CA2037136A1 - Sulphonylated pyrimidinecarboxamides - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Herbicidal sulphonylated pyrimidinecarboxamides of the formula (I) in which R represents in each case optionally substituted aryl, aralkyl or heteroaryl, X represents hydrogen, halogen, alkyl, halogeno-alkyl, alkoxyalkyl, alkoxy or halogenoalkoxy, Y represents halogen, alkyl, halogenoalkyl, alkoxy-alkyl, alkoxy or halogenoalkoxy and Z represents hydrogen, halogen, alkyl, halogeno-alkyl, alkoxy or halogenoalkoxy, and salts thereof.

* * *

Le A 27 532

Description

~ 5 The invention relates to new sulphonylated pyrimidine-carboxamides, to processes for their preparation, and to their use as herbicides.

It is already known that certain he~erocyclic N-acylsul-phonamides, for example, N-(2-methoxy-phenylsulphonyl)-4,6-dimethyl-pyrimidine-2-carboxamide and N-(2-chloro-phenylsulphonyl)-4,6-dimethoxy-pyrimidine-2-carboxamide, have herbicidal properties (cf. EP-A 353,640).

However, the herbicidal activity of these compounds is not always entirely satisfactory.

The new sulphonylated pyrimidinecarboxamides of the general formula (I) X
R-S02-NH-CO~;~Y t I ) in which 5 R represents in each case optionally substituted aryl, aralkyl or heteroaryl, X represents hydrogen, halogen, alkyl, halogenoalkyl, alkoxyalkyl, alkoxy or halogenoalkoxy, Y represents halogen, alkyl, halogenoalkyl, Le A 27 532 ' ' ' ' ' ' -- ' ' ~ '. ' ,, - ~ :

2 ~

alkoxyalkyl, alkoxy or halogenoalkoxy and Z represents hydrogen, halogen, alkyl, halogenoalkyl, alkoxy ox halogenoalkoxy, and salts of compounds of the formula (I), have now been found.

The new sulphonylated pyrimidi:necarboxamides of the general formula (I) are obtained when (a) pyrimidinecarboxamides of the general formula (II) N==~
H2N-CO~ />--Y
N--~ (II) in which X, Y and Z have the abovementioned meanings are reacted with sulphonyl halides or sulphonic anhydrides of the general formula (III) R-so2-Q (III) in which R has the abovementioned meaning and Q represents fluorine, chlorine, bromine or the group Le A 27 532 - 2 -... _ ' ' ` ' :
.
'`

2 0 ~ i ~ 3 ~3 -O-SO2-R where R has the abovementioned meaning, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or when (b~ pyrimidinecarboxylic acids of the general formula (IV) X
HOOC ~ /~-Y
N~ IV) in which X, Y and Z have the abovemantioned meanings, or reactive derivatives of compounds of the formula (IV), are reacted with sulphonamides of the general formula (V) R-SO2-NH2 tv) in which R has the abovementioned meaning, or with reactive derivatives of compounds of the formula (V), if appropriate in the presence of reaction auxili-aries and if appropriate in the presence of diluents, Le A 27 532 - 3 _ -.- : . : - :
. , . : - ~

~3~ ~q 3 ~, and, if desired, the products obtained by processes (a) or (b) are converted into salts by customary methods.

The new sulphonylated pyrimidinecarboxamides of the general formula (I) are distinguished by a powerful herbicidal activity.

Surprisingly, the sulphonylated pyrimidinecarboxamides of the formula (I~ according to the invention have a con-siderably more powerful herbicidal action than the heterocyclic N-acylsulphonamides which are known from the prior art such as, for example, N-(2-methoxy-phenylsul-phonyl)-4,6-dimethyl-pyrimidine-2-carboxamide and N-(2-chloro-phenylsulphonyl)-4,6-dimethoxy-pyrimidine-2-carboxamide.

The invention preferably relates to compounds of theformula (I~ in which Rl R represents the radical ~ where R1 and R2 are identical or different and represent hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, carboxyl, Cl-C6-alkyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, car-boxyl,Cl-C4-alkoxycarbonyl,Cl-C4-alkylamino-Le A 27 532 - 4 -. . ~ .
- ,,' .
.. : .

2 ~ ~ rgl i 3 ~

carbonyl, di-(Cl-C4-alkyl)-amino-carbonyl, hydroxyl, Cl-C4-alkoxy, formyloxy, Cl-C4-alkyl-carbonyloxy, C,-C 4 - alkoxy-carbonyloxy, Cl-C4-alkylaminocarbonyloxy, C1-C4-alkylthio, Cl-C4-alkylsulfinylt Cl-C4-alkylsulphonyl, di-~C~-C4-alkyl)-amino-sulphonyl, C3-C5-cycloalkyl or phenyl), or represent C2-C6-alkenyl (which is option-ally substituted by fluorine, chlorine, bromine, cyano, Cl-C4-alkoxycarbonyl, carboxyl or phenyl), or represent C2-C6-alkinyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, Cl-C4-alkoxy-carbonyl,carboxyl orphenyl), or represent Cl-C4-alkoxy (which is optionally substitutedby fluorine,chlorine,bromine, cyano, carboxyl, Cl-C4-alkoxy-carbonyl, C~-C4-alkoxy, Cl-C4-alkylthio, Cl-C4-alkyl-sulphinyl or C1-C4-alkylsulphonyl), or represent Cl-C4-alkylthio (which is option-ally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C4-alkoxy-carbonyl, Cl-C4-alkylthio, C1-C4-alkyl-sulphinyl or C1-C4-alkylsulphonyl), or represent C3-C6-alkenyloxy (which is optionally substituted by fluorine, chlorine, bromine, cyano or Cl-C4-alkoxy-carbonyl)l or represent C2-C6-alkenylthio ~which is optionally substituted by . :
fluorine, chlorine, bromine, cyano, nitro, ~ --:
.

Le A 27 532 - 5 ~ ;~

.`
, ' ~ ~' ' 2 $ 3 r~ 3 Cl-C3-alkylthio or Cl-C4-alkoxycarbonyl), C3-C6-alkinyloxy, C3-C6-alkinylthio, or represent the radical -S(o)p-R3 where p represents numbers 1 or 2 and R3 represents Cl-C4--alkyl (which is option-ally substituteclby fluorine, chlorine, bromine, cyano or Cl-C4-alkoxy-car-bonyl), C3-C6-alkenyl, C3-C6-alkinyl, Cl-C4-alkoxy, Cl-C4-alkoxy-Cl-C4-alkylamino, Cl-C4-alXylamino, di-(Cl-C4-alkyl)-amino, or represents the radical -NHoR4 where R4 represents Cl-C6-alkyl (which is optionally substituted by fluorine, chlorine, cyano, Cl-C4-alkoxy, Cl-C4-alkylthio, Cl-C4-alkylsulphinyl, Cl-C4-alkylsulphonyl, Cl-C4-alkyl-carbonyl, Cl-C4-alkoxy-carbonyl, Cl-C4-alkylamino-carbonyl or di-(Cl-C4-alkyl)-amino-carbonyl)l or repre-sents C3-C6-alkenyl (which is option-ally substituted by fluorine, chlorine or bromine), C3-C6-alkinyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-Cl-C2-alkyl, phenyl-Cl-C2-alkyl (which isoptionallysubstitutedbyfluorine, chlorine, nitro, cyano, Cl-C4-alkyl, Cl-C4-alkoxy or C~-C4-alkoxy-Le A 2~ 532 - 6 ~

' ` ' ' `
.
'~

2 ~ 3 ~

carbonyl), or represents benzhydryl, or represents phenyl (which is optionally substituted by fluorine, chlorine, nitro, cyano, Cl-C4-alkyl, trifluoromethyl, Cl-C4-alkoxy, Cl-C2-fluoroalkoxy, Cl-C4-alkylthio, trifluoromethylthio or Cl-C4-alkoxy-carbonyl), Rl and R2 furthermore represent phenyl or phenoxy, or represent Cl-C4-alkylcarbonylamino, Cl-C4-alkoxy-carbonylamino, Cl-C4-alkyl-amino-carbonylamino, di-(Cl-C4-alkyl)amino-carbonylamino or represent the radical -Co-R5 where R5 represents Cl-C6-alkyl, C1-C6-alkoxy (which is optionally substituted by fluorine, chlorine, methoxy or ethoxy), C3-C8-cycloalkoxy, C3-C6-alkenyloxy, Cl-C4-alkylkthio, amino, Cl-C4-alkylamino, Cl-C4-alkoxyamino, C~-C4-alkoxy-Cl-C4-alkyl-amino or di-(Cl-C4-alkyl)-amino :
(which are optionally substituted by fluorine and/or chlorine~, Rl and R2 furthermore represent Cl-C4-alkylsulphonyl oxy,di-(Cl-C4-alkyl)-aminosulphonylamino, or represent the radical -CH=N-R6 where Le A 27 532 _ 7 _ .. .. . . .

