JPS59167570A - Guanidine derivative - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel guanidine derivatives, processes for their preparation and their use as herbicides and plant growth regulators.

Patent specifications [for example, DE-AS (see German Patent Application Publication No. 1,089,210 and East German Patent Application No. 71,016 and East German Patent Application No. 84,530]) indicate that various guanidines are effective. However, these compounds have had relatively little importance as weed control agents and/or plant growth regulators.

According to the present invention, novel guanidine derivatives of the following general formula (I) have been found: In the formula, R1 represents hydrogen or a group -S(O)m-R5, where m represents the number 0, 1 or 2. , and R5 represents an optionally substituted group selected from the group consisting of alkyl, aralkyl, aryl, and heteroaryl, R2 represents a 6-membered aromatic heterocyclic group, and the structural formula has at least one containing a nitrogen atom and substituted with halogen, amine, cyanide or formyl, and/or an optionally substituted group selected from the group consisting of alkyl, alkoxy, alkylamino, dialkylamino, alkylcarbonyl and alkoxycarbonyl. R3, which may be substituted and/or optionally fused, is hydrogen, an optionally substituted group selected from the group consisting of alkyl, cycloalkyl, alkenyl, alkynyl and aralkyl, or the group -S(O )n-R6,
Here, n represents the number 0, 1 or 2, and R6 represents an optionally substituted group selected from the group consisting of alkyl, aralkyl, aryl and heteroaryl, and R
4 represents hydrogen or hydroxyl, with the proviso that at least one of the groups R1 and/or R3 is not hydrogen; and furthermore, if -R3 is not hydrogen, then -R
4 represents an optionally substituted group selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl and aryl, or R3 and R4 together represent alkanediyl;
The group optionally contains an intermediate oxygen atom or a bridge >N-R7, where R7 represents an optionally substituted alkyl, alkylcarbonyl or aryl; and R4 represents a group -X-R8, where X represents oxygen, sulfur, -SO- or -SO2, and R8 is an optionally substituted group selected from the group consisting of C1-C6-alkyl, alkenyl, alkynyl, cycloalkyl, phenylalkyl and aryl. Furthermore, R4 represents a group, where R9 represents hydrogen or optionally substituted alkyl, and R10 represents alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl, aryl, heteroaryl, alkyl- or alkoxycarbonyl. and alkyl- or arylsulfonyl, or R9 and R10 together represent alkanediyl, optionally containing an intermediate oxygen atom; Furthermore, R4 represents a group, where R11 represents hydrogen or optionally substituted alkyl, and R12 is an optionally substituted group selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl, and aryl. or R11 and R12 together represent alkanediyl; further R4 represents trialkylsilyl or a group, where q represents the number 0 or 1, and Y represents oxygen or represents sulfur, and R13 and R14 are the same or different,
Any individual individually selected from the group consisting of alkyl, alkenyl, aralkyl, alkynyl, aryl, alkoxy, alkenoxy, alkynoxy, aralkoxy, aryloxy, alkylthio, alkenylthio, aralkylthio, alkynylthio, arylthio, amino, alkylamino and dialkylamino. represents an optionally substituted group, or R13 and R14 together represent alkanedioxy, oxyalkyleneamino or alkanediamino; further R4 represents an optionally substituted heterocyclic group;
Furthermore, M represents hydrogen, one equivalent of metal or an ammonium group optionally substituted with alkyl, alkenyl, alkynyl and/or aralkyl, or -M represents R2
When bonded to the same nitrogen atom, such as - also represents an optionally instantly substituted group selected from the group consisting of alkyl, alkenyl, alkynyl and aralkyl.

Furthermore, formula (I), with the proviso that M represents hydrogen, and R1, R2, R3 and R4 have the above meanings, We have found a new 1:1 adduct of a compound of 1:1 with a strong acid.

When M represents hydrogen, the new guanidine derivatives of the general formula (I) occur as a mixture of tautomers of the formulas (IA) and (IB). The ratio in this mixture depends on aggregation-determining factors such as temperature, solvent and concentration.

If, in addition to M, R3 and/or R4 also represent hydrogen, the general formula (I) represents other possible tautomers as shown in formulas (IC) and (ID).

The novel guanidine derivatives of formula (I) are characterized in that (a) R1 represents hydrogen, R3 represents hydrogen or an optionally substituted pole selected from the group consisting of alkyl, cycloalkyl, alkenylalkynyl and aralkyl, and M is represents hydrogen or an optionally substituted group selected from the group consisting of alkyl, alkenyl, alkynyl and aralkyl, and when the groups R2 and R4 have the abovementioned meanings, the formula (II) in which M1 is hydrogen or represents an optionally substituted group selected from the group consisting of alkyl, alkenyl, alkynyl and aralkyl, and R2 has the above meaning. In the formula, R3 represents hydrogen or an optionally substituted group selected from the group consisting of alkyl, cycloalkyl, alkenyl, alkynyl and aralkyl, and R4 has the above meaning, or an amino compound of formula (III) ) and, if necessary, treating the reaction product with an acid acceptor; (b) R1 represents the group -S(O)n-R5, where m
and R5 have the above meanings, and M represents hydrogen or an optionally substituted group selected from the group consisting of alkyl, alkenyl, alkynyl and aralkyl,
Furthermore, if R2, R3 and R4 have the above meaning, or R3 represents the group -S(O)n-R6, where n
and R6 have the above meanings, and M represents hydrogen or an optionally directly substituted group selected from the group consisting of alkyl, alkenyl, alkynyl and aralkyl,
Furthermore, when R1, R2 and R4 have the above meanings, R1 represents hydrogen and R3 is hydrogen, alkyl, cycloalkyl,
represents an optionally substituted group selected from the group consisting of alkenyl, alkynyl and aralkyl; the figure represents hydrogen or an optionally substituted group selected from the group consisting of alkyl, alkenyl, alkynyl and aralkyl; and a guanidine derivative of the formula (I) in which the radicals R2 and R4 have the abovementioned meanings, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, of the formula (
IV) R5-S(O)m-X1(IV) in which X1 represents fluorine, chlorine or bromine, and m and R5 have the above meanings, and/or halogen/sulfur compounds of formula (V) R6-S
(O)n-X2(V) in which X2 represents fluorine, chlorine or bromine and n and R6 have the meanings given above; (c) R3 is hydrogen or represents an optionally substituted group selected from the group consisting of alkyl, cycloalkyl, alkenyl, alkynyl and aralkyl, and R1, R2 and R
4 has the abovementioned meaning, formula (VI) in which R15 represents optionally substituted alkyl or aralkyl, and M and the groups R1 and R2
has the above meaning, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, an isothiourea of the formula (III), where R3 is water or alkyl, cycloalkyl, alkenyl, alkynyl represents an optionally substituted group selected from the group consisting of and aralkyl, and R4 has the above meaning. (d) R3 represents hydrogen or an optionally substituted group selected from the group consisting of alkyl, cycloalkyl, alkenyl, alkynyl and aralkyl, and M and When R1, R2 and R4 have the above meanings,
Formula (I) in which R3 represents the group -S(O)n-R6, where n and R6 have the meanings given above, and M and the group R1
, R2 and R4 have the abovementioned meanings, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent.
) where R3 represents hydrogen or an optionally substituted group selected from the group consisting of alkyl, cycloalkyl, alkenyl, alkynyl and aralkyl, and R4 has the above meaning, or an amino compound of the formula ( (e) M represents one equivalent of the metal, or alkyl,
represents an ammonium group optionally substituted with alkenyl, alkynyl and/or aralkyl, and the groups R1, R
2, when R3 and R4 have the above meanings, formula (I)
, in which M represents hydrogen and the radicals R1, R2, R3 and R4 have the meanings given above, are combined with metal hydroxides, hydrides or alkanolates, if appropriate in the presence of diluents, or with organic or (f) if it is intended to prepare a 1:1 adduct of a guanidine derivative of formula (I) with a strong acid, formula (I), with M and the group R1. , R2, R3 and R4 have the meanings given above, if appropriate with an inert diluent,
Obtained by reaction with strong acids.

Novel guanidine derivative of formula (I) and strong acid Part 1
:1 adducts are distinguished by strong herbicidal activity and/or are suitable in regulating the growth of certain plants.

Surprisingly, the new compounds of formula (I) have substantially better herbicidal and plant growth regulating action than previously known guanidines with similar action, and are good in cotton and various cereals. shows high selectivity.

