DD237783A5 - HERBICIDE MEDIUM - Google Patents

Abstract

The invention relates to herbicidal compositions containing new substituted carbonylphenylsulfonylguanidines of the general formula (I), (wherein the radicals R1, R2, R3 and M have the meanings given in the description) and 1: 1 adducts of compounds of the formula (I) strong acids as active ingredients.

Description

is hydrogen or C ₁ -C ₄ alkyl and

C ₁ -C ₄ -alkyl [which is optionally substituted by halogen, cyano, nitro, C ₁ -C ₄ -alkoxy or C ₁ -C ₄ -alkoxycarbonyl],

_C3-C6 cycloalkyl, phenyl-C ₁ -C ₂ -alkyl, phenyl [which gegebenenfallstlurch halogen, cyano, nitro, C ₁ -C ₄ -alkyl, "Ci-C ₂ haloalkyl, C ₁ -C ₄ - AIkOXy, C ₁ -C ₂ -haloalkoxy, C ₁ -C ₄ -AlkYItMo, C ₁ -C ₂ haloalkylthio or C ₁ -C ₄ -alkoxycarbonyl is substituted], for d-Ci-alkyl-carbonyl, C ₁ -C ₄ -alkylcarbonyl, C ₁ -C ₄ -alkylsulfonyl, C ₁ -C ₄ -haloalkylsulfonyl or phenylsulfonyl [which is optionally substituted by halogen, cyano, nitro, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ - C ₄ alkoxy, Cr-Cr haloalkoxy or CHV alkoxy-carbonyl is substituted],

and 1: 1 adducts of compounds of formula (I) with strong acids;

in addition to extenders and / or surface-active agents.

2. Use of substituted carbonylphenylsulphonylguanidines of the general formula (I) according to item 1, characterized in that they are used for controlling unwanted plant growth.

3. A process for the preparation of herbicidal agents, characterized in that one mixes substituted carbonylphenylsulphonylganidines of the general formula (I) according to item 1 with extenders and / or surface-active agents.

Field of application of the invention

The invention relates to herbicidal compositions containing novel carbonylphenylsulfonylguanidines as active ingredients.

Characteristic of the known technical solutions

Various guanidine derivatives have become known as potential herbicides from patents (see DE-AS 1 089210, DD-PS 71 016 and 84530), but have hitherto received no greater importance as agents for weed control and / or regulation of plant growth. Other guanidine derivatives are the subject of a not belonging to the prior art prior art patent application of the applicant (see DE-OS 3334455).

Object of the invention

Surprisingly, the novel compounds of the formula (I) show considerably better herbicidal activity than previously known guanidines of the same direction of action.

Explanation of the essence of the invention

There have now been new substituted carbonylphenylsulfonylguanidines of the general formula (I)

(D

in which

M is hydrogen or a metal equivalent,

R ^{1 is} hydroxy, C ₃ -C ₃ -alkoxy and, in the case where R ² is other than hydrogen, also represents ethoxy and furthermore K ₁ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkyl-C ₁ -C -oxy- alkoxy, C ₁ -C ₆ -haloalkoxy, cyano-C ₁ -C ₆ -alkoxy, C ₁ -C ₄ -alkoxy C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio-C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylsulfinyl-C ^ C ^ alkoxy ^^ C ^ Ci-C ^ AIkylsulfonyl-alkoxy, C ₁ -C ₄ -alkoxy-C ₁ -C CaTbOnYl ^ ₂ -BIkOXy, C ₃ -C ₈ -alkyl ken oxy, C ₃ -C ₈ - AIkINOXy, phenyl-Ci-Cs-alkoxy, phenoxy [which is optionally halogen, cyano, nitro, C ₁ -C ₄ -alkyl, d-Ca-haloalkyl, C ₁ -C ₄ -alkoxy, C! -C ₂ -haloalkoxy is substituted or Ci-CrAlkoxycarbonyl] for Ci-Cs-alkylamino [which is optionally substituted by halogen, hydroxy, cyano, Ci-C ₄ -alkoxy or C ₁ -C ₄ -alkoxy-carbonyl substituted], Cr-Ce-cycloalkylamino, C3-C ₆ -cycloalkyl-Cl-C2-alkyl-amino, Cs-Ca-alkenylamino, C ₃ -C ₈ -alkynylamino, phenyl-C ^ Ca-alkylamino.für di- (C ₁ -C ₄ alkyl ) -amino [which is optionally substituted by halogen, cyano hydroxy or C ₁ -C ₄ -alkoxy substituted], di- (C ₃ -C ₆ -Gycloalkyl) amino, di _(C3-C5 alkenyl) -amino, di- (C ₃ -C ₅ -alkinyi) - amino ^ ürC ^ Cs-alkoxyamino [which is optionally substituted by halogen, Ci-C ₄ -alkoxy, C ^ C alkylthio, C ₁ -C ₄ -AIkYlSuI-finyl or C! -C ₄ alkylsulfonyl is substituted], for Cs Cs-alkenyloxyamino-Cs-alkynyloxyamino, C ₃ -C ₆ -cycloalkyl-oxyamino, C ₁ -C ₄ -alkoxy-carbonyl-C ₁ -C -alkoxyamino, phenyl-C ₁ -C ₂ -alkoxyamino [which is optionally substituted by halogen, cyano, NHrO ₁ C substituted ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy or d-CT-alkoxy-carbonyl], C ^ Ce-alkylhydrazino, di- (Ci-C ₄ alkyl) hydrazino, Cs-Ce Cycloalkylhydrazino, phenyl-Ci-C ₂ -alkylhydrazino, phenylhydrazino [which is optionally substituted by halogen, cyano, nitro, C ₁ -C ₄ -Alkyl, Cp-CrHalogenalkyl, C ₁ -C ₄ -alkoxy, CH ^ -haloalkoxy, dd -Aikylthio, C ₁ -C ₂ haloalkylthio or dC ^ alkoxycarbonyl substituted], for C ^ d-alkyl-carbonyl-hydrazino, dQ-alkoxycarbonyl-hydrazino ^ -C ^ alkylsulfonylhydrazino, d Q-Halogenalkylsulfonylhydrazino or Phenylsulfonylhydrazino [which is optionally substituted by halogen, cyano, nitro, C ₁ -C ₄ -alkyl, C | -C ₂ haloalkyl, C ₁ -C ₄ -alkoxy, C | -C ₂ haloalkoxy or C C ₄ alkoxycarbonyl su bstituiert] or is amino;

in which further

R ^{2 is} hydrogen, C ₁ -C ₆ -alkyl [which is optionally substituted by fluorine, chlorine, bromine cyano, hydroxy or C ₁ -C ₄ -alkoxy], C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -alkenyl, C ₃ C ₆ -AlkJnYl, benzyl [which is optionally substituted by fluorine, chlorine, nitro, cyano, Ci-C ₄ -A [kyl, Ci-C ₄ -alkoxy or Ci-C ^ alkoxycarbonyl] or the radical

SO2-, in which

R ^{1 has} the above stated meaning:

in which further

R ^{3 is} hydrogen, C ₁ -C ₆ -alkyl [which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxy, C ₁ -C ₄ -alkoxycarbonyl, hydroxy or C ₁ -C ₄ -alkoxy], C ₃ -C ₆ -CyClOaIkYl, Cs-Ce-alkenyl, C ₃ -C ₆ -AlkInYl, phenylethyl or benzyl [which is optionally substituted by fluorine, chlorine, nitro, cyano, C ₁ -C ₄ alkyl, Ci-C ₄ -alkoxy or Ci-Q alkoxy-carbonyl substituted] orfor phenyl [which is optionally substituted by fluorine, chlorine, bromine, hydroxy, cyano, nitro, amino, Ci-C ₄ -alkyl, Irifluormethyl, C ₁ -C ₄ -alkoxy, trifluoromethoxy, dQ-alkylthio, Trifluoromethylthio, aminosulfonyl or C ₁ -C ₄ -alkoxycarbonyl is substituted], or

R ² and R ³ together represent C ₄ -C ₆ alkanediyl [which is optionally interrupted by an oxygen bridge or by a bridge> NR ⁴ ], where

