DD262657A5 - PROCESS FOR PREPARING O-ARYL-N'-PYRIMIDIN-2-YL-ISOHARNSTRATES - Google Patents

Abstract

The invention relates to processes for the preparation of 0-aryl-N-pyrimidin-2-yl-isoureas, which are herbicidally active. The invention provides a novel process for the preparation of O-aryl-N-pyrimidin-2-yl isoureas. The object of the invention is to provide a new, simple process for the preparation of 0-aryl-N-pyrimidin-2-yl-isoureas. The herbicidally active 0-aryl-N-pyrimidin-2-ylureas of the general formula (I) ## STR3 ## (in which the radicals R 1, R 2, R 3, R 4 and R 5 have the meanings given in the description) are obtained in good yields, by reacting iminocarbonic acid esters of the formula (II) with amines of the formula (III) in the presence of acid acceptors and if appropriate in the presence of thickening agents at temperatures between 0C and 150C. Formulas (I), (II) and (III)

Description

"- A. <*? << * Jf

Berlin, 30th September 1987 69351/12

Process for the preparation of O-aryl-N'-pyrirnidin-2-ylisoureas

Field of application of the invention

The present invention relates to a novel process for the preparation of O-aryl-N'-pyrimidin-2-yl-isoharnatoffen and novel intermediates therefor. The process products are known and can be used as herbicides.

Characteristic of the known state of the art

It is known that 0-aryl-N'-pyrimidin-2-yl-isoureas can be prepared by reacting sulfonylguanidines with phenols or phenolates, disadvantageous in this process are the partially unsatisfactory yields in the preparation of the sulfonylguanidines to be used and / or in the preparation of the 0-aryl-N-pyrimidin-2-yl-isoureas (see EP-OS 173 957)

Object of the invention

The invention provides a novel process for preparing O-aryl-U'-pyrimidin-2-yl isoureas, the process product being obtained in a simple manner and in high yields.

Explanation of the essence of the invention

The object of the invention is to provide an improved, new process for the preparation of 0-aryl-lT'-pyrimidin-2-yl-isoureas.

• 1 1

It has now been found that O-aryl-N'-pyrimidin-2-yl · isoureas of the general formula (I)

R ³

R ¹ -SO ₂ -N ^ / NH-C VR ⁴ CN = <

LR ⁵

OR ²

in which

,

R ^{1 represents} an optionally substituted radical from the Series aralkyl, aryl and heteroaryl, P ^{2 is} optionally substituted aryl,

-

R ^{J is} hydrogen, halogen, hydroxy, C 1 -C 4 -alkylamino,

Di- (Cj-C ^ -alkyl) -amino or optionally substituted C ^ -C ^ alkyl, C ^ -C ^ alkoxy and Cj-C ^ - alkylthio,

,

R ^{4 is} hydrogen, halogen, optionally

substituted C ^ -C ^ alkyl, cyano, formyl, Cj-C ^ - alkylcarbonyl or C ^ -C ^ alkoxycarbonyl and

F ^{5 is} hydrogen, halogen, hydroxy, for optionally 30

substituted C ₁ -C ₆ -alkyl, C ₁ -C ₄ -alkoxy and C ₁ -C ₆ -alkylthio, C ₁ -C ₄ -alkylamino or di (C 1 -C 4 -alkyl) -amino, or

R ⁴ and R ⁵ together represent C 3 -C ₆ -alkanediyl,

Le A 24 512

obtained in high yields in a simple manner »when iminocarbonic acid esters of the formula (II)

R ^ SO ₇ -N = C (II) ² \ ²

in which

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

with amines of the formula (III)

R ³

H ₂ N- <7-R ⁴ (III)

N = ⁵ K _

R ⁵

in which r3 _t r4 _unc j r5 JjJ have _{6 o} jj _en given meanings,

in the presence of acid acceptors and optionally in the presence of diluents at temperatures between

O ⁰ C and 150 ⁰ C converts. 30

Surprisingly, it is possible with the aid of the method according to the invention to produce the compounds of the formula (I) in a simple manner in good yield.

Le A 2 4

With the aid of the method according to the invention, those compounds of the formula (I) are preferably prepared in which

HR ⁷

R ^{1 is} the radical -ζ > in which

R and R 'are the same or different and are hydrogen, halogen [in particular fluorine, chlorine, bromine and / or iodine], cyano, C ₁ -C 12 -alkyl [which is optionally substituted by fluorine, chlorine, bromine, Cyano, C ₁ -C ₄ -alkoxy, C ₃ -C ₆ -cycloalkyl or phenyl], for C ₁ -C ₄ -alkoxy [optionally substituted by fluoro, chloro, bromo, cyano or C ₁ -C ₄ -alkoxy ], for di- (C ₁ -C ₄ -alkyl) -aminosulfonyl, for phenyl or phenoxy, for C ₁ -C ₄ -alkylcarbonylamino, C ₁ -C ₄ -alkylamino-carbonyl-amino, di- (C ₁ - C ₄ bl

kyl) amino carbonylamino, di (C ₁ -C ₄ alkyl) aminocarbonyl or di (C ₁ -C ₄ alkyl) aminosulfonylamino, wherein

HR ¹⁰

R ^{1 is} the radical -C (J , where

R ⁸ R ⁹

Le A 24 512

-S

R ^{8 is} hydrogen or C ₁ -C ₄ -alkyl) cy- itent, 5

R ⁹ and R ^{10 are the} same or different and are hydrogen, fluorine "chlorine" bromine, nitro, cyano, C ₁ -C ₄ -Al) CyI [which is optionally substituted by fluorine and / or chlorine], C ₁ -C ₄ -alkoxy

[which is optionally substituted by fluorine and / or chlorine] or di- (C ₁ -C ₄ -Bl) CyI) -amino sulfonyl stand;

wherein further 15

R ^{1 is} the radical -f JT 4-R ¹² , wherein

R * * and R ^ are the same or different and are hydrogen, fluorine, chlorine, bromine, nitro, cyano, C ₁ -C ₄ -Al) CyI [which is optionally substituted by fluorine and / or chlorine] or C ₁ -C ₄ -

Alkoxy [which is optionally substituted by fluorine and / or chlorine]; where further

p2 yyyy ₁ . _e £ _NEN phenyl radical, which is optionally substituted by one or more radicals from the series

Halogen [in particular fluorine, chlorine, bromine and iodine], cyano, nitro, hydroxy, carboxy, C ₁ -C ^ -AlKyI

