AU610067B2 - 3-substituted 1-(2-halogenoalkoxy-benzenesulphonyl)-3- heteroaryl-(thio) ureas - Google Patents

Abstract

The invention relates to novel 3-substituted 1-(2-halogenoalkoxy- benzenesulphonyl)-3-heteroaryl(thio)ureas of the formula (I) <IMAGE> (in which Q, R, R<1>, R<2>, X, Y and Z are as defined in the description), their preparation, and their use as herbicides.

Description

29 JGS:CB.1493T.33

AUSTRALIA

PATENTS ACT 1952 COMPLETE SPECIFICATION

(ORIGINAL)

FOR OFFICE USE Application Number: Lodged: Complete Specification Lodged: Accepted: mends Published: Priority: Related Art: )0O LODGED AT SUB-OFFICE 2 3 JUN 1987 Sydney v U -C~r TO BE COMPLETED BY APPLICANT Name of Applicant: S'Address of Applicant: .Actual Inventor: t 1 Address for Service: 4 44

S

S BAYER AKTIENGESELLSCHAFT D-5090 Leverkusen, Bayerwerk, Germany Theodor PFISTER, Christa FEST, Klaus-Helmut MULLER, Hans-Jochem RIEBEL, Hans-Joachim SANTEL, Robert R. SCHMIDT ARTHUR S. CAVE CO.

Patent Trade Mark Attorneys Goldfields House 1 Alfred Street SYDNEY N.S.W. 2000

AUSTRALIA

"3-SUBSTITUTED uompeiie Specirication ror tne invention entitled 1-C 2^ALOGENOALKOXY-BENZENESULPHONYL)-3-HETEROARYL-(THIO)UREAS".

The following statement is a full description of this invention i including the best method of performing it known to me:- ASC 49'" 4i .4 The invention reLates to new 3-substituted 1-(2haLogenoaLkoxy-benzenesuLphonyL)-3-heteroaryL-(thio)ureas, severaL processes for their preparation and their use as herbicides.

it is known that certain 1-aryLsuLphonyL-3-heteroaryL-ureas, such as, for example, 1-(2-methoxy-benzenesuLphonyL )-3-(4,6-dimethyL-pyr iridin-2-yL )urea, 1-(2-tr ifLuoromethoxy-benzenesuLphonyL )-3-(4,6--dimethoxy-pyrimidin-2-yt )urea and 1-(2-tr ifLuoromethoxybenzenesuLphonyL 10 3-(4,6--dimethyL-pyrimidin-2-yL)urea, have a herbicidaL action. However, the action of these compounds is not a Lw a ys c o mp Let e Ly s at is fa ct o ry (c om pa r e, f or e xa m p Le, U .S.

Patent Specification 4,169,719 and European Patent A-173,3 12).

New 3-substituted 1-(2-haLogenoaLkoxy-benzenesuLphonyL)-3-heteroaryL-(thio)ureas of the generaL formuLa a aS0 2 Y

R

2 a #Oa in which R hrarla aoenoaLkYL Q represents oxygen or sulphur, R represents optionaLLy substituted radicaLs from the series comprising aLkyL, aLkenyL, aLkinyL A 90 oraaal

R

2 represents hydrogen, halogen, hydroxyL, alkyL, haLogenoaLkyL, aLkoxy,.\,haLogenoaLkoxy, aLkyLthio, 9~ 0*haLogenoaLkyLthio, amino akyLamino or diaLkyla am i no 0 90 X represents nitrogen or a -CH- grouping, Y represents nitrogen or a -R grouping, e--.24-483- la Ila 0- R represents halogeno-C -C4-alkyl, Q represents oxygen or sulphur, 1 R represents C -C6-alkyl [which is optioinally substituted by fluorine, cyano, C 1

-C

4 -alkoxy or Cl-C 4 -alkylthio], or represents C 3

-C

6 -alkenyl or C -C6-alkinyl [which are optionally substituted by fluorine or chlorine], or represents phenyl-C -C alkyl [which is optionally substituted in the phenyl part by fluorine, chlorine, nitro, cyano, methyl, methoxy or C -C -alkoxycarbonyl], R represents hydrogen, fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, ethoxy, difluoro- 00* methoxy, methylthio, ethylthio, amino, methylamino, S° ethylamino, dimethlyamino or diethylamino, .s X represents nitrogen, 00 3 Y represents nitrogen or a -CR grouping, wherein R represents hydrogen, fluorine, chlorine, bromine, methyl, formly, acetyl, methoxycarbonyl or ethoxycarbonyl, and 0000 4 0 Z represents a -CR grouping, wherein 4 R represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino, dimethlyamino or diethylamino, I and salts of compounds of the fjrmula with metals and basic organic nitrogen compounds have now been found.

-4 lb 0049s/gs k 1114 1 s>Lanah a I ngen---- k y L formyL, aLkyl- arbonyl or aLkoxy-carbonyL and 4 Z represents nit ogen or a -CR grouping, wherein R represents hydrogen,' aLtogen, hydroxyL, aLkyL, haLogenoaLkyL, alkoxy, haL enoalkoxy, aLkyLthio, aLkyLamino or diaLkyamino, and salts of compounds of the formuLa (I with metaLs and g-e-n--c o m-p o u n-d h- enA be f d.

The new 3-substituted 1-(2-haLogenoalkoxy-benzenet suLphonyL)-3-heteroaryL-(thio)ureas of the formuLa are obtained by a process in which 2-haLogenoaLkoxy-benzenesuLphonyL iso(thio)cyanates of the formula (II)

OR

(II)

SO

2

N=C=Q

in which Q and R have the abovementioned meanings, are reacted with heteroarylamines of the formuLa (III) rett <4 '4 N-Z- (I-I) R -NH- Y R2 in which 12 R R X, Y and Z have the abovementioned meanings, if appropriate in the presence of diLuents and if appropriate in the presence of cataLysts, and, if appropriate, *414 the products thus obtained are converted into saLts by customary methods, or by a process in which 2-haLogenoaLkoxy-benzenesuLphonic acid amides of the S formula (IV) Le A 24 483 -2

I

OR

(IV)

S0 2 -NH2 in which R has the abovementioned meanings, are reacted with N-heteroaryt-urethanes of the formuLa (V) O 81

N--Z

Y

R2 in which 1 2 R R X, Y and Z have the abovementioned meanings and R represents C 1

-C

4 -alkyL, benzyl or phenyL, if appropriate in the presence of diluents and if appropriate in the presence of acid acceptors, and, if appropriate, the products thus obtained are converted into saLts r r by customary methods, or by a process in which II rE N-(2-haLogenoalkoxy-benzenesutphonyL)-urethanes of S 15 the formuLa (VI)

V

)I (VI) S0 2

-NH-C-O-R

6 in which Q and R have the abovementioned meanings and R 6 represents C 1

-C

4 -aLky, benzyl or phenyl, are reacted with heteroarylamines of the formula (III)

(III)

R Y

R

2 so 6( 4* 4** in which 1 2 R R X, Y and Z have the abovementioned meanings, Le A 24 483 3 r if appropriate in the presence of diluents and if appropriate in the presence of acid acceptors, and, if appropriate, the products thus obtained are converted into salts by customary methods, or by a process in which 1-arylsulphonyl-3-heteroaryL-ureas of the formula

(VII)

O2H 1 N-Z Y 0 2

Y

7 2 I

(VII)

in which Q, R, R 2 X, Y and Z have the abovementioned meanings, are reacted with compounds of the formula (VIII) R 1-W (VIII)

S

St .5 S r S S 05 S Si Sos.

5054 0 0 850o *a ai o St aL 05 00 in which R has the abovementioned meanings and 15 W represents a nucleophilic leaving group, if appropriate in the presence of diluents and if appropriate in the presence of acid acceptors, and, if appropriate, the products thus obtained are converted into salts by customary methods.

The new 3-substituted 1-(2-halogenoalkoxy-benzenesuLphonyL)-3-heteroaryl-(thio)ureas of the formula are distinguished by a potent herbicidal activity.

Surprisingly, the new compounds of the formula (I) exhibit a considerably better herbicidal action than the 25 already known urea derivatives of the same type of action.

T he invent i o n b @W-a L y-rela t cmpounds-&-f the formula (I) in which R represents- logeno-C 1-C 4 -aL kyL, Q repr esnts oxygen or sulphur, I A n 0 Iv 4 0105s:AB More specifically, the new compounds of the Formula unlike the prior art compounds i) are valuable not only as selective wheat herbicides, but also, in particular, as selective corn (maize) herbicides; ii) display virtually no persistence in the soil since they are decomposed very rapidly by hydrolysis.

t i t I a t t I 4 4 t *4 14 9 9 t 4* L i., <9 t, i-1 1

I

I' i R-epese.nts-Cj-C6- -ayw-L-hsubstituted by fLuorine, cyano, C -C 4 -aLkoxy or

C

1

-C

4 -aLkyLthioD, or represents C -C 6 -akeny or C 3

-C

6 -aLkiny [which are opti natLy substituted by fluorine or chlorine], or re resents phenyL-

C

1

-C

2 -aLkyL [which is optional y substituted in the phenyl part by fluorin chlorine, nitro, cyano, methyL, methoxy or C 1

-C

2 -aLkoxycarbonyL1, R2 represents hydrogen, fLuorine, chLorine, bromine, methyL, trifLuorom thyl, methoxy, ethoxy, difLuoromethoxy, methylthi ethyLthio, amino, methylamino, ethyLamino, imethyLamino or diethylamino, X represents nitrogen or a -CH- grouping, Y represents nitrogen or a -CR 3- grouping, where in R3 represents hydroge fLuorine, chLorine, bromine, methyL, for yL, acetyl, methoxycaroonyL or ethoxycarbony, nd 4 Z represents nitro en or a -CR grouping, wherein R represents hyd ogen, fLuorine, chlorine, 4,44 bromine, methyl, ethyl, trifLuoromethyL, methoxy, ethoxy, propoxy isopropoxy, difluoromethoxy, methylthio, et ylthio, methyLamino, ethyLamino, Him the.t.yLamino.- r Aie-.thy Laminn The invention furthermore preferably relates to saLts of compounds of the formula as defined above S' with sodium, potassium, magnesium or caLcium and with S 30 monoalkyL-, dialkyL-, trialkyl-, benzyl-alkyL- and benzyLdiaLkylamines with in each case up to 4 carbon atoms in the alkyL radicals, the aLkyl radicals optionaLLy in each oa case containing a substituent from the series comprising fLuorine, chLorine, hydroxyL, methoxy, ethoxy and cyano.

35 Compounds of the formula which are particularly preferred are those Le A 24 483 1 in wh ich R represents trifLuoromethyL, difLuoromethyL, 2chioroethyL or 1, 1,2,2-tetrafLuoroethyL, Q represents oxygen or suLphur, Rlrepresents methyL, ethyL, n-propyL, i-propyL, n-butyL, aLLyL, propargyL, benzyL or phenyLethyL R 2 X Y and Z have the abovementioned preferred mean inrgs.