2 ~ 3 r~

R6 represents Cl-C6-alkyl which is option-ally substituted by fluorine, chlorine, cyano, carboxyl, Cl-C4-alkoxy, Cl-C4-alkylthio, Cl-C4-alkylsulphinyl or Cl-C4-alkylsulphonyl, or represents benzyl which is optionally substituted by fluorine or chlorine, or represents C3-C6-alkenyl or C3-C6-alkinyl, each of which is optionally substituted by fluorine or chlorine, or represents phenyl which is optionally substituted by fluorine, chlorine, bromine, Cl-C4-alkyl, Cl-C4-alkoxy, trifluoromethyl, trifluoromethoxy or trifluoromethyl-thio, or represents Cl-C6-alkoxy, C3-C6-alkenoxy, C3-C6-alkinoxy or benzyloxy each of which is optionally substituted by fluorine and/or chlorine, or repre-sents amino, Cl-C4-alkylamino, di-(C1-C4-alkyl~-amino, phenylamino, Cl-C4-alkyl-carbonyl-amino, Cl-C4-alkoxy-carbonylamino, Cl-C4-alkyl-sulphonyl-amino, or represents phenylsulphonyl-amino which is optionally substituted by fluorine, chlorine, bromine or methyl, where furthermore Le A 27 532 - 8 -, 2~3~

R represents the radical -CH ~ where R7 represents hydrogen or Cl-C4-alkyl, R8 and R9 are identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, carboxyl, Cl-C4-alkyl (which is optionally substituted by fluorine and/or chlorine), Cl~C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), Cl-C4-alkoxy-carbonyl, Cl-C4-alkylsulphonyl or di-(Cl-C4-alkyl)-amino-sulphonyl; where furthermore R represents the radical R10 ~ R11 where Rl~ and R~lare identical or different and represent hydrogen, fluorine, chlorine, bromine, nitro, cyano, Cl-C4-alkyl ~which is option-ally substituted by fluorine and/or chlorine) or Cl-C4-alkoxy (which is option-ally substituted by fluorine and/or chlorine); where furthermore Le A 27 532 - 9 -. . . ~
' ' ~ ' ~ ' ~3 -J~3 ~'J

R represents the radical ~ where ~N~

Rl2 and R13are identical or different and represent hydrogen, fluori:ne, chlorine, bromine, nitro, cyano, Cl-C4-alkyl (which is option-ally substitutecl by fluorine and/or chlorine) or C2-C4-alkenyl (which is optionally substitu~ed by fluorine and/or chlorine), Cl-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine)~ or represent Cl-C4-alkylthio, Cl-C4-alkylsulphinyl or Cl-C4-alkylsulphonyl (which are optionally substituted by fluorine and/or chlorine), and represent di-(Cl-C4-alkyl)-aminosulphonyl, Cl~C4-alkoxy-carbonyl, dimethylaminocarbonyl or dioxolanyl; where furthermore R represents the radical R1 4~R15 where Rl4 and R15are identical or different and represent hydrogen, fluorine, chlorine, bromine, Cl C4-alkyl (which is optionally substitu-ted by fluorine and/or bromine), C1-C4-alkoxy (which is optionally substi~uted by fluorine and/or chlorine), or represent Le A 27 532 - 10 - :

- ~ :
.

.
- : - . . .
. .. . ~, . - : -.

2~r~3~i C1-C4-alkylthio, Cl-C4-alkylsulphinyl or C1-C4-alkylsulphonyl (which are optionally substituted by fluorine and/or chlorine), or represents di-tCl-C~-alkyl)-amino-sulphonyl; where furthermore R represents the radical ~ ~ ~1 ? where .

Rl5 and R17are identical or different and represent hydroqen, fluorine, c~lorine, bromine, cyano, nitro, Cl-C4-alkyl (which is option-ally substituted by fluorine, chlorine, Cl-C4-alkoxy and~or Cl-C4-halogenoalkoxy), Cl-C4-alkoxy (which is optionally sub-stituted by fluorine and/or chlorine), Cl-C4-alkylthio, Cl-C4-alkylsulphinyl or Cl-C4-alkylsulphonyl (which is optional.ly substituted by fluorine and/or chlorine~, di-(Cl-C4-alkyl)-amino-sulphonyl or C,-C4-alkoxy-carbonyl, and Al represents oxygen, sulphur or the group N-Z1, where zl represents hydrogen, Cl-C4-alkyl (which is optionally substituted by fluorin~, chlorine, bromine or cyano), C3-C6-cyclo-alkyl, benzyl, phenyl ~which is optionally:

Le A 2~ 532 - 11 -:. ' ' - ~ . ....................... ' : .

- :

2~37~

substituted by fluorine, chlorine, bromine or nitro), Cl-C4-alkylcarbonyl, C1-C4-alkoxy-carbonyl or di-(Cl-C4-alkyl)-amino-carbonyl; where furthermore R represents the radical ~ ~ ~ Rl9 where Rl8 and Rl9are identical or different and represent hydrogen, C,-C4-alkyl, halogen, Cl-C4-alkoxycarbonyl, Cl-C4-alkoxy or Cl-C4-halogenoalkoxy, yl represents sulphur or the group N-R20 where R20 represents hydrogen or Cl-C4-alkyl; where furthermore R represents the radical ~ . where ~7 RZ2 R2l represents hydrogen, Cl-C4-alkyl, phenyl or (iso)quinolinyl, R22 represen~s hydrogen, halogen, cyano, nitro, Cl C4-alkyl (which is optionally substituted by Le A 27 532 - 12 -.
: --~. . : . . , :

2 ~ 3 ~

fluorine and/or chlorine), Cl-C4-alkoxy (which is optionally subs~ituted by fluorine and/or chlo-rine), dioxolanyl or Cl-L'4-alkoxy-carbonyl and R23 represents hydrogen, halogen or Cl-C4-alXyl; where S furthermore R represents the radical ~ ~ R24 where N~S

R24 represents hydrogen, halogen, Cl-C4-alkyl or C1-C4-alko~y-carbonyl; where furthermore R represents the radical ~ 2 where R260~ N-R
R25 represents Cl-C4-alkyl and R26 represents Cl-C4-alkyl, where furthermore ~}
R represents the radical ~ ~ where ~27 R27 represents hydrogen or methyl;
in which furthermore Le A 27 532 - 13 -, :. :. - .:

$

X represents hydrogen, halogen, Cl-C4-alkyl, Cl-C4-halogenoalkyl, C1-C2-alkoxy-C1-C2-alkYl, c1-C4-~lkoxy or C1-C4-halogenoalkoxy, Y represents halogen, Cl-C4-alkyl, Cl-C4-halogenoalkyl, C~-C2-alkoxy-Cl-C2-alkyl, Cl--C4-alkoxy, or Cl-C4-halo-genoalkoxy and Z represents hydrogen, halogen, Cl-C4-alkyl, Cl-C4-halogenoalkyl, Cl-C4-alkoxy or Cl-C4-halogenoalkoxy.

-The invention furthermore preferably relates to salts of compounds of the formula (I) ~) with protonic acids such as, for example, hydro-chloric acid, sulphuric acid, phosphoric acid, methanesulphonic acid, benzene- or p-toluenesulpho-nic acid, or naphthalene mono- or -di-sulphonic acids, or ~) with bases such as, for example, the hydroxides, hydrides, amides or carbonates of sodium, potassium or calcium, or sodium Cl-C4-alkanolates or potassium C1-C4 alkanolates, ammonia, C1-C4-alkylamines, di-(C1-C4-alkyl)-amines or tri-(C1-C4-alkyl)-amines.