[which is optionally substituted by fluorine, chlorine, bromine,

Le A 24 512

Nitro, cyano, hydroxyl, carboxyl, Cj-C ^ alkoxy-carbonyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -AlKyIthio or phenyl substituted], C ₃ -C _fe cycloalkyl, C ₁ -C ₄ -alkoxy [which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxy, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio or C ₁ -C ₄ -alkoxycarbonyl], C ₁ -C _4- alkylthio [which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxy, C ₁ -C ₄ -alkoxycarbonyl], amino, Cj-C ^ -alkyl-amino or di- (C ₁ -C ₄ [which are optionally substituted by fluorine, chlorine, bromine, cyano, carboxy, C ₁ -C ₄ -alkoxy or C ₁ ~ C ₄ -alkoxy-carbonyl] alkyl) amino, C ₁ -C ₄ -alkyl-carbonyl- amino, C ₁ -C ₄ -alkoxycarbonylamino, (di) C ₁ -C ₄ -alkylamino-carbonyl-amino, formyl, C ₁ -C ₄ -alkyl-carbonyl, benzoyl, C ₁ -C ₄ -alkoxy carbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenyl [which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, hydroxy or methyl], phenoxy, phenylthio, phenylsulfonyl, P henylamino or phenylazo [which are optionally substituted by fluorine, chlorine, bromine, cyano, nitro, methyl and / or trifluoromethyl], pyridoxy or pyrimidoxy [which are optionally substituted by fluorine, chlorine, bromine, cyano, nitro, methyl and / or trifluoromethyl ], C ₁ -C ₄ alkyl-carbonyloxy, C ₁ -C ₄ alkoxy-carbonyloxy, C ₁ -C ₄ -alkyl-amino-carbonyloxy and di- (C ₁ -C ₄ -alkyl) -amino-carbonyloxy, or which is optionally substituted by an alkylene chain [which is optionally branched and / or interrupted by one or more oxygen atoms] or a benzene

rest [which is optionally substituted by fluorine, chlorine, 35

Le K 24 512

"" 7 ^β

Bromine, cyano, nitro, methyl and / or trifluoromethyl is fused]; where further

R ^{3 is} hydrogen, fluorine, chlorine, bromine, hydroxyl, C ₁ -C ₄ alkylamino, di (C ₁ -C ₄ -BlKyI) amino, C ₁ -C ₄ -Al) CyI [which may be substituted by fluorine and / or chlorine is substituted], C ₁ -C ₄ -alkoxy [which is optionally substituted by fluorine and / or chlorine], C ₁ -C ₄ -alkylthio [which is optionally substituted by fluorine and / or chlorine],

R ^ is hydrogen, fluorine, chlorine, bromine, C ₁ -C ₄

[which is optionally substituted by fluorine and / or chlorine], cyano, formyl, C ₁ -C ₄ -AlKyI-CaT-carbonyl or C ₁ -C ₄ -alkoxycarbonyl and

R ^{5 is} hydrogen, fluorine, chlorine, bromine, hydroxy, C ₁ -C ₄ alkyl [which is optionally substituted by fluorine and / or chlorine], C ₁ -C ₄ -alkoxy [which optionally substituted by fluorine and / or chlorine is], C ₁ -C ₄ alkylthio [which is optionally substituted by fluorine and / or chlorine], C ₁ -C ₄ -A ^ yI amino or di (C ₁ -C ₄ alkyl) amino, or

R * and R ^ together represent C3 ~ C ₄ -alkanediyl.

If, for example, N- (2-chlorobenzenesulfonyl) -iminokohlensiurediphenylester and 2-amino-4-methoxy-6-methyl-pyrimidine are used as starting materials, the reaction can be

Le A 24 512

tion sequence according to the method according to the invention by the following formula:

SO ₂ -N = C

♦ Base

CH _;

+ H ₂ NC S

ochr

The iminocarbonic acid esters to be used in the process according to the invention are novel and are generally defined by the formula (II). The new iminocarbonic acid esters of the formula (II) are preferably

in which

for the rest

stands in which

and R 1 are the same or different and represent hydrogen, halogen [in particular fluorine, chlorine, bromine and / or iodine], cyano, C 1 -C 4 -alkyl, which is optionally substituted by fluorine,

Le A 24 512

Chlorine, bromine, cyano, C ₁ -C ₄ -alkoxy, C ₃ -C ₆ - Substituted cycloalkyl or phenyl],

for C ₁ -C ₄ -alkoxy [which is optionally substituted by fluorine, chlorine, bromine, cyano or C ₁ -C ₄ alkoxy], for di- (C ₁ -C ₄ -alkyl) -aminosulfonyl, for phenyl or phenoxy , for C ₁ -C ₄ -alkylcarbonylamino, C ₁ -C ₄ -

Alkylamino-carbonylamino, di- (C ₁ -C ₄ -alkyl) -amino-carbonylamino, di (C ₁ -C ₄ -alkyl) aminocarbonyl or for di- (C ₁ -C ₄ -alkyl) -

aminosulfonylamino, wherein further 15

HR ¹⁰

R ¹ for the radical -CH <f? stands in which

R ⁸ R ⁹ 20

R ^{8 is} hydrogen or C ₁ -C ₄ -alkyl,

R and R * are the same or different and represent hydrogen, fluorine, chlorine, bromine,

Nitro, cyano, C ₁ -C ₄ -A ^ yI [which is optionally substituted by fluorine and / or chlorine], C ₁ -C ₄ -alkoxy [which is optionally substituted by fluorine and / or chlorine] or

Di (C ₁ -C ₄ alkyl) aminosulfonyl; where further

Le A 24 512

R ^{1 is} the radical -f \\ 4-R ¹² »in which

R ** and R * ^{2 are the} same or different and represent hydrogen, fluorine, chlorine, bromine,

Nitro, cyano, C ₁ -C ₄ -alkyl [which ge

optionally substituted by fluorine and / or chlorine] or C ₁ -C ₄ alkoxy [which optionally substituted by fluorine and / or chlorine

Ιζ is], stand; and

R ^ is a phenyl radical which is optionally substituted by one or more radicals from the series

Halogen [in particular fluorine, chlorine, bromine and iodine], cyano, nitro, hydroxy, carboxy, C ₁ -C ^ -AlKyI [which is optionally substituted by fluorine, chlorine, bromine, nitro, cyano, hydroxy, carboxy, C ₁ -C ₄ -alkoxy-CBrbonyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio or phenyl-substituted], C ₃ -C ₆ -cycloalkyl, C ₁ -C ₄ -alkoxy [which is optionally substituted by fluorine, chlorine, bromine , Cyano, carboxy, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio or C ₁ -C ₄ -alkoxycarbonyl], C ₁ -C ₄ -alkylthio [which is optionally substituted by fluorine, chlorine, bromine , Cyano, carboxy, C ₁ -C ₄ -alkoxy-carbonyl], amino, C ₁ -C ₄ -alkyl-amino or di- (C ₁ -C ₄ -alkyl) -amino [which is optionally substituted by fluorine, Chlorine, bromine, cyano, carboxy, C ₁ -C ₄ -alkoxy or C ₁ -C ₄ -alkoxycarbonyl are substituted],