The invention preferably relates to compounds of formula (I) in which R1 represents hydrogen or the group -S(O)n-R5, where m represents the number 0, 1 or 2, and R5 is optionally halogen [ alkyl having up to 6 carbon atoms, which may be directly substituted, for example, in particular by fluorine, chlorine and/or bromine], furthermore R5 is a radical, in which R16 and R17 are the same or different; ,
hydrogen, halogen [for example in particular fluorine, chlorine and/or bromine], cyano, nitro, C1-C5-alkyl [the radicals can optionally be fluorine, chlorine, bromine, cyanide, carboxyl, C
1-C4-alkoxy-carbonyl, C1-C4-alkylaminocarbonyl, di(C1-C4-alkyl)
-Aminocarbonyl, hydroxyl, C1-C4-alkoxy, formyloxy, C1-C4-alkyl-carbonyloxy, C1-C4-alkoxy-carbonyloxy, C1-C4-alkylamino-carbonyloxy, C1-C4-alkylthio, C1 ~C4-alkylsulfinyl, C1-C4-alkylsulfonyl, di-(
C1-C4-alkyl)-aminosulfonyl, C3-C
6-cycloalkyl or phenyl], C2-C6-alkenyl [the group may optionally be substituted with fluorine,
[optionally substituted with chlorine, bromine, cyano, C1-C4-alkoxy-carbonyl, carboxyl or phenyl], C1-C4-alkoxy [the group may optionally be substituted with fluorine,
Chlorine, bromine, cyano, carboxyl, C1-C4-alkoxy-carbonyl, C1-C4-alkylthio, C1
~C4-alkylsulfinyl or C1-C4-alkylsulfonyl), C3-C6
-alkenoxy, which radicals may optionally be substituted with fluorine, chlorine, bromine, cyano or C1-C4-alkoxy-carbonyl], C3-C6-alkynoxy or the radical -S(O)p-R13, where p represents the number 0, 1 or 2, and R18 is C1-C4-alkyl [the group optionally represents fluorine, chlorine, bromine, cyano or C1-C4-alkyl].
optionally substituted with C4-alkoxy-carbonyl], C3-C6-alkenyl, C3-C6-alkynyl, C1-C4-alkoxy, C3-C6-al-alkylamino or di-(C1-C4-alkyl) -represents amino, or phenyl or phenoxy, C1
~C4-alkyl-carbonylamino, C1-C4-alkoxy-carbonylamino, C1-C4-alkylamino-carbonylamino, di-(C1-C4-alkyl)-amino-carbonylamino or group -CO-R19
, where R19 is C1-C6-alkyl, C1
~C6-alkoxy, C3-C6-alkenoxy, C1
~C4-alkylthio, C1-C4-alkylamino or di-(C1-C4-alkyl)-amino, which radicals may optionally be substituted with fluorine and/or chlorine; or C1-C4- represents alkylsulfonyloxy, di-(C1-C4-alkyl)-aminosulfonylamino or the group -CH=N-R20, where R
20 is fluorine, chlorine, cyano, carboxyl, C1 as needed
~C4-alkoxy-carbonyl, C1-C4-alkylthio, C1-C4-alkylsulfinyl or C1
-C optionally substituted with C4-alkylsulfonyl
1-C6-alkyl, benzyl optionally substituted with fluorine or chlorine, C3-C6-alkenylmo or C3 optionally substituted with fluorine or chlorine
~C6-alkynyl, optionally fluorine, chlorine, bromine, C1~
C4-alkyl, C1-C4-alkoxy, phenyl optionally substituted with trifluoromethyl, trifluoromethoquino or trifluoromethylthio, C3-C6-alkenoxy optionally substituted with fluorine and/or chlorine, C3-C6 -alkynoxy, benzyloxy or C1-C6-alkoxy; or amino, C1-C4-alkylamino, di-(C1-C4
-alkyl)-amino, phenylamino, C1-C4-
represents alkyl-carbonylamino, C1-C4-alkoxy-carbonylamino or C1-C4-alkyl-sulfonylamino, or represents phenylsulfonylamine optionally substituted with fluorine, chlorine, bromine or methyl, and furthermore R5 represents a group, where R21 represents hydrogen or C1-C3-alkyl, and R22 and R23 are the same or different,
Hydrogen, fluorine, chlorine, bromine, nitro, cyano, C1-C
4-alkyl [the group may be optionally substituted with fluorine and/or chlorine], C1-C4-alkoxy [the group may optionally be substituted with fluorine and/or chlorine], carboxyl, C1- C4-alkoxycarbonyl, C1-C4-alkylsulfonyl or di-(C1-
C4-alkyl)-aminosulfonyl; further R3 represents a group, where R24 and R25 are the same or different;
Hydrogen, fluorine, chlorine, bromine, nitro, cyano, C1-C
4-alkyl [the group may optionally be substituted with fluorine and/or chlorine] or C1-C4-alkoxy [
the group may optionally be substituted with fluorine and/or chlorine; further R5 represents a group, where R26 and R27 are the same or different;
Hydrogen, fluorine, chlorine, bromine, nitro, cyano, C1-C
4-alkyl [the ring group may be optionally substituted with fluorine and/or chlorine], C1-C4-alkoxy [the group may optionally be substituted with fluorine and/or chlorine], C1-C4- alkylthio, C1-C4-alkylsulfinyl or C1-C4-alkylsulfonyl, optionally substituted with fluorine and/or chlorine, and di(C1-C4-alkyl)-
represents aminosulfonyl or C1-C4-alkoxy-carbonyl, further R5 represents a group, where R28 and R29 are the same or different,
Hydrogen, fluorine, chlorine, bromine, C1-C4-alkyl (which group may optionally be substituted with fluorine and/or chlorine and/or bromine), C1-C4-alkoxy (which group may optionally be substituted with fluorine and/or bromine); May be substituted with chlorine]
, C1-C4-alkylthio, C1-C4-alkylsulfinyl or C1-C4-alkylsulfonyl [
These groups may optionally be substituted with fluorine and/or chlorine] or di-(C1-C4-alkyl)-aminosulfonyl, and further R5 represents a group, in which R30 and R31 are the same or different. are different,
Hydrogen, fluorine, chlorine, bromine, cyano, nitro, C1-C
4-alkyl [the ring group may be optionally substituted with fluorine and/or chlorine], C1-C4-alkoxy [the group may optionally be substituted with fluorine and/or chlorine], C1-C4- alkylthio, C1-C4-alkylsulfinyl or C1-C4-alkylsulfonyl [these groups may optionally be substituted with fluorine and/or chlorine], di-[C1-C4-alkyl)-aminosulfonyl- or C1 ~C4-alkoxy-carbonyl and Z is oxygen, sulfur or the group N-Z1
, where Z1 is hydrogen, C1-C4-alkyl, optionally substituted with fluorine, chlorine, bromine or cyano;
C3-C6-cycloalkyl, benzyl, phenyl (which radicals may optionally be substituted with fluorine, chlorine, bromine or nitro), C1-C4-alkyl-carbonyl, C
1-C4-alkoxy-carbonyl or di-(C1-
C4-alkyl)-aminocarbonyl, further R2 represents a group, R32 and R4 are the same or different, hydrogen, fluorine, chlorine, bromine, C1-C4-alkyl [the ring group is optionally fluorine and/or chlorine] or C1-C4-alkoxy [the group may optionally be substituted with fluorine and/or chlorine], and as a condition, at least one of the groups R32 and R34 shall not be hydrogen, and R33 is hydrogen, fluorine, chlorine, bromine, cyano or C1
~C4-alkyl, optionally substituted with fluorine and/or chlorine; further R2 represents a group, where R35 and R36 are the same or different;
Hydrogen, fluorine, chlorine, bromine, C1-C4-alkyl [the group may optionally be substituted with fluorine and/or chlorine], C1-C4-alkoxy [the group may optionally be substituted with fluorine and/or chlorine] ], C1 to C4-
alkylamino or di-(C1-C4-alkyl)-
represents amino, with the proviso that at least one of the groups R35 and R36 is not hydrogen; further R2 represents a group, where R37 is hydrogen, fluorine, bromine, C1-C4-alkyl [