In particular, the invention relates to compounds of the formula (I) in which Le A 27 532 - 14 -2 ~ 3 ~

R represents the radical ~ where Rl represents hydrogen, fluurine, chlorine, bromine, cyano, nitro, carbogyl, methyl, trifluoromethyl, methoxyr ethoxy, difluoromethoxy, trifluorometh-oxy, Cl-C3-alXylthio, Cl-C3-alkylsulphinyl, Cl-C3-alkylsulphonyl, dimethylaminosulphonyl diethyl-aminosulphonyl, N-methoxy-N-methylaminosulphonyl, phenyl, phenoxy or Cl-C3-alkoxy-carbonyl and R2 represents hydrogen, fluorine, chlorine, bromine, methyl, trifluoromethyl or methoxy; where fur-thermore R represents the radical -IH ~ where R7 represents hydrogen, Ra represents fluorine, chlorine, bromine, cyano, carboxyl, methyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, methylsulphonyl or dimethylaminosulphonyl and R9 represents hydrogen, fluorine or chlorine; where Le A 27 532 - 15 -.

furtherm~re R represents the radical R12 ~ where Rl2 represents dimethylaminocarbonyl or c,-C4-alkyl~
sulphonyl and Rl3 represents hydrogen, fluorine or chlorine;
where ~urthermore ~ _, R represencs the radic~l R280_ ~ s~ where R23 represents methyl or ethyl, or R R represents the radical RZ 90 - c ~ where N-N
~3 R29 represents methyl or ethyl, :~
in which furthermore X represents hydrogen, fluorine, chlorine, bromine, Le A 27 532 - 16 -2~7~ 3~i methyl, ethyl, trifluoromethyl, methoxymethyl, methoxy, ethoxy or difluoromethoxy, Y represent~ fluorine, chlorine, bromine, methyl, ethyl, fluoromethyl, chloromethyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl,fluorodichloromethyl,methoxy, ethoxy, difluoromethoxy or trifluoromethoxy and Z xepresents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy or difluoromethoxy.

Very particularly preferred are compounds of the formula (I) are those in which R has the meaning given above as being particularly preferred, X represents hydrogen, Y represents methoxy or methyl and Z represents hydrogen.

If, for example, 2-fluoro-benzenesulphonyl chloride and 5-methoxy-pyrimidine-2-carboxamide are used as starting substances in process (a) according to the invention, the course of the reaction can be outlined by the following equation;

e A 27 532 - 17 -'~

3 ~1 ~52 Cl , N CH3 /~< N =~
-HCl ~S02-NH-CO--~ ~OCH3 If, for example, 2-trifluoromethoxy-benzylsulphonamide and methyl 4,5,6-trimethyl-pyrLmidine-2-carboxylate are used as starting substances in process (b) according to the invention, the cours~ of the reaction can be outlined by the following equation:
OCF3 ~ CH3 -502-N~2 t 113C-O-CO~ ~CH~

-HOCH3 ~H2-S02-NH-CO~H3 Formula tII) provides a general definition of the pyrimi-dine carboxamides to be used a~ starting substances in process (a) according to the invention for the preparation of compounds of the formula (I).

In formula (II), X, Y and Z preferably, or in particular, have those meanings which have already bPen mentioned above in connection with the description of the compounds of the formula (I) according to the invention as being Le A 27 532 - 18 -~- .

3 1:~

preferred, or particularly preferred, for ~, Y and Z.

Examples of the ~tarting substances of the formula (II) which may be mentioned are:
5-fluoro-, 5-chloro-, 5-bromo-, S-methyl-, 5-ethyl-, 5-methoxy- and 5-ethoxy-pyrimidine-2-carboxamide, and 5-fluoro-4,6-dimethyl-, 5-chloro-4,6-dime~hyl-, 5-bromo-4,6-dimethyl- and 4,5,6-trimethyl-pyrimidine-2-carbox-amide.

The starting substances of the formula (II) are known and/or can be prepared by processes known per se ~cf.
British Patent Specification 777,465; Compt. Rend. 248 (1959), 250-252 - cited in Chem. Abstracts 53, 18049i;
Ann. Chim. (Paris) 5 (1960), 351-379 - cited in Chem.
Abstracts 56, 5961g; Collect. C~ech. Chem. Commun. 37 (1972), 1721-1733 - cited in Chem. Abstracts 77, 101522s;
Org. React. (Tartu) 20 (1983), 85-95 - cited in Chem.
Abstracts 99, 157694w).

Formula (III) provides a general definition of the sulphonyl halides or sulphonic anhydrides furthermore to be used as starting substances in process (a) according to the invention for the prepara~ion of the new compounds of the formula (I). In formula (III), R preferably, or in particular, has the meaning which has been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as being preferred, or particularly preferred, for R, and Q
preferably represents chlorine.

Le A 2? 532 - 19 -:

Examples of starting substances of the formula (III) which may be mentioned are:
benzenesulphonyl chloride, 2-chloro-, 3-chloro-, 4-chloro-, 2,5-dichloro-, 2-fluoxo-, 4-fluoro-, 2-bromo-, 4-bromo-, 2-cyano-, 2-nitro-, 4-nitro-, 2-methyl-, 4-methyl-, 2-chloroemthyl-, 2-tri~luoromethyl-, 2-meth-oxy-, 4-methoxy-, 2-methylthio-, 2-trifluoromethylthio-, 2-difluoromethylthio_,2-cyclopropyloxycarbonyl-,2-phen-oxy-, 2-difluoromethoxy-, 2-trifluorome~hoxy-, 2-(2-chloroethoxy)-~ 2-methylthiomethyl-, 2-dimethylamino-sulphonyl-, 2-phenyl-, 2-methoxycarbonyl-, 2-ethoxy-carbonyl-, 2-dimethylaminocarbonyl-lphonyl-, carbonyl-ben~enesulphonyl chloride and (2-chloro-phenyl)-, (2-cyano-phenyl)-, (2-methoxycarbonyl-phenyl)- and (2-trifluoromethoxy-phenyl)-methanesulphonyl chloride, 2-chloro-6-methyl-benzenesulphonyl chloride and 2,6-dichloro-benzenesulphonyl chloride.

The sulphonyl halides or sulphonic anhydrides of the formula (III) are known and/or can be prepared by pro-cesses known per se (cf. J. Org. Chem. 33 (1968), 2104;
J. Org. Chem. 25 (1960), 1824; DE-AS (Germar Published Specification) 2,308,262; EP-OS (European Published Specifications) 23,140, 23,141, 23,422, 35,893, 48,143, 51,466, 64,322, 70,041, 44,808 and 44,809; VS Patent Specifications 2,929,820, 4,282,242; 4,348,220 and 4,372,778, and Angew. Chem. 93 (1981), 151).

Process (a) according ~o the invention for the prepara-tionof the new compounds of the formula (I) is preferably Le A 27 532 - 20 -- .

. ~

' ,. ~ '- -.. ,: , , .
' carried out using diluents. Diluents which are suitable for this purpose are virtually all inert organic sol-Yents. These preferably include 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 and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, esters such as methyl acetate and ethyl acetate, nitriles such as, for example, acetonitrile and propionitrile, amides such as, for example, dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone, and also dimethyl sulphoxide, tetramethylene sulphone and hexamethylphosphoric triamide and pyridine.

Acid acceptors which can be employed in process (a) according to the invention are all acid-binding agents which can customarily be employed for reactions of this type. The following are preferably suitable: alkali metal hydroxides such as, for example, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as, for example, calcium hydroxide, 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 alkali metal alcoholates such as sodium carbonate, Le A 27 532 - 21 -3 !~i potassium carbonate, sodium tert.-butylate, potassium tert.-butylate, furthermore aliphatic, aromatic or heterocyclic amines, for example triethylaminel tri-methylamine, dimethylaniline, dimethylbenzylamine, pyridine, picoline, 1,5-diazabicyclo-[4.3.0~-non-5-ene (DBN), 1,8-diazabicyclo-[5.4.0]-undec-7-ene (D~U) and 1,4-diazabicyclo-[2.2.2]-octane (DABCO).

When carrying out process (a) according to the invention, the reaction temperatures can be varied within a substan-tial range. In general, the process is carried out at temperatures between -20C and ~100C, preferably at temperatures between O~C and +80C.

For carrying out process (a) according to the invention, between 1 and 5 moles, preferably between 1 and 3 moles, of sulphonyl halide or sulphonic ~nhydride of the formula (III) are generally employed per mole of pyrimidine-carboxamide of the formula (II).

The reactants can be combined in any desired sequence.
In a preferred embodiment of process (a) according to the invention, a starting compound of the formula (II) and an acid acceptor are stirred with a diluent, and a starting compound of the formula (III) is slowly metered into this mixture (if appropriate in portions). The reaction mixture is then stirred until the reaction is complete.