Le A 24 512

CJ-C ₄ -alkyl-carbonylamino, C _χ -C ₄ -alkoxy-carbonylamino, (di) -C ^ -C ^ alkylamino-carbonylamino, formyl, Cj-C ^ alkyl-carbonyl, benzoyl, Cj-C ₄ -alkoxy-carbonyl, phenoxy-carbonyl, benzyloxycarbonyl. Phenyl [which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, hydroxy or methyl], phenoxy, phenylthio, phenylsulfonyl, phenylamino or phenylazo [which may be substituted by fluorine, chlorine, bromine, cyano, nitro, methyl and / or Trifluoromethyl substituted], pyridoxy or pyrimidoxy [which are optionally substituted by fluorine, chlorine, bromine, cyano, nitro, methyl and / or trifluoromethyl], C ₁ -C ₄ -alkyl-carbonyloxy, C ₁ -C ₄ -alkoxy carbonyloxy, C ₁ -C ₄ -alkyl-amino-carbonyloxy and di- (Cj-C ^ -j-alkyl) -amino-carbonyloxy, or which may optionally be branched by an alkylene chain [optionally branched and / or by one or more oxygen atoms interrupted] or a benzo radical [which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, methyl and / or trifluoromethyl

is substituted] is fused. 25

Examples of the iminocarbonic acid esters of the formula (II) which may be mentioned are:

/ OR

F 1 -SO ₂ -N = C (II)

² \ ²

Le A 24 512

table

35

Cl

10

Cl

Cl

15

Cl

Cl

Cl

Cl

20

Cl

H-

25

Cl

CH-

Cl

H ₃ C

30

Cl

Le λ 24

Table 1 - continued

10

Cl

Cl

tert-H ₉ C ₄

15

Cl

^C 2 ^H 5

20

Cl

Cl

^H 5 ^C 2

br

25

Cl

br

30

Cl

Cl

br

35

Le A 24 512

Table 1 - continued

10

Cl

Cl

OCH

H ₃ CO

15

Cl

H ₃ C

20

Cl

Cl

25

Cl

H ₅ C ₂

30

35

Cl

Cl

Cl

Cl

Cl

Cl

Le A 24 512

Table 1 - continued

ί ; C

10

15

20

25

30

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

OC ₃ H ₇ -Ii

nH ₇ C ₃ 0

H ₃ CS

N (CHg) ₂ F

35

Le λ 24 512

Table 1 - continued

35

oCRF

10

oCRF

Cl

15

oCRF

Cl

OCF.

Cl

20

H-

25

CH-

OCF

H ₃ C

30

OCF

Le A 24

Table 1 oil

- Continuation

oCRF

OCF

OCF

OCF

OCF

OCF>

OCF,

tert-H ₉ C ₄

^C 2 «5

H ₅ C

br

br

Le A 24

Table 1 - continued

OCF,

OCH

10

OCF

H ₃ CO

15

OCF ^

H ₃ C

OCF,

OC ₂ H ₅

20

OCF

25

OCF

^H 5 ^C 2

OCF

Cl

Cl

30

35

OCF

Cl

Cl

Le A 24

Table 1 - continued

OCF.

10

OCF

OCF

15

OCF,

20

OCF

25

OCF.

OCF

30

OCF

PC ₃ H ₇ -H

Ji-H ₇ C ₃ O

nH ₇ C ₃

H ₃ CS

N (CHg) ₂ F

35

Le A 24

Table 1 - continued

OCHF ₂

Cl

OCHF ₂

Cl

OCHF ₂

OCHF-

Cl

H-.

OCHF ₂

CH-

OCHF-

OCHF ₂

0 -4.

OCHF-

Le λ 24

Table 1 - continued

OCHF ₂

OCHF-

tert-H ₉ C ₄

^H 5 ^C 2

OCHF-

^C 2 ^H 5

OCHF-

OCHF-

br

OCHF-

br

OCHF-

OCHF-

Le A 24

Table 1 - continued

OCHF ₂

OCH

OCHF-

H ₃ CO,

OCHF '