If, for exampLe, 2-trifLuoromethoxy-benzenesuLphonyL isoth jocyanate and 4-ethoxy-6-methyL-2-methyLamino-1,3,5-triazine are used as starting substances for process variant the course of the reaction can be outLined by the foLLowing equat ion:

OCF

3

CH

3

CH

3 S0 2 -N C =S HN-C-< N 0C 2

H

ti*1t

OCF

3 S CH3~ CH.3 t Nt acid if, for exampLe, 2-difLuoromethoxy--benzenesuLphonic acdamidle and 0-phenyL--N-methyL-N-(4--ethyLamino-6-methyLthio-l,3,5-triazin-2-yL)-urethane are used as starting substances for process variant the course of the reaction can be outLined by the foLLowing equation: oOCHF 2 0 CM 3

SCH

3 +4 C N---s HHC 2

H

OCHF

2 0 CM 3

SCM

3 0 2 i Le A 24 483 -6- If, for exampLe, O-phenyL-N-[2-(2-chLoroethoxy)benzenesuLphonyL ]-urethane and 2-benzyLamino-4--chLoro-6methoxy-pyrimidline are used as starting substances for process variant the course of the reaction can be outLined by the folLowing equation:

QCH

2 CHZ"1 0 Q$-so02 NHC-0-{D C 1

CH

2

O)CH

3 H 0-0

OCH

2

CH

2 Cl 0 Cl so2- 1N 4, 4 44 4 4 4 4 4444 4444 4 4444 44 4 4 444 if, for exampLe, 1-(2-trifLuoromethoxy-benzene- 10 suL~honyL )-3-(4,6-dimethoxy-1,3,5-triazin-2-yL )-urea and methyl iodide are used as starting substances for process variant the course of the reaction can be outlined by the following equation: 4 44 4 4 4 4 4'

OCF

3 0 OCH 3

OCH

3

CH

3

I

NaOH NaI 4 44 4 4 44% 4 44 44 44 4 4 44 4 4 4 4 4 44

OCF

3 0 CH 3

OCH

3 11_I

OCH

3 Le A 24 483 7- L 2 Formula (II) provides a general definition of the 2-halogenoalkoxy-benzenesulphonyL iso(thio)cyanates to be used as starting substances in process according to the invention. In this formula Q and R preferably or particuLarly represent those radicals which have already been mentioned as preferred or as particularly preferred for these substituents in connection with the description of the substances of the formula according to the invention.

Examples of the compounds of the formula (II) which may be mentioned are: 2-trifLuoromethoxy-, 2-(2-chloroethoxy)-, 2-difluoromethoxy- and 2-(1,1,2,2-tetrafLuoroethoxy-benzenesuLphonyL isocyanate and -benzenesuLphonyL isothiocyanate.

The compounds of the formula (II) are known and/or can be prepared by known processes (compare, for example, European Patent A-44,808 and 173,312 and U.S. Patent Specification 4,514,212).

S 20 Formula (III) provides a general definition of the heteroarylamines also to be used as starting substances in process according to the invention. In this for- 1 2 mula (III), R R X, Y and Z preferably or particu- Larly represent those radicals which have already been o 25 mentioned as preferred or as particularly preferred for these substituents in connection with the description of the substances of the formula according to the inven- S0" tion.

0 Examples which may be mentioned of the compounds of the formuLa (III) are: o Le A 24 483 Ii I S

N-Z:

R

1 y R2

(III)

TabLe 1 N-zz R2

HI

-CH

3

CH

3

CM

3

-CH

3

-CM

3

CH

3 .54, 45 a *52 a S 5a~ .544 .4 a,.

eQ a a a *L~ 24 a a S a SI

IL

a S S *4 $2 a 4 a a a a .5

-CH

3

-CH

3

CM

3

CM

3

CM

3 OC

H

3

N

-CH

N-

C

2

H

5

C

3

-CM

3

-CM

3

-CM

3

C

C

3

CM

3 3-

CH

3

CM

3 CHl

C

3

CH

3

CM

3 Le A 24 483 9- TabLe 1 Continuation

N-Z::

R2

R

1

II

-CH

3

CH

3

-CH

3 494t 9991 9$ 94 94 9 4 *4 $9 4 909$ 9999 $499 9994$ 9* 9 994 o 9$ 9 $4 99 o 9 9494 CH 3

-CH

3

-CH

3

O

2

H

5

N

N-

CH

3 OCHF2

N-

CH

3

CH

3

OCH

3

SC

2

H

-CM

3

-CH

3

-CM

3

-CM

3

-CH

3 0C 2

H

CM

3

N(CH

2

CH

3

N-K

NHCM

3

N-<

3

NH-C

2

M

OCR

3

N(CH

3 )2

-CM

3

-CM

3

-CM

3 99 99 9 9 9 99 9 9 9 9 9 9~0 A 24 483 10 TabLe 1 Continuation

P

1

Y

-CH

3

CH

3

-CH-

3

CF

3 Cl 0C 2

H

5

N-

SC

2

H

5

NHCH

3

CH

3

NK

NHC

2

H

C

2

H

N(C

2

H

5 2

SCM

3 N1HC 2

H

5

CM

3

CM

3

P

2

OCX

3

CH

N C 2

H

5 2 NH CH3 NC 2

H

N

N(CM

3 2 0$0~ 04*4 *a

I

44 a 0044 0400 t~004 o *00 00 a 400 O 04 0 4 0 44 44 4 0 4 0844

CH

3

_-CH

3

-CH-

3

-CM

3

-CM

3

CH

3

-CH

3

N-N

CM

3

CH

3

CM

3

-CM

3

-CM

3 *4 00 4 00 0 0 0 p Le A 24 483 11

I

I Tab~e 1 Continuation

N-Z--

<y -c MN-Zz P2

-CH

3

CH

3

SCH

3

N(CCH

3

NHCH

3

H

3

N(C

2

H

5 )2 N SC 2

H

N(CH

3 2 I5#1 4* $4 44 4 0 t 4 4' '4 0 4044 4004 444, 0 044

-CR

3

-CH

2 -0

S

2

H

NC C 2 HS 2

CH

3

CH

3

CH

3

N

OCH

3

OCH

3

N

QCH

3 0C 2

H

5

N

0C 2

H

5

-CR

3 CH2<

CH

3 H 3

CR

3

CR

3

C

2

H

OCHF

2

N

CH

3 0C 2 Hq

N

Cl 0 444 ,.t 4 4 0 4 40 4 C I 4 4~ 44 44 4 4 0 4 84 4 4 0 4 O 48 Le A 24 483 12 TabLe 1 Continuation N-Zz R2 R 1 -c-

R

2 I CH 2< CH2-<D -CH 2-0

I~

a. a a~ 4 4 P4~ 4~4 Q 4 44 o o a 44~ Ia a t.~ a I 4 I S 0 II IS I I I

I

IA I a

LI

C3

CH

3 3

CH

3 0C 2

H

5

CM

3

SCM

3

CH

3

CH

3

CH

3

QCH

3

OCH

3

OCH

3 -CH2--O -cH2--O

OCH

3 0CH 3

N-K

2

H

CH

3

O

2

M

0CH 3

-C

2

H

5

-C

2

H

OCH

3

NCN

OCH

3

CM

3 CH3

-C

2

H

5

-C

2

H

5

-C

2

H

Le A 24 483 13 TabLe 1 Continuation R

R

R2

-C

2

H

5

-CH

3

-C

2

H

5 00 0 ."U 00040 Go a

-C

2

H

5

-C

2

H

-C

2

H

5 N 0C2

H

5 Cc 2

H

5 N OCHF 2

CF

3

C

2 Hq

N

CCH

3

CH

3 0 2

H

5

CH

3

OCHF

2

CH

3 -c

-C

2

H

-cl- 3

-CH

3 N

C

2

H

ci N OCHF 2 Ci

CH

3

OCH

CH

3

CH

3

NCH

3 C2 Le A 24 483 14 4' Table 1 Continuation

P

1 -z -c 2

H

5

CH

3

S

2

H

5 S CH 3

OCH

3 N CH

SCH

3

NCH

3 C 2

H

-c 2

H

5

-C

2

H

CH

3 N C 2

H

5 2

OCH

3

NH

NC3

NCH

3 N(C 0C 2

H

OH

C 2

H

@000 0 0*00 *0 00 0 0 '4 0 0.0 0.0 0 0.

o o 00* 00 0*4 0 04 @0 0 o 04 0 *0 00 0 0080 00 0, 0 00 0 0 0 0

-C

2

H

5

-C

2

H

5

-C

2

H

-C

2

H

-Le A 24 483 15 TabLe 1 Continuation

NP

1 -c:

R

2 11I-

-C

2

H

-C

2

H

5

-C

2

H

5

-C

2

H

5

N-<

2

H

5 N (C 2

H

5 ~2

NHCH

3

SCH

3

NHC

2

H

SCH

3

N(CH

3 2 SC2

"NI

NCH

N(C

2

H

5 2

SCH

3

SCH

3

-C

2

H

-C

2

H

N-N

-C3

CH

3

CH

3

SCH

3

N(C

2

H

5 2

S

2

H

N(CH

3 2

N-N

CH

3

SC

2

H

SC

2

H

00~ @009 0* 09 0 0 0 0 00 9 0 0 9000 000k 00 0 004

C

2

H

5

-C

2

H

-C

2

H

t 4 L C 4 4

-C

2

H

Le A 24 483 16

'S

TabLe 1 Continuation M--Z2 -c R 2

-Q

if

CH

3

-CH

3

-CH

3

-C

3

H

7 -n

CF

3

OCH

3

CF

3

CH

3

C

2

H

5

N

-KH

CH

3

CH

3

N

-KH

OCH

3

N

OCH

3

N

0C 2

H

5

CH

2 -l0j

-C

3

H

7 -n

-C

3

H

7 -ri

-C

3

H

7 -n

-C

3

H

7 -n

OCH

3

CH

3

N

N

N-

CH

3

OCH

*0 Ce C C

CC

C C C 4*C~ CCC C

'CCC

C

*4t 4' 4 4 4 4 4 444, 44 4* 4 4 4 4 C C. C 4 C C

EC

-C

3

H

7 -n

-C

3

H

7 -n

-C

3

H

7 -n Le A 24 483 17 TabLe 1 Continuation -zz ply -c L

-C

3

M

7 -n -C3H-

-C

3

H

7 -r

CH

3

NH

CH

3

OCH

3 0C 2

H

5 0C 2

H

5

CM

3

N

CH

3

CM

3

N

OCH

N

OC-

CH

3

N-K

CH

3

-C

3

M

7 -n

-C

3

H

7 -n -cH-n

C

3

SCH

3

N-<

2

M

CH

3 CH3

N-

CM

3

C

3

-C"-CHCM

2 a. a~ 4444 *4 4~ a a a a 44 a *400 4444 4 444* 4.4 a.

a ata a' a a a a a at.

a aa a a a 4 4.4 a at a, C a a a 4a a a a I at

-CM

2

-CM=CM

2

-CM

2 -CM= CM 2

-CH

2

-CM=CM

2

-CM

2

-CM=CM

2

-CM

2 -CH= CM 2

-CM

2 -CM= CM 2

-CM

2 -CH= CM 2 Le A 24 483 18 Tab~e 1 Continuation HWZz R2 <2 I I

-CH

2

-CH=CH

2

-CH

2 -CH= CH- 2

QCH

3

CH

3 0C 2

H

5

CH

3

-CH

2

-CH=CH

2

-CH

2

-CH=CH

2

O

2

H

N-K

2

H

OCH

3

-CH

2

-CH=CH

2 44* I 1144 SI II I I S o I A 4 8040 4 lOll 01

IAI

.4 4 4 I 4 4 4~ 4 4 t4~4 44 to 4 1 1 4 I 10 0 C 0 0 I 04 Le A 24 483 19 The compounds of the formula (III) are known and can be prepared by processes which are known per se (compare, for example, Chem. Pharm. Bull. 11 (1963), 1382 and U.S. Patent Specification 4,299,960, European Patent A-121,082, 125,205 and 126,711 and European Patent A-152,378).

Formula (IV) provides a general definition of the 2-halogenoalkoxy-benzenesulphonic acid amides to be used as starting substances in process according to the invention. In this formula R preferably or particularly represents those radicals which have already been mentioned as preferred or as particularly preferred for this substituent in connection with the description of the substances of the formula according to the invention.

Examples which may be mentioned of the compounds of the formula (IV) are: 2-trifLuoromethoxy-, 2-difluoromethoxy-, 2-(2-chLoroethoxy)- and 2-(1,1,2,2-tetrafLuoroethoxy)-benzenesuLphonic acid amide.

The compounds of the formula (IV) are known (compare, for example, Zh. Org. Khim. Org. Chem. USSR], 8 (1972), 1023 1026 [English 1032 1034] and European Patent A-44,808).

