl-N- (diisopropyl -aminothio) -N-methylcarbamate as an oil.

An elementary analysis of the compound ClgH31Na02S gives the following values:

calculated: C 61.15 H 8.84 N 11.89 S 9.07 found: C 60.93 H 9.25 N 11.64 S 9.14

Example 11

Starting from the known compound 2-cyano-ethyl-N - {[(methylamino) carbonyl] oxy} ether imidothioate, the following aminothio derivatives according to the invention are obtained by appropriate processes, as described in Examples 1 and 2:

2-Cyanoethyl-N - <{[(dimethylaminothio) methylaminoj-carbonyl} -oxy> ethane imidothioate, mp. 78.5 ° to 80 ° C.

An elementary analysis of the compound C9H10N4O2S2 gives the following values:

calculated: C 39.11 H 5.84 N 20.27 S 23.20 found: C 38.96 H 5.81 N 19.87 S 23.34 2-cyanoethyl-N- <{[methyl (1 -piperidinylthio ) amino] car-bonyl} oxy> ethanimidothioate, mp. 118 ° to 119 ° C.

An elementary analysis of the compound C12H20N4O2S2 gives the following values:

calculated: C 45.54 H 6.37 N 17.71 S 20.27 found: C 45.36 H 6.39 N 17.71 S 20.36 2-cyanoethyl-N - <{[methyI (4-morpholinyIthio ) amino] car-bonyl} oxy> ethanimidothioate, mp. 121 ° to 123 ° C.

An elementary analysis of the compound C11H18N403S2 gives the following values:

calculated: C 41.49 H 5.70 N 17.60 S 20.14 found: C 41.35 H 5.99 N 17.15 S 19.91 2-cyanoethyl-N - <{[(2.6- dimethyl-4-morpholinylthio) me-thlamino] carbonyl} oxy> ethanimidothioate, mp. 64.5 ° to 65.5 ° C.

An elementary analysis of the connection Ci3H22N403S2 gives the following values:

calculated: C 45.06 H 6.40 N 16.17 S 18.51 found: C 44.73 H 6.75 N 16.09 S 18.52 2-cy anoethyl-N - <{[(di-n -butylaminothio) methylamino] -carbonyl} oxy> äthanimidothioat, mp. 59.5 ° to 60.5 ° C.

An elementary analysis of the compound C15H28N402S2 gives the following values:

calculated: C 49.97 H 7.83 N 15.54 S 17.79 found: C 49.68 H 7.83 N 15.16 S 17.73 If the latter compound is tested in the manner described in Example 3, this is achieved following results:

insect

Amount of chemicals

Mortality in%

SAW

33 ppm

100

HF

10 ppm

100

BW

10 ppm

85

YFM

0.02 ppm

100

CL

100 ppm

73

Example 12

0 - {[(Dimethylamino) thio] methylcarbamoyl} oxime of 2-methyl-l, 3-dithiolane-2-carboxaldehyde, mp. 66 ° to 68 ° C. An elementary analysis of the compound C3H17Nai02S3 er-5 gives the following values:

calculated: C 36.59 H 5.80 N 14.22 found: C 36.43 H 5.89 N 14.19 0 - {[(diethylamino) thio] methylcarbamoyl} oxime of 2-methyl-1,3 -dithiolan-2-carboxaldehyde as an oil.

10 An elementary analysis of the compound CnH ^ NjOaSj gives the following values:

calculated: C 40.84 H 6.54 N 12.99 found: C 40.99 H 6.61 N 13.10 A compound of particular interest is methyl-N-15 - <{fmethyl (4-morpholinylthio) amino] carbonyl} oxy> ethane imidothioate.

This compound works against the southern armyworm in an unexpectedly sustainable manner in a comparison laboratory test. For example, when 20 to 200 ppm of this compound is applied, 100% kill is achieved after 14 or 49 days. Other compounds in this subclass have the same or a similar activity against insect pests and moreover a relatively low phytotoxicity to plants, such as cotton.

25 The new aminothiocarbamates which can be prepared according to the invention can normally be used as pure compounds (cf. the examples), as technically pure compounds from industrial production or as mixtures of individual pure compounds. From a practical point of view, however, the compounds which can be prepared according to the invention are preferably blended with a diluting carrier, if appropriate together with other agents against insects, mites and nematodes. There are a number of thinning carriers suitable for the preparation of pesticides, e.g. dispersible carriers, as are usually used. Such carriers can optionally also contain auxiliaries, such as wetting agents, emulsifiers, adhesive substances and other constituents which indirectly promote effectiveness.