R ^{4 is} Ci-Gt-alkyl, C ₁ -C -alkyl-carbonyl, C ₁ -C ₄ -alkoxy-carbonyl or phenyl [which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C ₁ -C ₄ -alkyl, Ci C ₂ -fluoroalkyl or C ₁ -C ₄ -alkoxy is substituted];

in which further

R ^{3 is} the radical -O-R ⁵ , in which

R ⁵ is C ₁ -C 8 -alkyl [which is optionally substituted by halogen, C ₁ -C ₄ -alkoxy, dd-alkylthio, dQ-alkylsulfonyl] C ₃ -C ₆ -alkenyl [which is optionally substituted by fluorine or chlorine], C ₃ -C ₆ -alkyl-, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkyl-C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy-C ₁ -butyl-C ₁ -C ₂ -alkyl, aminocarbonylmethyl, C ₁ -C ₄ -AlkYlBmInO-Ca carbonyl-methyl, di-fC-i-Ci-alkyD-amino-carbonyl-methyl, phenyl, benzyl or phenylethyl [which is optionally substituted by halogen, cyano, nitro, Ci-C ₄ alkyl -C ₄ -alkoxy, C ₂ -haloalkoxy or Ci-C ₄ -alkyl koxycarbony is, dC ^ haloalkyl, C ₁ I substituted];

in which further

R ⁶

R is the radical -N ₇ , wherein

^ R ⁷

R ^{6 is} hydrogen or C ₁ -C ₄ -A ^ yI and

R ^{7 is} C 1 -C 4 -alkyl [which is optionally substituted by halogen, cyano, nitro, C 1 -C ₄ -alkoxy or C 1 -C ₄ -alkoxycarbonyl], C 1 -C ⁶ -cycloalkyl, phenyl-C 1 -C ₄ -alkyl, phenyl [which is optionally halogen, cyano, nitro, C ₁ -C ₄ alkyl, Ci-C ₂ -haloalkyl, C ₁ -C ₄ -alkoxy, dd-haloalkoxy, C ₁ -C ₄ -alkylthio, C ₁ -C _2- haloalkylthio or C 1 -C ₄ -alkoxycarbonyl is substituted], for C 1 -C ₄ -alkyl-carbonyl-C 1 -C 4 -alkoxy-carbonyl, C 1 -C ₄ -alkylsulfonyc-C 1 -C ₄ -haloalkylsulphonyl or phenylsulphonyl [which is optionally substituted by halogen, cyano, nitro, C ₁ -C ₄ -alkyl, d-Cj-haloalkyl, CiC ₄ -alkoxy, CiC ^ haloalkoxy or C ₁ -C ₄ -alkoxy-carbonyl substituted],

and 1: 1 adducts of compounds of formula (I) with strong acids.

The general formula (I), when M is hydrogen, stands for the individual tautomers of the formulas (IA) and (IB)

(IA)

R ²

CO-R ¹ . _Γμ

CH ₃

H ₃ (IB)

_R 2 ^ ^N \ _R 3

in which

R ¹ , R ² and R ^{3 have} the meanings given above, as well as mixtures of the tautomers (IA) and (IB).

The mixing ratio depends on aggregation determining factors, e.g. Temperature, solvent and concentration

In the event that, in addition to M, R ^{2 also represents} hydrogen, a further tautomeric form (IC) is possible:

UC)

The novel substituted carbonylphenylsulphonylguanidines of the formula I (a) are obtained in the case where M is hydrogen and R ^{2 is} the radical 1

stands, SO ₂ -

when guanidine derivatives of the formula (II)

(in

in which

R ^{3 has} the abovementioned meaning, with at least two molar equivalents of substituted arenesulfonyl chlorides of the formula (III)

(III)

in . u / hich

R ^{1 has} the abovementioned meaning, in the presence of acid acceptors and optionally in the presence of diluents;

- a- *.%> / / Ο »

(b) in the event that M is hydrogen and R ^{2 is} hydrogen, C ₁ -C ₆ -alkyl [which is optionally substituted as indicated above], C ₃ -C ₆ -cycloalkyl, C ₁ -C ₆ -alkenyl, C ₃ - C ₆ -alkyl or benzyl [which is optionally substituted as indicated above] or together with R ^{3 has} the abovementioned meaning, if the substituted carbonylphenylsulfonylguanidines of the formula (ID) obtainable by the process indicated under (a) are

(ID)

CO-R

in which

R ¹ and R ^{3 have} the meanings given above,

with amino compounds of the formula (IV)

R ² HN ^ (IU)

R ³ in which

R ^{2 has} the meaning given above under (b) and

R ^{3 has} the meaning given above,

or with hydrochlorides of amino compounds of the formula (IV), if appropriate in the presence of acid acceptors and

optionally in the presence of diluents; or (c) in the event that M and R ^{2 are} hydrogen, if compounds of the formula (V)

R ³

in which

R ^{3 has} the meaning given above

with compounds of the formula (VI)

MR ¹ (VI)

in which

M and R ^{1 have} the meanings given above, 'if appropriate in the presence of diluents; or

(d) in the event that Μ is equivalent to a metal !, if one obtains the compounds of the formula (I) in which by the processes indicated above under (a), (b) and (c)

IVl is hydrogen and

R ¹ , R ² and R ^{3 have} the meanings given above,

with metal hydroxides, hydrides or alkoxides or with organometallic compounds, if appropriate in the presence of diluents; or

(e) in the case where 1: 1 adducts of compounds of formula (I) with strong acids are to be prepared, if compounds of formula (I) in which M is hydrogen and R ¹ , R ² and R ^{3 are} the have the meanings given above,

optionally reacted with strong acids in the presence of diluents.

The new substituted Carvonylphenylsulfonylguanidine of formula (I) and their adducts with strong acids are characterized by strong herbicidal activity.

The invention preferably relates to compounds of the formula (I) in which M is hydrogen or a sodium, potassium or calcium equivalent,

R ^{1 is} C ₃ -C ₆ -alkoxy; and -for the case where R ² is other than hydrogen-also for ethoxy, -C 1 -Q-fluoroalkoxy, C ₁ -C ₄ -alkoxy, cyano-C ₁ -C ₄ -alkoxy, C ₁ -C ₂ Alkoxy-C ₁ -C ₂ -alkoxy, C ₁ -C -alkoxycarbonyl-d-cralkoxy, C ₃ -C ₅ -alkenoxy, C ₃ -C ₅ -alkoxy, benzyloxy, phenoxy [which is optionally substituted by fluorine, chlorine, bromine, cyano, Nitro, methyl, trifluoromethyl, methoxy, trifluoromethoxy or methoxycarbonyl], for C ₁ -C ₆ -alkylamino [which may be substituted by fluorine, chlorine, hydroxyl, cyano, C ₁ -C ₂ -alkoxy or C ₁ -C ₂ -alkoxy -CaTbOnYl is substituted], amino, C ₃ -C ₅ -alkenylamino, Benzvlamino. Phenvlamino.

for di- (Ci-C ₃ -alkyl) -amino [which is optionally substituted by fluorine, chlorine, cyano, hydroxy or C ₁ -C ₂ -alkoxy], for dC ₆ alkoxyamino [which is optionally substituted by fluorine, chlorine or Ci -C ₂ alkoxy], C ₃ -C ₅ -alkenoxyamino, C ₁ -C ₂ -alkoxycarbonyl-C ₁ -C ₂ -alkylamino, C ₁ -C ₂ -alkoxycarbonyl-C ₁ -C ₂ - alkoxyamino, phenyl-C 1 -C 4 -alkoxyamino [which is optionally substituted by fluoro, chloro, cyano, nitro, methyl, methoxy or methoxycarbonyl], for C ₁ -C ₄ -alkylhydrazino, di (C ₁ -C ₂ -alkyl) hydrazino, C C ₃ -C ₆ -cycloalkylhydrazino or phenylhydrazino [which is optionally substituted by fluorine, chlorine, cyano, nitro, methyl, methoxy or methoxycarbonyl] is C ₃ -C ₆ -cycloalkoxy or amino;

in which further

R ^{2 is} hydrogen, C ₁ -C ₄ -alkyl, which is optionally substituted by fluorine, chlorine, bromine, cyano, hydroxy or C ₁ -C ₂ -alkoxy, C ₃ -C ₆ -cycloalkyl, C ₃ - C ₅ alkenyl, C ₃ -C ₅ alkynyl, benzyl

.CO-R ¹

or the radical / 7 ~ A cn in which

l / \ > - b U 2 -

R ^{1 has} the abovementioned meaning, in which furthermore R ^{3 is} hydrogen, C ₁ -C ₄ -alkyl [which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxy, C ₁ -C 6 -alkoxycarbonyl, hydroxy or C ₁ -C _2- alkoxy is substituted], Cs-Cg-cycloalkyl, Ca-Cs-alkenyl, C ₃ -C ₅ -alkynyl. Phenylethyl, benzyl [which is optionally substituted by fluoro, chloro, nitro, cyano, methyl, methoxy or methoxycarbonyl] or phenyl [which is optionally substituted by fluoro, chloro, bromo, hydroxy, cyano, nitro, amino, C ₁ -C ₃ -A yl, trifluoromethyl, C ₁ -C ₃ -alkoxy, trifluoromethoxy, C ₁ -C ₃ -alkyl, trifluoromethylthio, aminosulfonyl or C ₁ -C 4 -alkoxycarbonyl is substituted]

or R ² and R ³ together are C ₄ -C ₅ alkanediyl, which may be replaced by an oxygen bridge or by a

Bridge> NR ^{4 is} interrupted, where R ^{4 is} C ₁ -C ₃ -alkyl, C ₁ -C 5 -alkyl-carbonyl or phenyl [which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro,

C ₁ -C 6 -alkyl, trifluoromethyl or C ₁ -C ₂ -alkoxy is substituted]; in which further

R ^{3 is} the radical -O-R ⁵ wherein R ^{5 is} C ₁ -C ₈ alkyl [optionally substituted by fluoro or chloro], C ₃ -C ₆ alkenyl, optionally substituted

fluoro or chloro-substituted],. '.