[the group may optionally be substituted with fluorine and/or chlorine] or C1-C4-alkoxy [the group may optionally be substituted with fluorine and/or chlorine], and R38 is hydrogen, fluorine, chlorine, bromine, C1-C4-alkyl (which radicals may optionally be substituted with fluorine and/or chlorine), cyano, formyl, C1-C4-alkyl-carbonyl or C1-C4-alkoxy-carbonyl; and R39 is C1-C4-alkyl [
[the group may optionally be substituted with fluorine and/or chlorine], C1-C4-alkoxy [the group may optionally be substituted with fluorine and/or chlorine], amino, C
1-C4-alkylamino or di-(C1-C4-alkyl)-amino, or R38 and R39 together represent C3-C4-alkanediyl, further R2 represents a group, in which R40 and R41 are the same or different,
represents C1-C4-alkyl [the group may optionally be substituted with fluorine and/or chlorine] or C1-C4-alkoxy [the group may optionally be substituted with fluorine and/or chlorine]; Furthermore, 38 is hydrogen, C1-C4-alkyl [the ring group is optionally fluorine, chlorine, bromine, cyano, hydroxyl or C1-C2
- may be substituted with alkoxy], C3-C6-
Cycloalkyl, C3-C6-alkenyl, C3-C6
-alkynyl, benzyl, optionally substituted with fluorine, chlorine or methyl, or the group -S(O)
n-R6, where n represents the number 0, 1 or 2, and R6 preferably has the meaning given above for R5, but is not in each case identical to R5; furthermore R4 represents hydrogen or hydroxyl, with the condition that
At least one of the groups R1 and R3 shall not be hydrogen; furthermore, when -R3 is not hydrogen - R4 is C1-C6-alkyl [the group may optionally be fluorine, chlorine, bromine, cyano, carboxyl, C1-C4 -alkoxy-carbonyl, hydroxyl or C1-C4-alkoxy], C3-C6-cycloalkyl [the ring group may optionally contain an intermediate -SO2- bridge], C3-C5- alkenyl, C3-C6-alkynyl, benzyl or phenylethyl, optionally substituted with fluorine, chlorine and/or methyl; or phenyl, optionally substituted with fluorine, chlorine, bromine,
Hydroxyl, cyano, nitro, amino, C1-C4-
Alkyl, trifluoromethyl, C1-C4 alkoxy, trifluoromethoxy, C1-C4-alkylthio,
trifluoromethylthio, aminosulfonyl or C1
~C4-alkoxy-carbonyl], or R3 and R4 together represent C4-C6-alkanediyl, optionally substituted with oxygen bridge or bridge >N-R7
may be included in the middle, where R7 is C1-C4-alkyl, C1-C4-alkyl-
carbonyl or phenyl [the group may optionally contain fluorine, chlorine,
optionally substituted with bromine, cyano, nitro, C1-C4-alkyl, trifluoromethyl or C1-C4-alkoxy; further R4 represents a group -X-R8, where X is oxygen, sulfur , -SO- or -SO2-,
and R8 is C1-C6-alkyl [the group is optionally fluorine, chlorine, C1-C4-alkoxy, C1-C4-alkylthio, C1-C6 alkylsulfinyl or C1-C4-
optionally substituted with alkylsulfonyl], C3-
C6-alkenyl, C3-C6-alkynyl, C3-C
6-cycloalkyl, benzyl [the ring group may optionally be substituted with fluorine, chlorine or methyl] or phenyl [the group may optionally be substituted with fluorine, chlorine, bromine, nitro, cyano,
C1-C4-alkyl, trifluoromethyl, C1-C
4-alkoxy, trifluoromethoxy, C1-C4-
furthermore, R4 represents a group, R9 represents hydrogen or C1-C4-alkyl, and R10 represents C1-C4-alkyl, optionally substituted with alkylthio or trifluoromethylthio; Fluorine, chlorine, bromine, cyano, C1-C4-alkoxy or C1
-C4-alkoxy-carbonyl], C3-C6-alkenyl, C3-C6-alkynyl, C3-C6-cycloalkyl [the group is optionally substituted with -SO2
[which may contain a bridge in between], benzyl or phenylethyl [these groups may optionally be substituted with fluorine, chlorine or methyl], phenyl [the ring groups may optionally be substituted with fluorine, chlorine, bromine, nitro, cyano , C1-C4-alkyl, trifluoromethyl, C1-C4-alkoxy, trifluoromethoxy, C1-C4-alkylthio or trifluoromethylthio]
, pyrimidyl, C1-C4-alkyl-carbonyl, benzoyl, C1-C4-alkoxy-carbonyl, C1
-C4-alkylsulfonyl or phenylsulfonyl, optionally substituted with fluorine, chlorine, bromine or methyl; or R9 and R10 together represent C4-C6-alkanediyl; may optionally contain an oxygen bridge in the middle]
furthermore, R4 represents a group, R11 represents hydrogen or C1-C4-alkyl, and R12 represents C1-C4-alkyl, C3-C6-alkenyl, C1-C6-alkynyl, C3-C6-cyclo Alkyl, benzyl or phenylethyl (these groups may optionally be substituted with fluorine, chlorine or methyl) or phenyl (these groups may optionally be substituted with fluorine, chlorine, bromine, C
1-C4-alkyl, trifluoromethyl, cyano, nitro, C1-C4-alkoxy or trifluoromethoxy], or R1
1 and R12 together represent C4-C6-alkanediyl; further R4 represents tri-(C1-C4-alkyl)-silyl or a group; where q represents the number 0, 1 or 2; Y represents oxygen or sulfur, and R13 and R14 are the same or different,
individually C1-C4-alkyl, which radicals may optionally be substituted with fluorine, chlorine, cyanide or methyl;
~C4-alkenyl, C3-C4-alkynyl, benzyl [the radical may optionally be substituted with fluorine, chlorine or methyl], phenyl [the radical may optionally be substituted with fluorine, chlorine or methyl] ], C1-C4-alkoxy [the group may optionally be substituted with fluorine, chlorine, cyano or methoxy], C2-C4-alkenoxy, C3-C4-alkynoxy, benzyloxy [the group may optionally be substituted with fluorine, chlorine and/or methyl], phenoxy [the group may optionally be substituted with fluorine, chlorine,
optionally substituted with bromine, cyano, nitro, methyl, trifluoromethyl or methoxy], C1-C4-
Alkylthio [the group may be optionally substituted with fluorine, chlorine, cyano or methoxy], C1-C4-alkenylthio, benzylthio [the ring group may be optionally substituted with fluorine, chlorine or methyl], C3 ~C4-alkynylthio, phenylthio [the group may optionally be substituted with fluorine, chlorine, bromine, cyano, nitro, methyl, trifluoromethyl or methoxy], amino, C
1-C4-alkylamino or di-(C1-C4-alkyl)-amino, or R13 and R14 together represent C2-C3-alkanedioxy, oxy-C1-C3-alkylamino or C1- C3-alkanediamino; further R4 represents a 5- or 6-membered heterocyclic structure containing 1 to 3 nitrogen atoms and/or oxygen or sulfur atoms and optionally containing fluorine, chlorine, or bromine; , C1-C4-
Optionally substituted with alkyl, trifluoromethyl, nitro, cyano or C1-C4-alkoxy: in addition M is hydrogen, sodium, potassium, magnesium, calcium, aluminum, manganese, iron, cobalt or 1 equivalent of nickel, optionally C1-C6-alkyl, optionally substituted with chlorine, C3-C6-alkenyl, C3-C6-alkynyl and/or benzyl, optionally substituted with fluorine, chlorine or methyl; represents an ammonium group substituted with
or when -M is bonded to the same nitrogen atom such as R2 - also C1-C6-alkyl [the ring group may optionally be substituted with fluorine, chlorine or cyano], C3-C6
- represents alkenyl, C3-C6-alkynyl or benzyl.