So FormuLa provides a general definition of the N-heteroaryL-urethanes also to be used as starting sub- 40o0 25 stances in process according to the invention. In 1 2 this formula R R 2 X, Y, Z and Q preferably or 0 6 particularly represent those radicals which have already been mentioned as preferred or as particularly preferred 8< for these substituents in connection with the description of the substances of the formula according to the 5 invention. R in this formula preferably represents S methyl, benzyl or phenyl, in particular methyl or phenyl.

Examples which may be mentioned of the compounds of the formula are: S2048 Le A 24 48 20

I

Q

R

5 IH N-z-z' R -O0- Y

R

5

-CH:

3

-C

Q =0 or S TabLe 2 Kfh-Zz' -c R 2

-CH

3

CH

3

CH

3

-Q

OCH

3

OCH

3

-CH

3 4.4, @4 44 4 4 c~4 0 0 ~4~4 4 4.~ 1Z ~t 4~ 4 I 4 4 4 S. I t 4

IS

Le A 24 483 21 O r§Wm

'A

k TabLe2 2- Continuation N-zz- -c R 2

-Q

H I

OH

3

-OH

3

-OH

3

-CH

3

CH

3

QCH

3

OCH

3

OCH

3 0C 2

H

5

N-=

CH

3

N-<

2

H

CH

3 00H 3

-OH

3

OH

3

CH

3

OH

3

-OH

3

OH

3

-CH

3

CH

3 -a 0 0.0 0 0 oaoa 0000 a a oao a a a?.

-CH

3

-OH

3

CH

3

N==

N-

OCH

SCH

3 -C3 -083 -083 to a I a a a? t a a a 0 IL Le A 24 483 22 TabLe 2 Continuation N-zz

R

2 2

CM

3

CM

3

-CH

3

-CH

3

OCHF

2

N

CK,

CH

3

SC

2

H

5

SCH

3

SCH

3

SC

2

H

N

-CH

OCH

N-

SC

2

H

5

-CH

3

-CM

3

CH

3

-CH

3

-CH

3

-CM

3

-CH

3

N-N

NC CH 3 )2 IC3 N (cC 2

H

5 2

N-K

3

-KN

NHCH

3

NHC

2

HS

OC3 N (CM 3 2 Cl

N'N

N(C

2

H

5 )2

I..

*4 6

A

4

A

A

'A

6.

#'6

-CH

3

CM

3

-CM

3 tA

A

I A 61 A I U A

A

Le -A 24 483 23 TabLe 2 -Continuation N-Zk-

R

1

R

2 R 1 R2

-CR

3

-CH

3

-CH

3

-CH

3

,CH

3

NHCH

3 C3 NRC 2

H

0C 2

H

5

N(C

2

H

5 2

SCH

NHCH

SCH

3

N(C=

3

NHC

2

H

5

N-

N-<N

NH CR 3

CH

3

-CR

3

OC

2

NHCH

3

O

2

H

NR

N (CR 3 2

-CR

3

-CH

3

CR

3 64 ~C

C

Ce C o 6 a

C

a

C

C C C CC#

CC

C

tt~ 4 C t~ L C~ 44 1 4 44 *4 1. C 4 4 C 44 4 C CC C CC

-CH

3

-CR

3

CR

3

CR

3

CR

3

CR

3

SCR

3

N(C

2

H

5 )2

C

2

H

N(CH

3 )2

-CR

3

CR

3 Le A, 24 483 24 27 'ill- TabLe2 2-Continuation

N-Z:

-C

R

R

-CH

3 C

H

2-0- CH 2-<D CH2- CH 2-Q N-K C 2

N

CH

3

N

-C3

N-

OCH

OCR

3

N

OCH

3

OC

2

H

5

N

N-

CR

3

OCR

3

N-

CR

3

-CR

3 -CR3

N-N

H3

CR

3

CR

3

N

C

2

R

N-

OC HF 2

N

CR

3

OC

2

H

Cl

OCR

3

C

3 0040 Goo 0 0400 4, 4 0 .4 04 .4 .4 .4 0 4.? 4 44 O 4 0 .~44 00 $4 0 0 0 04 0 0 4 0S Le A 24 483 25 2 Ta bL e Continuation -z

-Q

OH2 OH2 9000 0 990 Ga &o 00 0 9 0 0 40 0 0 000* 4000 00 4 9 041 14 41 4 *1~ I 14 II 4 4 14 1 40 4 4 4440

-C

2

H

5 0C 2

H

5 0C 2

H

5

CH

3

OCH

3

N

N==

CH

3

CH

3

N

OCH

3 N

OH

-CH

Cc 2

H

5

N

CF

3

-C

2

H

5

N-(

2

H

00H

-C

2

H

5

-C

2

H

5 -c 2

H

5

OCH

3 'N4

OCH

3 CH3

CHF

2 CH3

C

2

H

5

-CH

3

-OH

3

-OH

3 44 40 4 0 6 4 4 1 4 4 1 41 Le A 24 483 26 TabLe 2 Continuation N-zz Rl R2R 1 -cz R2

C

2

H

5

-C

2

H

5

-C

2

H

C

2

H

N

OCH

-NN

CH

3

N-

CH

3

N-K

2

H

OCH

OCHF

2 N

CM

3

CH

3

SC

2

H

SCH

3

-C

2

H

5

-C

2

H

5

-C

2

H

CH

3

CH

3

OCH

SCH

3

N

CH

3

N

N(CH3 2

M

OCH

NCM

4 o 0*t 00 00 00 4 0 #0 0004 0000 0000 00 444 o 411 01 0 0.

41 04 0400

-C

2 )4 5

-C

2

H

-C

2

H

-C

2

H

5 4. *4 4 04 Le A 24 483 27 TabLe 2 Continuation

-C

2

H

5

-C

2

H

5

-C

2

H

5 -y 0C 2

H

5

SCH

3 OC3

SC

2

H

5

SC

2

H

5 N HH N(c 2

H

5 NKC

H

3

NHCH

3

C

2

H

C

2

H

-c 2

H

R

1 R2

OCH

3 NH C 2

H

OCH

3

N(CH

3 2

OCH

N-

N (C 2

H

5 2

N-

NHCH

3

OC

2 Hc,

NHC

2

H.;

N-K

2

H

N(CH

3 2

-C

2

H

444w 4 4.0~0 04 44 0 0 0 4 40 99 0 0444 4000 5404 4 404 to 0 0 0 0 0 0 (0 I I 4 -c 2

H

5

-C

2

H'

-C

2

H

-c 2

H

-C

2

H

5

N--N

CH

3 t04 9 c 4 ILe A 24 483 28 9- TabLe 2 Continuation N--Zz RR2 R 1 C -c 2H5

-C

2

H

C

2

H

5

SCH

NHC

2

H

5

SCH

3

N(CH

3 2 N SC 2

H

NHCH

3

N(C

2

H

5 ~2

SCH

3

CF

3

N

OCH

CF

3

N

CH

3

CH

3

CH

3

N(C

2

H

5 )2

N(CH

3 )2

N--N

H H 3

CH

3

N-N

SC

2

H

OCH

3

N

CH

3 00 os S 044 04 44 4 4 0 0 44 44 4 0*44 440* 40*0 00 k 0 011 C,5

-CH

3

-C

2

H

04 0 .44 0 04 00 00 00 0 4040 -CH4 3 0* 00 0 0 0 0 0 00 Le A 24 483 29 TabLe 2 Continuation

N-Z

-cH

N

-CH

3 0CH 3

CM

3

N

-C

3

H

7 -n

CH

3

CH

3

N

-c3H7-

OCH

3 0CM 3

N

-C

3

H

7 -n C

OCH

3 0C 2

H

5

-C

3

H

7 -n 0C 2

H

5

-C

3

H

7 -n

N

CH

3

-C

3

H

7 -n

N

CM

3

N

-COC

CH

3 N 3

-C

3

H

7 -n-K 4 4*0 *4 *4 *0 4 o o 64 4 4 4 *440 4 i itt I it i I i44~

-C

3

H

7 -n

-C

3

H

7 -n

-C

3

H

7 -n

-C

3

H

7 -n

-C:

3

H

7 -n N

C

2

H

N-

N OCHF 2

NH

OCH

3

WCM

3

SC

3

SCH

3 00 40 1 0 4 4 4 0 4.

Le A 24 483 30 TabLe2 2- ContinUation 0C 2

H

5

-C

3

H

7 -n I 0C 2

H

5

CH

3

I

N

-CH

2 -CH=C-

-K

CH

3

CH

3

N

-CH

2

-CHCH

2 -K,

OCH

3

OCH

N

-CH

2

-CH=CH

2

-K

OCH

3 C3

-CH

2

-CH=CH

2

CH

3

-CH

2 -CH4=CH 2

N

CH

3

-CH

2

-CH=CH

2 0C 2

H'

5

-Q

oC 2

H

OC3

CH

3

N

-CH

2

-CH=CH

2

-K

".4 CoO 4 4* *0

CO

4 4~ 0 0 0*00 004* 4440 *0 4 It

-CH

2

-CH=CH

2

-CH

2

-CH=CH

2

-CH

2

-CH=CH

2

-CH

2

-CH=CH

2

-CH

2

-CH=CH

2 N cH

OHF

2

CH

3

OCH

3

-KN

OCH

3

CH

3

N-<

OCH

t It 4 01 I I I 0 4 0£ Le A 24 483 31 dA Table 2 Continuation Y Y XN-( R 1 2 R1 2

CH

3

-CH

2

-CH=CH

2 -K -N

SCH

3 The compounds of the formula are known and can be prepared by processes which are known per se (compare, for example, European Patent A-101,670, 121,082, 125,205, 126,711 and European Patent A-152,378).

Formula (VI) provides a general definition of the N-(2-haogenoaLkoxy-benzenesu phonyl)-urethanes to be used as starting substances in process according to the invention. In this formula R and Q preferably or Sparticularly represent those radicals which have already So" been mentioned as preferred or as particularly preferred for these substituents in connection with the description of the substances of the formula according to the a6o i invention. R in formula (VI) preferably represents methyl, benzyl or phenyl, in particular methyl or phenyl.

Examples which may be mentioned of the compounds Sof the formula (VI) are: N-(2-trifluoromethoxy-benzene- S 20 sulphonyl)-, N-[2-(2-chloroethoxy)-benzenesulphonyl]-, t N-(2-difluoromethoxy-benzenesulphonyl)-, tetrafluoroethoxy)-benzenesulphonyl]-O-methyl-urethane, -0-phenyl-urethane, -0-methyl-thiourethane and -0-phenylthiourethane.

The compounds of the formula (VI) are known (com- Le A 24 483 32 pare, for example, European Patent A-125,205, 121,082, 44,808 and European Patent A-44,809).

The heteroarylamines of the formula (III) also to be used as starting substances in process according to the invention have already been described in the description of process variant Formula (VII) provides a general definition of the 1-arylsulphonyl-3-heteroaryl-ureas to be used as starting substances in process according to the invention. In this formula (VII), R, R 2 Q, X, Y and Z preferably or particularly represent those radicals which have already been mentioned as preferred or as particularly preferred for these substituents in connection with the description of the substances of the formula according to the invention.