C 1 -C 8 -alkoxycarbonyl-C 1 -C 4 -alkyl, phenyl, phenylethyl or benzyl [which is optionally substituted by fluorine, chlorine, nitro,

Cyano, C ₁ -C ₂ -alkyl, C ₁ -C ₂ -alkoxy or C ₁ -C ₂ -alkoxy-CaTbOnYl is substituted] 'stands; in which further

for the rest "N ^ _7. stands, in which

R ^{6 is} hydrogen or methyl and

R ^{7 is} Ci-C ₂ -alkyl [which is optionally substituted by fluorine, chlorine, cyano, C- | -C ₂ -alkoxy or C ₁ -C ₂ -alkoxycarbonyl], Qr-Ce-cycloalkyl, phenylethyl, benzyl or Phenyl [which is optionally substituted by fluorine, chlorine, bromine, nitro, cyano, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy or C ₁ -C ₂ -alkoxy-CaTbOnYl].

The invention further preferably 1: 1 adducts of compounds of formula (I) - as defined above, wherein M is hydrogen - with hydrohalic acids, such as hydrogen chloride, hydrogen bromide and hydrogen iodide, with sulfuric acid, trifluoroacetic acid, optionally with fluorine or chlorine substituted alkanesulfonic acids with up to 4 carbon atoms or also with benzene or naphthalene-sulphonic acids, which are optionally substituted by fluorine, chlorine, bromine or methyl.

The invention relates in particular to compounds of the formula (I) in which

(A) M is hydrogen or a sodium, potassium or calcium equivalent,

R ^{1 is} C ₃ -C ₄ -alkoxy, C ₁ -C ₃ -fluoroalkyl, C ₁ -C ₃ -chiolactoxy, cyanoethoxy, methoxyethoxy, C ₁ -C ₄ -alkoxy-carbonyl, C ₃ -C ₄ -alkenoxy, benzyloxy or phenyloxy,

2 W

R stands for the rest // \\ _ cn, in which

R ^{1 has} the meaning given above, and

R ^{3 is} the radical -O-R ⁵ , in which

R ^{5 is} C ₁ -C ₄ -alkyl [which is optionally substituted by fluorine or chlorine], C ₃ -C ₄ -alkenyl, C ₁ -C ₂ -alkoxycarbonyl-d ^ -alkyl. Phenyl, phenylethyl or benzyl [which is optionally substituted by fluorine, chlorine, nitro, cyano, methyl, methoxy, methoxycarbonyl or ethoxycarbonyl],

or in which

(B) M for hydrogen is sodium, potassium or calcium equivalent,

R ¹ ^ rC ₃ -C ₄ -alkoxy, C ₁ -C ₃ -fibrekoxy, C ₁ -C ₃ -chiolaxoxy, cyanoethoxy, methoxyethoxy, C ₁ -C -alkoxy-carbonyl-C ₁ -C ₂ -koxy, C ₃ - C ₄ alkylkoxy, C ₃ -C ₄ alkoxy, benzyloxy or phenoxy, for C ₁ -C ₄ -alkylamino, allylamino, propargylamino, benzylamino, for di- (C ₁ -C ₂ -alkyl) -amino, for C ₁ -C ₄ -alkylamino; C ^ AIkoxyamino, Allyloxyamino, C ₁ -C ₂ -AIkOXycarbonyl-C-C2-alkylamino, phenyl - ^ - C ₂ -alkoxyamino, C ₁ -C ₂ alkoxy-carbonyl-C ₁ -C 2 1 alkoxyamino, for dimethylhydrazino or phenylhydrazino;

in which further

R ^{2 is} hydrogen and

is the radical -O-R ⁵ , wherein

W ₁ -C ₁ -C ₄ -alkyl [which is optionally substituted by fluorine or chlorine], Q ₁ -C -alkenyl, C ₁ -C ₂ -alkoxycarbonyl-C ₁ -C ₄ -alkyl, phenyl, phenylethyl or benzyl [which is optionally substituted by fluorine, chlorine, Nitro, cyano, methyl, methoxy, methoxycarbonyl or ethoxycarbonyl is substituted],

and, in the case where M is hydrogen, the 1: 1 adducts of the previously defined compounds with hydrochloric acid, sulfuric acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid. If, for example, for the process variant (a) 2-propoxycarbonyl-benzenesulfonyl chloride and N '- (4,6-dimethyl-pyrimidin-2-yl) -N "-allyloxy-guanidine as starting materials, the reaction sequence can be outlined by the following equation :

0-CH ₂ -CH = CH ₂

COOC ₃ H ₇ ^r f \\ SO ₂ -N ^

-2HC

ι- *

C ^ \ N = C

NH-

.N- ^ ^CH 3 CH ₃

SO ₂ ^ ^ 0-CH ₂ -CH = CH ₂

COOC ₃ H ₇

For example, for process variant (b), use is made of N '- (4,6-dimethylpyrimidin-2-yl) -N "-methoxy-N", N "' - bis- (2-butoxycarbonyl-benzenesulfonyD-guanidine and methoxyamine as starting materials, the reaction sequence can be outlined by the following formula scheme:

COOCz ₊ H ₃

O ₂ -N.

^{N =} ^ CH ₃

H ₂ NOCH.

OCH ₃

COOCz ₊ H ₉

SO ₂ -NHOCH ₃ COOCi ₊ H ₉

- Ο- «^ fej / 1

If, for example, the cyclic diamide and N, N-dimethylhydrazine specified below are used as starting materials for process variant (c), the reaction sequence can be outlined by the following formula scheme:

OC ₂ H ₅

CO-N.

SO ₂ -N

CH ₃

H ₂ NN (CH ₃ ) ₂

'CH;

• C0-NHN (CH _{3) 2}

"CH-

0C ₂ H ₅

If, for example, for the process variant (d) N '- (4,6-dimethyl-pyrimidin-2-yl) -N "-phenoxy-N"' - (2-dimethylaminocarbonyl-benzenesulfonylj-guanidine and potassium ethoxide as starting materials, so the course of the reaction is outlined by the following formula scheme:

CO-N (CH ₃ ');

H ₃ CH ₃

KOC ₂ H ₅

/ V

- HOC ₂ H ₅

C0-N (CH _{3) 2} ©

CH ₃

CH ₃

H- ^N -o / ^

For example, for process variant (e), use is made of N '- (4,6-dimethylpyrimidin-2-yl) -N'-benzyloxy-N ", N"' - bis- (2-ethoxycarbonyl-benzenesulfony-O-guanidine and hydrochloric acid as starting materials, the reaction sequence can be outlined by the following formula scheme:

ooc ₂ h ₅

SO ₂ -N

NH

CH-

CH ₃

COOC ₂ H ₅

HCl

COOC ₂ H ₅

LH

χ HCl

0-CH ₂ ^ J)

COOC ₂ H ₅

The guanidine derivatives to be used as starting materials for process variant (a) are generally defined by the formula (II). In formula (II), R ³ preferably or in particular has the same meaning as given above in the context of the substituent definition of the formula (I) is preferably or as particularly preferred. As starting materials of the formula (II), mention may be made, for example:

N '- (4,6-dimethylpyrimidin-2-yl) -N "-methoxy-guanidine, -N" -ethoxy-guanidine, -N "-propoxy-guanidine, -Ν" -isopropoxy-guanidine, Ν "- butoxy-guanidine, -Ν" -isobutoxy-guanidine, -Ν "-sec-butoxy-guanidine, -Ν" -pentoxy-guanidine, -Ν "-isopentoxy-guanidine, -Ν ' '-sec.-pentoxy-guanidine, -Ν "-hexyloxy-guanidine, -Ν" -isohexyloxy-guanidine, -Ν "-heptyloxyguanidine, -IST-isoheptyloxy-guanidine, -Ν" -octyloxy-guanidine, -Ν "- isooctyloxy-guanidine, -Ν" -allyloxy-guanidine, -Ν "-crotyloxyguanidine, -N" - (2-chloro-ethoxy) -guanidine, -N "- (2-fluoro-ethoxy ( -guanidine, -N "- (2-chloro-propoxy) -guanidine, -N" - (3-chloro-propoxy) -guanidine, -N "- (4-chloro-butoxy) -guanidine, -Ν" - methoxycarbonylmethyloxy-guanidine, -Ν "-ethoxycarbonylmethoxy-guanidine, -N" - (1-methoxycarbonyl-ethoxy) -guanidine, -N "- (1-ethoxycarbonyl-ethoxy) -guanidine, -N" -aminocarbonyl -methoxy-guanidine, -N "- (2-phenylethoxy) -guanidine, -N" -phenoxy-guanidine, -N "- (4-methyl-benzyloxy-guanidine, -N" - (4-fluoro-benzyloxy) - guanidine, -N "- (4-chloro-benzyloxy) -guanidine, -N" - (4-nitr o-benzyloxy) -guanidine, -N "- (2,6-dichloro-benzyloxy) -guanidine, -N" - (4-ethoxycarbonyl-benzyloxy) -guanidine, and -N "- (4-methoxycarbonyl-benzyloxy) -guanidine ,

The starting materials of the formula (II) are known in some cases (compare J. Chem. Soc. 1962, 3915); in part, they are the subject of a not belonging to the prior art prior art patent application of the applicant (see DE-OS 3334455). The compounds of the formula (II) are obtained when rrfan 2-cyanamino-4,6-dimethyl-pyrimidine of the formula (VII)

nc-nhY' ^x ) (VII)

with amino compounds of the formula (VIII)

H ₂ NR ³ · (VIII)

in which

R ^{3 has} the abovementioned meaning, or with their hydrochlorides,

optionally in the presence of diluents, such as. As ethanol, isopropanol or butanol, at temperatures between 20 and 150 ⁰ C, preferably between 50 and 120 ° C, and if appropriate, the reaction products with acid acceptors, such as. As ammonia, caustic soda or soda treated.