Furthermore, the present invention preferably comprises a compound of formula (1) as defined above and a hydrohalic acid such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, sulfuric acid, phosphoric acid, carbon atom 4
or with benzene- or naphthalene-sulfonic acids optionally substituted with fluorine, chlorine or methyl.

The invention particularly relates to compounds of formula (I): (A)R
1 represents a group -S(O)m-R5, where m represents the number 2, and R5 represents a group, where R16 represents fluorine, chlorine, bromine, methyl, trifluoromethyl, C1-C2- alkoxy, difluoromethoxy,
trifluoromethoxy, phenyl or C1-C2-alkoxycarbonyl, and R17 represents hydrogen; further R37 represents hydrogen, methyl or methoxy, R38 represents hydrogen, chlorine, methyl, acetyl or methoxycarbonyl, and R39 represents C1-C4-alkyl or C1-C4-alkoxy or together with R38 represents C3-C4-alkanediyl; further R3 represents hydrogen, methyl or the group -S(O)n-R6 where n represents the number 2 and R6 particularly preferably has the meaning indicated above for R3; furthermore R4 is hydroxyl, C1-C2-alkoxy, C3-
represents C4 alkenoxy, -C3-C4-alkynoxy, benzyloxy or a group, where R9 represents hydrogen or methyl and R10 represents C1
~C3-alkyl, phenyl, acetyl, methoxycarbonyl, phenylsulfonyl or p-toensulfolinyl; furthermore, M represents hydrogen, sodium, potassium or 1 equivalent of magnesium or calcium; and -M represents hydrogen; - 1:1 adducts of the compounds defined above with hydrochloric acid, sulfuric acid, benzenesulfonic acid and p-toluenesulfonic acid: or ha(B) where R1 is hydrogen or the group -S
(O)m-R5, where n represents the number 0, 1 or 2, and R5 represents a group, where R16 and R17 represent hydrogen, or R16 represents chlorine, nitro, methyl, tri fluoromethyl or methoxy, and R19 represents fluorine, chlorine, bromine, methyl, trifluoromethyl, cyano, nitro or methoxy; and R37 represents hydrogen, methyl or methoxy; R3
8 represents hydrogen, chlorine, methyl, acetyl or methoxycarbonyl and R39 represents C1-C4-alkyl or C1-C4-alkoxy or R38 and R39 together represent C3-C4-alkanediyl , furthermore R3 represents hydrogen, methyl or the group -S(O)n-R6, where n represents the number 0, 1 or 2, and R6 particularly preferably has the meaning indicated above for R5. has: further R4 represents hydroxyl, with the proviso that at least one of the groups R1 and R3 is not hydrogen; further R4 represents C1-C4-alkoxy, C3-C4-alkenoxy, C3-C4-alkynoxy, benzoyl represents oxy or a group, where R9 represents hydrogen or methyl, and R10 represents C1
~C3 represents alkyl, phenyl, acetyl, methoxycarbonyl, phenylsulfonyl or p-toluenesulfonyl; furthermore M represents hydrogen, sodium, potassium or one equivalent of magnesium or calcium, and -M represents hydrogen- defined compounds and hydrochloric acid, sulfuric acid,
1 with benzenesulfonic acid and p-toluenesulfonic acid
:1 adduct; or (C)R1 represents hydrogen or the group -S(O)m-R5, where m represents the number 0, 1 or 2, and R5 represents hydrogen, fluorine, chlorine, bromine, nitro , methyl, trifluoromethyl, C1-C2-alkoxy, difluoromethoxy, trifluoromethoxy, phenyl- or C1-C2-alkoxy-carbonyl, and R17 is hydrogen, fluorine, chlorine, bromine, nitro, methyl,
represents trifluoromethyl, C1-C7-alkoxy, difluoromethoxy or trifluoromethoxy, furthermore R2 represents a group, R37 represents hydrogen, methyl or methoxy, R38 represents hydrogen, chlorine, methyl, acetyl or methoxycarbonyl and R39 represents C1-C4-alkyl or C1-C4-alkoxy, or R38 and R39 together represent C3-C4-alkanediyl, furthermore R3 represents hydrogen, with the proviso that R1 is not hydrogen or optionally hydroxyl-substituted C1-C4-alkyl, C5-C6-cycloalkyl, C3-C4-alkenyl or C3-C4-alkynyl; benzyl or the group -S(O ) n-R', where n represents the number 0, 1 or 2 and R6 particularly preferably has the meaning indicated above for R5; furthermore R4 is optionally chlorine, cyano, C1- C3-alkoxy-carbonyl, C1-C4-alkyl optionally substituted by hydroxyl or C1-C2-alkoxy, or C3-C6-cycloalkyl, C3-C4-alkenyl, C3-C4-alkynyl or benzyl or optionally substituted with fluorine, chlorine, bromine, nitro, cyano, aminosulfonyl, hydroxyl, amino, methyl, trifluoromethyl, methoxy, trifluoromethoxy, methylthio, trifluoromethylthio or C1-C2-alkoxy-carbonyl. or if -R1 is not hydrogen, it also represents hydrogen; and M is hydrogen, one equivalent of sodium or potassium or magnesium or calcium, C1-C4-alkyl-, di-(C1-C4 -alkyl)- or tri-(
C1-C4-alkyl)-represents ammonium; and when -M represents hydrogen - 1:1 adducts of the compounds defined above with hydrochloric acid, sulfuric acid, benzenesulfonic acid and p-toluenesulfonic acid;
or (D) R1 represents a group -S(O)m-R5, where m represents the number 2, and R5 represents a group, where R15 is fluorine, chlorine, bromine, methyl, trifluoromethyl, C1-C2-alkoxy, difluoromethoxy,
Trifluoromethoxy or C1-C2-alkoxy-
carbonyl and R17 represents hydrogen; further R2 represents a group, R40 represents methyl, methoxy or ethoxy and R41 represents methyl, methoxy or ethoxy; furthermore R3 represents hydrogen, methyl or the group - S(O)n-R6, where n represents the number 2 and R6 particularly preferably has the meaning indicated above for R5; furthermore R4 is hydroxyl, C1-C4-alkoxy, C ~C
4-alkenoxy, C3-C4-alkynoxy, benzyloxy or a group, where R9 represents hydrogen or methyl and R10 represents C1
~C3-alkyl, phenyl, acetyl, metquincarbonyl, phenylsulfonyl or p-toluenesulfonyl; and M represents one equivalent of hydrogen, sodium or potassium or magnesium or calcium; and -M
represents hydrogen - 1:1 adducts of the compounds defined above with hydrochloric acid, sulfuric acid, benzenesulfonic acid and p-toluenesulfonic acid; or (E) R1 is hydrogen or the group -S(O)m -R5, where m represents the number 0, 1 or 2, and R5 represents a group, where both R16 and R17 represent hydrogen, or R16 is chlorine, nitro, methyl, trifluoromethyl or methoxy, and R17 is fluorine, chlorine,
bromine, methyl, trifluoromethyl, cyano, nitro or methoxy; furthermore, R2 represents a group, R40 represents methyl, methoxy or ethoxy and R41 represents methyl, methoxy or ethoxy; furthermore R3 represents a group; represents hydrogen, methyl or the radical -S(O)n-R6, where n represents the number 0, 1 or 2 and R6 particularly preferably has the meaning indicated above for R5; and R4 represents hydroxyl, with the proviso that groups R1 and R
at least one of 3 is not hydrogen; further R4 represents C1-C4-alkoxy, C3-C4-alkenoxy, C1-C4-alkynooxy, benzyloxy or a group, where R9 represents hydrogen or methyl; , and R10 is C1
~C3-alkyl, phenyl, acetyl, methoxycarbonino, phenylsulfonyl or p-toluenesulfonyl; and M represents one equivalent of hydrogen, sodium or potassium or magnesium or calcium, and -M
represents hydrogen - 1:1 adducts of the compounds defined above with hydrochloric acid, sulfuric acid, benzenesulfonic acid and p-toluenesulfonic acid; or (F) R1 is hydrogen or the group -S(O)- represents R5,
m here represents the number 0, 1 or 2, and R16 is hydrogen,
Fluorine, chlorine, bromine, nitro, methyl, trifluoromethyl, C1-C2-alkoxy, difluoromethoxy,
represents trifluoromethoxy or C1-C2-alkoxy, and R17 is hydrogen, fluorine, chlorine, bromine, nitro, methyl,
represents trifluoromethyl, C1-C2-alkoxy, difluoromethoxy or trifluoromethoxy, furthermore R2 represents a group, R40 represents methyl, methoxy or ethoxy and H41 represents methyl, methoxy or ethoxy; and R3 is hydrogen, C2-C4-alkyl optionally substituted with hydroxyl, C5-C6-cycloalkyl,
C3-C4-alkenyl, C3-C4-alkynyl, benzyl or the group -S(O)n-R6, where n is the number 0, 1- or 2 and R6 is particularly preferably relative to R5; has the meaning given above; in addition R4 represents C1-C4-alkyl optionally substituted with chlorine cyano, C1-C3-alkoxy-carbonyl, hydroxyl or C1-C2-alkoxy, or C5-C6 - cycloalkyl, C3-C4-alkenyl, C3-C4-alkynyl or benzyl, optionally fluorine, chlorine, bromine, nitro, cyano, aminesulfonyl, hydroxyl, amino, methyl, trifluoromethyl, metquin, trifluoromethoxy , phenyl optionally substituted with methylthio, trifluoromethylthio or C1-C2-alkoxy-carbonyl, or - when at least one of the groups R1 and R2 is not hydrogen - also represents hydrogen; furthermore M is hydrogen, 1 equivalent of sodium or potassium or magnesium or calcium, or C1-C4
- represents alkyl-, di-(C1-C4-alkyl)- or tri-(C1-C4-alkyl)-ammonium; and when -M represents hydrogen - a compound as defined above with hydrochloric acid, sulfuric acid, 1:1 adduct with benzenesulfonic acid and p-toluenesulfonic acid.