H ₃ C

OCHF-

OCHF-

OCHF-

^H 5 ^C 2

OCHF-

Cl

Cl

OCHF-

Cl

Cl

Le A 24

Table 1 - continued

10

OCHF ₂

Ti-H ₇ C ₃ O

15

OCHF-

nH ₇ C ₃

OCHF-

H ₃ CS

20

OCHF-

OCHF-

OCHF-

OCHF-

OCHF ₂

OC ₃ H ₇ -Ii

Le A 24

Table 1 - continued

OCH ₂ CH ₂ Cl

OCH ₂ CH ₂ Cl

Cl

OCH ₂ CH ₂ Cl Cl

OCH ₂ CH ₂ Cl Cl

OCH ₂ CH ₂ Cl

OCH ₂ CH ₂ Cl CH-

PCH ₂ CH ₂ Cl H ₃ C

OCH ₂ CH ₂ Cl

Le A 24 512

Table 1 - continued

OCH ₂ CH ₂ Cl

tert-H ₉ C ₄

10

OCH ₂ CH ₂ Cl

^H 5 ^C 2

, OCH ₂ CH ₂ Cl

^C 2 ^H 5

, 0CH ₂ CH ₂ Cl

OCH ₂ CH ₂ Cl Br

OCH ₂ CH ₂ Cl Br

OCH ₂ CH ₂ Cl

OCH ₂ CH ₂ Cl

Le A 24 512

Table 1 - continued

OCH ₂ CH ₂ Cl OCHr

OCH ₂ CH ₂ Cl H ₃ CO

OCH ₂ CH ₂ Cl H ₃ C

OCH ₂ CH ₂ Cl

OC ₂ H ₅

OCH ₂ CH ₂ Cl H ₅ C ₂ O

OCH ₂ CH ₂ Cl

OCH ₂ CH ₂ Cl Cl

Cl

OCH ₂ CH ₂ Cl Cl

Cl

Le A 24 512

Table 1 - continued

10

15

OCH ₂ CH ₂ Cl

OCH ₂ CH ₂ Cl

OC ₃ H ₇ -H

, OCH ₂ CH ₂ Cl nH ₇ C ₃ O

v_ ) χ

I ₁ -H ₇ C ₃

20

OCH ₂ CH ₂ Cl

OCH ₂ CH ₂ Cl

OCH ₂ CH ₂ ClH ₃ CS

N (CHg) ₂ F

OCH ₂ CH ₂ Cl

OCH ₂ CH ₂ Cl

Le A 24 512

Table 1 - continued

10

Cl

20

Cl

25

Cl Hj ₃ C

30

35

Le A 24

Table 1 - continued

15 V =

20

tert-H ₉ C ₄

25

^H 5 ^C 2

^C 2 ^H 5

30

H ₅ C

35

10

H ₃ C

Le A 24 512

Table 1 - continued

10 br

br

20

25

30

OCH

H ₃ CO,

Le A 24

Table 1 - continued

10

H ₃ C

15 \ =

20

H ₅ C ₂ O

25

^H 5 ^C 2

Cl

Cl

30 35

Cl

Cl

Le A 24

Table 1 - continued

15 ^ - =

0C ₃ H ₇ -n

nH ₇ C ₃ 0,

nH ₇ C ₃

H ₃ CS

N (CH ₃ ) ₂

Le A 24 512

Table 1 - continued

15

35

br

20

br

Cl

br

25 \ =

H ₃ CO

br

30

br

10

Le A 24

Table 1 - continued

35

Cl

10

Cl Cl

15

Cl

H, Cl

Cl

Cl

20

Cl

H ₃ C

25

Cl CH-

Cl

H, -H ₃ C

30

Cl

Le K 24

Table 1 - continued

35

Cl

tert, -H ₉ C ₄

10

Cl

H ₂ -

15

Cl

, ^C 2 ^H 5

Cl

H ₂ -

_2n

20

Cl

br

25

Cl

H ₂ "Br

Cl

30

Cl

Le A 24

Table 1 - continued

Cl

HIGH-

10

Cl

H ₂ "H ₃ CO

15

Cl

H, -H ₃ C

Cl

Ho-

OC ₂ H ₅

20

Cl

Ho-H ₅ C ₂ O

25

Cl

Cl

Ho-Cl

Cl

30

35

Cl

Ho-Cl

Cl

Le A 24

Table 1 - continued

35

Cl

OC ₃ H ₇ -η

10

Cl

nH ₇ C ₃ 0

15

Cl

H, -Ti-H ₇ C ₃

Cl

H, -H ₃ CS

20

25

Cl

H,-

Cl

N (CHg) ₂

30

Cl

Cl

Le A 24

Table 1 - continued

262 A7

H-

Cl

H ₃ CO

CF

CF

Cl

H ₃ CO,

Le A 24

Table 1 - continued

.10

CF,

CFr

Hi

15

CN

20

CN

CN

Cl

25

CN

30

35

CN

Cl

Cl

Le A 24

Table 1 - continued

10

15

20

25

30

Cl

H,-

Cl

Cl

H,-

Cl Cl

Cl Cl

Cl

OCH ^

ochr

4

OCH

Cl

H ₃ CO,

Cl

H ₃ CO

35

Le A 24

£. W & ξ

Table 1 - continued

OCH;

CH.

CH.

CH.

Cl

H ₃ CO

CH-

CH.

CO-N (CH ₃ )

H ₃ C

Le A 24

Tabelie 1 - continued

CO-N (CHg) ₂

\ Sss = t /

CO-N (CHg) ₂ CO-N (CHg) ₂ SO ₂ N (CHg) ₂ SO ₂ N (CHg) ₂ SO ₂ N (CHg) ₂ SO ₂ N (CHg) ₂ SO ₂ N (CHg) ₂

Cl

CO-N (CH ₂ ) ₃ H ₃ CO,

Cl

H ₃ CO

Le A 24 512

The compounds of the formula (II) are obtained when iminocarbon dichlorides of the formula (IV)

R ^ SO ₇ -N = C (IV)

²

in which 10

R * has the meanings given above,

with compounds of the formula (V) R ² -OM (V)

in which

R has the meanings given above and 20

M is hydrogen or an alkali metal atom,

optionally in the presence of acid acceptors, such as. For example, sodium or potassium hydroxide, and optionally in the presence of inert diluents, such as. As acetone, methyl ethyl ketone or acetonitrile, at temperatures between 10 ⁰ C and 100 ⁰ C implemented.

The iminocarbonic acid dichlorides to be used as starting materials for the preparation of the compounds of the formula (II) are generally defined by the formula (IV). In this formula, R preferably represents those radicals which have already been mentioned as preferred in the context of the substituent definition of the formula (I). 35

Le A 24 512 ·

26

The iminocarbonic acid dichlorides of the formula (IV) are known in some cases and / or can be prepared by known processes (cf., for example, Chem. Ber. 22, 2900 (1966), CA 90: 137826b; Angew. Chem. T7_ _t 430 (1965)). New are the iminocarbonic acid dichlorides of the formula (IVa)

R ¹³ -SO ₂ -N = C (IVa)

in which _{b) 1}

is the radical -C ^λ ), in which

_R 14

R is halogen [in particular fluorine, chlorine, bromine 2Q and / or iodine], cyano, C ₂ -C ₆ -alkyl, C ₁ -C ₆ -alkyl

[which is substituted by fluorine, chlorine, bromine, cyano, C ₁ -C ₄ -alkoxy, C ₃ -C ₆ -cycloalkyl or phenyl], for C ₁ -C ₄ -alkoxy [which is optionally substituted by fluorine, chlorine, bromine, Cyano or C ₁ -C ₄ -alkoxy], for di (C ₁ -C ₄ -syl)

kyl) -aminosulfonyl, for di- (C ₁ -C ₄ -alkyl) -aminocarbonyl, for phenyl or phenoxy, for C ₁ -C ₄ -alkylcarbonylamino, Cj ^ -C ^ -alkylamino-carbonylamino, di- (C ₁ C ₄ -alkyl) -amino-carbonylamino, di-2Q (C ₁ -C ₄ -alkyl) -aminocarbonyl or for di- (C ₁ -C ₄ -

alkyl) -aminosulfonylamino wherein further

Le A 24 512

HR ¹⁷

R ^{13 is} the radical -CH X _- "/ where

pl5 _R 16

R ^{15 is} hydrogen or C ₁ -C ₄ -A ^ yI,

« _{A 17}

R ¹⁶ and R ^{1 are the} same or different and for

Hydrogen, fluorine, chlorine, bromine, nitro, cyano, C ₁ -C ₄ -alkyl [which may be replaced by fluorine and / or

Chlorine is substituted], C ₁ -C ₄ -alkoxy 15

[which optionally by fluorine

and / or chlorine is substituted] or di (C ₁ -C ₄ alkyl) aminosulfonyl; where further

R ^{13 is} the radical - Y | j "4-R ¹⁹ , wherein

R * ^ and R * ^{9 are the} same or different and represent hydrogen, fluorine, chlorine, bromine,

Nitro, cyano, C ₁ -C ₄ -A ^ yI [which is optionally substituted by fluorine and / or chlorine] or C ₁ -C ₄ alkoxy [which optionally by

³ ^ substituted fluorine and / or chlorine

is], stand.