2-Cyanamino-4,6-dimethyl-pyrimidine of the formula (VIl) is already known (compare J. Chem. Soc. 1953, 1725). The amino compounds of the formula (VIII) are also already known and can be prepared by processes known per se (compare Chem. Pharm. Bull. 15 [1967], 345; Bull. Soc. Chim. France 1958,664; Synthesis 1976, 682, J. Chem. Soc., 1930, 2228, and HeIv. Chim. Acta 45 [1962], 1387).

The arenesulfonic acid chlorides to be further used as starting materials for the process variant (a) are generally defined by the formula (III). In formula (III) R preferably represents ¹ KJrC ₃ -C ₆ -alkoxy, _{Ci-C4-fluoroalkoxy,} dC ₄ -Chloralkoxy, cyano-C ^ Ct-alkoxy, Ci-C ₂ -Al koxy-C ₁ -C ₂ -a I koxy, C ₁ -C ₂ -alkoxy-carbony 1-C ₁ -C ₂ -bikoxy, C ₃ -C ₅ -alkyl-kNOXy, C ₃ -C ₅ -alkynoxy, benzyloxy or phenoxy [which is optionally substituted by fluorine, chlorine, Bromine, cyano, nitro, methyl, trifluoromethyl, methoxy, trifluoromethoxy or methoxycarbonyl is substituted].

In formula (III), R ¹ is in particular K ¹ -C ₃ -C ₄ -alkoxy, C ¹ -C 5 -fluoroalkoxy, C ¹ -C 8 -chloroalkoxy, cyanoethoxy, methoxyethoxy-C ¹ -C ₄ -alkoxy-carbonyl-C ¹ -C ₄ -alkyl.

alkoxy, Cs-d-alkenoxy, C ₃ -C ₄ -alkyl, benzyloxy or phenoxy

 As starting materials of the formula (III), mention may be made, for example:

2-ethoxycarbonyl, 2-propoxycarbonyl, 2-isopropoxycarbonyl, 2-butoxycarbonyl, 2-isobutoxycarbonyl, 2-sec-butoxycarbonyl, 2- (2-fluoroethoxy) carbonyl, 2- (2-chloroethoxy) carbonyl, 2- (2-cyanoethoxy) carbonyl, 2- (2-methoxyethoxyl-carbonyl, 2-methoxycarbonylmethoxycarbonyl, 2-ethoxycarbonylmethoxycarbonyl, 2-allyloxycarbonyl, 2-crotyloxycarbonyl, 2-propargyloxycarbonyl The 2-benzyloxycarbonyl and 2-phenoxycarbonyl-benzenesulfonyl chloride The arensulfonyl chlorides of the formula (III) are known (compare Chem. Ber., 90 [1957], 841-852; J. Org. Chem. 27 [1962], 1703 -1709) and / or can be prepared by processes which are known per se, giving the compounds of the formula (III) if bis (2-carboxyphenyl) disulphide of the formula (IX)

(IX)

with thionyl chloride, optionally in the presence of a catalyst, such as. For example, dimethylformamide, and optionally in the presence of a diluent, such as. B. chloroform, at temperatures between 20 and 80 "C, after the end of the reaction, which is to detect the cessation of gas evolution, volatile components distilled off, the residue, which consists essentially of bis (2-chlorocarbonyl-phenyl) - disulfide of the formula (X)

(X)

(Via)

R ^{1 has} the meaning indicated above,

optionally in the presence of an acid binder, such as. For example, triethylamine, and optionally in the presence of a diluent, such as. For example, toluene or methylene chloride, at temperatures between 0 and 100 ⁰ C, the here · formed substituted bis (2-carbonyl-phenyl) disulfides of the formula (Xl)

(XI) S-S

in which

R ^{1 has} the meaning given above,

optionally after concentration by filtration with suction, these products of formula (XI) in water or aqueous hydrochloric acid, or in a mixture of water and an organic solvent such. As acetic acid or methylene chloride, dispersed and at temperatures between 0 and 30 ⁰ C, optionally in the presence of a catalyst such. B. tetrabutylammonium bromide, chlorine to saturation initiates.

The workup can be carried out by conventional methods, for example by the organic phase, optionally after dilution with a water-immiscible organic solvent such. As methylene chloride, separated, washed with water, dried, filtered, concentrated and optionally the product is purified by distillation under reduced pressure.

The substituted carbonylphenylsulphonylguanidines to be used as starting materials for process variant (b) are generally defined by the formula (ID). In Formula (ID), R ¹ and R ³ preferably or in particular have the same meanings as (I) above in the context of the substituent of the formula are preferred or particularly preferred as.

As examples of the compounds of the formula (I D) may be mentioned:

N '- (4,6-dimethylpyrimidin-2-yl) -N "-methoxy-N", - N "' - bis- (2-ethoxycarbonyl-benzenesulfonyl) -guanidine, N", N- '' bis (2-propoxycarbonyl-benzenesulfonyl) -guanidine - N "" N "'- bis- (2-isopropoxycarbonyl-benzenesulfonyl) -guanidine and -N", N "' - bis- (2-butoxycarbonyl-benzenesulfonyl) guanidine.

The compounds of the formula (ID) can be prepared by the process described above under (a). The amino compounds to be used further as starting materials in process variant (b) are generally defined by the formula (IV). In formula (IV), R ² and R ³ preferably or in particular have the same meanings as are given above in the context of the substituent definition of the formula (I) preferably or as particularly preferred. As starting materials of the formula (IV), mention may be made, for example:

N, N-dimethylhydrazine, isopropylhydrazine, phenylhydrazine, O-methyl, O-ethyl, O-propyl, O-isopropyl, O-butyl, O-isobutyl, O-sec-butyl, O- Pentyl, 0-isopentyl, O-sec-pentyl, 0-hexyl, 0-isohexyl, O-heptyl, O-isoheptyl, 0-octyl, 0-isooctyl, 0-allyl , O-crotyl, O- (2-chloroethyl) -, O- (2-fluoroethyl) -, O- (2-chloro-propyl) -, O- (3-chloro-propyl) -, O- (4-chloro-butyl) -, 0- 'methoxycarbonylmethyl, O -ethoxycarbonylmethyl, 0- (1-methoxycarbonyl) -ethyl, 0- (1-ethoxycarbonyl) -ethyl, 0-aminocarbonylmethyl, O- ( 2-phenyl-ethyl) -, 0-phenyl-, O- (4-methyl-benzyl) -, 0- (4-fluoro-benzyl) -, 0- (4-chloro-benzyl) -, 0- (4 -Nitrobenzyl) -, 0- (2,6-dichlorobenzyl) -, 0- (4-methoxycarbonyl-benzyl) - and 0- (4-ethoxycarbonyl-benzyl) -hydroxylamine. Amino compounds of the formula (IV) are known and can be prepared by processes known per se (compare Chem. Pharm. Bull. 15 [1967], 345; Bull. Soc. Chim. France 1958,664; Synthesis 1976,682; Chem. Soc. 1930,228 and HeIv. Chim. Acta 45 [1962], 1387).

The compounds to be used as starting materials for process variant (c) are generally defined by the formula (V). In formula (V), R ³ preferably or in particular has the same meaning as given above in the context of the substituent definition of the formula (I) preferably or as particularly preferred. Examples which may be mentioned are compounds of the formula (V) in which R ^{3 is} methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, see.-butoxy, benzyloxy, allyloxy, 3-chloropropoxy, methoxycarbonylmethoxy, 2-phenylethoxy, 4-methyl -benzyloxy, 4-fluorobenzyloxy, 4-chloro-benzyloxy, 4-nitro-benzyloxy or 4-methoxycarbonyl-benzyloxy.

The compounds of formula (V) are not yet described in the literature. The novel compounds of the formula (V) are obtained when guanidine derivatives of the formula (II)

(II)

in which

R ^{3 has} the abovementioned meaning, with 2-chlorosulfonyl-benzoyl chloride of the formula (XII)

CO-CL

(XII)

SO ₂ CL * ~ »<

optionally in the presence of acid acceptors, such as. As pyridine or diazabicyclooctane (DABCO), and optionally in the presence of diluents, such as. As methylene chloride or chloroform, at temperatures between -20 ⁰ C and + 30 ° C.

The preparation of the intermediates of the formula (II) has already been described above in connection with the process indicated under (a).

2-chlorosulfonyl-benzyl chloride of the formula (XII) is known (cf., DE-OS 2036171) The amino compounds to be used further as starting materials in process (c) are generally defined by the formula (VI). In formula (VI), M and R ¹ preferably or in particular have the same meanings as are given above in the context of the substituent definition of the formula (I) preferably or as being particularly preferred.