40 The new aminothiocarbamates which can be prepared according to the invention are, for example, against insects, nematodes and mites in a wide variety of preparations, e.g. effective as dust, wettable powders, emulsifiable concentrates, aqueous dispersions, solutions and flowable creams for application to a site, to the ground, to plants, foliage, seeds and other parts of plants. Granular preparations or granules can normally also be produced and applied to the floor or to surfaces. In addition, the compounds which can be prepared according to the invention can form the only active ingredient in a recipe or can be combined with other insecticides, mite killers or nematocides.

From the compounds which can be prepared in solid form according to the invention and which can be prepared according to the invention, it is possible, for example, to readily produce dust-like preparations by jointly grinding a mixture of the same and a powdered carrier. The milling is usually carried out in a ball mill, a hammer mill or by airflow 60 micronization. A suitable final particle size is less than 60 microns. Preferably 95% of the particles have a particle size of less than 50 microns and about 75% of the particles have a particle size of 5 to 20 microns. Dust-like application forms of such a degree of grinding are usually free-flowing and can be applied to living beings, inanimate material, fruit trees, crop plants and the soil for thorough distribution and covering. Dust-like application forms are particularly suitable

625 209

20th

for effective control or killing of insects and mites on large areas when applied by an airplane. Such application forms are also indicated, for example, for use on the underside of foliage.

Suitable powdered carriers are, for example, naturally occurring clays, such as china, georgia, bard, attapulgite, kaolin and bentonite clays, minerals in their natural form, as can be obtained from the soil, e.g. Talc, pyrophyllite, quartz, diatomaceous earth, Fuller earth, chalk, phosphate rock and sulfate rock, sulfur, silicon dioxide and silicates, chemically modified minerals, such as washed bentonite, and colloidal silicon dioxide, as well as organic flours such as wood flour, walnut shell flour, soybean meal and tobacco flour , as well as free-flowing hydrophobic starches.

Dust-like preparations are also obtained, for example, by dissolving the aminothiocarbamates which can be prepared according to the invention in a volatile solvent, such as methylene chloride, mixing the solution obtained with a powdered carrier and evaporating the solvent.

The proportions of powdered carrier and active compound can vary over a wide range depending on the intended use, the harmful nematodes or mites to be controlled and the treatment conditions. As a rule, dust-like preparations can contain up to about 90% by weight of active ingredient. Preferably, the active ingredient content is from about 0.50 to about 20%.

Dispersible powder or powder preparations are obtained, for example, by incorporating a surface-active agent or wetting agent in a dust-like preparation produced in the manner described. Incorporation of 0.1 to about 12% of surface-active agent or wetting agent into a dust-like preparation normally gives a dispersible powder or a dispersible powder. This or these is particularly suitable for further mixing with water for spraying inanimate materials and products, fruit trees, crops, the soil and the livestock. Such dispersible powders can be mixed or diluted with water to any concentration of the active compound which can be prepared according to the invention, whereupon the mixture obtained is applied in an amount sufficient to ensure a given application amount and an even distribution. From these points of view, the dispersible powders or powders according to the invention may preferably contain about 5 to about 80% of the active ingredient.

Examples of surface-active agents or wetting agents which can usually be used in the preparation of dispersible powder forms are alkyl sulfates and sulfonates, alkyl aryl sulfonates, sulfosuccinate esters, polyoxyethylene sulfates, polyoxyethylene sorbitan monolaurate, alkylaryl polyether sulfates, alkylaryl polyether ether alcoholates, sulfonate sulfates, alkynonate sulfates, alkynonate sulfates, alkynonate sulfates, alkynonate sulfates, alkynonate sulfates, alkynonate sulfates, alkynonate sulfates, alkynonate sulfates, sulfonate sulfates, Fatty acid amides, glycerin mannitan laurate, polyalkyl ether condensates of fatty acids, lignosulfonates and the like. Preferred surfactants or wetting agents are mixtures of sulfonated oils and polyalcohol carboxylic acid esters (Emcol H-77), mixtures of polyethoxyethanols (Triton X-151, X-161, X-171), e.g. about equal parts of sodium kerylbenzenesulfonate and isooctyl-phenoxypolyäthoxyäthanol with about 12 ethoxy groups, and mixtures of calcium alkylarylsulfonates and polyethoxylated vegetable oils (Agrimul N4S). Of course, the sulfate and sulfonate wetting agents of the type described are preferably used in the form of their soluble salts, for example their sodium salts. All of the surface-active agents or wetting agents mentioned are generally suitable for lowering the surface tension of water in concentrations of about 1% or below. The dispersible powder or powder preparations can also optionally be prepared using mixtures of the surface-active agents mentioned.