Examples which may be mentioned of the compounds of the formula (VII) are: OR 0 II N- Z VI I j /-SO 2

Y

R2 t 4 a e o 9a Le A 24 483 33

A

.1 ii ~1

II

I

TabLe 3

-CF

3

-CF

3

-CF

3 R2

CH

3

N

-c3

CH

3

N

OCH

3 OC

H

3

N

OC H 3

C

2

H

N

-CF

3 444 49*4 44 ,i A I a a ~9 49 a 4k4a Ia4a

C,

9, a 445

-CF

3

-CF

3 0C 2

H

N

0C 2

H

DC

H

3

CH

3

N-<

2

H

CH

3 94 42 I 21t 4 45 a S (S 4 04 a a a 49 41 a a 4 a a a Le A 24 483 34 Tabte3 3 -Continuation R 0 -c-

-CF

3

-CF

3 N C3 0CM o CH3

CH

3 N CH 3 0N -CF 3

-CF

3 *004 *44 *0 04 0t 0 0 44 0 #00-4 0 9000 #0 04 tt~ 44

I

O 00 0. 1 toot

-CF

3

-CF

3

-CF

3

-NN

CM

3

CF

3

OH

3

OCH

3

O

2

H

0C 2

H

0t 40 0 0 0 00 4 4 00 0 00 Le A 24 483 35 Table 3 -continuation -y R

Q

R

2

-CF

3 0

OCH

3

-CF

3 0N

CF

CH

3

-CF

3 0

SC

2

H

-CF

3 0-K

SCH

3 0C 2

H

-CF

3 0

N

SCH

3 4 04 4 ~*4OCH 3 a a4 A CF 3 0 N

SC

2

H

is*

CF

3

-CF

3 0

OCHF

2 Le A 24 483 t t I -36- TabLe 3 -Continuation

CH

3

-CF

3 0 K S CH 3

CH

3

-CF

3 0

N(CH

3 2

-CF

3 0

N(C

2

H

5 )2

N-K

-CF

3 0-(

NHCH

3 0CH 3

-CF

3 0 NHC 2

H

-CF

3 0-K

N(CH

3 Le A 24 483 I It 37 TabLe 3 -Continuation

R

R2

-CF

3 0 N OCN I

SC

2

H

-F0 NK CH NH

CH

N CH3

-CF

3 0-C N

NHC

2

H

O

2

H

-CF

3 0

N(C

2 H 2 *oft SCH3

-CF

3 0 SH

SCH

3

-CF

3 0 C ItN(CH 3 2 Le A 24 483 -38- TabLe 3-Continuation 7

-CF

3

CF

3

CF

3

-CF

3

N-Z--

OCH

3

N(C

2

H

5 )2

N-K

NHCH13

NHC

2

H

N

N(CH

3 2

N-N

CH

3

CH

3

CH

3

N(C

2

H

5 2 484 .444 #8 44 4 8 4 8 8

'I

4444 44*4 8948 4 ~,44 44 o 841 48 8 8 4 4.44 I 44 8 4 8 44 4 44 8 4 4 4 84 48 6 8 4 8 *4 6 64 4 64

-CF

3

-CF

3

-CF

3 Le A 24 483 39 TabLe 3 -Continuation N-Zz

RR

NN

-CF

3 0

SC,

-CF

3 0 -c Cl N

-CF

3 0-c

N-<

Cl

N

40993 -0 -CFCF0

C

C

3

-CF

3 0 3- 0C 2

H

4 4 4 Le A 24 483 TabLe 3 -Continuation R Q R2

SC

2

H

-CF

3 0 -V~

N(CH

3

N--N

-CF

3 0 KNY H3 CH4 3

CH

3

N:

-CF

3 0- 3

N-

C'

N 2

H

-CF

3 0 Cl N C 2

H

-CF

3 0

OCH

3 Le A 4 8 Pa41 TabLe 3 -Continuation -y

CH

3

-CHF

2 0 0CM 3 -CH2 0N 0CM 3

OCH

3 N

C

2

H

1<~e

N

-CHF

2 0-, c2H

-CHF

2 0

CH

3

-CHF

2 0 1C

IN==-

I I I Lee 24 483 42 TabLe 3 Continuation Ky R 2

OCH

3

CH

3

CH

3

N

-C3 -C HF 2

-CHF

2 Re', 4, 4* a 4 4 4,4* 4,4,4 4 *4* 44 a 44.~

-CHF

2

-CHF

2

N~-

CH

3

OCH

OCH

3 N O 2

H

0C 2

H

I'

4

I

4 1 4 4 41 44 1 4 4 1 4 1 41

I

Le A 24 483 43 TabLe 3 -Continuation

N-ZZ

P R 2

O

2

H

-CHF

2 0-C

N

OCH

3 -CH2 0N OC HF 2

CM

3

CH

-CHF

2 0-C

SC

2

H

N-K

-CHF

2 0

SCM

3

-CHF

2 0 -v ft SC M 3

-CHF

2 0

SC

2

H

f f 4 ft Le A 24 483 44 TabLe 3 -Continuation

N-Z-,

R

CH

3

-CHF

2

N

SCH

3

CH

3

-CHF

2 0 C

N(CH

3 2

CH

3 0 -C \0 N (C 2

H

5 2

N-

-CHF'

2 0

NHCH

3

N-K

-Cl-F 2 0 NHC H OCH3

-CHF

2 0 -C

N(CH

3 2 Le A 24 483 C 45 ~4 Table 3 Continuation

-CHF

2

-CHJF

2

-CHF

2

-CHF

2 N

SC

2

H

CH

3

NHCH

3

N-K

NHC

2

H

O

2

H

N (C 2

H

5 ~2

SCH

3

NHCH

3

NHC

2

H

NKC

H

3 N N

N(CH

3 2 4*41 04 s a S S

S

5540 4445$ 4 sass #0 0 9 *54 0O sas

S.

9 5 5# #0 9 0 *4 54 0 0 9 5* 5 5*

-CHF

4

CH-F

2

-CHF

2 Le A 24 483 46 TabLe 3- Continuation R Q

OCH

-CHF

2 0

NHC

2

H

5 o -C \0 N(4CH 3

-CHF'

2 0-C K

CH

-CHF 0HN

S(CH

3

-CHF

2 0 00 4 a p ot 3 Le 24 483 £~CHt 474 TabLe 3-Continuation

NHCH

3

-CHF

2

N

N(C

2 Hi 5 )2 Cl

N

-CHF

2 0 Cl Cl

N

-CHF

2 0 c

OCH

3 Cl

-CHF

2 0 o 0C 2

H

CF

3

N

-CHF

2 0 Cl 44.4

CF

3

N

-CHF

2 0

OCH

3 Le A 24 483 -48- TabLe 3 -Continuation o -<y

C

2

H

N

N--

6-CHF 2 0 H< 3 6 0CH 3 4CF 0 14 *CH 0 N C2 JO2 c 82H 6' 6N 6 Le A 2 48 I3 -49ij 7 TabLe3 3-Continuation

-CH

2

CH

2 C 1

-CH

2

CH

2 C1

N-Z::

CH

3

CH

3

N

OCH

3

OCH

3

N

C3 Nc

-CH

2

CH

2 C 1

-CH

2

CM

2 C 1 4444 4 4C4 44 44 4 C 4 4 .a 4 4 4444 4441

I

4441 44

I

14

I

I I I I I II 44 I 4 4 4444

-CH

2

CH

2 C 1

-CH

2

CH

2 C 1

-CH

2

CH

2 c1 0C 2

M

N.

0C 2

H

CM

3

N-K

2

H

N

Le A 24 483 44 44 44 4 I 4 44 1 4 II 4 CI 50

-I

Table 3 Continuation R2 -CR 2

CH

2 C 1

-CH

2

CH

2 C 1

-CH

2

C'H

2 C1

-CH

2

CH

2 C 1 N-k

C

3

CR

3

CH

3

N

0000 0 0040 00 00 OQ 0 0 0 0 00 00 0 040* 004* 4*40 00 04 0 lb 01 O 0 O I lb 0 4 44 4 04 ~00S

-CH

2

CH

2 C1

-CH

2

CH

2 C1 C3

CH

3

OCH

OCH

3 HZ2H 0C 2

H

34 04 4 4 40 0 O 00 I I Le A 24 483 51

I

t 0 hi 4 Li Li

A

TabLe3 3-Continuation

-CH

2

CH

2 C 1

-CH

2

CH

2 C1

-CH

2

CH

2 C1

-CH

2

CH

2 c 1

-CH

2

CH

2 C 1 z P2 OcH

OCH

3

OCHF

2

N

-c3

CH

3

SC

2

H

OCH

3

-C

NSC=<

SCH

3 Z0 2

H

-NN

OCH

3 0400 0 0.0~ 00 00 o 0 0 0 0 0 00 0000 4001 0000 01 0 40~

-CH

2

CH

2 C 1

-CF

2 cXF 2 00 I 0~ 00 0 0 00 0 00 (0 0 0001 00 00 0 0 0 1 04 0 0 0 0~ Le A 24 483 52 Tab~e3 3-Continuation R 0

-CH

2

CH

2 C 1

-CH

2

CH

2 C1

-CH

2

CH

2 C 1

-CH

2

CH

2 C 1

-CH

2

CH

2 C 1

-CH

2

CH

2 C 1

-CF

2

CHF

2

N-

CH

3

N(CH

3 2 NC C 2

H

5 )2 OC

H

3

NC~

NHCH

3

OCH

CH

3

CH

3 4*41 4*4 4* 44 4~ 4 4 4 4 4 444, 444~ 4444

I

4 t~ 4 4 4 1 4 4 4 41 4 4 4 4.44 *4 44 1 4 4 #4 4 14

I

Le A 24 483 53 4 TabLe 3 -Continuation -z R 0 y

-CH

2

CH

2 C1

-CH

2

CH

2 C 1

-CH

2

CH

2 C1

-CH

2

CH

2 C1

NC~

SC

2

H

CH-

3-<

NHCH

3

CH

3 N IiC 0C 2

H

N(C

2

H

5 )2 N II

SCH

3

NHC

2

H

SCH

3 N (CH 3 2 *0 *o 00 *000 t

A'

I A A A'

-CH

2

CH

2 c 1

-CH

2

CH

2 C 1

-CH

2

CH

2 C1 A 00 A A

''IA

Le A 24 483 0~ t A a, A A' 54 TabLe 3 -Continuation

-CH

2

CH

2 C1

-CH

2

CH

2 C 1

-CH

2

CH-

2 C 1

-CH

2

CH

2 C 1

-NN

N(C

2

H

5 )2 0C 2

H

N *CH

NHC

2

H

-NN

N(CH

3 )2

N--N

-C

CH

3

CH

3

CH

3

N(C

2

H

5 )2 0004 0 0000 00 00 0 0 0 0 0 0 00 0 0 4000 0004 0000 *0 0 0 0 01 14 0 1 4 14

CI

I. 0 0 1001 it II 00 4 0 4 01 4 O 04 14

-CH

2

CH

2 C1

-CH

2

CH

2 C 1

-CH

2

CH

2 C 1 Le A 24 483 55 TabLe3 3-Continuation

-CH

2

CH

2 C1

-CH

2 CfH 2 Cl

-CH

2

CH

2 C 1

-CH

2 Cq 2 C 1

R

2

SC

2

H

NHCH

3 SC 2H

CN

N(C

2

H

CH

DC2H Cl3 -cZI

CF

3

CF

3 *44, 4 I144 44 *4 I I I I I 4* 41 4 4444 4*44 1444 44 4 4 4 4 4 II I 4 4 14I 4

-CH

2

CH

2 C 1

-CH

2 CHqC 1

-CH

2

CH

2 C 1 Le A 24 483 *4 44 4 4 4 1 44 4 44 £4 56

I!