Examples of the compounds of the formula (VI) are:

Propanol, isopropanol, butanol, isobutanol, sec-butanol, 2-fluoroethanol, 2-chloro-ethanol, 3-chloropropanol, 2-cyano-ethanol, 2-methoxy-ethanol, methyl glycolate, allyl alcohol, crotyl alcohol, propargyl alcohol , Benzyl alcohol, phenol, methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, allylamine, propargylamine, benzylamine, dimethylamine, diethylamine, O-methyl, O-ethyl, O-propyl, O-isopropyl, O-butyl -, 0-isobutyl, O-sec-butyl, 0-allyl, O-methoxycarbonylmethyl, O-ethoxycarbonylmethyl, O- (1-methoxycarbonylethyl) -, Od-ethoxycarbonyl-ethyl) -, O-phenyl -, O-benzyl-, O- (2-phenyl-ethyl) - and 0- (4-methyl-benzyl) -hydroxylamine and Ν, Ν-dimethylhydrazine, isopropylhydrazine, phenylhydrazine and N, 0-dimethylhydroxylamine.

The compounds of the formula (VI) are known and can be prepared by processes known per se (cf., Chem.

Pharm. Bull. 15 [1967], 345).

The substituted carbonylphenylsulfonylguanidines to be used as starting materials in process variant (d) are generally defined by the formula (I) with the proviso that M is hydrogen. In formula (I) - insofar as it relates to the compounds to be used as starting materials for process (d) - M is hydrogen and the radicals R ¹ , R ² and R ³ preferably or in particular have the same meanings as above in the context the substituent definition for formula (I) are preferably or particularly preferred.

The compounds of the formula (I) to be used as starting materials for process (d) may be prepared by the methods described under (a), (b) and

(c).

Examples of the metal hydroxides, hydrides, alkoxides or organometallic compounds to be used in process (d) are: lithium, sodium, potassium, magnesium and calcium hydroxide, lithium, sodium and calcium hydride, sodium methanolate and ethoxide, potassium methoxide, ethoxide and potassium tert-butoxide, and butyl lithium and isopropyl magnesium chloride.

The carbonylphenylsulfonylguanidines to be used as starting materials in process variant (e) are generally defined by formula (I) provided that M is hydrogen. In formula (I) - insofar as it relates to the compounds to be used as starting materials for process (e) - M is hydrogen and the radicals R ¹ , R ² and R ³ preferably or in particular have the same meanings as above in the context the substituent definition of the formula (I) are preferably or specified as particularly preferred. The compounds of the formula (I) to be used as starting materials for process (e) can be prepared by the processes described above under (a), (b) and (c).

In process (e) strong acids are used as starting materials. Preferably, these are hydrogen halides, such as hydrogen chloride, hydrogen bromide, or hydrogen iodide, sulfuric acid further or optionally substituted by fluorine or chlorine alkanesulfonic acids having up to 4 carbon atoms, such as. For example, methanesulfonic acid, ethanesulfonic acid, chloromethanesulfonic acid, 2-chloroethanesulfonic acid and trifluoromethanesulfonic acid, trifluoroacetic acid, further benzenesulfonic acid, p-toluenesulfonic acid, naphthalene-1,4-, -1,5-, -1,6-, -2,6- and -2,7-disulfonic acid.

The process (a) according to the invention for the preparation of the novel compounds of the formula (I) is preferably carried out using diluents. As such, virtually all inert organic, but preferably aprotic polar solvents come into consideration. These include optionally substituted hydrocarbons, such as. B.

Methylene chloride, chloroform, 1,2-dichloroethane, toluene, xylene and chlorobenzene, nitriles, e.g. Acetonitrile and propionitrile, ethers, such as. For example, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, and dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, pyridine and 2-methyl-5-ethyl-pyridine.

As acid acceptors in process (a) virtually all commonly used acid binders can be used.

These include, in particular, alkali metal hydroxides and alkaline earth metal hydroxides, alkali metal and alkaline earth metal hydrides, organometallic compounds, such as butyllithium, and also aliphatic, aromatic or heterocyclic amines, such as trimethylamine, triethylamine, N, N-dimethylaniline, Ν, Ν-dimethylbenzylamine, diazabicyclooctane (DABCO) , Diazabicyclononene (DBN), diazabicycloundecene (DBU), pyridine, 2-methyl-5-ethyl-pyridine and 4-dimethyl-amino-pyridine.

The reaction temperatures can be varied within a wide range in process (a). In general, one works between -80 and + TOO ⁰ C, preferably between -30 and + 5O ⁰ C. The inventive method (a) is generally carried out at atmospheric pressure.

To carry out process (a), in each case between 2 and 5 mol, preferably between 2.1 and 3 mol, of arensulfonyl chloride of the formula (III) are employed per mole of guanidine intermediate of the formula (II).

The reaction components are usually combined at room temperature or with external cooling and the reaction mixture is stirred until the end of the reaction.

The workup and isolation of the new compounds by conventional methods: optionally after distilling off volatile components with water and a water-immiscible solvent such. As methylene chloride, chloroform or toluene, shaken, the organic phase washed with water, dried, filtered and concentrated. The remaining products of the formula (I) are obtained by digestion with organic solvents, such. B.

Diethyl ether, ethyl acetate, ethanol or isopropanol brought to crystallization and optionally purified by recrystallization.

The process (b) according to the invention is preferably carried out using diluents. As such, virtually all inert organic solvents and optionally also water are suitable. These include, in particular, alcohols, such as methanol, ethanol, n- and iso-propanol, ethers, such as tetrahydrofuran, dioxane and 1,2-dimethoxyethane, esters, such as methyl acetate and ethyl acetate, nitriles, such as. As acetonitrile or propionitrile, and dimethylformamide and water.

Acid acceptors which can be used in process (b) are acid binders which do not appreciably compete in their nucleophilic properties with the amino compounds of the formula (IV).

As such are alkali metal and alkaline earth metal carbonates, such as. As potassium carbonate and calcium carbonate, tertiary amines, such as

z. For example, triethylamine, N, N-dimethylaniline and Ν, Ν-dimethylbenzylamine, and nitrogen heterocycles, such as. Pyridine, diazabicyclooctane (DABCO) and diazabicycloundecene (DBU).

The reaction temperature can be varied within a wide range in process (b). In general, it is carried out between 0 ⁰ C and 150 ° C, preferably between 10 ⁰ C and 100 ⁰ C. Process (b) is generally carried out at atmospheric pressure.

For carrying out the process (b) according to the invention, in general between 1 and 10 mol, preferably between 2 and 5 mol, of the amino compound of the formula (IV) or its hydrochloride are employed per mole of guanidine derivative of the formula (ID).

In general, the guanidine derivative of the formula (I D) is initially charged with the diluent at room temperature or with gentle cooling, and the amino compound of the formula (IV) or the hydrochloride thereof and, if appropriate, a suitable acid acceptor are added thereto. The reaction mixture is then generally stirred at room temperature or elevated temperature until the end of the reaction.

The work-up can be carried out by customary methods. As far as the products of formula (I) are crystalline from the reaction mixture, they can be isolated by suction. Otherwise, it is diluted with water, optionally after concentration, and diluted with a water-immiscible solvent, e.g.

Methylene chloride, extracted. By washing the extraction solution with water, drying, filtering, concentrating the filtrate and recrystallizing the residue, the products of formula (I) can be obtained in pure form.

The process (c) according to the invention for the preparation of the novel compounds of the formula (I) is preferably carried out using diluents. As such, virtually all inert organic solvents come into consideration, as mentioned above in connection with the description of process (b) according to the invention.

The reaction temperature can be varied within a wide range in process (c). In general, it is carried out between -20 ⁰ C and +150 ⁰ C, preferably between 0 ⁰ C and 80 ⁰ C. Process (c) is generally carried out at atmospheric pressure.

For carrying out process (c), in general between 1 and 3 mol, preferably between 1 and 2 mol of compound of the formula (VI) are employed per mole of compound of the formula (V).

In general, the compound of formula (V) is presented with the diluent and the compound of formula (Vl) - optionally dissolved in the diluent - added thereto. The reaction mixture is stirred until the end of the reaction.

The work-up can be carried out by customary methods.

As far as the products of formula (I) are crystalline they are isolated by suction. Otherwise - optionally after concentration - with water and a water-immiscible solvent such. B. methylene chloride shaken, the organic phase dried, filtered and concentrated. The residue essentially contains the products of the formula (I).

The process (d) according to the invention is preferably carried out using diluents. As such, virtually all inert organic solvents come into consideration. These include in particular alcohols, such as. Ethanol, n- and isopropanol, ethers, e.g. Tetrahydrofuran, dioxane and 1,2-dimethoxyethane, esters, e.g. Ethyl acetate and methyl ester and nitriles, such as. For example acetonitrile.

The reaction temperature can be varied within a wide range in process (d). In general, it is carried out between -20 "C and + 50 ° C, preferably between 0 ⁰ C and 30 ⁰ C. Process (d) is generally carried out at atmospheric pressure.

For carrying out the process (d) according to the invention, in general between 0.9 and 1.2 mol, preferably between 0.95 and 1.1 mol, of metal compound are employed per mole of guanidine derivative of the formula (I).