A suitable dispersible powder or powder preparation is obtained by mixing and grinding 148.3 kg of Georgia clay, 2.04 kg of isooctylphenoxypolyethoxyethanol (Triton X-100) as a wetting agent, 4.08 kg of a polymerized Sodium salt of a substituted benzene long chain sulfonic acid (Daxad 27) as a dispersant and 15 51.25 kg of the active ingredient, for example a compound of Examples 2 and 5. The preparation obtained has the following percentage composition:

active ingredient 25

Isooctylphenoxypolyäthoxyäthanol polymerized sodium salt of a substituted benzene long-chain sulfonic acid 2

Georgia tone 72

30th

If this preparation is dispersed in an amount of 4.54 kg in 378.5 l of water, a sprayed preparation with about 0.3% (3000 ppm) of active ingredient is obtained. This can be applied, for example, to insects, mites, 35 plants, eastern trees or other habitats (the insect pests) or sprayed onto the ground against nematodes.

If necessary, dispersants such as methyl 40 cellulose, polyvinyl alcohol, sodium lignin sulfonates and the like can be incorporated into the powder or powder preparations according to the invention. Other additives are, for example, adhesives or adhesives, such as vegetable oils, naturally occurring gums, casein and the like. Finally, the preparations can also contain corrosion inhibitors, 45 such as epichlorohydrin, and anti-foaming agents, e.g. Contain stearic acid.

The new aminothiocarbamates which can be prepared according to the invention can also be applied to insects, mites, objects or a site in the form of aqueous sprays 5Q without a solid carrier. However, since the compounds as such are relatively insoluble in water, they are preferably dissolved in a suitable inert organic solvent. The solvent carrier should expediently not be miscible with water, so that an emulsion of the solvent carrier in water can be prepared. If, for example, a water-miscible solvent carrier, such as ethanol, is used, the solvent carrier dissolves in water, an excess of the compound which can be prepared according to the invention then precipitating out of the solution. In an oil-in-water emulsion, the solvent phase is generally dispersed in the aqueous phase, the dispersed phase containing the active ingredient. In this way it is usually possible to ensure a uniform distribution of the water-insoluble active ingredient in an aqueous spray. It is expedient to use solvent carriers in which large amounts of the aminothiocarbamates which can be prepared according to the invention dissolve, so that the active ingredient is relatively reduced

21st

625209

can prepare highly concentrated solutions. In some cases, one or more solvent carriers with or without cosolvent can be used to prepare concentrated solutions of the active ingredient. The main consideration here is to expediently use a water-immiscible solvent for the active ingredient so that it is kept in solution over the concentration range suitable for application to insects and mites.

The emulsifiable concentrates are consequently generally obtained by dissolving the active ingredient and a surfactant or wetting agent in a practically water-immiscible solvent carrier, e.g. a solvent carrier which is soluble in water in an amount of less than 2.5% by volume at temperatures in the range from 20 ° to 30 ° C, e.g. Cyclohexanone, methyl propyl ketone, summer oils, ethylene dichloride, aromatic hydrocarbons such as benzene, toluene and xylene, as well as high-boiling petroleum hydrocarbons such as kerosene, diesel oil and the like. Optionally, a cosolvent such as methyl ethyl ketone, acetone, isopropanol and the like can be incorporated into the solvent carrier to increase the solubility of the active ingredient. Aqueous emulsions are then preferably obtained by mixing the solution obtained with water and observing the desired concentration of active ingredient. The same surface-active agents or wetting agents or mixtures thereof as have already been mentioned can be used as surface-active agents or wetting agents.