TabLe 3 Continuation N-zzk

R

2

SC

2

H

N(CH

3 )2

-CH

2

CH

2 C I

-CH

2

CH

2 C 1

-CH

2

CH

2 C 1

-CH

2

CH

2 C 1

-CH

2

CH

2 C 1

-CF

2

CHF

2

-CF

2

CHF

2

N--N

CN= H 3

,CH

3 CH3

N

C2H

N

OCH

CH

3

NCH

OCH

3 414 o 00 o 0 I 4 I II 44 000* 4>400 044* 44 4 4~ 4 I 40 4 t 0 £040 00 I~ 0 0 Le A 24 483 57 Tab~e 3 Continuation R -K y

-CF

3 s N< \H

CH

3 N CH 3

-CF

3 s 3CH OCH3 -CF 3 s N

OH

OCH

3 C 2

H

-CF

3 0 C 2

H

-CF

3 s 4 0C 2

H

-CF s

-C

3

CH

3 Le A 24 483 4 r t-58- 4 4 4 Table 3 Continuation

-CF

3 R 2 N OCH3

CH

3

CH

3

CH

3

-CF

3

-CF

3

-CF

3 r 0 0 2 00 0 0 0 zoo o

-CF

3

-CF

3

CH

3

NCH

CH

3

CHN

0C 2

H

'044 440 44 44440 00 44 44 4444 440 0 0 *404 44* 444 0* 44 44 44 4444 44 44 44~ Le A 24 483 59 TabLe 3 -Continuation

H-Z::

R R2 R2H

-CF

3 S-C

QCH

3 OC KF 2

-CF

3 s

CH

3 CH4 3 -CF3S

SC

2

H

SCH

3

-CF

3 S

N

OCH

3

-CF

3 S .S C 2 H 3 42C (3 Le A 24 483 '2 '2 60 TabLe3 3-Continuation

CF

3

-CF

3

-CF

3

-CF

3

CH

3

SCH

3 Nc

N(CH

3 2

CH

3

N

N(C

2

H

5 )2

OCH

3

NHH

3

OCH

3 NC M

AAA

A

I AA A PA WA A A A A A A A A f~AA

AAA

CF

3

-CF

3 Le A 24 483 61 -7 Table_3 -Continuation

-CF

3

-CF

3

-CF

3

-CF

3

R

2

H

SC

2

H

CH

3

NHCH

CH

3 NH C 2

H

N(C

2

H

5 )2

SCH

3

NK

NHCH

SCH

3 NHC2H

SCH

?4(CH 3 2 I 4*4 4 4 *4 44 4 4 tg 4 4 I ~44 *41 t '.4

-CF

3

-CF

3

-CF

3 Le A 24 483 62 TaqbLe 3-Continuation

RR

OCH

3

-CF

3 s 0(C 2

H

5 3s <c "N

NHCH

-CF

3 s

N(CH

3 )2

N--N

-CF

3

S

CH

3

CH

3

-CF

3 S N

N(C

2

H

5 2 Le A 24 483 -63 TabLe 3 -Continuation Ro

-CF

3

-CF

3

-CF

3

-CF

3

SC

2

H

-NN

NHCH

3

SC

2

H

N(C

2

H

5 2 C 1 C 1 C 1 0CM 3 C I 0C 2

H

CF

3

N

-c1 CF3

C

3 ,Iti liii I t 1 I 4,t I 4, I I I It Ii I t t t I. I~2 4 ii I I I 411

-CF

3

-CF

3

-CF

3 a. *s S S 4 4 I I Le A 24 483 64 TabLe3 3-Continuation

-CF

3

-CF

3

-CF

3

-CF

3 R2

N(CH

3 2

K-N

C

3

CH

3 CH3 Cl

C

2

H

OCH

3 44,4 4 4444 #4 44 4 4 4 4 4 4 ~~0 4444 44a4 4444 #4 444

-CF

3 4, 44 4 415.

4 4 4 4~ I 44 44 4 4444 44 44 4 4 4 4 4 4 4 4 1 44 Le A 24 483 65 TabLe 3 Continuation

CHF

2

-CHF

2

-CHF

2

CHF

2 R2

CH

3

N

-c3

CH

3

NH

OCH

3

QCH

3

OCH

3 C 2

H

0C 2

H

N

0C 2

H

OCH

3

CH

3

CH

3 t 4 44 44 4 1 I 4 I S *0*S *44S I I 1 44'.

4, 4 4 4 4.

4 4 S St 1 4 4 4444

-CHF

2

-CHF

2

-CHF

2 4-4 4* I I I

I

14 4 4 I 4 4 II Le A 24 483 66

N.

TabLe 3 -Continuation

-CHF

2

-CHF

2 N-zz

OCH

3

CH

3

-CNN

CH

3 N

H

-CHF

2

CHF

2 4444 444 44 41 4 4 4 4 4444 4*44 .444 44 4

-CHF

2

CHF

2 C3

CH

3

OCH

3 0C 2

H

0C 2

H

I

Le A 24 483 67 R22 N-4C 2

H

-CHF

2 S

"N~

OCH

3

-CHF

2 s C

CH

3

-CHIF

2 S

"N

SC

2

H

N-k 3

-CHF

2 S -C N

SCH

3 4 0 2 H

SCH

3 N-OCH3 4 99,-CHF 2 S-C

N

S

2

H

Le A 24 483 -68 TabLe3 3-Continuation -C y

-CHF

2

,CHF

2 C HF2

CHF'

2

CH

3

SCH

3

CH

3

-NN

N(CH

3 2

CH

3

N(C

2

H

5 2 OC3 NH CH 3 N (CH 3 2 400.

04 *0 4 a a a a 0 aa a a o 8~48 4.40 a.

4 a a *ts

-CHF

2

-CHF

2 4* 4 4 a a -a *0 4 0 4 0 a a; Le A 24 483 69 T ab L

R

e 3 Continuation z 0y CHF2

-CHF

2

-CHF

2

-CHF

2

O

2

H

N( sc 2

H

H3

NR

CH

3

N-

K(C

2

H

5 N HH

SCH

3 vNC

SCH

3

NCH

3 4416 444 04 ii 4 4 4

I

4 44 4 4 44,, 4444 444 4.

04 4 444 44 4. 4 4 4 4 4 44 4 1444

CHF

2

-CHF

2

-CHF

2 44. 44 C 4 4 4 4 44 4 4 44 4 f* Le A 24 483 70 Table_3 -Continuation

OCH

3

-CHF

2 s

N(C

2

H

5 2 OC 2

H

-CHF

2 S-C N

NHC

2 H3 0C 2

H

N-

-CHF

2 S -47 N*=49 9-CHF 2 s

N--

CH

3

-CHF

2 S NCH 19 4H3 Le A 24 483 71 I

I

It Ii Tab~e 3 -Continuation

-CHF

2

_CHF

2

-CHF

2

-CHF

2 z C

NHCH

3

N(C

2

H

5 2 -c1 Cl

OCH

Cl 0C 2

H

CF

3

CF

3

OCH

3 ~t 4 4tt A AA At

A

4 A 4~

A

4,.

*14 44 4 ,,r it A I C A A A At A,.

4 f 4 4t 4 t4 At

CHF

2

-CHF

2

CHF

2 Le A 24 483 72 TabLe 3 -Continuation

-CHF

2

CHF

2

-CHF,

-CHF

2 y R2

N(CH

3 2 c H 3

CH

3 C3 c 2

H

C==l

C

2 14

N

OCH

3 4414 4 Ii 4, 4

I

4 II I I I

II.,

44~ 4

I

I 414

II

t I I

-CHF

2 '4 ~e It 4* I I It I It I II Le A 24 483 73 TabLe 3 -Continuation

-CH-')CH

2 C 1

-CH

2 Cli~C1 #411 #414 II 44 I I I I I 14 I I 0440 *08* Sob *0

II

I 041

II

I 44 4 4' I I I I 44 14 4 44.4 11 04 I 4 4 44 I o 44 4 14

-CH

2

CH

2 C 1

-CH

2

CH

2 C 1

-CH

2

CH

2 C 1

-CH

2

CH

2 C 1

-CH

2

CH

2 C 1 N-Z-

CH

3

N

OCH

3

OCH

3

N

N-

C

2

H

N=-

-C3 0C 2

H

N==

CH

3 Le A 24 483 74 TabLe 3 -Continuation R 0

-CH

2

CH

2 C1

OH

3

-NN

OCH

3

CH

3

CH

3

N-

-CH

2

CH

2 C 1

-CH

2

CH

2 C 1

-CH

2

CH

2 C 1 *#eO e 0 o ~o o o a

C

0 *000 Co o 0 C qa.

-CH

2

CH

2 C1

CH

3

CH

3

OCH

3 2' 00 2

H

-CH

2 cH 2 C 1 4,

CO

C,

CC OC Ct 0 C 00 I I I I I CO Le A 24 483 75 *044 4 44.4 44 44 4 4 0 O 4 44 4 4 0 4444 4044 4444 4 4 441 Tab~e 3 -Continuation

-CH

2

CH

2 C 1

-CH

2

CH

2 C1

-CH

2

CH

2 C1

-CH

2

CH

2 C 1

-CH

2

CH

2 C 1

-CH

2

CH

2 C 1 -Cy

OCH

3

QCHF

2

N

-c3

CH

3

SC

2

H

OC3

SCH

3

O

2

H

SCH

3

OCH

3

SC

2

H

t Le A 24 483 76

I

I

TabLe 3 -Continuation

-CH

2

CH

2 C1

-CH

2

CH

2 C 1

-CH

2

CH

2 C 1

-CH

2

CH

2 C1

CH

3

N(H)

SCH

3

N(C

2

H

5 )2

CH

3 Nc

OCH

3 NHC H3

OCH

3

N(CH

3 2 444' 446 *6 4.

4 0 44 4 0 4444 4444 4404 *0 4 144

-CH

2

CH

2 C 1

-CH

2

CH

2 C1 4, 4 4 4.4 64 4 4 4 4. 4 ~4 4 4. 4 C Le A 24 483 77 Tab~e3 3-Continuation

-CH

2

CH

2 C1

-CH

2

C!H

2 C 1

-CH

2

CH

2 C 1 -C y

SC

2

H

CH

3

HHCH

3 H3

NHC

2

H

SCH

3 NHC

H

3

SCH

3 HHiC 2

H

SCH

3

-CH

2

CH

2 C 1 444

-CH

2

CH

2 C1 S 444 4 4.

4 4 4 4~ 4 44 4 4 4 444*.

44 44 4 4 0 4 4 44 4 4 4 4 4 44

-CH

2

CH

2 C1 Le A 24 483 78 TabLe 3 -Continuation -z R 0

-CH

2

CH

2 C 1

-CH

2

CH

2 C 1

-CH

2

CH

2 C 1

-CH

2

CH

2 C 1

OCH

3

N(C

2

H

5 2

O

2

H

NN

NH

2

H

O

2

H

N.

NCH

3 2

CH

3

CH

3

CH

3

N(C

2

H

5 2 'St.

t.I~ I A A t A S S t~t S S I

'IA.

'ASS

'Itt

I

I It

-CH

2

CH

2 C1

-CH

2

CH

2 C 1

-CH

2

CH

2 C 1 At *4 S S A S St S A S S A tS Le A 24 483 79 Aj Table 3 -Continuation

-CH

2 CHZC 1

-CH

2

CH

2 C1

-CH

2

CH

2 C 1

-CH

2

CH

2 C 1

-CH

2

CH

2 C 1

-CH

2

CH

2 C1

NZ

NHCH

3

C

2

H

N (C 2

H

5 ~2

N-

-4,

OCH

3 Cl1 0C 2

H

CF

3

N-

-c1

CF

3

OCH

3 Ii 0*0* 0 0 o so 04 0 *000 *400 04 o *04 04 t I t 4CC

-CH

2

CH

2 C1 C C C C C C (C Le A 24 483 80 TabLe 3 -Continuation

-CH

2

CH

2 C 1

-CH

2

CH

2 C 1

-CH

2

CH

2 C 1

-CH

2

CH

2 C 1

-CH

2 CH4 2 C 1

CF

2

CHF

2

SC

2

N(CH

3 2

N--N

-c

H

3

CH

3

CH

3

N

C 2

H

Cl

C

2

H

CH

3

CH

3

OCH

3

OCH

3 9040 *094 90 99 4 0

S

0 00 99 0 9940 900 0 *496 t0 4 9*4 4 4 -tt~

-CF

2

CHF

2 Le A 24 483 81 TabLe 3 -Continuation R 02

CH

3

-CF

2

CHF

2 S

-N

OCH

3

-CF

2

CHF

2

OCH

3

OCH

3 4 4 4 44 4 4 444 444t 44 44 4 44 41 Le A 24 483 82 ii The compounds of the formula (VII) are known and/ or can be prepared by known methods (compare, for example, European Patent A-44,808, 44,809 and European Patent A-173,312).