For example, when using o-isopropyl-hydroxylamine hydrochloride and 2-cyanoamino-4-methoxy-6-methyl-pyrimidine as starting materials for process (a), the reaction process can be illustrated by the following reaction scheme: For example, process Starting from (b), 2-difluoromethoxy-benzenesulfonyl chloride and N' as substances
-(4-methoxy-6-methyl-s-triazine-2-
When using N'-(4-
methoxy-6-methyl-pyrimidin-2-yl)-N''
-(2-fluorobenzenesulfonyl-S-methyl-isothiourea and diethylamine and when the first obtained ammonium salt is treated with hydrochloric acid,
The reaction process can be illustrated by the following reaction equation: For example, N′-(4,
6-dimethoxy-s-triazin-2-yl)-N″-
When using methoxy-N'',N''-bis(2-trifluoromethyl-benzenesulfonyl)-guanidine and ammonia, the reaction process can be illustrated by the following reaction scheme: e.g. N as starting material for process (e). ′
-(4,6-dimethoxy-pyrimidin-2-yl)-N
″-methoxy-N″′-(2-trifluoromethoxy-
When using benzenesulfonyl)-guanidine and potassium ethanolate, the reaction process can be illustrated by the following reaction scheme: For example, N'-(4,6-dimethyl-pyrimidin-2-yl )-N″-methyl-N″′-(2-methoxycarbonyl-benzenesulfonyl)-guanidine and trifluoromethanesulfonic acid, the reaction process can be illustrated by the following reaction formula: Formula (II) is the method A general definition of cyano compounds used as starting materials for (a) is shown. In this formula, M1 is preferably hydrogen, C1-C6-alkyl (which radicals may optionally be substituted with fluorine, chlorine or cyano), C3-C6-alkenyl, C3-C6-alkynyl or pendyl, especially represents hydrogen and R2 is preferably or especially
Preferably or particularly preferably the formula (I
) have the meanings given above within the scope of the substituents.

The following starting sequences of formula (II) may be mentioned: 2-cyanoamino-4,6-dimethyl-pyrimidine, 2
-cyanoamino-4-methoxy-6-methyl-pyrimidine, 2-cyanoamino-4,6-dimethoxy-pyrimidine, 2-cyanoamino-4-ethoxy-6-methyl-pyrimidine, 2-cyanoamine-4-methyl-6-poropoxy -pyrimidine, 2-cyanoamino-4-methyl-6
-isopropoxy-pyrimidine, 2-cyanoamino-4
-Methyl-6-butoxy-pyrimidine, 2-cyanoamino-4-methyl-6-imbutoxy-pyrimidine, 2-
(cyano-N-methyl-amino)-4,6-dimethyl-
Pyrimidine, 2-(cyano-N-methyl-amino)-4
-methoxy-6-methyl-pyrimidine, 2-cyanoamino-4,6-dimethyl-s-triazine, 2-cyanoamino-4-methoxy-6-methyl-s-triazine, 2
-cyanoamino-4,6-dimethoxy-s-triazine, 2-cyanoamino-4-ethoxy-6-methyl-s-
Triazine, 2-cyanoamino-5-chloro-4,6-
dimethyl-pyrimidine and 2-cyanoamino-4,5,
6-Trimeter-pyrimidine.

Some of the cyano compounds of formula (II) are known (J
．． Chem. Soc. 1953, 1725-1730). Compounds of formula (II) are obtained essentially by the following synthetic route: (a1) generally an alkali metal or alkaline earth metal salt of a cyanamide, such as sodium cyanamide or calcium cyanamide, if appropriate with an inert diluent, such as acetone; in the presence of acetonitrile or dimethylformamide between 0°C and 150°C, preferably 10°C
At temperatures between 100° C. and 100° C., halogen compounds of the formula (VII) Hal1-R2(VII) in which R2 has the abovementioned meaning and Hal1 represents fluorine, chlorine, bromine or iodine, in particular chlorine. After distilling off the volatile constituents and dissolving the residue in water, the compound of formula (II) can be precipitated by acidification, for example with hydrochloric acid, and can be isolated by suction filtration. or (a2) when R2 represents a substituted pyrimidinyl group, cyanoguanidine ("dicyanodiamide") can be
- dicarbonyl compounds, such as acetylacetone (J.
Chem. Soc. 1953, 1725-1730), acetoacetate (J. Prakt. Chem.
77, (1908), 542 and J. Chem. soc
．． 1948, 586), or malonic acid esters (see
German Patent Specification No. 158,591).

The 2-cyanoamino-4-hydroxy-6-methyl- or -4,5-dihydro-pyrimidine obtained from the acetoacetate or malonate ester is treated in the usual manner with a diluent, if appropriate, such as water, methanol, ethanol, in the presence of n- and isopropanol, acetone, dioxane or dimethylformamide and acid binders such as sodium hydroxide, potassium hydroxide,
In the presence of sodium carbonate or potassium carbonate,
The corresponding 2-cyanoamino-4-alkoxy-6-methyl- or -4,6-dialkoxy- by reaction with an alkylating agent, e.g. dimethyl sulfate or diethyl sulfate.
Can be converted to pyrimidine. N as necessary
- To avoid alkylation, the acylation can be carried out using an acylating agent,
For example, it is carried out with acetic anhydride or acetyl chloride, and after alkylation, deacetylation is carried out with aqueous acids or bases.

The halogen compound of formula (VII) is known [J. Ch
em. Soc. (C) 1966, 2031; Chem.
pharm. Bull. 11 (1963), 1382-
1388: and Arch. pharm. 295 (196
2), 649-657].

Furthermore, formula (II) used as starting material for process (a)
The amino compounds of I) are mostly known or can be prepared by methods known per se [Chem, Pharm. Bull. 15 (1967)
, 345-349; Bull. Soc. Chem. Fr.
ance 1958, 664; and Synthesis
1976, 682].

In formula (III), R4 preferably has the meaning given above within the definitions of the substituents for formula (I), and R3 preferably has hydrogen, C1
~C4-alkyl, optionally substituted with fluorine, chlorine, bromine, cyano, hydroxyl or C1-C4-alkoxy, C3-C5-cycloalkyl,
represents C3-C6-alkenyl, C3-C6-alkynyl or benzyl, optionally substituted with fluorine, chlorine or methyl.

Particularly preferred starting materials of formula (III) are particularly preferred where R4 has the same meanings indicated above within the definition of substituents for formula (I) and R3 is hydrogen, optionally hydroxyl. - Compounds representing optionally substituted C1-C4-alkyl, C5-C6-cycloalkyl, C3-C4-alkenyl, C3-C4-alkynyl or benzyl.

As examples of starting materials of formula (III), the following may be mentioned: ammonia, methylamine, ethylamine, n- and isopropylamine, n-, iso-, sec.
- and t-butylamine, cyclopentylamine, cyclohexylamine, allylamine, propargylamino, benzylamine, aniline, 2-fluoro-, 3-fluoro- and 4-fluoro-aniline, 2-chloro-,
3-chloro- and 4-chloro-aniline, 2-bromo, 3-bromo- and 4-bromo-aniline, 2-nitro-, 3-nitro- and 4-nitro-aniline, 2-amino-, 3- amino- and 4-amino-benzonitrile,
4-Amino-benzenesulfonamide, o-, m- and p-cresol, o-, m- and p-phenylenediamine, o-, m- and p-toluidine, 2-trifluoromethyl-, 3-tri fluoromethyl- and 4-trifluoromethyl-aniline, 2-methoxy-, ■-methoxy- and 4-methoxy-aniline, 4-trifluoromethylthio-aniline, 2-amino- and 4-amino-benzoic acid methyl ester, Dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, dicyclopentylamine, dicyclohexylamine, diallylamine, cyclopargylamine, dibenzylamine, N-methylaniline, O-methylhydroxylamine, O-ethylhydroxylamine, O-propylhydroxylamine, O-isopropylhydroxylamine, o-butylhydroxylamine, O-isobutylhydroxylamine, O-allylhydroxylamine, O-propargylhydroxylamine, O-benzylhydroxylamine, N,O-dimethylhydroxylamine, Methylhydrazine, N,N-dimethylhydrazine, N,N'-dimethylhydrazino, ethylhydrazine, n- and isopropylhydrazine and hydrochloride salts of these compounds: phenylhydrazine, acetylhydrazide, methylhydrazinoformate, benzenesulfonate Hydrazide and p-toluenesulfonohydrazide.