The concentration of active ingredient in the emulsifiable concentrates should expediently be in the range from about 5 to 50, preferably in the range from about 10 to about 40,% by weight. A concentrate with 20% by weight of the compound dissolved in a water-immiscible solvent of the type described can be mixed in an amount of 13 ml with 3.79 l of an aqueous medium, a mixture with 700 parts of active ingredient then being obtained per million parts of liquid carrier. Correspondingly, for example 0.946 l of a 20% concentrate with 151.41 water provide a mixture with about 1200 ppm of active ingredient. In a corresponding manner, even more concentrated solutions of the active ingredient can usually be prepared.

The concentrates for use in the form of aqueous dispersions or emulsions can be a humectant, i.e. an agent that delays the drying of the preparation in contact with the material to which it is applied. Suitable humectants are glycerin, diethylene glycol, solubilized lignins such as calcium lignin sulfonate, and the like.

If a long-term effect is desired, granular preparations or granules are particularly suitable for application to the floor. Such preparations can be easily made, for example, by wide sawing machines or locally, e.g. in a furrow, apply. The single ones. Granules can have any size between 0.246 and 1.651 mm, expediently 0.417 to 0.833 mm. The granules or the granules are preferably obtained by dissolving the active compound in a solvent such as methylene chloride, xylene or acetone and applying the solution to a certain amount of a granular absorbent carrier. Examples of granular absorbent carriers are ground corn cobs, ground walnut shells, ground peanut shells and the like. If desired, the impregnated granular absorbent carrier can be coated with a coating agent which ensures the integrity of the grain or granulate until application to an object or site which is suitable for releasing the active ingredient.

The amount of application to insects, mites, the soil or another site depends, for example, on the type s of the pest to be controlled, the presence or absence of fauna worth preserving, the temperature conditions during the treatment and the type and effectiveness of the application. In general, activity against insects or mites is achieved when the compounds which can be prepared according to the invention are applied in concentrations of from about 5 to about 2000 ppm, preferably from about 30 to about 1000 ppm. 45.4 to 226.8 kg / 0.4046 ha of active compound is normally required for nematodes.

The preparations containing the aminothiocarbamates which can be prepared according to the invention can be applied in a customary known manner to insects, mites, nematodes, the soil or another site. For example, a floor surface, a building or plants can be sprayed with wettable powders from powder sprayers or manually operated knapsack sprayers. Baths are usually suitable for livestock. Dust-like preparations can usually be applied using powder sprayers or hand-operated atomizers. Cream and ointment-like preparations can be applied to the skin or objects for longer protection against insects or mites. .

The active compounds can also be prepared in a relatively highly diluted form in a dispersible insecticidal vehicle for use in the home. For example, the active constituents can be prepared as dust-like preparations with approximately 0.1 to 5.0% of active constituent with deodorized kerosene for aerosol application.

Choosing the application conditions suitable in practice in each case should generally not pose any difficulties for the person skilled in the art. The variables that need to be considered include, for example, the level of pest infestation, the level of control to be controlled. Type of pest, the site to be treated specifically, the plant species, the weather forecast for temperature, relative humidity, rain, dew and similar environmental conditions. and the same.

The compounds which can be prepared according to the invention are generally effective pesticides for controlling vertebrate-free pests in agriculture, industry and in the home. The compounds have been found to be active against invertebrates, for example from the class of insects, e.g. against the order Coleoptera, in particular the cotton beetle (Anthonomus grandis Boheman), a kind of meal beetle (Tribolium confusum Jacquelin deVal) and the Mexican bean beetle (Epilachna varivestis Mulsant), the order Diptera, especially the house fly (Musca domestica Linnaeus), the order Orthoptera , in particular the house cricket (Acheta domesticus Linnaeus) and the kitchen cockroach (Blatella germanica Linnaeus), as well as the order Lepidoptera, in particular the southern army worm (Pro-denia eridania Cramer), especially the colon spider mite (Tetranychus urticae Koch) .

The effectiveness against invertebrate pests has been commonly confirmed for concentrations of 100, 500, 75, 40 and even 10 ppm according to the respective insect or mite. For example, some invertebrate pests are more sensitive than others to the compounds which can be produced according to the invention, and others can even be completely resistant.

Further compounds which can be prepared according to the invention are, for example, those of the formula:

625209

22

wherein R2 and R3 have the meaning given. These compounds are usually obtained in a manner analogous to the previously described compounds, i.e. the respective aminothio derivative is obtained, starting from the basic Furadan® compound. These compounds can usually be used in a manner corresponding to the compounds described above. Examples of the latter compounds are:

Example 13

The following new aminothiocarbamate derivatives can be prepared starting from the known compound 2,3-dihydro-2,2-dimethyl-7-benzofuranylmethylcarbamate:

2,3-Dihydro-2,2-dimethyl-7-benzofuranylmethyl (l-piperidinylthio) carbamate, mp 62 ° to 63 ° C.