The novel compounds of the formula (IVa) are obtained when dimethyl iminodithiocarbonate of the formula (VI) 35

Le A 24 512

/ SCH ₃

P ¹³ -SO ₂ -N = C (VI)

² \

in which

R * ^{3 has} the meanings given above for formula (IVa),

in the presence of inert Verdiinnungsmitteln, such as carbon tetrachloride, at temperatures between ^{0 0} C and 25 ⁰ C with a chlorinating agent such as sulfuryl chloride or chlorine gas, implemented.

The dimethyl iminodithiocarbonates of the formula (VI) are known and / or can be prepared by known methods (cf., for example, EP-A 121 082, EP-A 151 554 and EP-A 173 957).

As examples of the new Iroinokohlensäuredichloride of formula (IVa) may be mentioned:

-S ^ ¹¹

R ¹³ -SO ₂ -N = C (IVa)

² \

Le A 24 512

table

13

Cl

Cl

OCH ₂ CH ₂ Cl

CN

CV

OC ₂ H ₅

CO-N (CHg) ₂

C0-N (C ₃ H ₇ -n) ₂

- 47 -

»13

OCF,

cv "

OCHF-

br

OCH

cv

OC ₃ H ₇ -Ii

CO-N (C ₂ H ₅ )

Le A 24

The compounds which are furthermore to be used as starting materials for the preparation of the compounds of the formula (II) are generally defined by the formula (V). In this formula, R ² preferably represents those radicals which have already been mentioned as preferred in the context of the definition of substituents of the formula (I). M in this formula is hydrogen or an alkali metal atom, such as preferably sodium or potassium. In the event that M is an alkali metal atom, the process for preparing the compounds of formula (II) is preferably carried out without acid acceptor.

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

The amines also to be used as starting materials in the process according to the invention are generally defined by the formula (III). In this formula (III), R, r4 and R preferably represent those radicals which have already been mentioned as preferred in the context of the substituent definition of the formula (I)

 25

As examples of the amines of the formula (III) may be mentioned s

-R ⁴ (III)

Le A 24 512

table 3 RS R ³ R ⁴ R ⁵ R ³ R ⁴ CH ₃ CH ₃ H ^C 2 ^H 5 Chg H OCH ₃ OCH ₃ H OC ₂ H ₅ OCHg H OCH ₃ CH ₃ H H CH ₃ H OC ₂ H ₅ CH ₃ H Cl CH ₃ H OCH ₃ Cl H OC ₂ H ₅ Cl H OCHF ₂ CH ₃ H SCH ₃ CH ₃ H schg CH ₃ H N (CHg) ₂ OCH ₃ H N (CHg) ₂ ^C 2 ^H 5 H H OCH ₃ H Cl CH ₃ Cl CH ₃ ^C 2 ^H 5 H H OC ₂ H ₅ H OC ₂ H ₅ H H H CH ₃ H OH CH ₃ COOC ₂ H ₅ H Cl H N (CH ₃ J ₂ CH ₃ CH ₃ ^C 2 ^H 5 ^C 2 ^H 5 H OCH ₃ ^C 2 ^H 5 H OC ₂ H ₅ OCH ₃ H NHCH ₃ ^C 2 »5. H

Le A 24

The amines of the formula (III) are known and / or can be prepared by processes known per se (cf., eg, Chem. Pharm, Bull. H (1963), 1382-1388, J. Chem. Soc., 1946 . 81, U.S. Patent 4,299,960 and EP-A 173 957).

The process according to the invention is preferably carried out using diluents. Suitable thinners are virtually all inert organic solvents. These preferably include aliphatic and aromatic, optionally halogenated

Hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, Tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, esters such as methyl acetate and ethyl acetate, nitriles such as. B, acetonitrile and propionitrile, amides such as. B. dimethylformamide, dimethylacetamide and N-

** Methyl pyrrolidone and dimethyl sulfoxide, tetramethylene sulfone and hexamethylphosphoric triamide.

Acid acceptors which can be used in the process according to the invention for the preparation of the compounds of the formula (I) are all acid binders customarily used for such reactions. Preferably in question alkali metal hydroxides such. For example, sodium and potassium hydroxide, alkaline earth metal hydroxides such. As calcium hydroxide, alkali carbonates and alcoholates such as. Sodium and potassium car-

Le A 24 512

carbonate, sodium and potassium methoxide or ethylate or potassium tert-butoxide.

The reactions are generally carried out at temperatures between -20 ° C and 150 ⁰ C, preferably at temperatures between ^{0 0} C and 80 ° C. The reactions * 0 are generally carried out at atmospheric pressure.

To carry out the process according to the invention, the starting materials of the formulas (II) and (III) and, if appropriate, the appropriate acid acceptor are used in equimolar amounts.

Preference is given to a compound of formula (III), the acid acceptor and the diluent such as. B. tetrahydrofuran and stirred for a few hours. Subsequently, the compound of the formula (II) is added. After the reaction, the reaction solution is concentrated, mixed with water, filtered with suction through silica gel and treated with a mineral acid such as. B. hydrochloric acid slightly acidified. The solution is dissolved in an organic diluent such. B.

** methylene chloride added. The organic phase is washed with saturated sodium carbonate solution and then with water, dried and concentrated. The purification of the crude products is done by conventional methods.

The ^J accessible by this process compounds of formula (I) are known and can be used as plant protection agents, especially as herbicides (see FIG. Z. B. EP-A 173 957).