Working-up can be carried out by customary methods (cf.
the Preparation Examples).

Le A 27 532 - 22 -'~

~3~ 3 Formula (IV) provides a general definition of the pyrimi-dinecarboxylic acids to be used as starting substances in process (b) according to the invention for the prepara-tion of compounds of the formula (I).

In formula (IV), X, Y and Z preferably, or in particular, ha~e those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as being preferred, or as being particularly preferred, for X, Y
and Z.

Examples of the starting substances of the formula (IV) which may be mentioned are:

5-fluoro-, 5-chloro-, 5-bromo-, 5-methyl-, 5-ethyl-, 5-methoxy- and 5-ethoxy-pyrimidine-2-carboxylic acid, and also 5-fluoro-4,6-dimethyl-, 5-chloro-4,6-dimethyl-, 5-bromo-4,6-dimethyl- and 4,5,6-trimethyl-pyrimidine-2-carboxylic acid.

The starting substances of the formula (IV) are known and/or can be prepared by process known per se (cf.
British Patent Specification 777,465; Compt. Rend~ 248 (1959), 250-252 - cited in Chem. Abstracts 53, 18049i;
Ann. Chim. (Paris) 5 (1960), 351-379 - cited in Chem.
Abstracts 56, 5961g; Collect. Czech. Chem. Commun. 37 (1972), 1721-1733 - cited in Chem. Abstracts 77, 101522s;
Org. React. (Tartu) 20 (1983), 85-95 - cited in Chem.
Abstracts 99, 157694w; Chem. Pharm. Bull. 28 (1980), 1408-1414 - cited in Chem. Abstracts 94, 47251p).

Le A 27 532 - 23 -2 ~ . 3 ~

In process (b) according to the ;Lnvention, the carboxylic acid chlorides or alkyl esters (preferably methyl esters or ethyl esters), aralkyl esters (preferably benzyl ester) or aryl esters (preferably phenyl esters, option-ally substituted in the phenyl group by cyano, nitro,chlorine, fluorine, bromine and/or methyl) which are derived from the pyrLmidinecarboxylic acids of the formula (IV) are optionally employed as starting substan-ces ("reactive derivatives") in place of these pyrimi-dinecarboxylic acids.

The carboxylic acid chlorides which are derived from th~compounds of the formula ~IV) are obtained from the corresponding carboxylic acids by customary methods, for example by rea~tion with acid chlorides which are custo-marily used as ~chlorination agents" such as, forexample, phosgene, oxalyl chloride or thionyl chloride, if appropriate in the presence of reaction auxiliaries such as, for example, pyridine, and if appropriate in the presence of diluents such as, for example, chloroform or tetrachloromethane, at temperatures between 0C and 100C.

The esters, which are furthermore mentioned as reactive derivatives of the compounds of the formula (IV), can be obtained from the corresponding carboxylic acid chlorides and suitable alcohols or phenol~ using customary methods, in general by reaction in the presence of an acid accep-tor such as, for example, triethylamine or pyridine, and in the presence of a diluent such as, for example, Le A 27 532 - 24 -2 ~ 3 ii.~

acetonitrile, at ~emperatures between 0C and 100C.

However, the abovementioned esters can also be obtained directly from the carboxylic acids of the formula (IV) in the presence of condensation auxiliaries such as, for example, dicyclohexylcarbodiimicle, if appropriate in the presence of reaction auxiliaries such as, for example, 4-dimethylamino-pyridine, and if appropriate in the presence of diluents such as, for example, methylene chloride or chloroform, at temperatures between 0C and 100C.

Formula (V) provides a general definition of the sul-phonamides furthermore to be used as starting substances in process (b) according to the invention for the pre-paration of compounds of the formula (I).

In formula (V) R preferably, or in particular, has the meaning which has already been mentioned above in connec-tion with the description of the compounds of the formula (I) according to the invention as being preferred, or as being particularly preferred, for R.

Examples of the starting substances of the formula (V) which may be mentioned are:
benzenesulphonamide, 2-chloro-, 3-chloro-. 4-chloro-, 2,5-chloro-, 2-fluoro-, 4-fluoro-, 2-bromo-, 4-bromo, 2-cyano-, 2-nitro-, 4-nitro-, 2-methyl-, 4-methyl-, 2-chloromethyl-, 2-trifluoromethyl-, 2-methoxy-, 4-methoxy-, 2-methylthio-, 2-trifluoromethylthio-, Le A 27 532 - 25 -, 2 ~ ?~

2-difluoromethylthio-, 2-cyclopropyloxycarbonyl-, 2-phenoxy-, 2-difluoromethoxy-, 2-~rifluoromethoxy-, 2-(2-chloroethoxy)-, 2-methylt!hiomethyl-, 2-dimethyl~
aminosulphonyl-, 2-phenyl-, 2-mel;hoxycarbonyl-, 2-ethoxy-carbonyl-, 2-dimethylaminocarbonyl- and 2-diethylamino-carbonyl-benzenesulphonamide, and also (2-chloro-phenyl)-, (2-cyano-phenyl)-, (2-methoxycarbonyl-phenyl)- and (2-trifluoromethoxy-phenyl)--methanesulphonamide, 2-chloro-6-methyl-benzenesulphonyl chloride and 2,6-dichloro-benzenesulphonamide.

The sulphonamides of the formula (V) are known and/or can be prepared by processes known per se (cf. J. Org. Chem.
33 (1968), 2104; J. Org. Chem. 25 (1960), 1824; DE-AS
(German Published Specification) 2,308,262; EP-A 23,140, 23,141, 23,422, 35,893, 48,143, 51,466, 64,322, 70,041, 44,808 and 44,809; US Patent Specifications 2,929,820, 4,282,242; 4,348,220 and 4,372,778, and Angew. Chem. 93 (1981), 151).

In process (b) accordi.ny to the invention, the sulphonyl isocyanates which are derived from the sulphon2mides of the formula (V) ("reactive derivatives") are optionally employed as starting substances in place of these sul-phonamides. These compounds are known and/or can be prepared by processes known per se (cf. J. Org. Chem. 31 (1966), 2658-2661; EP-A 7,687; EP-A 46,626; EP-A 21,641;
EP-A 23,140; EP-A 23,141; EP-A 70,041; EP-A 23,422;
EP-A 64,322; EP-A 34,431; EP-A 35,893; EP-A 51,466;
EP-A 44,808; EP-A 173,312; DE-OS (German Published Le_A 27 532 - 26 -: .. . . ..
-: ' 31l~

Specification~ 3,132,944; EP-A ~7,780; EP-A 271,780~.

Process (b) according to the invention for the prepara-tion of the new compounds of the formula (I) is pre-ferably carried ou~ using diluents. Diluents which are suitable for this purpose are preferably the same diluents which are mentioned above in the case of process (a) according to the invention.

If appropriate, process (b) according to the invention~is car~ied out in the presence of a reaction auxiliary.
Suitable reaction auxiliaries for this purpose are compounds with which carboxylic acids are converted into reactive intermediates which are then reacted in situ with nucleophilic compounds such as, for example, the sulphonamides of the formula (V), to give corresponding carboxylic acid derivatives. Examples of reaction auxili-aries of this type which may be mentioned are carbonyl diimidazole and 2-chloro-1-methyl-pyridinium iodide.

Other suitable reaction auxiliaries for the reaction of the esters and carboxylic acid chlorides mentioned as reactive derivatives of compounds of the formula (IV) with sulphonamides of the formula (V) are acid acceptors as they are mentioned above in the case of process (a) according to the invention.

When carrying out process (b) according to the invention, the reaction temperatures can be varied within a substan-tial range. In general, the process is carried out at Le A 27 532 - 27 -:- ' .' . " : . :

temperatures between O~C and 150~, preferably at tem-peratures between 10C and 100C.

Process (b) according to the invention is generally carried out under atmospheric pressure. However, it is also possible to carry out the process under increased or reduced pressure.

For carrying out process (b) according to the invention, the starting substances required in each case are generally employed in approximately equimolar amounts.
However, it is also possible to use one of the two components employed in each case in a larger excess. In general, the reactions are carried out in a suitable diluent, if appropriate in the presence of a reaction auxiliary, and the reaction mixture is stirred for several hours at the particular temperature required.
Working-up in process (b~ according to the invention is carried out in each case by customary methods (cf. the Preparation Examples).