The conditions shown in formula (I) and method (b) above are the same as method (b).
gives a general definition of guanidine derivatives used as starting materials. In the case of the guanidine used in this formula as starting material for process (b), R1 preferably represents hydrogen and R3 preferably represents hydrogen, C1-C4-alkyl, optionally fluorine, chlorine, bromine, cyano, hydroxyl or optionally substituted with C1-C4-alkoxy], C
3-C5-cycloalkyl, C3-C6-alkenyl,
C3-C6-alkynyl or benzyl, optionally substituted with fluorine, chlorine or methyl, M is hydrogen, C1-C6-alkyl, optionally substituted with fluorine, chlorine or cyano; ], C3
~C6-alkenyl, C3-C6-alkynyl or benzyl, and R2 and R4 preferably represent formula (I
) have the meanings given above within the definitions of substituents.

Particularly preferred starting materials for process (b) are of formula (I),
provided that R1 represents hydrogen, R3 represents hydrogen, optionally hydroxyl-substituted alkyl, C5-C6-cycloalkyl, C3-C4-
represents alkenyl, C3-C4-alkynyl or benzyl, M represents hydrogen and R2 and R4 have, with particular preference, the same meanings given above in the structure of the definitions of the substituents for formula (I); is a guanidine derivative.

Formula (I) used as starting material in production method (b)
As an example of a guanisine derivative, the following may be mentioned: N'-(4,6-dimethyl-pyrimidine-2-
yl)-, N'-(4-methoxy-6-methyl-pyrimidin-2-yl)-, N'-(4-ethoxy-6-methyl-pyrimidin-2-yl)-N'-(4-propoxy -6-methyl-pyrimidin-2-yl)-, N'-(4
-isopropoxy-6-methyl-pyrimidin-2-yl)-N'-(4-butoxy-6-methyl-pyrimidine-
2-yl)-, N'-(4-isobutoxy-6-methyl-pyrimidin-2-yl)-, N'-(4,6-dimethoxy-pyrimidin-2-yl)-, N'-(4, 6-dimethyl-s-triazin-2-yl)-, N'-(4-
methoxy-6-methyl-s-triazin-2-yl)-
, N'-(4-ethoxy-6-methyl-s-triazin-2-yl)-N'-(4,6-dimethoxy-s-triazin-2-yl)-, N'-methyl-N'- (4-methoxy-6-methyl-pyrimidin-2-yl)-, N'
-(4,5,6-trimethyl-pyrimidin-2-yl)
- and N'-(5-chloro-4,6-dimethyl-pyrimidin-2-yl)-guanidine, -N''-methyl-guanidine, -N''-ethyl-guanidine, -N''-propyl-guanidine, - N″-isopropyl-guanidine,
-N''-butyl-guanidine, -N''-isobutyl-guanidine, -N''-sec-butyl-guanidine, -N
"-t-butyl-guanidine -N"-cyclopentyl-guanidine, -N"-cyclohexyl-guanidine,
-N″-allyl-guanidine, -N″-propargyl,
-guanidine, -N''-benzyl-guanidine, -N''
-phenyl-guanidine, -N''-(2-fluorophenyl)-, -(3-fluorophenyl)- and -(4-
fluorophenyl)-guanidine-, -N''-(2-chlorophenyl)-, -(3-chlorophenyl)- and -
(4-chlorophenyl)-guanidine, -N''-(2
-bromophenyl)-, -(3-bromophenyl)- and -(4-bromophenyl)-guanidine, -N″-(
2-nitrophenyl)-1-(3-nitrophenyl)-
and -(4-nitrophenyl)-guanidine, -N''-
(2-aminophenyl)-, -(3-aminophenyl)
- and -(4-aminophenyl)-guanidine, -N''
-(2-cyano-phenyl)-, -(3-cyano-phenyl)- and -(4-cyano-phenyl)-guanidine, -N''-(4-amino-sulfonyl-phenyl)-guanidine, -N'' -(2-hydroxy-phenyl)-,
-(3-hydroxy-phenyl)- and -(4-hydroxy-phenyl)-guanidine, -, N''-(2-methyl-phenyl)-, -(3-methyl-phenyl)- and -(4-methyl -phenyl)-guanidine, -N″-(
2-trifluoromethyl-phenyl)-, -(3-trifluoromethyl-phenyl)- and -(4-trifluoromethyl-phenyl)-guanidine, -N''-(2-methoxy-phenyl)-, -( 3-methoxy-phenyl)
- and -(4-methoxy-phenyl)-guanidine, -
N''-(2-trifluoromethoxy-phenyl)- and -(4-trifluoromethoxy-phenyl)-guanidine, -N''-(4-trifluoromethylthio-phenyl)-guanidine, -N''-(2- Methoxycarbonyl-
phenyl)- and -(4-methoxycarbonyl-phenyl)-guanidine, -N'',N''-dimethyl-guanidine, -N'',N''-diethyl-guanidine, -N'',N
″-dipropyl-guanidine, -N″,N″-diisopropyl-guanidine, -N″,N″-dibutyl-guanidine, -N″,N″-diisobutyl-guanidine, -N
″,N″-dicyclopentyl-guanidine, -N″,N
″-dicyclohexyl-guanidine, -N″,N″-diallyl-guanidine, -N″,N″-dipropargyl-
Guanidine, -N'',N''-dibenzyl-guanidine-
, N″-methyl-N″-phenyl-guanidine, -N″
-Methoxy-guanidine, -N''-ethoxy-guanidine, -N''-propoxy-guanidine, -N''-isopropoxy-guanidine, -N''-butoxy-guanidine, -N''-isobutoxy-guanidine, -N''- Allyloxy-guanidine, -N''-propargyloxy-guanidine, -N''-benzyloxy-guanidine, -N
"-Methyl-N"-methoxy-guanidine, -N"-methylamino-guanidine, -N"-dimethylamino-guanidine, -N"-methyl-N"-methylamino-guanidine, -N"-ethylamino- Guanidine, -N″-
Propylamino-guanidine, -N''-isopropylamino-guanidine, -N''-morpholino-guanidine,
-N''-acetamino-guanidine, -N''-methoxycarbonylamino-guanidine, -N''-benzenesulfonylamino-guanidine and -N''-p-toluenesulfonylamino-guanidine.

The guanidine derivatives of formula (I) used as starting materials for process (b) have not yet been described in the literature for the most part and these can be prepared by process (a) according to the invention.

Formulas (IV) and (V) further give a general definition of the halogen/sulfur compounds used as starting materials in process (b). In this formula, m, n, R5 and R6 preferably and especially have analogous meanings as indicated above within the definition of the substituents for formula (I) as each preferred or particularly preferred. , and X1 and X
2 preferably and particularly preferably represents chlorine.

The following may be mentioned as starting materials for formulas (IV) and (V): 2-chloro-, 2-fluoro-, 2-bromo-, 2-nitro-, 2-methyl-, 2-methoxycarbonyl -, 2
-ethoxycarbonyl-, 2-methoxy-, 2-ethoxy-, 2-phenyl-, 2-trifluoromethyl-, 2
-difluoromethoxy-, 2-trifluoromethoxy-
, 2-phenoxy-, 2-methyl-5-chloro-, 2,
5-dichloro- and 2-chloro-5-trifluoromethyl-benzenesulfonyl chlorides and the corresponding sulfenyl and sulfinyl chlorides.