In general, the guanidine derivatives of the formula (I) and the diluent are introduced and - optionally with slight external cooling - the metal compound - optionally dissolved in the diluent - metered. The reaction mixture is stirred until the end of the reaction. The salt products of formula (I) are generally crystalline and can be isolated by suction. The process (e) according to the invention is preferably carried out using diluents. As such, virtually all inert organic solvents come into consideration. These include, in particular, alcohols, such as methanol, ethanol, n- and iso-propanol, ethers, such as tetrahydrofuran, dioxane and 1,2-dimethoxyethane, esters, such as methyl acetate and ethyl acetate, and ketones, such as acetone, methyl ethyl ketone and methyl isobutyl ketone.

Insofar as the acids used as starting materials are used in aqueous solution, advantageously acetic anhydride can also be used as diluent.

The reaction temperature can be varied within a wide range in process (e). In general, it is carried out between -20 ⁰ C and +50 ⁰ C, preferably between 0 ⁰ C and 30 ⁰ C. Process (e) is generally carried out at atmospheric pressure.

For carrying out the process (e) according to the invention, in general between 1 and 10 mol, preferably 1 and 5 mol, of a strong acid are employed per mole of the compound of the formula (I).

In general, the compounds of the formula (I) and the diluent are initially charged and, if appropriate with slight external cooling, the strong acid is metered in. The reaction mixture is stirred until the end of the reaction. The 1: 1 adducts are generally crystalline and can be isolated by suction.

The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and especially as weed killers. Weeds in the broadest sense are all plants that grow in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides essentially depends on the amount used.

The active compounds according to the invention can, for. B. be used in the following plants:

Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa , Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea.

Dicotyledonous cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.

Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum , Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.

Monocotyledonous cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

However, the use of the active compounds according to the invention is by no means restricted to these genera, but extends in the same way to other plants.

The compounds are useful depending on the concentration for total weed control e.g. on industrial and railway tracks and on paths and squares with and without tree cover. Likewise, the compounds for weed control in permanent crops, z. As forestry, ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, gum, oil palm, cocoa, berry fruit and hop plants and used for selective weed control in annual crops become.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension-emulsion concentrates, active-ingredient-impregnated natural and synthetic substances and superfine encapsulations in polymeric substances. These formulations are prepared in a known manner, for. Example, by mixing the active compounds with extenders, that is liquid solvents and / or solid carriers, optionally with the use of surfactants, emulsifiers and / or dispersants and / or foam-forming agents.

In the case of using water as an extender z. As well as organic solvents can be used as auxiliary solvent. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for. As petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.

Suitable solid carriers are:

z. Ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as fumed silica, alumina and silicates, as solid carriers for granules: e.g. cracked and fractionated natural rocks, such as calcite, marble, pumice,

Sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material, such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foam-producing agents are in question: z. Nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates; suitable dispersants are: e.g. Lignin-sulphite liquors and methylcellulose.

It can be used in the formulations adhesives such as carboxymethylcellulose _t, natural and synthetic powdered, granular or latex-like polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins and synthetic phospholipids. Other additives may be mineral and vegetable oils.

There may be dyes, such as inorganic pigments, for. For example, iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and Metallphthalocyaninfarbstoffe and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such or in their formulations also in mixture with known herbicides for controlling weeds, ready-to-use formulations or tank mixes being possible.

For the mixtures known herbicides such. N- (2-benzthiazolyl) -N, N'-dimethylurea, 3- (3-chloro-4-methylphenyl) -1,1-dimethylurea, 3- (4-isopropylphenyl) -1,1-dimethylurea , 4-Amino-6- (1,1-dimethylethyl) -3-methylthio-1,2,4-triazine-5 (4H) -one, 4-amino-6- (1,1-dimethyl-ethyl) - 3-ethylthio-1,2,4-triazine-5 (4H) -one, 1-amino-6-ethylthio-3- (2,2-dimethylpropyl) -1,3,5-triazine-2,4- 1H, 3H) -dione, 4-amino-3-methyl-6-phenyl-1,2,4-triazine-5 (4H) -one, 2-chloro-4-ethylamino-6-isopropyl-amirio-1 , 3,5-triazine, the R-enantiomer of the 2- [4- (3,5-dichloro-pyridin-2-oxy) -phenoxy] -propionic acid (trimethylsilyl) methyl ester, the R-enantiomers of the 2- [4- (3,5-dichloropyridyl-2-oxy) -phenoxy] -propionic acid (2-benzyloxy) ethyl ester, 2,4-dichlorophenoxyacetic acid, 2- (2,4-dichlorophenoxy (-propionic acid, 4-chloro-2-methyl phenoxy-acetic acid, 2- (2-methyl-4-chlorophenoxy (-propionic acid, 3,5-diiodo-4-hydroxy-benzonitrile, 3,5-dibromo-4-hydroxy-benzonitrile and diphenyl ether and phenylpyridazines such. Some mixtures surprisingly also show syn ergotic effect.

Also a mixture with other known active ingredients, such as fungicides, insecticides, acaricides, nematicides, protective substances

bird repellancy, plant nourishment and soil conditioners is possible. .

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. The application is done in the usual way, for. B. by pouring, spraying, spraying, spreading.

The active compounds according to the invention can be applied both before and after emergence of the plants.

They can also be incorporated into the soil before sowing.

The amount of active ingredient applied may vary within a substantial range. It depends essentially on the type of effect desired. In general, the application rates are between 0.001 and 10 kg of active ingredient per hectare of soil surface, preferably between 0.05 and 5 kg per ha.

Compounds of formula (I) also show fungicidal activity. The preparation and the use of the active compounds according to the invention are evident from the following examples.

Preparation Examples example 1

, COOC ₂ H ₅

'/ Λ / ^N ~~ v \ ^L

\\ _ rn. ι. .NH - // ^N >

(Method [a])

18.6 g (0.075 mol) of 2-ethoxycarbonyl-benzenesulfonyl chloride are added to a cooled to -10 ⁰ C mixture of 4.9 g (0.025 mol) of N '- (4,6-dimethyl-pyrimidin-2-yl) -N " -methyoxy-guanidine and 30 ml of pyridine with stirring. The reaction mixture for 3 days stirred at 20 ⁰ C and then concentrated in a water jet vacuum. The residue is dissolved in 100 ml of methylene chloride, this solution is washed with water, dried, filtered and concentrated. The in Trituration of the residue with ethanol crystalline product is isolated by suction.

This gives 3.6 g (23% of theory) of N '- (4,6-dimethyl-pyrimidin-2-yl) -N "-methoxy-N", N "' - bis- (2-ethoxycarbonyl-benzenesulfonyl) -guanidine of melting point 106 ⁰ C.

- IO - £ .01 / OO

Example 2

NH-N (CH ₃ J ₂

(Method [b])

A mixture of 18.5 g (0.029 mol) of N '- (4,6-dimethylpyrimidin-2-yl) -N "-methoxy-N", N "' - bis- (2-propoxycarbonylbenzenesulfonyD-guanidine, 4, 2 g (0.07 mol) of Ν, Ν-dimethylhydrazine, 40 ml of water is refluxed for 90 minutes and then concentrated, the residue is eluted through a silica gel column with ethyl acetate to give 4.8 g (39% of theory) N '. - (4,6-dimethylpyrimidin-2-yl) -N'-dimethylamino-N '' - (2-propoxycarbonylbenzenesulfonyl-guanidine as a yellow oil.

Example 3

, CO-NHCz ₊ H ₉

"VSO ₂ -N. Nh // \\\

C \ N

H . OCH ₃

(Method [c])

4.0 g (0.025 mol) of butylamine are added at 20-3O ⁰ C to a mixture of the compound of the following formula (9.1 g

OCH ₃

and 60ml diethyl ether and 5ml dioxane with stirring. The reaction mixture is stirred for 15 hours at 20-25 ⁰ C and isolated the crystalline product by suction. This gives 8.1 g (75% of theory) of N '- (4,6-dimethylpyrimidin-2-yl) -N "-methoxy-N"' - (2-butylamino-carbonyl-benzenesulfonyl) -guanidine of melting point 169 ⁰ C.

Example 4

SO ₃ H

COOC ₃ H ₇ :.

(Method [e])

A mixture of 4.5p (0.007 mol) N '- (4,6-dimethylpyrimidin-2-yl) -N "-methoxy-N" -, N "' - bis- (2-propoxycarbonylbenzenesulfonyD-guanidine , 30 ml of acetone and 1.4 g (0.007 mol) of p-toluenesulfonic acid hydrate is stirred for 4 hours at 20 ⁰ C. The crystalline product is isolated by suction.

This gives 4.1 g (72% of theory) of the 1: 1 adduct of N '- (4,6-dimethylpyrimidin-2-yl) -N "-methoxy-N", N "' - bis- ( 2-propoxycarbonyl-benzenesulfonyl) -guanidine and p-toluenesulfonic acid of melting point 172 ° C.