If appropriate, salts can be prepared from the compounds of the general formula (I) according to the invention.
Such salts are obtained in a simple manner by customary salt formation methods, for example by dissolving or dispersing a compound of the formula (I) in a suitable solvent such as, for example, water, methanol, ethanol, methylene chloride or acetone, and adding a suitable acid or base. The salts can then be isolated by concentration or filtration with suction, if appropriate after pro-Le A 27 532 - 28 -- - - ~ ' , :
- ~ .
-: ' ':
. -.

2 ~

longed stirring.

The active compounds according to the invention can beused as defoliants, desiccants, agents for destroying broad-leaved plants and, especially, as weed-killers. By weeds, in the broadest sense, ~here are ~o be understood all plants which grow in locations where they are undesired. Whether the substances according to the inven-tion act as total or selective herbicides depends essen-tially on the ~mount 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, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, ~amium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.

Dicotyledon cultures of the qenera: Gossypium, Glycine, Beta, Daucusl Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Le A 27 532 - 29 -2 ~

Panicum, Digitaria, PhleumJ Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, A~ena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocot~ledon cultures of the qenera: Oryza, Zea, Triticum~ Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.

However, the use of th~ active compounds according 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 concentra-tion, for the- total combating of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed ~or combating weeds in peren-nial 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, on lawns, turf and pasture-land, and for the selective combating of weeds in annual cultures.

The compounds according to the invention are very suit-able for selectively combating monocotyledon and dicoty-ledon weeds in monocotyledon and diootyledon crops, both Le A 27 532 - 30 --. : :-2 ~ 3 ~

pre- and post-emergence.

The active compounds can be converted into the customary formulations, such as solutio:ns, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, sus;pension-emulsion concen-trates, 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 r that is liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that is emulsi-fying agents and/or dispersing agents and/or foam-formins agents.

In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary 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, chloro-ethylenes 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 sol-vents, such as dimethylformamide and dimethyl sulphoxide, Le A 27 532 - 31 -', ' ' ' ~. .
- ' . .:
- , , 2~7:~3~

as well as water.

As solid carriers there are suitable:
for example ammonium salts and ~round natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground syn-thetic minerals, such as highly disperse silica, alumina and silicates, as solid carriers for granules there are suitable: for example crushed and frac~ionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of or~anic material such as sawdust, coconut shells, maize cobs and tobacco stalks;
as emulsifying and/or foam-forming agents ~here are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethy-lene fatty alcohol ethers, for example alkylaryl poly-glycol ethers, alkylsulphonates, alkyl sulphates, aryl-sulphonates as well as albumen hydrolysis products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural andsynthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and s~nthetic phospholipids, can be used in the formulations. Further additives can be mineral and vegetable oils.

Le A 27 532 - 32 -.
. . :
.

21~3rl ~

It is possible to use colorants such as inorganic pig-ments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dye-stuffs, 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 90%.

For combating weeds, the active compounds according to the invention, as such or in the form of their formula-tions, can also be used as mixtures with known herbi-cides, finished formulations or tank mixes being possible.

Suitable herbicides for the mixtures are known herbi-cides, such as, for example, 1-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4(lH,3H)-dione (AMETHY-DIONE) or N-(2-benzothiazolyl)-N,N'-dimethylurea (META-BENZTHIAZURON) for combating weeds in cereals; 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one (METAMITRON) for combating weeds in sugar beet and 4-amino-6-(l,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one (METRIBVZIN) for combating weeds in soya beans, further-more also 2,4-dichlorophenoxyacetic acid (2,4-D); 4-(2,4-dichlorophenoxy)-butric acid (2,4-DB); 2,4-dichloro-phenoxypropion~c acid (2,4-DP); 5-(2-chloro-4-trifluoro-methyl-phenoxy)-2-nitro-benzoic acid (ACIFLUORFEN);

Le A 27 532 - 33 -` ~ , . ' 2 ~ 3 2-chloro-2',6'-diethyl-N-methoxy-methylacetanilide (ALACHLOR); methyl-6,6-dimethyl-2,4-dioxo-3-[1-(2-propenyloxyamino)-butylidene]-cyclohexanecarboxylic acid (ALLOXYDIM); 4-amino-benzenesu:lphonyl methylcarbamate (ASULAM); 2-chloro-4-e~hylamino-6-isopropylamino-1,3,5-triazine (ATRAZINE); methyl 2-[[[[[(4,6-dLmethoxypyrimi-dine-2-yl)-amino]-carbonyl]-ami.no]-sulphonyl]-methyl]-benzoate (BENSULFURON); 3-isopropyl-2,1,3-benzo-thiadiazin-4-one 2,2-dioxide (BENTA20NE); methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate (BIFENOX); 3,5-dibromo-4-hydroxy-benzonitril; (BROMOXYNIL); N-(butoxymethyl)-2-chloro-N-(2,6-diethylphenyl)-acetamide (BUTACHLOR);
5-amino-4-chloro-2-phenyl-2,3-dihydro-3-oxypyridazine (CHLORIDAZONE);ethyl2-{[(4-chloro-6-methoxy-2-pyrimidi-nyl)-aminocarbonyl]-aminosulphonyl}-benzoate (CHLORI-MURON); N-(3-chlorophenyl)-isopropyl carbamate (CHLOR-PROPHAM); 2-chloro-N-{[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl}-benzenesulphonamide (CHLOR-SULFURON); N,N-dimethyl-N'-(3-chloro-4-methylphenyl)-urea (CHLORTOLURON); exo-l-methyl-4-(1-methylethyl)-2-t2-methylphenyl-methoxy)-7-oxabicyclo-(2~2/l)-heptane (CINMETHYLIN); 3,6-dichloro-2-pyridinecarboxylic acid (CLOPYRALID); 2-chloro-4-ethylamino-6-(3-cyanopropyl-amino)-1,3,5-triazine (CYANAZINE); N,S-diethyl N-cyclo-hexylthiocarbamate (CYCLOATE); 2-[1-(ethoximino)-butyl]-3-hydroxy-5-[tetrahydro-(2H)-thiopyran-3-yl]-2-cyclo-hexen-l-one (CYCLOXYDIM); 2-[4-(2,4-dichlorophenoxy)-phenoxy]-propionic acid, its methyl ester or its ethyl ester (DICLOFOP); 2-[(2-chlorophenyl)-methyl]-4,4-di-methylisoxazolidin-3-one (DIMETHAZONE); S-ethyl N,N-di-Le A 27 532 - 34 -2 ~ $

n-propyl-thiocarbamidate (EPTAME); 4-amino-6-t-butyl-3-ethylthio~ ,4-triazin-5(4H)-one (ETHIOZIN); 2-{~-[(6-chloro-2-benzoxazolyl)-oxy]-phenoxy}-propanoic acid, its methyl ester or its ethyl ester (FENOXAPROP); 2-[4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy]-propanoic acid or its butyl ester (~LUAZIFOP); N,N-dimethyl-N~-(3-tri-fluoromethylphenyl)-urea (FL~OMETURON); l-methyl-3-phenyl-5-(3-trifluoromethylphenyl)-4-pyridone (FLURI-DONE); [(~-amino-3,5-dichloro-6-fluoro-2-pyridinyl)-oxy]-acetic acid or its l-methylheptyl ester (FLUROXYPYR); 5-(2-chloro-4-trifluoromethyl-phenoxy)-N-methylsulphonyl-2-nitrobenzamide (FOMESAFEN); 2-{4-[(3-chloro-5-(tri-fluoromethyl)-2-pyridinyl)-oxy]-phenoxy} propanoic acid or its ethyl ester (HALOXYFOP); 3-cyclohexy1-6-dimethyl-amino-1-methyl-1,3,5-triazin-2,4-dione (HEXAZINONE);
methyl 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-lH-imidazol-2-yl]-4(5)-methylbenzoate (IMAZAMETHABENZ);
2-[5-methyl-5-(1-methylethyl)-~-oxo-2-imidazolin-2-yl]-3-quinolinecarboxylic acid (IMAZAQUIN); 2-[4,5-dihydro-4-methyl-4-isopropyl-5-oxo-(lH)-imidazol-2-yl]-5-ethyl-pyridin-3-carboxylic acid (IMAZETHAPYR); 3,5-diiodo-4-hydroxybenzonitril (IOXYNIL); N,N-dimethyl-N'-(4-iso-propylphenyl)-urea (ISOPROTURON); (2-ethoxy-1-methyl-2-oxo-ethyl 5-t2-chloro-4-(trifluoromethyl)-phenoxy]-2-nitrobenzoate (LACTOFEN); (2-methyl-4-chlorophenoxy)-acetic acid (MCPA); (4-chloro-2-methylphenoxy)-propioni~
acid (MCPP); N-methyl-2-(1,3-benzothiazol-2-yloxy)-acetanilide(MEFENACET);2-chloro-N-(2,6-dimethylphenyl)-N-~(lH)-pyrazol-1-yl-methyl]-acetamide (METAZA~HIOR); 2-ethyl-6-methyl-N-(l-methyl-2-methoxyethyl)-chloro-Le A 27 532 - 35 -S'id rJ ~