Some of the halogen/sulfur compounds of formulas (IV) and (V) are known [Chemistry Lett, 19
78,951; European Patent No. 23,422, European Patent No. 35,893, European Patent No. 42,731, European Patent No. 44,80
No. 8, No. 44,809, No. 51,466, No. 64,804, and No. 70. , 041; U.S. Patent No. 2,929,820. Nos. 4,282,242 and 4,372,778; and J. Org. Ch
em. 33 (1968), 2104].

Formulas (IV) and (V) where m and n each represent the number 2
The compound can be obtained essentially by the following two synthetic methods: (b1) the corresponding sulfonic acid R5-SO3H or R6
-SO3H or an alkali metal or alkali metal salt thereof, if appropriate in the presence of a catalyst such as pyridine or dimethylformamide and if appropriate an inert diluent such as methylene chloride, chloroform, acetonitrile, chlorobenzene and /Also using sulfolane, between -20°C and +150°C, preferably between 0°C and +
At temperatures between 100°C and halogenating agents such as phosphorus chloride (
V) reacting with (phosphorus pentachloride), phosphoryl chloride (phosphorus oxychloride), thionyl chloride, phosgene or benzotrichloride; after dilution with water, the sulfonyl chloride, if these are obtained in crystalline form;
can be isolated by suction filtration or non-aqueous compatible solvents,
For example, extracting with methylene chloride, diethyl ether or hexane, washing and drying the extract, evaporating and purifying by recrystallization or distillation: or (b2) X1 and X2 represent chlorine and R5 and R6 represents an aromatic group, it can be used in a manner known per se [J. Org. Chem. 25 (1960), 18
24: DE-OS (German patent application publication specification) No. 2
, 308,262 and European Patent No. 59,241
], the appropriate amine compounds R5-NH2 and R5-NH2, respectively, in the presence of acetic acid if appropriate, -
Between 10°C and +20°C, preferably between -5°C and +10°C
between 0° C. and 80° C., then (in situ) in the presence of a joint compound such as copper chloride or copper sulfate as a catalyst.
Preferably by reaction with a salt of sulfur dioxide or sulfite, such as sodium sulfite or sodium bisulfite, at a temperature of 10°C to 60°C.

The work-up can be carried out in the usual manner: upon dilution with water, the sulfonyl chloride is generally obtained in crystalline form, which can be isolated by filtration with suction.

However, this compound can also be used in non-hydratable solvents,
For example, it can be extracted from an aqueous dispersion with methylene chloride or diethyl ether, dried and purified by vacuum distillation.

Formula (VI) shows the definition of the isothiourea used as starting material in process (c). In this formula,
R5 preferably represents C1-C4-alkyl or benzyl, in particular methyl, and R1, R2 and M are preferably or especially preferably within the definition of the substituents for formula (1). have the same meaning as indicated above.

As examples of starting materials of formula (VI), the following may be mentioned: N'-(4,6-dimethoxy-s-triazin-2-yl)-, N'-(4,6-dimethyl-pyrimidine) -2-
yl)-, N'-(4-methoxy-6-methyl-pyrimidin-2-yl)-, N'-(4-ethoxy-6-methyl-pyrimidin-2-yl)-, N'-(4- propoxy-6-methyl-pyrimidin-2-yl)-, N'-(
4-Inpropoxy-6-methyl-pyrimidin-2-yl)-, N'-(4-butoxy-6-methyl-pyrimidin-2-yl)-, N'-(4-isobutoxy-6-methyl-pyrimidine -2-yl)-, N'-(4,6-dimethoxy-pyrimidin-2-yl)-, N'-(4,6
-dimethyl-s-triazin-2-yl)-, N'-(
4-Methoxy-6-methyl-s-triazin-2-yl)-, N'-(4-ethoxy-6-methyl-s-triazin-2-yl)-, N'-(4,5,6- trimethyl-pyrimidin-2-yl)- and N'-(5-chloro-
4,6-dimethyl-pyrimidin-2-yl)-, -N''
-(2-fluoro-benzenosulfonyl)-, -N″-
(2-chloro-benzenesulfonyl)-, -N″-(2
-Bromo-benzenesulfonyl)-, -N''-(2-nitro-benzenesulfonyl)-, -N''-(2-methyl-benzenesulfonyl)-, -N''-(2-methoxycarbonyl-benzenesulfonyl)- , -N″-(2-ethoxycarbonyl-benzenesulfonyl)-, -N″-(
2-Methoxy-benzenesulfonyl)-, -N″-(2
-ethoxy-benzenesulfonyl)-, -N″-(2-
phenyl-benzenesulfonyl)-, -N''-(2-trifluoromethyl-benzenesulfonyl)-, -N''-
(2-difluoromethoxy-benzenesulfonyl)-,
-N''-(2-trifluoromethoxy-benzenesulfonyl)-, -N''-(2-phenoxy-benzenesulfonyl)-, -N''-(2-methyl-5-chloro-benzenesulfonyl)-, -N ″-(2,5-dichlorobenzenesulfonyl)- and -N″-(2-chloro-5-trifluoromethyl-benzenesulfonyl)-s-methyl-
Isothiourea.

Certain isothioureas of formula (M) are known (see European Patent No. 5,986). These compounds can be prepared in a manner known per se by combining suitable isodithiocarbamic acid derivatives of the formula (VIII) in which R1 and R15 have the meanings given above, if appropriate with strong, but slightly nucleophilic -philic) in the presence of a base, such as sodium hydride, and if appropriate in the presence of a diluent, such as tetrahydrofuran, dioxane, 1,2-dimethoxyethane, dimethylformamide or dimethylsulfoxide, -2
Reaction with an amino-hetalene of the formula (IX) M-NH-R2(IX), where M and R2 have the meanings given above, at a temperature between 0°C and 100°C, preferably between 0°C and +80°C. obtained by The treatment can be carried out by a perspiration method, for example by dilution with water and acidification, for example with hydrochloric acid, after which the product of formula (VI) obtained in crystalline form can be isolated by suction filtration. .

Formula (VIII) shows the definition of the indithiocarboxylic acid derivative required as an intermediate product. In this formula,
R1 and R15 preferably also particularly have the same meanings as indicated above within the definition of the substituents for formula (I) or (VI) as preferred or especially preferred.

As examples of compounds of formula (VIII), the following may be mentioned: N-(2-fluoro-benzenesulfonyl), N-(2-chloro-benzenesulfonyl), N-(
2-Bromo-benzenesulfonyl), N-(2-nitro-benzenesulfonyl), (N-(2-methyl-benzenesulfonyl), N-(N-methoxycarbonyl-benzenesulfonyl), N-(2-ethoxycarbonyl) -benzenesulfonyl), N-(2-methoxy-benzenesulfonyl), N-(2-ethoxy-benzenesulfonyl), N-(2-phenylbenzenesulfonyl), N-
(2-difluoromethoxy-benzenesulfonyl), N
-(2-trifluoromethoxy-benzenesulfonyl)
, N-(2-phenoxy-benzenesulfonyl), N-
(2-methyl-5-chloro-benzenesulfonyl), N
-(2,5-dichloro-benzenesulfonyl) and vinyl-
(2-Chloro-5-trifluoromethyl-benzenesulfonyl)S',S''-dimethylisodithiocarbamate.

Isodithiocarbamic acid derivatives of formula (VIII) are still hardly described in the literature. These compounds can be prepared in a manner known per se [Chem. Ber. 99(
1966), 2885], of the formula (x) R1-NH2(x) in which R1 has the meaning given above, in the presence of a strong base, such as sodium hydroxide, and if appropriate a diluent, For example, in the presence of water and dimethylformamide, from -20°C to +1
Reaction with carbon disulfide at a temperature between 50°C, preferably between 0°C and 100°C, and then (in situ) between -20°C and +1
At a temperature between 50°C, preferably between 0°C and 100°C, the formula (
XI) Hal2-R15 (XI) in which R15 has the abovementioned meaning and Hal2 represents chlorine, bromine or iodine.

The product of formula (VIII), which is obtained in crystalline form after dilution with water, can be isolated by suction filtration.

In formula (X), R1 preferably or particularly has the same meaning as given above within the definition of the substituents for formula (I).

As examples of compounds of formula (X), the following may be mentioned: 2-fluoro-, 2-chloro-, 2-bromo-,
2-nitro, 2-methyl-, 2-methoxycarbonyl-
12-ethoxycarbonyl-, 2-methoxy-, 2-ethoxy-, 2-phenyl-, 2-difluoromethoxy-
, 2-trifluoromethoxy-, 2-phenoxy, 2-
Methyl-5-chloro-2,5-dichloro- and 2-chloro-5-trifluoromethyl-benzenesulfonamide.