Le A 24 512

EXAMPLES Production Examples Example 1

3.4 g (0.027 Hol) 2-Amino-4,6-dimethyl-pyrimidin inΊ00 ml tetrahydrofuran bei.20 ^0, mixed C-butoxide, 3.2 g (0.027 mole) of potassium tert and 3 hours at 20 ⁰ G is then stirred. 11 g (0.027 mol) of N- (2-chlorobenzylsulfonyl) -iminokohlensäurediphenylester are then added, the temperature rises to 35 ⁰ O, After the exothermic reaction has subsided, the reaction mixture is stirred at 20 ⁰ G for 15 hours. The reaction mixture is filtered off and concentrated. The residue is taken up in water, filtered off with suction through kieselguhr and the filtrate is slightly acidified with dilute hydrochloric acid. The aqueous solution is extracted with methylene chloride. The organic phase is washed with saturated sodium bicarbonate solution and with water, dried and concentrated in vacuo. The residue is recrystallized from isopropanol.

9.7 g are thus obtained (82% of theory) of ^I> - (4,6-dimethyl-pyrimidin-2-yl) -N'M2-chloro-benzylsulfonyl) -O-phenylisourea melting point of 152 ⁰ C.

Analogously to Example 1, it is also possible, for example, to prepare all 0-aryl-N'-pyrimidin-2-ylisoureas described in the abovementioned document EP-A 173 957.

- 53 -

example

Mp: 100 ^° C. Yield: 58.2 % of theory

Equivalent Compounds of the Formula (II) Example (II-1)

H ₂ -SO ₂ -N = C

23.1 g (0.08 mol) of 2-chloro-benzylsulfonylisocyaniddichlorid are dissolved in 200 ml of acetone and treated at 20 ⁰ C with 18.8 g (0.16 mol) of sodium phenolate. The exothermic reaction is cooled. The reaction mixture is stirred overnight at room temperature, then filtered with suction. The filtrate is concentrated in vacuo, the resulting greasy residue crystallizes slowly. The crystal pulp is triturated with diisopropyl ether, filtered off with suction, washed and dried.

Le A 24

This gives 26.6 g (83 X of theory) of 2-chloro-benzylsul-5-Fonylirainokohlensäure OiO-diphenyl ester of melting point 130 ⁰ C.

Analog Example (II-1), the following compounds of formula (II) can be prepared:

F ^ -SC ₅ -N = C

/ OR "

table

Ex. No. R ¹

Physical

 constant

II-2

II-3

II-4

II-5

II-6

Cl

Cl

Cl Cl

Cl

OCF

Fp 130 ⁰ C mp. 177 ⁰ C

Mp. 185 ⁰ C mp. 183 ⁰ C mp. 112 C ⁰

Le A 24

Table 4 - Continued

15

II-9

20

11-10

25

11-11

11-12

br

CN

30

11-13

OCH,

11-14

35

Ex. No., R ³ Physical. constant

11-7

10

II-8

, OCH ₂ CH ₂ Cl

OCHF ₂

Le A 24

Table 4 - Continued

Ex, -No.

Physical. constant

11-15

11-16

CHr

CON (CHg) ₂

11-17

SO ₂ N (CHg) ₂

11-18

11-19

OCH ₂ CH ₂ Cl

OCHF-

11-20

11-21

11-22

br

Le A 24

Table 4 - Continued

Example no. F ¹ phytic. constant

11-2311-24

11-25

11-2611-2711-28

CN

OCH

CF

Cl

OCF

11-29

Cl

CH

CHO

11-31

SO ₂ N (CH ₃ ) ₂

_y C0N (CH ₃₎ C 11-30 "> - H

Le A 24

- 58 -

Table 4 - Continued

Ex-No. R ¹ Physical. constant

Cl

11-32

11-33

H,-

OCHF-

11-34

11-35

11-36.

br

CN

11-37

OCH

11-38

CF

11-39

Le A 24

Table 4 - Continued

11-42

CHr

br

11-43

11-44

CON (CHg) ₂

SO ₂ N (CHg) ₂

11-45

Cl

11-46

OCHF ₂

11-47

9 £ ^ I

Ex-No.

Physical. constant

11-40

11-41

Cl

OCF

Le A 24

262 IS

Table 4 - Continued

Ex-No. R ³ Physical. constant

11-48

11-49

br

HoCHoC

11-50

CNH ₃ C

11-51

11-52

OCH

Cr '

CF,

H ₃ CHOC

Cl

11-53

H ₃ C

oCRF

11-54

11-55

CHr

H ₃ CH ₃ C

Le A 24

Table 4 - Continued

Example no.

Phyeikal. constant

11-56

11-57

CON (CHg) ₂

SO ₂ N (CHg) ₂

H, CH, C

Cl

11-58

H ₂ "Cl

OCHF-

11-59

11-60

11-61

br

11-62

CN

11-63

Le A 24

Table 4 - Continued

OAO £ B7

»W dm W <a * /

Ex-No. R ¹

Phyeikal. constant

11-6411-65

OCH

CF

Cl

Cl

11-66

Cl

11-67

11-68

OCF

CH-

Cl

Cl

11-69

CON (CH ₃ ) ₂

Cl

11-70

11-71

SO ₂ N (CH ₃ ) 2

Cl

Cl

H ₃ CS

Le A 24

Table 4 - Continued

Ex, -No. R ¹ Physical. constant

11-72

OCHF-

hocs

11-73

11-74

Ö

H ₃ CS

11-75

br

H ₃ CS

11-76

11-77

CN

ochr

H ₃ CS

H ₃ CS

11-78

CF,

H ₃ CS

11-79

Cl

H ₃ CS '

Le A 24

 - 64 -

Table 4 - Continued

Ex-No.

Physical. Xonstante

11-80

11-81

CHr

CON (CH ₃ J ₂ : i-82 \ _ / ""

11-83

SO ₂ N (CH ₃ )

Cl

11-84

11-85

OCHF ₂ H ₃ CSH ₃ CSH ₃ CSH ₃ CS

/%

11-86 '

11-87

Le A 24

Table 4 - Continued

Ex-No. P ¹ Fhyeikal. Xonstante

11-88

11-89

br

CN

11-90

OCH- (

11-91

11-92

Cl

H ₃ C

11-93

OCF

11-94

11-95

CH,

CON (CHg) ₂

H ₃ C

Le A 24

Table 4 - Continued

Ex, -No. R ¹ Physical. constant

11-96

11-97

SO ₂ N (CH ₃ )

Cl

t ♦ -H ₉ C ₄

106 ⁰ C

OCHF-

11-98

11-99

11-100

11-101

br

O-

CN

11-102

OCH

11-103

Le A 24

Table 4 - Continued

11-106

OCF

11-107

CH-

11-108

11-109

SO ₂ N (CH ₃ ) ₂

Ex, -No.