acetanilide (METOLACHLOR); 2--{[[((4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino)-carbonyl]-amino]-sulphonyl}-benzoic acid or its methyl ester (METSULFURON); S-ethyl N,N-hexamethylenethiocarbamate (MOLIN~TE); 1-(3-tri-fluoromethyl-phenyl)-4-methylamino-5-chloro-6-pyridazone (NORFLURA3ON); 4-(di-n-propylamino)-3,5-dinitrobenzene-sulphonamide(ORYZALIN);2-chloro-4-trifluoromethylphenyl 3-ethoxy-4-nitro-phenyl ether (OXYFLUORFÆN); N-(l-ethyl-propyl)-3,4-dimethyl-2,6-dinitroaniline (PENDIMETHALIN), 3-(ethoxycarbonylaminophenyl) N-(3'-methylphenyl)-car-bamate (PHENMEDIPHAM); 2-chloro-N-isopropylacetanilide (PROPACHLOR); isopropyl N-phenyl-carbamate (PROPHAM);
O-(6-chloro-3-phenyl-pyridazin-4-yl) S-octyl thiocar-bonate (PYRIDATE); ethyl 2-[4-(6-chloro-quinoxalin-2-yl-oxy)-phenoxy]-propionate (QUIZALOFOP-ETHYL); 2-[1-(ethoxamino)-butylidene]-5-(2-ethylthiopropyl)-1,3-cyclohexadione (SETHOXYDIM); 2-chloro-4,6-bis-(ethyl-amino)-1,3,5-triazine(SIMAZINE);2,4 bis-[N-ethylamino]-6~methylthio-1,3,5-triazine (SIMETRYNE); 4-ethylamino-2-t-butylamino-6-methylthio-s-triazine(TERBUTRYNE);methyl 3-~[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl]-amino]-sulphonyl]-thiophene-2-carboxylate (THIANETURON); S-[(4-chlorophenyl)-methyl]- N,N-diethyl-thiocarbamate (THIOBENCARB); S-(2,3,3-trichloroallyl) N,N-diisopropylthiocarbamate (TRI-ALLATE); 2,6-dinitro-4-trifluoromethyl-N,N-dipropylaniline (TRIFLURALIN).
Surprisingly, some mixtures also show a synergistic action.

Mixtures with other known active compounds, such as Le A 27 532 - 36 -2 ~?~

fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, are also possible.

The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by fuxther dilution~ such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules.
They ar~ used in the customary mannerr for example by watering, spraying, atomizing 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 lS substantial range. It depends essentially on the nature of the desired effect. In general r the amounts used are between 0.1 g and 2,000 g of active compound per hectare of soil surface, preferably between 1 g and 1,000 g per ha.

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

Le A 27 532 - 37 -: ~ .
:

2 ~

Preparation Examples:

Example 1 ~ O2-NH-C ~ ~ C~3 (Process (a)) A mixture of 3.1 g (0.02 mol) of 5-methoxy-pyrimidine-2-carboxamide, 3.4 g (0.06 mol) of potassium hydroxide (powder) and 50 ml of dioxane is heated to 80C And stirred at this temperature for 10 minutes. The mixture is cooled to 20C, and 10.4 g (0.04 mol) of 2-trifluoro-methoxy-benzenesulphonyl chloride are then added, and the reaction mixture is stirred for 20 hours at 20C. It is then concentrated, the residue is stirred with 100 ml of 10% strength potassium carbonate solution, the mixture is filtered, and the filtrate is acidified with 2N hydro-chloric acid. The product which is separated in oil form is taken up in methylene chloride, and this solution is dried with sodium sulphate and filtered. The filtrate is concentrated, the residue is triturated with diethyl ether, and the product which is obtained in crystalline form during this process is isolated by filtration with suction.

O.7 g (9~ of theory) of N-(2-trifluoromethoxyphenyl-sulphonyl)-5-methoxy-pyrimidine-2-carboxamide of melting point 187C is obtained.

Le A 27 532 - 38 -. ::
' ' .

,, .

- . - - , ~ .
.. . . .

Example 2 ~ SO2-NH-C ~ ~ ~3 (Process (b)) A mixture of 1.46 g (6.8 mmol) of phenyl 5-methyl-pyrimidine-2-carboxylate, 1.64 g (6.8 mmol) of 2-tri-fluoromethoxy-benzenesulphonamide, 1.04 g (6.8 mmol) of 1,8-diazabicyclo-t5,4,0]-undec-7-ene (DBU) and 40 ml of acetonitrile is stirred for 7 hours at 70C and sub-sequently concentrated. The residue is stirred with 2N
hydrochloric acid, and the product which has remained undissolved is isolated by filtration with suction.

1.74 g (71% of theory) of N-(2-trifluoromethoxy-phenyl-sulphonyl)-5-methyl-pyrimidine-2-carboxamide of melting point 123C are obtained.

Other examples of the compounds of the formula (I) which can be prepared analogously to Examples 1 and 2 and following the general description of the preparation processes according to the invention are listed in Table 1 below.

Le A 27 532 - 39 -2 ~ 'J~ ~ ~

R 502-N~-Co~ ~r ( I ) z Table 1: Examples of the compounds of the formula ( I ) Ex. R X Y z Melting No. point ( ~) . .
502NtCH3)2 3 ~ H OCH3 H 226 4 ~ H CH3 H 141 6 ~ CH3 CH3 CH3 130 7 ~ H OCH3 H 106 Le A 27 532 - 4D -:: . ... ~ .. .
- ` . `

2 ~ 3 ~

Example for the preparation of startinq substances:

/~=~\ N=c~
~ -C~-~ ~ H3 4 g (0.029 mol) of 5-methyl-pyr:Lmidine-2-carboxylic acid and 3 g (0.032 mol) of phenol ar~ initially introduced into 50 ml of methylene chloride, and 0.36 g (0.003 mol) of 4-dimethylamino-pyridine and 6.67 g (0.032 mol) of N,N'-dicyclohexylcarbodiimide are added in succession.
The reaction mixture is stirred for 12 hours at room temperature and filtered. The filtrate is washed with 5%
strength acetic acid and water, the organic phase is separated off, dried over sodium sulphate and filtered, and the filtrate is concentrated.

3.5 g (56% of theory) of phenyl 5-methylpyrimidine-2-carboxylate remain as a solid of melting point 115C.

Le A 27 532 - 41 - ~-- .

Use Examples:
In the use examples, the compounds tA) and (B) listed below are used as comparison substances:

SO2-NH-CO ~ ~ (A) CH~
N-(2-Methoxy-phenylsulphonyl)-4,6-dimethyl-pyrimidine-2-carboxamide (disclosed in EP-A 353,640) Cl OCH3 r==~N ~
sO2-NH-C~~~ ~ (B) N-(2-Chloro-phenylsulphonyl)-4,6-dimethoxy-pyrimidine-2-carboxamide (disclosed in EP-A 353,640).

Le A 27 532 - 42 -s~

Example A

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 1,000 1 of water/ha.
After three 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 In this test, a clearly superior activity compared with the prior art is shown, for example, by the compounds of Preparation Examples 1 and 3.

Le A_27 532 - 43 -, ;- .,, - - ~

~ ~v ~

Example B

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 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 being decisive. After three 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 In this test, a clearly superior activity compared with the prior art is shown, for example, by the compound of Preparation ~xample 1.

Le A 27 532 - 44 -

Claims (23)

1. A sulphonylated pyrimidine carboxamide of the formula (I) in which R represents in each case optionally substituted aryl, aralkyl or heteroaryl, X represents hydrogen, halogen, alkyl, halogeno-alkyl, alkoxyalkyl, alkoxy or halogenoalkoxy, Y represents halogen, alkyl, halogenoalkyl, alkoxy-alkyl, alkoxy or halogenoalkoxy,and Z represents hydrogen, halogen, alkyl, halogeno-alkyl, alkoxy or halogenoalkoxy, or a salt thereof.