The compounds of the formula (I) listed in Table 1 below can be prepared by the processes described by way of example in the preceding examples:

(Ι)

-16- Z37 783

table

Example No. M

Melting point (° C;

H is -OCi + Hg-n

H is -OC ₃ H ₇ -n

H-NHOCH ₃

H-NHCH ₃

H -NHN (CH ₃ ) ₂

H -NHOC ^ Hg-n

H is -OCH (CH ₃ ) ₂

.H -OC ₂ H ₅

-OCi + Hg-n

SO ₂ -COOC ₃ H ₇ -n

C00CH _{(CH3) 2} COOC ₂ H ₅

COOC ^ Hg-n

-OC ₃ H ₇ -Ii

COOC ₃ H ₇ -n

H is -OCH (CH ₃ ) ₂ H -OC ₂ H ₅

H is -OC ₃ H ₇ -n

C00CH _(CH3) 2

7-VsO ₂ -

COOC ₂ H ₅

COOC ₃ H ₇ -n

SO ₂ - -OCH ₃ "OCH ₃

-OCH ₃ -OCH ₃ -OCH ₃

-OCH ₃

-UC ₂ H ₅ -OC ₂ H ₅ -OC ₂ H ₅ -OC ₂ H ₅ -OCH ₂ - ^ jN

-OCH ₂ - (^) -OCH ₂ - ^ "

104 134

151 177 178

-OCeH- _l7 -n (amorphous)

65

96 135

Table! Continuation

Example No. M melting point! ⁰ ^)

0CH (CH ₃ ) ₂ OC ₂ H ₅

COOCH (CH ₃ ) ₂

COOC ₂ H ₅

: -_ y-so ₂ -

COOC ^ Hg-n

H is -OC ₃ H ₇ -n

H is -OCH (CH ₃ ) ₂

H is -OC ₂ H ₅

COOC ₃ H ₇ -n

^ yso ₂ -

_COOCH (CH ₃ ) ₂

COOC ₂ H ₅ -

OOCz + Hg-n

-N (CH ₃ ) ₂ , CH ₃

H -N

OCH ₃ CH ₃

COOC ₃ H ₇ -n

CO-N (CH ₃ ) ₂

O ₂ - / CH ₃

^X OCH ₃ CH ₃

C0_

SO ₂ - -OCH ₂ - // _ \\

-OCH ₂ -CH = CH ₂ -OCHZ-CH = CH ₂ -OCH ₂ -CH = CH ₂ .OCH ₂ -CH = CH ₂ , OCH ₂ COOC ₂ H ₅ -OCH ₂ COOC ₂ H ₅ -OCH ₂ COOC ₂ H ₅ -OCH ₃

-OCH ₃

-OCH ₃

120

153

Table 1 M continuation R ¹ -OH R ² R ³ Melting point ^.) Example no. H -OCH (CH ₃ ) ₂ H -OCH ₃ 30 H OC ^ Hg-n H -N (CH ₃ ) ₂ 142 31 H -NHOC ₃ H ₇ H -N (CH ₃ ) ₂ 110 32 H -NHOCH (CH ₃ ) ₂ H -OCH ₃ 138 33 H , -NHOCH ₃ H -OCH ₃ 178 34 H -NHOCH ₃ H -OCH ₂ ^ j) 35 H -NHOCH ₂ - (^ N H -OCH (CH ₃ ) ₂ 36 H -OCH (CH ₃ ) ₂ H -OCH ₃ 37 H -OCi ₊ H ₉ H -OH 38 H -N (CH ₃ ) ₂ H -NH ^ 2> ' 39 H -NHOCH ₃ H -OC ₂ H ₅ 143-14B 40 H , -NHOC ₄ H ₉ -O H (amorphous) 41 H 1: 1 adduct of compound p-toluenesulfonic acid H -OCH ₂ - ^ (amorphous) 42 1: No. 7 with 189 7a ii No. 7 with sulfuric acid (amorphous) 7b : 1 adduct of compound No. 8 with sulfuric acid 160 8a : 1 adduct of compound

- Ib -

(Dec.)

Table 1 (continued )

UO

• η · ω S-I CQ S

00

(N  Η ιη (N I OO (N ΓΟ

:O

ro

οο

(N

VD

iH

* 3 *

00 (N

(N

e ln ι- (  -ι ro .-Ι ι I O e U U e U U I (N (N (N U (N (N (N ^ J e e (N e e " O U U e U U ro ι (N (N U (N (N e e e (N e e U U U e U U O O U O O 2 I ' ι O I ι ι I

ΓΟ

"Β *

VO

00

(N

E U

(N

ο ιη

(N

in

Table 1 (continued)

Example no.

Melting point ( ⁰ O

1: 1 adduct of Compound No. 16 with methanesulfonic acid 1: 1 adduct of Compound No. 16 with sulfuric acid 1: 1 adduct of Compound No. 19 with methanesulfonic acid 96

74

107

Preparation of starting materials of the formula (II) Example (U-I)

CH3

H - ~ ^v O -CHCH-CH, I ^l * CH ₃

A mixture of 143 g (0.97 mol) of 2-cyanamino-4,6-dimethyl-pyrimidine, 94.3 g (1.06 mol) of O-sec-butyl-hydroxylamine and 190 ml of ethanol is refluxed for 6 hours heated. The mixture is then filtered off with suction, the filtrate is concentrated and the residue is mixed with 500 ml of water. The resulting crystalline product is isolated by suction.

This gives 131 g (57% of theory) of N '- (4,6-dimethylpyrimidin-2-yl) -N "- (1-methyl-propoxy) -guanidine of melting point

Example (II-2)

HN ^ v> N ^

A mixture of 109 g (0.67 mol) of O-methylhydroxylamine hydrochloride, 99 g (0.67 mol) of 2-cyanamino-4,6-dimethyl-pyrimidine and 600 ml of ethanol is refluxed for 7 hours. Subsequently, the alcohol is distilled off in a water jet vacuum, the residue dissolved in hot water and added to this solution to 100 ml of concentrated ammonia. The crystallized product is filtered off and recrystallized from ethanol.

One obtains 71,8g (55% derTheorie) N '- (4,6-dimethyl-pyrimidin-2-yl) -N "-methoxy-guanidine of melting point 134 ⁰ C to

Analogously, the compounds of the formula (II) listed in Table 2 below can be prepared:

H / ^N ~ ^

c ^ W.

CH ₃

CH ₃ (II)

Table 1] e 2:

^Bs P ·, melting

punk t ( ⁰ C)

No. R ³

I 1-3 -OCH ₂ CH (CH ₃ ) ₂ 7S

II- * · -OCH ₂ CH = CH ₂ 103

I 1-5 -0 CH (CH ₃ ) ₂ gi,

I 1-6 -OCH ₂ CH ₂ - ^ Ol

Table 2 - continued

Example, melting

No. Rl point (° C )

II-7 -Oci, H ₉ -n OeI

11-8 -0C ₈ H ₁₇ -n 58

II-9 -OCH ₂ CH ₂ CH ₂ Cl 137

ii-io "

11-11 -OCH ₂ -COOCH ₃ 148-149

11-12 -O-CH ₂ -COOC ₂ H ₅ 98-99

11-13 -O-CH-COOCH ₃ '147-148

CH ₃

11-14 -0-CH ₂ - <^ 103

11-15 -0-CH ₂ - © 114-116

11-16 -0- (H

11-17 -0-CH ₂ -ZhX

11-18 -D-CH ₂ CON (CH ₃ ) ₂

11-19 -O-CH ₂ - (^) - CH ₃ 86

11-20 -O-CH ₂ -O-CH ₃

11-21 -O-CH ₂ -S-CH ₃

11-22 -O-CH ₂ - (^) - COOC ₂ H ₅ 138

Table 2 - continued

- tt- - £ .01 / 00

Example no.

Melting point ^)

11-23

11-24 11-25 U-26

145

172

88

102

11-27

-0-C ₃ H ₇ (-n)

11-28

-O-CH ₂ -COOC ₃ H ₇ (-n)

112

II-29

-O-CH ₂ -CF ₃

Preparation of starting materials of the formula (III) Example (III-1)

A mixture of 10Og (0.33 mol) of bis (carboxyphenyl) disulphide and 10OmI thionyl chloride is slowly heated to 70 ° C and held at this temperature until the evolution of gas is practically complete. It is then concentrated. Of the residue remaining as a residue crude bis (2-chlorocarbonyl-phenyl) disulfide -101 g (91% of theory) - 50g (0.14 mol) are removed and heated with 100 ml of ethanol for 3 hours under reflux to boiling. The bis (2-ethoxycarbonyl-phenyl) -disulfide obtained after cooling - 41 g (89% of theory), melting point 103 ⁰ C - is isolated by suction and taken up in 100 ml of water and 100 ml of methylene chloride. After addition of igTetrabutylammoniumbromid is introduced at an internal temperature between 0 ° C and 10 ⁰ C chlorine to saturation. Then the organic phase is separated, washed with water, dried, filtered and concentrated

 48 g (84% of theory) of 2-ethoxycarbonyl-benzenesulfonyl chloride (GC 97% pure) are obtained as yellow OeI.