Physical. constant

10

11-104

11-105

CF

Cl

UH ₉ C ₄

11-110

11-111

Cl

OCHF-

Le A 24

Table 4 - Continued

Ex-No. R ¹

Physical. constant

11-112

11-113

11-114

br

11-115

CN

11-116

11-117

CFr

11-118

Cl

11-119

cy

Le A 24

Table 4 - Continued

262 457

Example no. R ¹

Phyeikal. constant

11-12011-121

CH,

CON (CH ₃ )

11-122

SO ₂ N (CH ₃ )

Cl

11-12311-124

H ₂ -

OCHF-

11-125

11-126

11-127

br

Le A 24

Table 4 - Continued

Ex-No. R ¹ Physical. constant

11-128

11-129

CN

OCH

11-130

CF

11-131

11-132

Cl

OCF

11-133

CH-

11-134

11-135

CON (CH ₃ )

SO ₂ N (CH ₃ )

Le A 24

- 71 - ¹

Table 4 - Continued

Ex-No. R ¹ Physical. constant

Cl

11-13611-137

OCHF-

Cl

Cl

11-138

Cl

11-139

Cl

br

11-14011-141

CN

Cl

Cl

OCH

11-142

Cl

CF

11-143

Cl

Le A 24

Table 4 - Continued

Beiερ, -No.

Phyeikal. constant

11-144

11-145

11-146

Cl

oCRF

CH,

Cl

Cl

Cl Cl

Mp 184 ⁰ C

11-147

CON (CHg) ₂ Cl

11-149

SO ₂ N (CH ₃ ) ₂ Cl

Cl

OCHF-

11-150

11-151

Le A 24

Table 4 - Continued

Ex-No. R ¹ Physical. constant

10

11-152

11-153

br

15

CN

11-154

^H 5 ^C 2

il-155

OCH f

CFr

11-156

^H 5 ^C 2

Cl

11-157

OCF

11-158

II-1S9

CH,

Le A 24

Table 4 - Continued

Ex-No. R ¹ Physical. constant

11-160

11-161

CON (CH ₃ ) ₂

SO ₂ N (CH ₃ ) ₂

^H 5 ^C 2

Cl

O ₂ N

Mp 182 ⁰ C

11-163

OCHF ₂

CH,

11-164

OCF,

11-165

Cl

11-166

H,-

CH-

CH-

CH-

Le A 24

Table 4 - Continued

Ex-No. R ¹ Physical. Xonstante

OCH

11-167

CH-

CH-

11-168

CF

11-169

Cl

11-170

CH-

CH-

Q-CH

OCHF-

25 XI-171 <S

H ₃ C

11-172

H ₃ C

OCF

11-173

H ₃ C

Le A 24

Table 4 - Continued

11-176

H ₃ CÖ-

CF

11-177

11-178

Cl

H, C

H ₃ C

11-179

OCHF ₂ Cl

11-180

Cl

11-181

OCF,

Cl

OAOE

Ex-No.

Physical, constant

Cl

11-174

11-175

OCH

H ₃ C

H, C

Le A 24

Table 4 - Continued

Ex, -No. R ¹ Physical. constant

Cl

11-182

11-183

H,-

OCH

Cl

Cl

11-184

Cl

11-185

11-186

CF

Cl

Cl

Cl

11-187

OCHF-

1-H ₇ C ₃

11-188

XH ₇ C ₃

11-189

oCRF

iH ₇ C ₃

Le A 24

Table 4 - Continued

CHr

11-192

iH ₇ C ₃

11-193

11-194

Cl

Ö-iH ₇ C ₃

OCHF-

11-195

OCH

11-196

OCH,

oCRF

11-197

OCH

Ex. Physical, constant

Cl

11-190

11-19.1

OCH

a- ' 1 -H ₇ C ₃

1-H ₇ C ₃

Le A 24

Table 4 - Continued

Ex, -No. R ¹ Physical. constant

Cl

10

11-198

11-199

OCH

OCH

OCH.

11-200

CH-

11-201

11-202

CF

Cl

ochr

OCH

11-203

OCHF-

H ₃ CO

11-204

H ₃ CO

11-205

OCF

H ₃ CO

Le A 24

^ w 2 6sf

Table 4 - Continued

Example no.

Physical. constant

11-20611-207

Cl

OCH

H ₃ CO,

H ₃ CO

11-208

CH-

11-20911-210

Cl

H ₃ CO

hoco

11-211

OCHF ₂

H ₅ C

11-212

H ₅ C

11-213

oCRF

HCC

Le A 24 512

Table 4 - Continued

Ex-No. R ³ Physical. Xonstante

Cl

H ₅ C

11-215

OCH

H ₅ C

11-216

CH-

H ₅ C

11-217

CF

H ₅ C

11-218

Cl

H ₅ C

11-219

OCHF ₂

^C 2 ^H 5

11-220

CH ₁

11-221

OCF,

^C 2 ^H 5

Le A 24

Table 4 - Continued

Ex-No. R ¹ Physical «Constant

11-222

11-223

Cl

OCH

^C 2 ^H 5 ^C 2 ^H 5

11-224

CH-

C ₂ H ₅

11-225

11-226

CF

Cl

2 "5

Le A 24

Ausoanosverbindunoen of formula (IV) and (IVa) 5

Example (IV a-I)

OCF ₃

(^) - SO ₂ -N =

34.5 g (0.1 mol) of 2-trifluoromethoxy-benzenesulfonyl-iminothiokohlensaure S, S-dimethyl ester are dissolved in 300 ml of carbon tetrachloride and at 20 ⁰ C 568 g (8 mol) of dry chlorine gas are introduced. The reaction mixture is heated to about 40 ⁰ C. It is stirred for an hour, filtered off, the filtrate concentrated in vacuo and the residue is fractionally distilled in vacuo.

23.2 g (72.4 × of theory) of 2-trifluoromethane are thus obtained.

Thoxy-benzenesulfonyl-isocyanide dichloride of boiling point Kp: 126 ⁰ CM mbar.

Analogously to Example (IVa-I), the following compounds

of the formulas (IVa) or (IV) are obtained:

R ¹³ -SO ₂ -N = C (IVa)

(IV)

Le A 24

Z6 2 dO 7

table

Ex-No.

, 13 melting point / C ⁰ C]

IVa-2

IVa-3

Cl

OCHF-

79

IVa-4

IVa-5

IVa-6

IVa-7

br

CN

83

IVa-8

OCH

IVa-9

CF,

Le A 24

Table 5 - Requirements

Ex. No. -r.