2. A sulphonylated pyrimidine carboxamide or salt thereof according to claim 1, in which Le A 27 532 _ 45 _ R is the radical where R1 and R2 are identical or different and are hydrogen, fluorine, -chlorine, bromine, iodine, cyano, nitro, car-boxyl, C1-C6-alkyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C4-alkoxy-carbonyl, C1-C6-alkylamino-carbonyl, di-(C1-C4-alkyl)-amino-carbonyl, hydroxyl, C1-C4-alkoxy, formyloxy, C1-C4-alkyl-carbonyloxy, C1-C4-alkoxy-carbonyloxy, C1-C4-alkylamino-carbonyloxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, C1-C4-alkylsulphonyl, di-(C1-C4-alkyl)-amino-sulphonyl, C3-C5-cycloalkyl or phenyl), or are C2-C6-alkenyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, C1-C4-alkoxy-carbonyl, carboxyl or phenyl), or are C2-C6-alkynyl (which is optionally substituted by fluorine, chlorine, bromine, cyano, C1-C4-alkoxy-carbonyl, carboxyl or phenyl), or are C1-C4-alkoxy (which is option-ally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C4-alkoxy-carbonyl, C1-C4-alkoxy, C1-C4-alkylthio, Le A 27 532 - 46 -C1-C4-alkylsulphinyl or C1-C4-alkyl-sulphonyl),or are C1-C4-alkylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, carboxyl, C1-C4-alkoxy-carbonyl, C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl), or are C3-C6-alkenyloxy (which is optionally sub-stituted by fluorine, chlorine, bro-mine, cyano or C1-C4-alkoxy-carbonyl), or are C2-C6-alkenylthio (which is optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C1-C3-alkylthio or C1-C4-alkoxy-carbonyl), C3-C5-alkynyloxy, C3-C6-alkynylthio, or are the radical -S(0)p-R3 where p is the number 1 or 2 and R3 is C1-C4-alkyl (which is optionally substituted by fluorine, chlorine, bromine, cyano or C1-C4-alkoxy-carbonyl), C3-C6-alkenyl, C3-C6-alkynyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkylamino,C1-C4-alkyl-amino, di-(C1-C4-alkyl)-amino, or is the radical -NH0R4 where R4 is C1-C6-alkyl (which is optionally substituted by Le A 27 532 - 47 -fluorine, chlorine, cyano, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl, Cl-C4-alkyl-sulphonyl, C1-C4-alkyl-carbonyl, C1-C4-alkoxy-carbonyl, C1-C4-alkylamino-carbonyl or-di-(C1-C4-alkyl)-amino-carbonyl), or is C3-C5-alkenyl (which is optionally substituted by fluor-ine, chlorine or bromine), C3-C6 alkynyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C2-alkyl, phenyl-C1-C2-alkyl (which is optionally substituted by fluorine, chlor-ine, nitro, cyano, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-alkoxy-carbonyl), or is benz-hydryl, or is phenyl (which is optionally substituted by fluorine, chlorine, nitro, cyano, C1-C4-alkyl, trifluoro-methyl, C1-C4-alkoxy, C1-C2-fluoro-alkoxy, C1-C4-alkylthio, tri-fluoromethylthio or C1-C4-alkoxy-carbonyl), or R1 and R2 furthermore are phenyl or phen-oxy, or are C1-C4-alkylcarbonyl-amino, C1-C4-alkoxy-carbonylamino, C1-C4-alkylamino-carbonyl-amino, di-(C1-C4-Le A 27 532 - 48 -alkyl)-amino-carbonylaminor are the radical -CO-R5 where R5 is C1-C6-alkyl, C1-C6-alkoxy (which is optionally substituted by fluorine, chlorine, methoxy or ethoxy), C3-C6-cycloalkoxy, C3-C6-alkenyloxy, C1-C4-alkylthio, amino, C1-C4-alkylamino, C1-C4-alkoxyamino, C1-C4-alkoxy-C1-C4-alkyl-amino or di-(C1-C4-alkyl)-amino(which are option-ally substituted by fluorine and/or chlorine), or R1 AnA R2 furthermore axe C1-C4-alkyl-sulphonyloxy, dl-(C1-C4-alkyl)-amino-sulphonylamino, or are the radical -CH=N-R5 where R8 is C1-C8-alkyl which is optionally substituted by fluorine, chlorine, cyano, carboxyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkyl-sulphinyl or C1-C4-alkylsulphonyl, or is benzyl which is option-ally subqtituted by fluorine or chlorine, or is C3-C8-alkenyl or C3-C8-:alkynyl, each of which is optionally substituted by fluorine or chlorine, or is phenyl Le A 27 532 -49-which is optionally substituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, trifluoromethyl, trifluoromethoxy or trifluoromethyl-thio, or is C1-C6-alkoxy, C3-C8-alkenoxy, C3-C6-alkinoxy or benzyloxy each of which is optional-ly substituted by fluorine and/or chlorine, or is amino, C1-C8-alkylamino, di-(C1-C4-alkyl)-amino, phenylamino, C1-C4-alkyl-carbonyl-amino, C1-C4-alkoxy-car-bonylamino, C1-C4-alkyl-sulphonyl-amino, or is phenylsul-phonylamino which is optionally substituted by fluorine, chlorine, bromine or methyl, or R represents the radical where R7 is hydrogen or C1-C4-alXyl, R6 and R9 are identical or different and are hydrogen, fluorine, chlorine, bromine, nitro, cyano, carboxyl, Le A 27 532 - 50 -C1-C4-alkyl (Which is `optionally sub-stituted by fluorine and/or chlorine), C1-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), C1-C4-alkoxy-carbonyl, C1-C4-alkylsulphonyl or di-(C1-C4-alkyl)-aminosulphonyl, or R is the radical where R10 and R11 are identical or different and are hydrogen, fluorine, chlorine, bromine, nitro, cyano, C1-C4-alkyl (which is optionally substituted by fluorine andtor chlorine) or C1-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), or R is the radical where R12 and R13 are identical or different and are hydrogen, fluorine, chlorine, bromine, nitro, cyano, C1-C4-alkyl (which is optionally substituted by fluorine and/or chlorine) or C2-C4-alkenyl (which is optionally Le A 27 532 - 51 -substituted by fluorine and/or chlo-rine), C1-C4-alkoxy (which is optionally substituted by fluorine and/or chlo-rine), or are C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkyl-sulphonyl twhi.ch are optionally sub-stituted by fluorine and/or chlorine), or are di-(C1-C4-alkyl)-amino-sulphonyl, C1-C4-alkoxy-carbonyl, dimethylaminocarbonyl or dioxolanyl, or R is the radical where R14 and R15 are identical or different and are hydrogen, fluorine, chlorine, bromine, C1-C4-alkyl (which is optional-ly substituted by fluorine and/or bromine), C1-C4-alkoxy (.which is option-ally substituted by fluorine and/or chlorine),or are C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkyl-sulphonyl (which are optionally substi-tuted by fluorine and/or chlorine), or are di-(C1-C4-alkyl)-amino-sulphonyl, or R is the radical where Le A 27 532 - 52 -R16 and R17 are identical or different and are hydrogen, fluorine, chlorine, bromine, cyano, nitro, C1-C4-alkyl (which is optionally substituted by fluorine, chlorine, C1-C4-alkoxy and/or C1-C4-halogenoalkoxy), C1-C4-alkoxy (which is optionally substituted by fluorine and/or chlorine), C1-C4-alkyl-thio, C1-C4-alkylsulphinyl or C1-C4- .
alkylsulphonyl (which is optionally substituted by fluorine and/or chlo-rine), di-(C1-C4-alkyl)-amino-sulphonyl or C1-C4-alkoxy-carbonyl, and A1 is oxygen, sulphur or the group N-Z1, where Z1 is hydrogen, C1-C4-alkyl (which is optionally subssituted by fluorine, chlorine, bromine or cyano), C3-C6-cycloalkyl, benzyl, phenyl (which is optionally substituted by fluorine, chlorine, bromine or nitro), C1-C4-alkylcarbonyl, C1-C4-alkoxy-carbonyl or di-(C1-C4-alkyl)-aminocarbonyl, or Le A 27 532 -53-R is the radical where R18 and R19 are identical or different and are hydrogen, C1-C4-alkyl,. halogen, C1-C4-alXoxycar:bonyl, C1-C4-alkoxy or C1-C4-halogenoalXoxy, Y1 is sulphur or the group N-R20 where R20 is hydrogen or C1-C4-alkyl;
or R is the radical where R21 is hydrogen, C1-C4-alkyl, phenyl or (iso)quinolinyl, R22 is hydrogen, halogen, cyano, nitro, C1-C4-alkyl (which is optionally substituted by fluorine and/or chlorine), C1-C4-alkoxy (which is optionally sub-stituted by fluorine and/or chlorine), dioxolanyl or C1-C4-alkoxy-carbonyl,and Le A 27 532 -54-R23 is hydrogen, halogen or C1-C4-alkyl, or R is the radical where R24 is hydrogen, halogen, C1-C4-alkyl or C1-C4-alkoxy-carbonyl, or R is the radical where R25 is C1-C4-alkyl and R26 is C1-C4-alkyl, or R is the radical where R27 is hydrogen or methyl, in which furthermore X is hydrogen, halogen, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C2-alkoxy-C1-C2-alkyl, C1-C4-alkoxy or C1-C4-halogenoalkoxy, Le A 27 532 - 55 -y is halogen, C1-C4-alkyl, C1-C4-halogeno-alkyl, C1-C2-alkoxy-C1-C2-alkyl, C1-C4-alkoxy or C1-C4-halogenoalkoxy,.and z is hydrogen, halogen, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C4-alkoxy or C1-C4.haLogeno-alkoxy.