An elementary analysis of the compound C17H24N203S gives the following values:

calculated: C 63.71 H 7.55 N 8.74 S 10.01 found: C 63.75 H 7, -32 N 8.61 S 9.87 2,3-dihydro-2,2-dimethyl-7 -benzofuranyl-N-methyl (4 - morpholinylthio) carbamate, mp. 80 ° to 81 ° C.

An elementary analysis of the compound C10H22N2O4S gives the following values:

calculated: C 56.78 H 6.55 N 8.28 S 9.48 found: C 56.60 H 6.84 N 8.13 S 9.58 2,3-dihydro-2,2-dimethyl-7- benzofuranyl (dibutylamino-thio) methyl carbamate as an oil

An elementary analysis of the compound CaoH ^ NaO ^ S gives the following values:

2,3-Dihydro-2,2-dimethyl-7-benzofuranyl [(diethylamino) thio] methyl carbamate as an oil.

An elementary analysis of the compound C1GH24N2OaS gives the following values:

s calculated: C 59.23 H 7.46 N 8.63 found: C 59.14 H 7.21 N 8.65 If the latter compound is tested in the manner described in Example 3, the following results are obtained:

10th

15

20th

25th

insect

Amount of chemicals

Mortality in%

SAW

100 ppm

87 '

HC

1.3 [ig / plate

97

HF

30 ppm

100

BW

10 ppm V

100

YFM

»0.67 ppm

100

CL

100 ppm

93

calculated: found:

C 63.12 C 62.87

H 8.48 H 8.71

N 7.36 N 7.30

S 8.43 S 8.69

2,3-Dihydro-2,2-dimethyl-7-benzofuranyl (diisopropyl- 'amino-thio) methyl carbamate, mp 67-69 ° C.

An elementary analysis of the compound C18H28N2Q3S gives the following values:

calculated: C 61.33 H 8.01 N 7.95 S 9.10 found: C 61.27 H 8.15 N 7.98 S 9.38

Of course, all compounds can be formulated according to the general definition or according to the specified subclasses to suitable preparations with pesticidal activity:

• In Example 12, the aminothio derivatives from the known compound 0- [methylcarbamoyl] oxime of 2-methyl-1,3-dithiolane-2-carboxaldehyde are used according to the corresponding methods, as described in Examples 1 and 2 are manufactured.

30th

35

Claims (2)