Formula (VIII) provides a general definition of the compounds also to be used as starting substances in process according to the invention. In this formula (VIII), R preferably or particularly represents those radicals which have already been mentioned as preferred or as particularly preferred for this substituent in connection with the description of the substances of the formula according to the invention. W in formula (VIII) represents a nucleophilic leaving group, preferably chloride, bromide, iodide, -0-S0 2

-OCH

3 -0-S0 2

CH

3 or -0-SO2- -CH3 Examples which may be mentioned of the compounds of the formula (VIII) are: methyl, ethyl, n-propyl, ipropyl, n-butyl, i-butyl, benzyl, allyl and propargyl chloride, bromide and iodide, as well as dimethyl sulphate and methyl p-toluenesulphonate.

The compounds of the formula (VIII) are generally known compounds of organic chemistry.

Process according to the invention for the preparation of the new compounds of the formula is 25 preferably carried out using diluents. Possible diluents here are virtually all the inert organic solvents. These include, preferably, aliphatic and aromatic, optionally halogenated, hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chLorobenzene and o-dichlorobenzene, ethers, such as diethyl ether, dibutyl ether, glycol dimethyl ether, diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, esters, such as methyl and ethyl acetate, Le A 24 483 83 *ri

I

4 4O 4; 44 44 4 .9444

I..

4i

Q

r i i i rt 1 i41 -x nitriLes, such as, for example, acetonitrile and propionitrile, amides, such as, for example, d-methylformamide, dimethylacetamide and N-methyL-pyrrolidone, and dimethylsuLphoxide, tetramethylene sulphone and hexamethylphosphoric acid triamide.

If appropriate, process according to the invention is carried out in the presence of a catalyst.

Catalysts include, in particular, aliphatic, aromatic or heterocyclic amines, such as triethylamine, N,N-dimethylaniline, pyridine, 2-methyl-5-ethyl-pyridine, 4-dimethylamino-pyridine, diazabicyclooctane (DABCO), diazabicycLononene (DBN) and diazabicycloundecene (DBU).

The reaction temperatures can be varied within a substantial range in process according to the invention. The reaction is in general carried out at temperatures between 0°C and 1500C, preferably at temperatures between 200C and 100 0

C.

Process according to the invention is in general carried out under normal pressure. However, it is also possible for the process to be carried out under increased or reduced pressure.

For carrying out process according to the invention, in general 1.0 to 3.0 mol, preferably 1.0 to mol, of 2-halogenoalkoxy-benzenesulphonyl iso(thio)- 25 cyanate of the formula (II) are employed per mol of heteroarylamine of the formula (III).

The starting substances of the formulae (II) and (III), and if appropriate the catalyst and the diluent, are in general brought together at room temperature or with gentle external cooling and the reaction mixture is stirred, if appropriate at elevated temperature, until the reaction has ended.

The new compounds of the formula are worked up and isolated by customary methods: if the compounds of 35 the formula are obtained as crystals, they are isolated by filtration with suction. Otherwise if approp- Le A 24 483 84 99,9 1E 9 1 9 9 1

III

4 9 ~c 01 Ce 4

I

C

riate after concentration water and an organic solvent which is virtually water-immiscible are added and, after thorough shaking, the organic phase is separated off, dried, filtered and evaporated, the products of the formula remaining in the residue.

The preparation process described above under (b) for the compounds of the formula is preferably carried out in the presence of diluents. The same organic solvents as have been mentioned above in connection with the description of process according to the invention are possible here.

Acid acceptors which can be employed in process (b) according to the invention are all the acid-binding agents which can usually be used for such reactions. Preferred suitable acid-binding agents are alkali metal hydroxides, such as, for example, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides, such as, for example, calcium hydroxide, alkali metal carbonates and alcoholates, such as sodium carbonate and potassium carbonate and sodium methylate and ethylate and potassium methylate and ethylate, and furthermore aliphatic, aro- .n matic or heterocyclic amines, for example triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine, S pyridine, 1,5-diazabicyclo-C4,3,03-non-5-ene (DBN), 1,8diazabicyclo-[5,4,0]-undec-7-ene (DBU) and 1,4-diazabicyclo-[2,2,2]-octane (DABCO).

SThe reaction temperatures can be varied within a substantial range in process according to the invention. The reaction is in general carried out at temperatures between -20 0 C and +1000C, preferably at temperatures between 0 C and 500C.

Process according to the invention is in general carried out under normal pressure. However, it also possible for the process to be carried out under 35 is increased or reduced pressure.

t, For carrying out process according to the Le A 24 483 85 ad .ra dprm~ invention, in general 1.0 to 1.5 mol, preferably 1.0 to 1.2 mol, of 2-halogenoalkoxy-benzenesulphonic acid amide of the formula (IV) are employed per mot of N-heteroarylurethane of the formula The starting substances of the formulae (IV) and and if appropriate the acid acceptor and the diluent, are in general brought together at room temperature or with gentle external cooling and the reaction mixture is stirred, if appropriate at elevated temperature, until the reaction has ended. Working up and isolation of the new compounds of the formula can be carried out by customary methods: in general if appropriate after concentration the mixture is stirred with water and if appropriate acidified with hydrochloric acid. If the compounds of the formula are obtained here as crystals, they are filtered off with suction. Otherwise, the mixture is extracted with a solvent which is virtually water-immiscible, such as, for example, ethyl acetate or methylene chloride, and the organic phase is separated off, dried, filtered and concentrated, the products of the formula remaining in the residue.

The preparation process described above under (c) for the compounds of the formula is preferably carried out in the presence of diluents. The same organic sol- 25 vents as have been mentioned above in connection with the description of process according to the invention are possible here.

Process according to the invention is preferably carried out in the presence of an acid acceptor.

30 Possible acid acceptors here are the same inorganic acidbinding agents and organic bases as have been mentioned above in connection with the description of process (b) according to the invention.

The reaction temperatures can be varied within a substantial range in process according to the invention. The reaction is in general carried out at tempera- Le A 24 483 86 000 So o 0 0 O 0 o 0 0 6* 00 0 0 0 0 00 0B 0 0 u 0 00 SoJ m «r ,J r .1 tures between -20 0 C and +100 0 C, preferably at temperatures between 0°C and 50 0 C. Process according to the invention is in general carried out under normal pressure. However, it is also possible to carry out the process under increased or reduced pressure.

For carrying out process according to the invention, in general 1.0 to 1.5 moL, preferably 1.0 to 1.2 moL, of heteroarylamine of the formula (III) are employed per mol of N-(2-halogenoalkoxy-benzenesulphonyl)urethane of the formula (VI).

The reaction can be co-ried out and the mixture worked up in process as described above for process Polar organic solvents can preferably be employed as diluents in carrying out process according to the invention. Preferred possible solvents here are ketones, such as, for example, acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, and furthermore nitriles, and in addition amides, such as dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone, as well as ethers, such as diethyl ether, dibutyl ether, glycol dimethyl ether, diglycol dimethy'. ether, tetrahydrofuran and dioxane.

Strongly basic but weakly nucleophilic substances can preferably be employed as acid acceptors in carrying 25 out process according to the invention. Acid acceptors which are preferably suitable are alkali metal hydrides, such as, for example, sodium hydride and potassium hydride, alkaline earth metal hydrides, such as, for example, calcium hydride, alkali metal carbonates and alcoholates, such as sodium carbonate and potassium carbonate, sodium methylate and ethylate and potassium methylate and ethylate and potassium tert.-butylate, and furthermore 1,5-diazabicycLo-[4,3,01-non-5-ene (DBN), 1,8diazabicyclo-C5,4,0]-undec-7-ene (DBU) and 1,4-diazabi- 35 cyclo-E2,2,23-octane (DABCO).

The reaction temperature can be varied within a Le A 24 483 87 rrtr rtrr s:r ni Il r II i rrr, rirt ii ti r u I ,r rr C C 4I 1 C t el i 1 4, substantial range in process according to the invention for the preparation of the new compounds of the formula The reaction is in general carried out at temperatures between 0°C and +100 0 C, preferably between 00C and 800C. Process according to the invention is in general carried out under normal pressure.

For carrying out process according to the invention, the particular starting substances required are in general employed in approximately equimolar amounts.

However, it is also possible for one of the two particular components employed to be used in a larger excess. The reactions are in general carried out in a suitable diluent in the presence of an acid acceptor, and the reaction mixture is stirred for several hours at the particular temperature required. Working up is in each case carried out by customary methods in process according to the invention.

The compounds of the formula can be converted into salts with metals or with basic organic nitrogen compounds by customary methods. For this, the compounds of the formula are in general dispersed in inert solvents, such as are mentioned above for preparation pro- Scesses to and reacted with approximately equi- S't:4' molar amounts of soluble metal compounds, such as, for 25 example, sodium methylate, potassium ethylate or calcium 444 hydroxide, or with basic organic nitrogen compounds, such as, for example, isopropylamine, 2-hydroxy-ethylamine, dibutylamine, triethylamine or N,N-dimethyl-benzylamine, and the mixture is stirred at room temperature.

S 30 If the salts are obtained here as crystals, they are isolated by filtration with suction. Otherwise, they are obtained in crystalline form after distilling off the solvents.

rttI$, 35,3 L i 44 4 4 44 The active compounds according to the invention can be used as defoliants, desiccants, agents for destroying broad-leaved plants and, especially, as weed- Le A 24 483 88 kiLLers. By weeds, in the broadest sense, there are to be understood all pLants which grow in Locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentiaLLy on the amount used.

The active compounds according to the invention can be used, for example, in connection with the foLLowing plants: Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, GaLinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, ConvoLvuus, Ipomoea, PoLygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, SoLanum, Rorippa, RotaLa, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, GaLeopsis, Papaver and Centaurea.

DicotyLedon cultures of the genera: Gossypium, GLycine, Beta, Daucus, PhaseoLus, Pisum, SoLanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

MonocotyLedon weeds of the genera: Echinochloa, Setaria, lt Panicum, Digitaria, Phleum, Poa, Festuca, ELeusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, SELeocharis, Scirpus, Paspalum, Ischaemum, SphenocLea, Dactyloctenium, Agrostis, ALopecurus and Apera.

Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and ALLium.

However, the use of the active compounds accord- 30 ing to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.

The compounds are suitable, depending on the concentration, for the total combating of weeds, for example 35 on industrial terrain and rail tracks, ar4 on paths and squares with or without tree plantings. Equally, the Le A 24 483 89 compounds can be employed for combating weeds in perennial cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, and for the selective combating of weeds in annual cultures.

The active compounds can be converted to the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.

These formulations are produced 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 surface-active agents, that is emulsifying agents and/or dispersing agents and/or foam-forming agents.

4 In the case of the use of water as an extender, Sorganic solvents can, for example, also be used as auxiiary solvents. As liquid solvents there are suitable in the main: aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethylsulphoxide, as well 35 as water.

As solid carriers there are suitable: for example Le A 24 483 90 i: i ammonium salts and ground natural minerals, such as kao- Lins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silicic acid, alumina and silicates, as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calI te, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates as well as albumin hydrolysation products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phosphoi lipids, such as cephalins and lecithins, and synthetic t phospholipids, can be used in the formulations. Further 25 additives can be mineral and vegetable oils.

t4 t« It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and The active compounds according to the invention, t as such or in the form of their formulations, can also Le A 24 483 91 be used for combating weeds, as mixtures with known herbicides, finished formuLations or tank mixes being possible.