Preparation of starting materials of the formula (V)

Example (V-1)

-SO ₂ -N

CH ₃

CH ₃

A solution of 60g (0.25 mol) of 2-chlorosulfonylbenzoyl chloride is added under stirring at -10 ⁰ C to-5 ° C to a mixture of 49 g (0.25 mole) of N '- (4,6-dimethyl-pyrimidin-2- yl) -N "-methoxyguanidine, 50 g (0.63 mol) of pyridine and 200 ml of methylene chloride are then stirred in for 3 hours at 20 to 25 ° C. After washing the methylene chloride solution with dilute hydrochloric acid and ice water, drying, filtration and Concentration gives a residue which is made to crystallize by trituration with ethanol, the product which is obtained by crystallization being isolated by suction.

This gives 65 g (72% of theory) of the compound of the above structural formula of melting point 185 ° C. The compounds of the formula (V) listed in Table 3 below can be prepared by the process described by way of example in the preceding example.

SO ₂ -N-

(V)

table example

No melting point ( ^D C,

U-4 V-5 V-6 V-7 V-8 V-9 V-IO V-II

-0-C ₈ H ₁₇ -n

-0-O ₊ H ₉ -II

-OC ₂ H ₅

-0C ₃ H ₇ -n

-O-CH (CH ₃ ) ₂

-OCH ₂ CH (CH ₃ ) ₂

-O-CH ₂ -COOC ₂ H ₅

-O-CH-CH ₂ CH ₃ 162 136 (amorphous)

175 81

155

CH

V-12

-O-CH ₂ -CH = CH ₂ 153-155

Example A

Pre-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the indicated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Seeds of the test plants are sown in normal soil and watered after 24 hours with the preparation of active ingredient.

It is advisable to keep the amount of water per unit area expediently constant. The concentration of active ingredient in the preparation does not matter, only the application rate of the active ingredient per unit area is decisive. After three weeks, the degree of damage of the plants is rated in% damage in comparison to the development of the untreated control. It means:

0% = no effect (as untreated control) 100% = total destruction

The active compounds according to the invention show a very good herbicidal activity in this test. This applies in particular to z. B. for the compounds according to Preparation Examples 1,4,6.

Example B

Post-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the indicated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

With the preparation of active compound is injected test plants, which have a height of 5-15cm so that the respective desired amounts of active ingredient per unit area are applied. The concentration of the spray mixture is chosen so that in 2000I water / ha, the respective desired drug quantities are applied. After three weeks, the degree of damage of the plants is rated in% damage in comparison to the development of the untreated control.

It means:

0% = no effect (as untreated control) 100% = total destruction

The active compounds according to the invention show a very good herbicidal activity in this test. This applies in particular to z. B. for the compounds according to Preparation Examples 1,4, 6th

Claims (1)

Invention claim: in which M stands for hydrogen or a metal equivalent, "Π ¹ for hydroxy, C ₃ -C ₈ -alkoxy and, for the case where R ^{2 is} different from hydrogen, also represents ethoxy and furthermore for C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkyl <yl -C _l -C 2 alkoxy, CRC6-Halogenall <oxy, cyano-C ₁ -C 6 oxy-all <, CrC ^ alkoxy-CrC ^ alkoxy, C ₁ -C ₄ -alkyl alkylthio-CrC ^ alkoxy ^ rC ^ alkylsulfinyl C ₁ -C 4 -alkoxy, C ₁ -C 4 -alkylsulfonylCI-gralkoxy-C ₁ -C ₆ -alkoxy-carbonyl-C ₁ -C 4 -alkoxy, C ₃ -C ₈ -alkhenoxy, C ₅ -C 5 -alkoxy, phenylChoO-alkoxy, phenoxy [which may be replaced by Halogen, cyano, nitro, Ci-C ^ AlkyljCr ^ -haloalkyl, CrC ₄ -alkoxy, Ci-C ₂ -haloalkoxy or C ₁ -C ₄ -AlkoxyCarbonyl is substituted], for C ₁ -C ₈ -alkylamino which is optionally substituted by halogen , hydroxy, cyano, C _r C ₄ alkoxy or C ^ alkoxy-carbonyl is substituted], Cs-Ce-cycloalkylamino, C ₃ -C ₆ alkyl -CyCIo-Ci-d-alkylamino, C ₃ -C ₈ -alkenylamino, Ca-Cs-alkynylamino ^ -phenyl-Ci-Cs-alkylamino, for di (Ci-C ₄ -alkyl) -amino [which is optionally substituted by halogen, cyano, hydroxy or C ₁ -C ₄ -alkoxy sub is di-fCs-Ce-Cycloalkalaminoj ^ Di-ICs-CB alkenyD-amino, di-ICs-Cä-alkynyll-amino, for C ^ Ce alkoxyamino [which is optionally substituted by halogen, C ₁ -C ₄ - AIkOXy, Ci-C ₄ -alkylthio, C ₁ -C ₄ -alkylsulfinyl or C ₁ -C ₄ -alkylsulfonyl substituted], for Qr-Cs-alkenyloxyamino, Qr-Cs-alkynyloxyamino, Cs-Cβ-cyclo-alkyloxyamino, C C ₁ -C 6 -alkoxy-carbonyl-C ₁ -C ₄ -alkoxyamino, phenylC ₁ -C ₂ -alkoxyamino [which is optionally substituted by halogen, cyano, nitro, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkyl, AIkOXy or dC ^ alkoxycarbonyl], for C ^ Ce-Alkylhydrazino, di-IC ^ Ct-alkyll-hydrazino, Cs-Ce-Cycloalkylhydrazino, phenyl-C ₁ -C ₂ -alkylhydrazino, phenylhydrazino [which is optionally substituted by halogen, cyano, nitro, d-Cr-alkyl, Ci ^ haloalkyl, Ci-C ₄ alkoxy, C ₁ -C ₂ -halogen-alkoxy, Ci-Cj-alkylthio, _Ci-C2 haloalkylthio or C ^ C ^ alkoxycarbonyl is substituted], for d-Cit-alkyl-carbonylhydrazino, Ci-C ^ alkoxycarbonyl-hydrazino, Ci-C ^ alkylsulfonylhydrazino, dC ₄ haloalkylsulfo nylhydrazino or Phenylsulfonylhydrazino [which is optionally substituted by halogen, cyano, nitro, Ci-C ₄ alkyl, C ^ C ^ haloalkyl, C ₁ -C ₄ -alkoxy, C ^ C ^ haloalkoxy or Ci-C ^ alkoxycarbonyl] amino orfor stands; in which further R ^{2 is} hydrogen, C ₁ -C ₆ -alkyl [which is optionally substituted by fluorine, chlorine, bromine, cyano, hydroxy or C ₁ -C ₄ -alkoxy], C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -alkenyl, C ₃ -C ₆ -AIkInY ^ benzyl [which is optionally substituted by fluorine, chlorine, nitro, cyano, Ci-C ₄ -AlkYl ₁ C ₁ -C ₄ -alkoxy or d-Ci-alkoxycarbonyl] or the radical stands in which R ^{1 has} the meaning given above; in which further R ^{3 is} hydrogen, C ₁ -C ₆ alkyl [which is optionally substituted by fluoro, chloro, bromo, cyano, carboxy, C ₁ -C ₄ alkoxycarbonyl, hydroxy or C ₁ -C ₄ alkoxy], C ₃ -C ₆ -CyClOAlkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ -AlkJnYl, phenylethyl or benzyl [which is optionally substituted by fluorine, chlorine, nitro, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ -alkoxy or C ₁ -C ₄ -alkoxy-carbonyl substituted] or phenyl [which is optionally substituted by fluorine, chlorine, bromine, hydroxy, cyano, nitro, amino, Ci-C ₄ alkyl, Irifluormethyl, Ci-C ₄ - AIkOXy, irifluoromethoxy, Ci-C ₄ -Al kylthio, lrifluormethylthio, aminosulfonyl or Ci-Ct-alkoxycarbonyl is substituted]
stands, or R ² and R ³ together represent C ₄ -C ₆ alkanediyl [which is optionally interrupted by an oxygen bridge or by a bridge NR ⁴ ],
in which R ^{4 is} Ci-Ct-alkyl ^ -Ct-alkyl-carbonyl ^ i-Ct-alkoxycarbonyl or phenyl [which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, dC ₄ alkyl, Ci-CrFluoralkyloderCi-C ^ Alkoxy is substituted]; in which further R ^{3 is} the radical -O-R ⁵ , in which R ⁵ is Ci-C ₈ -alkyl [which is substituted ₄ alkylsulfonyl optionally substituted by halogen, C ₁ -C ₄ -alkoxy, d-CT-alkyl-thio, Ci-C IQtI C _n - C. ~ Al \ (0 n \ / l / olrhoc nonahaninfalloHnrnh Cliint-λΗωι-Γ ^ Ιλγ pniM ^ tittiioi ^; "! l, Ca-Ce-cyclo-alkyl, C ^ Ce-cycloalkyl-Q-cralkyl, C ^ C ^ alkoxy-carbonyl-d-cralkyl, aminocarbonylmethyl, Ci-C ^ alkylamino-carbonyl-methyl, di-ICi-C ^ alkyll-amino-carbonyl-methyl, phenyl, benzyl, or phenylethyl [which is optionally substituted by halogen, cyano, nitro, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₂ - Haloalkoxy or CiC / j-alkoxycarbonyl substituted] stands;
in which further for the rest -IT stands in which