625209 2nd PATENT CLAIMS 1. Process for the preparation of new amino thio-carbamates of the formula (ch2) - O Ii c- ■ ch. n: N> in which mean: R is a radical of the formula in which n represents 2 or 3 and the alkylene part of the ring is optionally substituted by one or two methyl radicals, or in which X and Y together with the carbon atom to which they are attached contain one containing two sulfur atoms heterocyclic ring of the formula: 15 . (ch.) - (a) 20th in which R4, Rs and R0 are the same or different and are hydrogen or halogen atoms, alkyl radicals with 1 to 5 carbon atoms, alkoxy radicals with 1 to 5 carbon atoms, alkylthio radicals with 1 to 5 carbon atoms, dialkylamino radicals with identical or different alkyl parts each with 1 to Can represent 3 carbon atoms or a radical -N = CHN (CH3i) 2; or the formula: wherein m is 2 or 3 and the alkylene part of the ring is optionally substituted with one or two methyl radicals, R2 and R3, which may be the same or different, a 25 alkyl radical with 1 to 6 carbon atoms, a cycloalkyl radical with 3 to 6 carbon atoms, a radical of the formula: 30th c = n in which Q and Ru are the same or different and can represent hydrogen or chlorine atoms or methyl radicals (b) 35 nen; or a remainder of the formula: in which X and Y are the same or different and alkyl radicals with 1 to 5 carbon atoms, alkylthio radicals with 1 to 5 carbon atoms, monocyano-substituted alkylthio radicals with 1 to 5 carbon atoms or phenylthio radicals with an unsubstituted or mono- to trisubstituted phenyl moiety, the substituents being identical or different are and can consist of halogen atoms, alkyl radicals with 1 to 4 carbon atoms, cyano radicals, alkoxy radicals with 1 to 5 carbon atoms, phenyl radicals or dialkylaminocarbonyl radicals with the same or different alkyl parts each with 1 to 3 carbon atoms, and in the case that that X represents a hydrogen atom, Y represents a radical of the formula 4ch2 -} - yy 40, in which D is 1 or 2, or Ra and Rs together with the nitrogen atom to which they are attached form an alkylene ring with 4 or 5 ring carbon atoms, a radical of the formulas: 45 n 0 50 0 and. f N . 12th r 12 r, V means in which R7 represents an alkyl radical with 1 to 3 carbon atoms or a phenyl radical, R8 stands for an alkyl radical with 1 to 3 carbon atoms and R9 represents an alkyl radical with 1 to 3 carbon atoms or a radical -SR10 with RI0 equal to an alkyl radical consisting of the same alkyl radical consists like the alkyl radical R7, and R7 and R10 together with the atoms to which they are attached form a heterocyclic ring containing two sulfur atoms of the formula: Form 55, wherein R12 represents a hydrogen atom or an alkyl radical having 1 to 3 carbon atoms, or a 4-methylpiperazinorest, characterized in that a compound of the formula 60 65 with a) R * R, ; N-S-C1 in an organic solvent, 3rd 625209 or with R-2 b) ^ N-H in sulfur dichloride in an organic R3 Implement solvent. 2. Use of the new aminothiocarbamates of the formula together with the atoms to which they are attached form a heterocyclic ring of the formula which contains two sulfur atoms: r (ch,) / V in which mean: Rj is a radical of the formula wherein n represents 2 or 3 and the alkylene part of the ring is optionally substituted with one or two methyl radicals, or in which X and Y together with the carbon atom to which they are attached have one two sulfur atoms containing heterocyclic ring of the formula: . (CH,); 20th (a) in which R4, R5 and R8 are the same or different and are hydrogen or halogen atoms, alkyl radicals with 1 to 5 carbon atoms, alkoxy radicals with 1 to 5 carbon atoms, alkylthio radicals with 1 to 5 carbon atoms, di-alkylamino radicals with identical or different alkyl parts each with 1 to Can represent 3 carbon atoms or a radical -N = CHN (CH3) 2; or the formula: c = n - 25th wherein m is 2 or 3 and the alkylene part of the ring is optionally substituted with one or two methyl radicals, R2 and R ,, which may be the same or different, an alkyl radical with 1 to 6 carbon atoms, a cycloalkyl-30 radical with 3 to 6 carbon atoms, a radical of the formula: 35 (b) in which Q and Rtl are the same or different and can represent hydrogen or chlorine atoms or methyl radicals; or a remainder of the formula: in which X and Y are the same or different and alkyl radicals with 1 to 5 carbon atoms, alkylthio radicals with 1 to 5 carbon atoms, monocyano-substituted alkylthio radicals with 1 to 5 carbon atoms or phenylthio radicals with an unsubstituted or mono- to trisubstituted phenyl moiety, the substituents being identical or different are and can consist of halogen atoms, alkyl radicals with 1 to 4 carbon atoms, cyano radicals, alkoxy radicals with 1 to 5 carbon atoms, phenyl radicals or dialkylaminocarbonyl radicals with the same or different alkyl parts, each with 1 to 3 carbon atoms, and it applies that in the event that X represents a hydrogen atom, Y represents a radical of the formula -fch, 4th O ü " 45, in which D is 1 or 2, or R2 and Rs together with the nitrogen atom to which they are attached form an alkylene ring with 4 or 5 ring carbon atoms, a radical of the formulas: r - ^ * i: 0 n 0 and / n 1: \ 12 r, c - s r. 11 r, means, in which RT represents an alkyl radical with 1 to 3 carbon atoms or a phenyl radical, Rg stands for an alkyl radical with 1 to 3 carbon atoms and R "represents an alkyl radical with 1 to 3 carbon atoms or a radical -SR10 with Rl0 equal to an alkyl radical consisting of the same Alkyl radical is like the alkyl radical R-, and form R7 and R10, where R12 represents a hydrogen atom or an alkyl-60. rest with 1 to 3 carbon atoms, or a 4-methylpiperazinorest means, as an active ingredient in pesticides. 65