Possible components for the mixtures are known herbicides, such as, for exampLe, N-(2-benzothiaz".LyL)- N,N'-dimethyLurea, 3-(3-chLoro-4-methyLphenyL dimethyLurea, 3-(4-isopropyLphenyL 1-dimethyLurea, 2chLoro-N--{E4-methoxy-6-methyL-1,3,5-triazin-2-yL )-amino>carbonyLJ--benzenesuLphonamide, ethyL 2-tE (4-chLoro-6methoxy-2-pyr imidyL )aminocarbonyL ]aminosuLphonyL--benzoate, 2-ethyLamino-6( 1,1-dimethyLethyL-amino)-4-methyLthio- 1,3,5-triazine, 4-amino-6-( 1,1-dimethyLethyL)-3-methyLthio-1,2,4-triazin-5C4H)-one, 4-amino-6-C 1,1-dimethyLethyl )-3-ethyLthio-1,2,4-triazin-5C4H)-one, 1-amino-6ethyLthio-3-C2,2-dimethyLpropyL)-1,3,5-triazine-2,4-( 1H, 3H)-dione, 5-(2-chLoro-4-tr ifLuoromethyL-phenoxy )-N-methyLsuLphonyL-2-nitrobenzamide,(2-ethoxy-l-methyL-2-oxo-ethyL)- 2-c h 10ro-4- t rif Luo rome thy I-p heno xy )-2-nit ro-ben zoat e, methyL 2-[4-C2,4-dichLorophenoxy)-phenoxi]-prop ionate, 2- 14-[C3-chLoro-5-trifLuoromethyL-2-pyridinyL )oxyl-phenoxyl- Otte propionic acid, the R-enantiomer of (trimethylsiLyL)methyl 2-{4-E(3,5-dichLoro-2-pyridinyL )oxy]-phenoxyl- 4p propionate, 2,4-dichLorophenoxyacetic acid, 2-(2,4-dichLorophenoxy)-propionic acid, 4-chLoro-2-methyL-phenoxy- 6: 25 acetic acid, 2-C4-chLoro-2-methyL-phenoxy)-propionic acid, iodo-4-hydroxy-benzonitriLe, 3,5-dibromo-4-hydroxybenzoni tri Le, 2-ES-methyl-S-C 1-methyLethyL )-4-oxo-2imidazoL in-2-yLJ-3-pyr idinecarboxyL ic acid, 2-C 1-ethoxya m ino-butyLidene)-5-C2-ethyLthiopropyL)-1,3 -cycLohexanedione, EC4-amino-3,5-dichLoro-6-fLuoro-2-pyridyL)oxylacetic acid and 3-isopropyL-2, 1,3-benzothiadiazin-C4)-one- O,~1 2,2-dioxide. Surprisingly, some mixtures also show a synergistic act ion.

Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides,4 bird repeLLants, plant nutrients and agents which improve Le A 24 483 -92 soiL structure, is also possible.

The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomising or scattering.

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

They can also be incorporated into the soil before sowing.

The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 0.01 and 10 kg of active compound per hectare of soil surface, preferably between 0.05 and 5 kg per ha.

The preparation and use of the active compounds according to the invention can be seen from the following examples.

sr: Preparation Examples Example 1 I It a OCF 3 0 CH3 OCH 3 Ii j -SO2-HH-C C- SOCH3 S 25 (Process variant A solution of 11.2 g (0.05 mol) of 2-trifluoromethoxy-benzenesulphonyL isocyanate in 50 ml of methylene chloride is added to a solution of 8.5 g (0.05 mol) of 4,6-dimethoxy-2-methylamino-pyrimidine in 50 ml of methylene chloride and the mixture is stirred at 20 0 C for 12 hours. It is then concentrated and the residue is trifturated with ether, filtered off with suction and dried.

Le A 24 483 93 Ilcl-~ ~-r~nmnMnrsnmorao-ann~ 2.6 g (12% of theory) of 3-(4,6-dimethoxy-pyrimidin-2-yL)-3-methyl-1-(2-trifLuoromethoxy-benzenesuLphonyl)urea of melting point 1620C are obtained.

Example 2

OCF

3 0 CH 3

OCH

3 >-S02-NH-C-N--

CH

3 (Process variant 4.1 g (0.01 moL) of 3-(4-methoxy-6-methyl-1,3,5triazin-2-yL)-1-(2-trifluoromethoxy-benzenesuLphonyl)-urea are taken up in 50 ml of tetrahydrofuran, and 2.4 g (0.02 mol) of potassium tert.-butylate and 1.7 g (0.018 mol) of dimethyl sulphate are added in succession. After the mixo*;o ture has been stirred at 250C for 2 hours, it is concentrated, the residue is acidified with 10% strength hydrochloric acid and ethanol is added. The product obtained 15 as crystals is filtered off with suction and dried.

o 3.0 g (71% of theory) of 3-methyL-3-(4-methoxy-6methyl-1,3,5-triazin-2-yl)-1-(2-trifluoromethoxy-benzenesulphonyl)-urea are obtained as white crystals of melting point 162 0

C.

t 20 The compounds of the formula listed in the t tfollowing Table 4 can be prepared by the processes described by way of example in the preceding examples: OR 0 R 1 S-SO2-NH-C-N--C Y (I) R2 tc Le A 24 483 94 Tab~e 4 ExampLe H..MeLting No. po in t R 0 I

R

2 /c]

CH

3 3 -CF 2

CHF

2 0 -CH 3 117

DCH

HC

3 4 -CF 3 0 -CH 3 173 C I 0C 2

H

-CF

3 0 -CH 3 138 0C 2

H

0C 2

H

6 -CF 3 0 -H 127 3 01 1C Cl

C

2

H

7 -CF 3 0 -CH 3 134

CH

3 112 8BCF 0 -CH 3 12 0 2

H

CM

9 -CF 3 0 -CM 3 148

OCH

3 Le A 24 483 2

L.

Table 4 -Continuation ExampLe No.

49.4.

0 4.440 .4 40 4 4 I 44 44 4 4444 4.444 4. 4. 4.

4.4 4 4.

C 4 444 4. 4.4 4. 4. .4.

4. 44.

4~ 4. 4.

4 4.

4.4.4.

-CF

3

-CF

3

-CF

3

-CF

3

-CF

3

-CF

3

-CF

2

CHF

2 o -cH 3 o -CH 3 o -CH 3 o -CH 3 o -CH 3 o -CH 2

CH=CH

2 o -CH 3

R

2

CH

3

CH

3

CH

3 C I

C

2

H

Cl1

CF

3 C 1

CF

3

OCH

3

CH

3

OCH

3

CH

3 c 1 M eLt in g p oi n t 1[0 C]I 169 142 Le A 24 483 96 TabLe_4-Continuation Example MeLting No. 0ont R Rop 1

C]

C

2

H

17 -CH 2

CH

2 Cl 0 -CH 3

OCH

3

OCH

3 18 -CHF 2 0 -CH 3 156 c 1 0C 2

H

19 -CHF 2 0 -CH 3 ~141 000 20 2 0 -CH 3 '/140 000OCH 3 9

C

2

H

l:21 -CHF2 0 -CH3 147

CH

3 44 22 -CHF 2 0 -CH 3 'IN\ 142

CH

3

OCH

3 23 -CH2 0 L11 3 4156

CH

3 Le A 24 483 -97- TabLe 4 Continuation Example N o.

0 R *999 a ta* a, a.

a a, a a .ta, I $11 t It~ t a I It I 14 a a alit

CHF

2

-CHF

2

CHF

2

CHF

2

CHF

2

-CHF

2 o -CH 3 o -CH 3 S -CH 3 S -CH 3 S CH S -CH 3 point/

OCH

3

OCH

3

N(CH

3 )2

CH

3

OCH

3 OC

H

OCH

3 0C 2

H

0C 2

H

0C 2

H

OCH

3

OCH

3

-CF

3 0 -C 2

H

Le A 24 483 98 TabLe 4 Continuation Example N o.

a0

-CF

3

-CF

3

-CF

3 o -C 3

H

7 -n o c2- 0o H

COOS

00 00

C

0 00 C C C 0090

CCCC

'C

9

S.,

00 00 0 *0 0 09 C 00 0 9 0000 00 St 0~ S St 9 -t S -t 0, R2

OCH

3

N

OCH

3

OCH

3 OC

K

3

CH

3 0C 2

H

CH

3

OCH

3

C

2

H

CH

3

CH

3

OCH

3 10 C I

-CH

2 ClA 2 Cl 0 -CH 3

_CH

2

CH

2 Cl S -CH 3

-CH

2

CH

2 Cl 0 -CH 3

-CH

2

CH

2 C1 0 -CH 3 120 Le A 24 483 99 I 1 1 -7 Tab~e 4 Continuation Example No R Q R

-CM

2

CH

2 c1 0

-CH

3

-CF

2

-CHF

2 0 -CM 3

-CF

2

-CHF

2 0 -CH 3 000t 0 000 0S £0 0 0 *0 4000 4000 41 41*1 04 4 *4 -cz

R

2

OCH

3

CH

OCH

3 0C 1

CH

3

CH

3

C

3

CM

3

CH

3

CH

3 M e Ltin g p o int/ 0

C]I

-CF

3 0

-CM

3 t t t

-CM

2

CM

2 Cl 0 -HI

-CF

3 0 -CM 3

-CM

2

CM

2 Cl 0 -CM 3 120 Le A 24 483 100 Tab~e 4- Continuation E xampL e No R Q 0

-CF

2

CHF

2 0 -CM 3

-CH

2

CM

2 C1 0 -CM 3 0000 *400 0e Ca a a a *4O t a a asi 4 aa a a *1 4 a a. S

-CF

2

CHF

2

-CF

3

-CF

3

-CF

3

-CF

3 o -CH 3 o -CH 3 o -cH- 3 o -CH 3 o CH

CH

3

OCH

3 0CM 3 OC3

C

3 0C 2

H

C

3 0c 2

H

MleL t i ng p oi n t 1[0 C]I 143 La a a Le A 24 .483 101

XII

I

ii d Table 4 Continuation Example No 0 Rl

CF

3 9 0 0 00 I 0 0 *0$ 4001 0*44 to I I 4 00~

-CF

3

-CF

3

-CF

3

-CF

3

-CF

3

-CF

3 o -CH 3 o -CH 3 o -cM 3 o -CH 3 o -CH 3 o -CH 3 o -CH 3

R

2

C

2

H

0C 2

H

c 2

H

C

2

H

OCH

3

OCH

3 NHC 2

H

0C 2

H

NH C H 0C 2

H

NMC

2

H

OCH

3 M eLt in g p oi n t

'I

0 0 04 0 0 1 o 0*40

N(CH

3 2 Le A 24 483 102 7 TabLe 4 Continuation Ex amp 1e No R 0 P 1 t4*# C tee

I.

S

a I as C S S a CS S It..

It

-CF

3

-CF

3

-CF

3

-CF

3

-CF

3

-CF

2

CHF

2

-CF

2

CHF

2

-CF

3 o -CH 3 o -CM 3 o -C 2

H

5 o -Cl 2

H

2 5 0o H o -CM 3 o -CM 3 o -CH 3

R

2

CM

3

SCM

3

SCM

3

OCH

3

CM

3

CM

3

CH

3 0CM 3

CM

3

CM

3 0CZH

CM

3

CH

3

OCH

3 0CM 3 t 4 t M e L t i n g p o n t 107 100 115 136 105 138 Le A 24 483 103 *4~4 a 4t0 *4 64 4 a 4 4 4 .4,4 44*4 4* *44 4- 1-1 Trable 4 ConLinuation Examnpl1e No. R Q P 1 N-Z Melt ingpoint 0

C)

67

CF

3 68

CF

3 69

CF

3 70

CF

3 71

CF

3 72

CF

3 73

CF

3 0 -CH 2

-CH=CH

2 0 C 2

H

0 -CH 2

-CH=CH

2 0 -CH 2

-C=-CH

0 -CH(CH 3 2 0 C 2

H

0-CH -H N< OC H 3

N-

OCH

3

OCH

3

N<~

OCH

3

"N

OCH

3

OCH

3

OCH

3

CH

3

CH

3

N-

OCH

3 a 4$ 0* *4 41 t Le A 24 483 104

I

1~1-cccclcrrcl-~llcl~~-.....1.... Table 4 Continuation Example No.