»13

Melting point / C ⁰ C]

IVa-IO

IVa-Il

Cl

Cl

Cl

IVa-12

PCH ₂ CH ₂ Cl

IV-13

CON (CH ₃ )

IV-14

SO ₂ N (CH ₃ )

Example (IV-I)

CH,

T-SO ₂ -N = C,

Le A 24

Claims (5)

claims 1 2 R and R have the meanings given above, with. Amines of the formula (III) in which R, R and R have the meanings given above, in the presence of acid acceptors and optionally in the presence of diluents at temperatures between 0 ⁰ C and 150 ⁰ C. 1. Process for the preparation of O-aryl-H'-pyrimidin-2-yl-isohamates of the general formula (I) R ¹ -SO ₀ -IT ^ ^ M - </ VR ⁴ (I) in which R is an optionally substituted radical from the series aralkyl, aryl and heteroaryl, R is optionally substituted aryl, R '- represents hydrogen, halogen, hydroxy, C 1 -C 6 -alkylamino, di (C 1 -C 6 -alkyl) amino or optionally substituted C ₁ -C 8 -alkyl, C ₁ -C 6 -alkoxy and C ₁ -C 4 -alkyl; -Cg-alkylthio stands, R is hydrogen, halogen, optionally substituted C.j-Cg-alkyl, cyano, pormyl, Cj-Cg-alkylcarbonyl or C ^ -Cg-alkoxycarbonyl and R ^ is hydrogen, halogen, hydroxy, optionally substituted Cj-Cg-alkyl, C ^ -Cg-alkoxy and Cj-Cg-alkylthio, for C ^ Cg-alkylamino or di- (C ^ Cgamino stands, or R ^ and R together are C - Cg-alkanediyl, characterized in that iminocarbonic acid esters of the formula (II) OR ² (II) 2 · Method according to claim. 1, characterized in that compounds of the formula (II) in which R is an optionally substituted radical from the series aralkyl, aryl and heteroaryl and ρ R is optionally substituted aryl, is used. 2T in which 3. The method according to claim 1, characterized in that compounds of the formula (II), according to claim 2, in which H
R ^{1 is} the radical · - (( ' ^N >, in which 7
R and R are the same or different and are hydrogen, Halogen / "in particular fluorine, chlorine, bromine and / or iodine, cyano, Cj-Cg-alkyl / which is optionally substituted by fluorine, chlorine, bromine, cyano, Cj-C4-alkoxy, CyCg-cycloalkyl or phenyl isjjT" » for C ₁ -C ₄ -alkoxy which is unsubstituted or substituted by fluorine, chlorine, bromine, cyano or C ₁ -C ₄ -alkoxy, 7 for di- (C ₁ -C ₄ -alkyl) -aminosulfonyl, phenyl or phenoxy, for C.C.-alkylcarbonylamino, C.sub.1 -C. -alkylaminocarbonylamino, di- (C.sub.1 -C. -alkyl) -amino-carbonyl- OA ^ Λ amino, di- (G .. -C. alkyl) -amino carbonyl or di- (C 1 -C 4 alkyl) -aminosulfonylamino wherein H 10 R ¹ for the radical -CH- / ¹ ^. stands in which R ⁸
R ^{8 is} hydrogen or C ₁ -G ₄ -alkyl, Q -IQ R ^ and R are the same or different and are hydrogen, iluor, chlorine, bromine, nitro, gyano, C ₁ -G ₄ alkyl / which is optionally substituted by KLuor and / or chlorine /, C ₁ -C ₄ -alkoxy / "which is optionally substituted by iluor and / or chlorine / or di- (C.-C.-alkyl) -aminosulfonyl; where further R ^{1 is} the radical -f ^ l4 -H ¹² wherein 12 R and R are the same or different and are hydrogen, fluorine, chlorine, bromine, nitro, cyano, C ₁ -C -alkyl / which is optionally substituted by chloro and / or chlorine / or C ₁ -C ₄ - / which 4 · The method of claim 1 or. 2, characterized in that compounds of the formula III, wherein the substituents Ro »Ra VB-ä- R5 ei ^{e have the} meaning given above, is used. 4 optionally substituted by fluorine and / or chlorine; and R is a phenyl radical which is optionally substituted by one or more radicals from the series Halogen £ "me in particular fluorine, chlorine, bromine and iodine /, cyano, nitro, hydroxy, carboxyl, Cj-Cg-alkyl £ ~ vrelGhea optionally substituted by fluorine, chlorine, bromine, nitro, cyano, hydroxyl, carboxyl, Cj-C. Alkoxy-carbonyl, C ₁ -C 4 -alkoxy, C ₁ -C -alkylthio or phenyl-substituted, C ₃ -C 6 -cycloalkyl, C ₁ -C -alkoxy, optionally substituted by fluorine, chlorine, bromine, cyano C is, carboxyl, Cj-C alkoxy, C ^ -C.-alkylthio or C.-C, -alkoxy-carbonyl / - C ₄ alkylthio 2r ^"welc ^ ^ea optionally substituted by fluorine, chlorine, bromine , Cyano, carboxy, C 1 -C 4 -alkoxycarbonyl, amino, C 1 -C 4 -alkylamino or di- (C 1 -C 4 -alkyl) -amino which may be substituted by fluorine, chlorine , Bromine, cyano, carboxy, C .- C. alkoxy or C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkylcarbonylamino, C 1 -C 4 alkoxycarbonylamino , (Di) -C ^ -C. -alkylamino-carbonyl-amino, formyl, C 1 -C 4 -alkyl-carbonyl, benzoyl, C 1 -C -alkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenyl w ~ ^el cb- ^it is optionally substituted by F luor, chlorine, bromine, cyano, nitro, hydroxy or methyl is substituted /, phenoxy, phenylthio, phenylsulfonyl, phenylamino or phenylazo / ~ wel- ö2 a before optionally substituted by fluorine, chlorine, bromine, cyano, ITitro, methyl and / or trifluoromethyl7, pyridoxy or pyrimidoxy / which are optionally substituted by fluorine, chlorine, bromine, cyano, nitro, methyl and / or trifluoromethyl /, Cj- C. alkyl -carbonyloxy, C.sub.1 -C.sub.-alkoxy-carbonyloxy, C.sub.1 -C.sub.8 -alkyl-amino-carbonyloxy and di- (C.sub.1 -C.sub.8, -alkyl) -anino-carbonyloxy, or which may be substituted by Alkylene chain "" which is optionally branched and / or interrupted by one or more oxygen atoms, or a benzo radical which is optionally fused to fluorine, chlorine, bromine, cyano, nitro, methyl and / or quifluoromethyl · 5 · Process according to claims 1-4 »characterized in that one carries out the reaction in the presence of an acid binder.