3. A sulphonylated pyrimidine carboxamide or salt thereof according to claim 1, in which R is the radical where R1 is hydrogen, fluorine, chlorine, bromine, cyano, nitro, carboxyl, methyl, trifluoromethyl, methoxy, ethoxy, difluoro-methoxy, trifluoromethoxy, C1-C3 alXylthio, C1-C3-alkylsulphinyl, C1-C3-alkylsulphonyl, dimethylaminosulphonyl, diethylaminosulphonyl, N-methoxy-N-methylaminosulphonyl, phenyl, phenoxy or C1-C3-alkoxy-carbonyl,and R2 is hydrogen, fluorine, chlorine, bro-mine, methyl, trifluoromethyl or methoxy, or Le A 27 532 - 56 -R is the radical where R8 is fluorine, chlorine, bromine, cyano, carboxyl, methyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, methylsul-phonyl or dimethylaminosulphonyl and R9 is hydrogen, fluorine or chlorine, or R is the radical where where R12 is dimethylaminocarbonyl or C1-C4-alkylsulphonyl and R13 is .hydrogen, fluorine or chlorine, or R is the radical where where Le A 27 532 - 57 -R28 is methyl or ethyl, or R is the radical where R29 is methyl or ethyl, X is hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxymethyl, methoxy, ethoxy or difluoromethoxy, Y is rluorine, chlorine, bromine, methyl, ethyl, fluoromethyl, chloromethyl, difluoro-methyl, dichloromethyl, trifluoromethyl, tri-chloromethyl, chlorodifluoromethyl, fluoro-dichloromethyl, methoxy, ethoxy, difluoromethoxy or trifluoromethoxy,and Z is hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy or difluoromethoxy.

4. A sulphonylated pyrimidine carboxamide or salt thereof according to claim 3, in which Le A 27 532 - 58 -X is hydrogen, Y is methoxy or methyl and Z is hydrogen.

5. The compound N-(2-trifluoromethoxyphenylsulphonyl)-5-methoxy-pyrimidine-2-carboxamide of the formula or salt thereof.

6. The compound N-(2-dimethylaminosulphonylphenylsulphonyl)-5-methoxy-pyrimidine-2-carboxamide of the formula or salt thereof.

7. A compound according to any one of claims 1 to 6 wherein the compound is in the form of a salt of hydrochloric acid, sulphuric acid, phosphoric acid, methanesulphonic acid, benzene- or p-toluenesulphonic acid, or naphthalene mono- or -di-sulphonic acids or the hydroxides, hydrides, amides or carbonates of sodium, potassium or calcium, or sodium C1-C4-alkanolates or potassium C1-C4-alkanolates, ammonia, C1-C4-alkylamines, di-(C1-C4-alkyl)-amines or tri-(C1-C4-alkyl)-amines.

8. A herbicidal composition comprising a herbicidally effective amount of a compound according to any one of claims 1 to 6 in admixture with a suitable carrier or diluent.

9. A herbicidal composition comprising a herbicidally effective amount of a compound according to any one of claims 1 to 6 in admixture with a solid diluent or carrier, a liquified normally gaseous diluent or carrier, or a liquid diluent or carrier containing a surface active agent.

10. A composition according to claim 8 wherein the compound is in the form of a salt of hydrochloric acid, sulphuric acid, phosphoric acid, methanesulphonic acid, benzene- or p-toluene-sulphonic acid, or naphthalene mono- or -di-sulphonic acids or the hydroxides, hydrides, amides or carbonates of sodium, potassium or calcium, or sodium C1-C4-alkanolates or potassium C1-C4-alkanolates, ammonia, C1-C4-alkylamines, di-(C1-C4-alkyl)-amines or tri-(C1-C4-alkyl)-amines.

11. A composition according to claim 9 wherein the compound is in the form of a salt of hydrochloric acid, sulphuric acid, phosphoric acid, methanesulphonic acid, benzene- or p-toluene-sulphonic acid, or naphthalene mono- or -di-sulphonic acids or the hydroxides, hydrides, amides or carbonates of sodium, potassium or calcium, or sodium C1-C4-alkanolates or potassium C1-C4-alkanolates, ammonia, C1-C4-alkylamines, di-(C1-C4-alkyl)-amines or tri-(C1-C4-alkyl)-amines

12. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 6.

13. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a composition containing a compound according to any one of claims 1 to 6 in admixture with a suitable carrier or diluent.

14. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a composition containing between 0.1 and 95% by weight of a compound according to any one of claims 1 to 6 in admixture with a suitable carrier or diluent.

15. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective mount of a composition containing between 0.5 and 90% by weight of a compound according to any one of claims 1 to 6 in admixture with a suitable carrier or diluent.

16. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 6 wherein the compound is applied as a pre-emergence herbicide.

17. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 6 wherein the compound is applied as a post-emergence herbicide.

18. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 6 wherein the compound is applied to an area of cultivation at a rate of between 0.1 and 2000 g/ha.

19. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 6 wherein the compound is applied to an area of cultivation at a rate of between 1 and 1000 g/ha.

20. A method according to claim 12 wherein the compound is in the form of a salt of hydrochloric acid, sulphuric acid, phosphoric acid, methanesulphonic acid, benzene- or p-toluene sulphonic acid, or naphthalene mono- or -di-sulphonic acids or the hydroxides, hydrides, amides or carbonates of sodium, potassium or calcium, or sodium C1-C4-alkanolates or potassium C1-C4-alkanolates, ammonia, C1-C4-alkylamines, di-(C1-C4-alkyl)-amines or tri-(C1-C4-alkyl)-amines.

21. A method according to claim 18 wherein the compound is in the form of a salt of hydrochloric acid, sulphuric acid, phosphoric acid, methanesulphonic acid, benzene- or p-toluene sulphonic acid, or naphthalene mono- or -di-sulphonic acids or the hydroxides, hydrides, amides or carbonates of sodium, potassium or calcium, or sodium C1-C4-alkanolates or potassium C1-C4-alkanolates, ammonia, C1-C4-alkylamines, di-(C1-C4-alkyl)-amines or tri-(C1-C4-alkyl)-amines.

22. A process for preparing a compound of formula I or salt thereof as defined in claim 1, wherein R, X, Y and Z are as defined in claim 1, which process comprises (a) reacting a pyrimidine carboxamide of the general formula II
(II) in which X, Y and Z have the above-mentioned meanings with a sulphonyl halide or sulphonic anhydride of the general formula III
R-SO2-Q (III) in which R has the above-mentioned meaning and Q represents fluorine, chlorine, bromine or the group -O-SO2-R where R has the above-mentioned meaning, or (b) reacting a pyrimidinecarboxylic acid of the general formula IV
(IV) in which X, Y and Z have the above-mentioned meanings, or a reactive derivative of a compound of the formula IV, with a sulphonamide of the general formula V

R-S02-NH2 (V) in which R has the above-mentioned meaning, or with a reactive derivative of a compound of the formula V, and, where reguired, forming a salt of the compound of formula I
so obtained.

23. A process for preparing a herbicidal composition which comprises admixing a compound of the formula I according to claim 1 or a salt thereof with a diluent, carrier and/or surface-active agent.