N-ZZ

Y

R2 Meltingpoint

C]

0 R 1 74

CF

3

CH

2

CH

2 Cl 0 -CH(CH 3 2 0 CH 3

CH

3

N--

OCH

3

OCH

3 N3

OCH

3

CH

3

NCH

CH3 76 CH 2

CH

2 Cl 0 CH 3 *r ot *rr IIf 1£ 1 441; 1' Example Example Example Example Example Example 77: Sodium 78: Sodium 79: Sodium 80: Sodium 81: Sodium 82: Sodium salt salt salt salt salt salt the the the the the the product of Example product of Example product of Example product of Example product of Example product of Example The active compounds according to the invention not only display very powerful action against dicotyledonous weeds but are also very well tolerated by monocotyledonous crops such as, in parcicular, wheat, barley, rice and corn (maize), and in addition display virtually no persistence since they are decomposed very rapidly.

Le A 24 483 105 L i _j Example A Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated 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, after 24 hours, watered with the preparation of the active compound. It is expedient here to keep constant the amount of water per unit area. The concentration of the active compound in the preparation is of no importance, only the amount of active compound applied per unit area S being decisive. After three weeks, the degree of damage 00 0,44 0 to the plants is rated in damage in comparison to the Sdevelopment of the untreated control. The figures denote: 20 0% no action (like untreated control) 0o 100% total destruction In this test, the active compounds according to 0o Preparation Examples 2, 22, 23 and 66 exhibit a very good o herbicidal activity; for instance they can be used for 0 00 oi the selective combating of Abutilon, Datura, Sinapis and oo Stellaria in wheat cultures.

Le A 24 483 S106 Example B Post-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Test plants which have a height of 5 15 cm are sprayed with the preparation of the active compound in such a way as to apply the particular amounts of active compound desired per unit area. The concentration of the spray liquor is so chosen that the particular amounts of active compound desired are applied in 2,000 L of water/ha. After thi e weeks, the degree of damage to the plants is rated in damage in comparison to the development of the untreated control. The figures denote: 0% no action (like untreated control) 100% total destruction S In this test, the active compounds according to t Preparation Examples 2 and 66 exhibit a very good herbicidal activity. They can be used, for example, as selective herbicides for the combating of Datura, Galinsoga, Ipomoea, Matricaria, Stellaria and Lolium in wheat cultures.

t Test results, wherein compounds according to Examples 2 and 66- I t are compared with similar compounds of the prior art, are set forth in Table B-1 herebelow with some additional results, in respect of further compounds of the invention, set forth in Table B-2 thereafter.

These results clearly demonstrate the superiority of the compounds of the present invention.

Le A 24 483 107 1,4 A2 8

I

S

F

Table B-1PosL-eerence--LtsL Active Compound cjreonho; Ge Appl icatzion rate g/ha Wheat Corn AbuLilon DaLura Mentha Sida Solanun Prior ArL:

OCF

3 0 OCH 3 (known from OCH 3 AU 46651/85)

OCF

3 0 OCH 3 c S0 2

-NH-C-NH-('

(known from CH 3 AU 46651/85) 125 125 20 70 100 30 90 100 95 70 70 95 70 70 f 4 Invent ion'.

OCF

3 0 CR 3

OCR

3 II I

-K

CH

3 (2)

OCF

3 0 CHq OCR 3 I I I -K,

S

2 125 125 0 100 0 100 100 100 80 90

OCR

3 (66)

I

C Ce.. S C e. r S C C C CC C C C t C C C C C C S a C 4* 0 C C CCSC SO S C C C C S C S C S PCC 555 5 C Sw CC S Table B-i: PosL-ernerc~erice-Le~L areenhou~e 03 J

,P

Active Compound Application Wheat Galinsoga Ipomoea Matricaria Stellaria Lolium Rate glha

OCF

3 0 CH.

3

OCH

3 S0 2

CH

3

OCF

3 0 CU 3

OCH

3 S0 2 -NH-C (66)

OCH

3 90 so 0 100 LeA 24483 a 4* 4.

Table B-2: PosL-emergence-LesL I g~reenhouse Active compound ApplicaLion raLe Wheat Corn Aniaranthus Chenopodlun Calinsoga Ifelianthus Ipomoea Matricaria Stellaria giha 0 -4 0 OCI4F 2 0 CH, OCH 3 i I I according to the invention Example 23 ocHF 2 0 CH OC)3 11 1 ocH- 3 according to the invention Example 24 0105s:AB As, indicated heretofore, the compounds of the present invention display virtually no persistence in the soil since they are decomposed very rapidly by hydrolysis. The following Comparative Hydrolysis Test demonstrates the clearly superior and very favourable degradation pattern exhibited by the compounds of the present invention. The inventive compounds are decomposed rapidly by hydrolysis. On the other hand, comparable prior art compounds prove to be very persistent in the soil. Persistence is an undesirable property for an agricultural herbicide.

Comparative Hydrolysis Test: t i To determine the relative stabilities of the compounds being tested towards hydrolysis, the determinations were performed siliar to the methods described in the official OECD-Guidelines for Testing Chemicals, "Hydrolysis as a Function of pH", but with the following modifications.

ii t S I t S Si s s, 107d- A) Materials and Methods a) Buffer solutions The following aqueous standard buffer solut'ions as purchased from E. Merck, (Darmstadt,

FRG).

pH 4 Citrate-HCl (Art.-No. 9435) pH 6 Citrate-NaOH (Art.-No. 9437) pH 9 Boric acid/KC1-NaOH (Art.-No. 9461) b) Test solution 4 An aliquote of an organic solvent stock solution t t t of the test compound was mixed with the aqueous t t buffer solution.

t The amount of organic co-solvent depends on the water solubility of the test compound. A typical test solution contains 1-10%, in some cases up to c r 50%, of co-solvent.

The typical concentration of the chemical compound in the test solution was between 10 and 50 mg/1000 It t t t ml ppm), maximum molarity of 5 x 10 4 4 4 Le A 24 483, 107e

D

2

I

I -lic :i B) Analytical method The concentration of test compound was quantified by HPLC (high pressure liquid chromatography) using the external standard method.

C) Test conditions Temperature: 40 0

C

Sampling intervals: dependent on hydrolytic behaviour of the test compound Total observation time: variable, max. 80 h.

D) Treatment of results Assuming pseudo first-order kinetics in degradation of the test compounds, the concentration of the test compoundswere plotted against time. The reaction rate constant k and the corresponding half-life value was caculated by regress.ion analysis.

Half-life values longer than 250 h are generally indicated as 250 h".

14 Ir 4 I I I i i I1 t*I 4(411

I

4 11

I

t Le A 24 483 107f E) The test compounds and their hydrolysis half-life values at various p1-1 values are shown in the following table, proving that the prior art compounds at pH 6 a pH value within the pH range of typical soils) are very persistent againsL hydrolytic degradation whereas the compounds of the invention are readily decomposed by hydrolysis, i.e.

they are not persistent against hydrolysis.

I

444*1

I

Its ~t 41 4 4 4 1.

1. 1.

1.

I 1.

141.1.

1.

At It 1.

4.4 II Al A 4. 1.

444 III

I

Le A 24 483 107g ~1 CI., "-i i.l r ;i, +5 4 0~ Sa I a aaa 0004 a aa cap, a 9 a ar 0 0 0 ace a 4 4 0 %er 0 S 0 @*0 4 0 Oa 4 4 Hydrolysis Halfi-Life Value (in hours) AcLivo Compound I at pH: 4 6 9 Prior Art:

OCF

3 0 OCH3 II N-K S0 2 NH-C-NW.C

N

(known from CH 3 AU 46651/85)

CCF

3 0 OCH 3 (known from OCH 3 AU 46651/85) Invent ion:

OCF

3 0 CH OCH 3 II! N- 2 N C2) CH 3

OCF

3 0 CH 3 OCH3 S0 2 (66) OC1{ 3 18a 250 27a 250 <1 6 a <1 6 a 250 250 250 250 (a approxLmabely)

Claims (1)

1. 2-halogenoalkoxy-benzenesuiphonyl iso(thio)cyanates of the formula (II) 6 0 2 N=C=Q (11) A A.~C (A C I 004 9s/gs 109a i in which Q and R have the meanings given in Claim 1, are reacted with heteroarylamines of the formula (III) (III) SR Y R 2 1 2 in which R R X, Y and Z have the meanings given in Claim 1, if appropriate in the presence of diluents and if approp- riate in the presence of catalysts, and, appropriate, the products thus obtained are converted into salts by customary methods, or in that 2-halogenoalkoxy-benzenesulphonic acid amides of the formula (IV) OR S(IV) CJ>S0 2 -NH 2 in which R has the meanings given in Claim 1 are reacted with N-heteroaryl-urethanes of the formula (V) Q R1 (V) R Y i R2 in which 1 2 SR R 2 Q, X, Y and Z have the meanings given in Claim 1 and R represents C 1 -C 4 -alkyl, benzyl or phenyl, if appropriate in the presence of diluents and if approp- riate in the presence of acid acceptors, and, if approp- riate, the products thus obtained are converted into salts by customary methods, or in that Le A 24 483 110 N-(2-halogenoa koxy-benzenesu phony )-urethanes of the formula (VI) OR Q SO 2 -NH-C-O-R 6 in which Q and R have the meanings given in Claim 1 and R6 represents C 1 -C 4 -alkyL, benzyL or phenyl, are reacted with heteroarylamines of the formula (III) N--Z (III) R1-NH--< Y R 2 in which R R X, Y and Z have the meanings given in Claim 1, if appropriate in the presence of diluents and if approp- riate in the presence of acid acceptors, and, if approp- riate, the products thus obtained are converted into saLts by customary methods, or in that 1-aryLsulphonyL-3-heteroaryl-ureas of the formuLa (VII) II N--Z 02-NH-C-NH--C Y 2 (VII) R R 2 in which Q, R, R2, X, Y and Z have the meanings given in Claim 1, are reacted with compounds of the formula (VIII) R has the meanings given in Claim 1 and Le A 24 483 111 L, 1 1 i I 4 44 1<4 4I I On o 44P 49(E 4R 4 444 W represents a nucLeophilic Leaving group, if appropriate in the presence of diluents and if approp- riate in the presence of acid acceptors, and, if approp- riate, the products thus obtained are converted into saLts by customary methods. 7 K1 Herbicida agents, characterized in that they con- tain at Least one 3-substituted 1-(2-haLogenoakoxy- benzenesulphonyL)-3-heteroaryL-(thio)urea of the general to ca.coifdre Lh e er Aes-s o- ar5o~ce cjeosr formula according to Claim 1 S 1 Use of 3-substituted 1-(2-haLogenoalkoxy-benzene- suLphonyL)-3-heteroaryL-(thio)ureas of the general formula according to Claim 1 for combating undesired plant growth. 9 7) Process for the preparation of herbicidal agents, characterized in that 3-substituted 1-(2-haogenoalkoxy- benzenesulphonyl)-3-heteroaryL-(thio)ureas of the general formula according to CLaim 1 are mixed with extenders and/or surface-active agents. A c ound accordingto cLaimnt. oI r rocess according to cla' 3 or 6, or an agent according to claim 4, or a method accor iag to claim 5 substantially as herein described with reference t any one of the foregoing examples thereof. 8) Any novel compound (includin starting and/or intermediate) compounds set forth herein, r any novel process set forth herein, or any novel mcthod step thereof set forth herein, the said compound, proces fmeheod- or -step-be i-ng-s-ubs-t-anti-a-lly-. ,as h-rein descri bk- DATED this 22nd day of June 1987. BAYER AKTIENGESELLSCHAFT By Its Patent Attorneys Le A 24 483 ARTHUR S. CAVE CO. -A 24 483 -112 0 k- z;