The composition of the amino compound of formula (X) is known (European Patent No. 23,422, European Patent No. 30,140, European Patent No. 35,422, European Patent No. 44,807, European Patent No. 44,
No. 808, No. 44,809, No. 51,466,
Same No. 64,804, No. 70,041 and No. 70
, 802; and U.S. Pat. No. 4,372,778).

These compounds can be prepared in a manner known per se with suitable chlorine compounds R1-Cl, if appropriate using an inert diluent such as diethyl ether or tetrahydrofuran, between -20°C and +100°C, preferably between 0°C and 5
Obtained by reaction with ammonia at temperatures between 0°C. The product of formula (X) obtained in this process in crystalline form can be isolated by suction filtration.

Examples of suitable precursors of formula R1-Cl and methods for their preparation are given above in the description of the starting materials for process (b).

In formula (XI), R1 preferably represents C1-C4-allyl or benzyl, especially methyl, and Ha
12 represents chlorine, bromine or iodine.

As examples of compounds of formula (XI), the following may be mentioned: methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide and ethyl iodide, and benzyl chloride and benzyl bromide.

The compound of formula (XI) is a known compound.

Formula (IX) furthermore shows the definition of the amino-hetalenes used as intermediates. In this formula, R2 preferably or particularly represents the same radicals as indicated within the definition of the substituents for formula (I), and M is hydrogen, sodium or potassium. or one equivalent of magnesium or calcium, especially hydrogen.

As examples of compounds of formula (IX), the following may be mentioned: 4,6-dimethyl-, 4,5,6-trimethyl-, 5-chloro-4,6-dimethyl-, 4-methoxy-
6-methyl-, 4-ethoxy-6-methyl-, 4-propoxy-6-methyl-, 4-isopropoxy-6-methyl-, 4-butoxy-6-methyl-, 4-isobutoxy-6-methyl- and 4,6-dimethoxy-2-amino-
pyrimidine, and 4,6-dimethyl-, 4-methoxy-6-methyl-, 4-ethoxy-6-methyl- and 4,
6-dimethoxy-2-amino-s-triazine.

Compounds of formula (IX) are known and/or can be prepared by methods known per se [Chem. Pharm. Bull. 11 (1963)
, 1382-1388: and U.S. Patent No. 4,299,9
See No. 60].

Formula (III) defines the amino compound used as starting material in process (c) according to the invention. Formula (II
Preferred and particularly preferred meanings of I) were given above in the description of the starting materials for process (a).

Formula (I) and the conditions of process (d) above give a general definition of the guanidine derivatives used as starting materials in process (d).

In formula (I), for the guanidine derivatives used as starting materials for process (d), R1 and R3 are preferably groups -S(O)m-R5 and -S(O), respectively.
n-R5, where m and n and R5 and R6
preferably and particularly preferably have the same meanings as indicated above within the definition of the substituents for formula (I); furthermore R2, R4 and M preferably and especially , preferably or particularly preferably have the same meanings as given above within the definition of the substituents for formula (I).

Examples of compounds of formula (I) used as starting materials in process (d) include: N'-
(4,6-dimethyl-pyrimidin-2-yl)-N″-
Methoxy-N'',N'''-bis(2-chlorobenzenesulfonyl)-, -N'',N'''-bis(2-bromo-benzenesulfonyl)-, -N''N'''-bis(2-fluoro- benzenesulfonyl)-, -N'', N'''-bis(2-methoxy-benzenesulfonyl)-, -N'', N
"'-bis(2-methyl-benzenesulfonyl)- and -N",N"'-bis(2-methoxycarbonyl-benzenesulfonyl)-guanidine.

The guanidine derivatives of formula (I) used as starting materials for process (d) have not been previously described in the literature. These can be manufactured by the manufacturing method described in method (b).

Formula (III) shows the definition of the amino compound starting material in process (c) according to the invention.

The preferred and particularly preferred meanings of R3 and R4 and the sequence of compounds of formula (III) were given above in the description of the starting materials for process (a).

The conditions shown in formula (I) and method (c) above correspond to method (e).
The definition of the guanidine derivative used as a starting material is shown in . In formula (I), for the guanidine derivatives used as starting material for process (e), M is hydrogen and R1, R2, R3 and R4 are preferably or particularly preferably of the formula ( Within the definitions of the substituents for I) have the same meanings as given above.

As examples of compounds of formula (I) used as starting materials in process (e), mention may be made of: N'-
(4,6-dimethyl-pyrimidin-2-yl)-A″-
Methoxy-N″,N″′-bis(2-fluoro-benzenesulfonyl)-, N″,N″′-bis(2-bromo-
benzenesulfonyl)-, -N'',N'''-bis(2-
methoxy-benzenesulfonyl)-, -N″,N″′-
Bis(2-methyl-benzenesulfonyl)- and -N″
, N″′-bis(2-methoxycarbonyl-benzenesulfonyl)-guanidine, and N′-(4,6-dimethyl-pyrimidin-2-yl)-N″-methoxy-N″
'-(2-fluoro-benzenesulfonyl)-, -N''
'-(2-chloro-benzenesulfonyl)-, -N'''
-(2-bromo-benzenesulfonyl)-, -N″'-
(2-methyl-benzenesulfonyl)-, -N″′-(
2-methoxy-penzenesulfonyl)- and -N″'-
(2-methoxycarbonyl-benzenesulfonyl)-guanidine.

The guanidine derivatives of formula (I) used as starting materials for process (e) have hitherto not been described in the literature. The derivatives can be prepared by the above methods (a), (b), (c) and (d).
) can be obtained by the manufacturing method described above.

Examples of metal hydroxides, hydrides or alcoholates or organometallic compounds used in process (e) include: lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide and water. Calcium oxide, lithium hydride, sodium hydride and calcium hydride, sodium methylate and ethylate,
Potassium methylate and ethylate and potassium t-butyrate, and butyllithium and isopropyl-magnesium chloride.

As examples of amines which may be used, if appropriate, in process (e), the following may be mentioned: isopropylamine, diisopropylamine, isobutylamine, sec-butylamine, tert-butylamine, diisobutylamine, trimethylamine, triethylamine, dibenzyl. Amine and ethyl-diisopropylamine.

Formula (I) shows the definition of the guanidine derivative used as starting material in process (f). In formula (I), R1, R2, R3, R4 and M preferably or particularly have the same meanings as given above within the definition of substituents for formula (I). has. Examples of compounds of formula (I) which can also be used as starting materials in process (f) are given above in the description of the starting materials for process (e).

In method (f), strong acids are used as starting materials.

These acids are preferably hydrohalic acids such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide, as well as sulfuric acid and phosphoric acid, or having up to 4 carbon atoms and optionally substituted with fluorine or chlorine. Alkanesulfonic acids, which may be present, such as methanesulfonic acid, ethanesulfonic acid, chloromethanesulfonic acid, 2-chloroethanesulfonic acid and trifluoromethanesulfonic acid, and also benzenesulfonic acid, p-toluenesulfonic acid, naphthalene-1-
These are sulfonic acid, naphthalene-2-sulfonic acid, naphthalene-1,4-, 1-1,5-, -1,6-, -2,6- and -2,7-disulfonic acid.

Particular preference is given to hydrohalic acid (hydrogen chloride), sulfuric acid, benzenesulfonic acid and p-toluenesulfonic acid.

Process (a) is preferably carried out using a diluent.

Suitable diluents are all inert organic solvents. Particular preference is given to alcohols such as methanol, ethanol, n- and isopropanol, and n-, iso-, sec- and tert-butanol. Ethanol is particularly preferred as solvent.

Practically all commonly used acid binders can be used as acid acceptors. Acid binders include in particular alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal carbonates, ammonia (if appropriate aqueous ammonia), and aliphatic, aromatic or heterocyclic amines, such as Triethylamine, N,N-dimethylaniline, N,
Includes N-dimethylbenzylamine, pyridine, diazabicyclooctane and diazabicycloundecene (DHU).

In process (a), the reaction temperature can be varied within a relatively wide range. Generally, this reaction takes place between 0°C and 150°C.
The temperature is preferably between 20°C and 120°C. Process (a) is generally carried out under atmospheric pressure.

To carry out the process (a) according to the invention, the formula (II
) per mole of cyanide compound of formula (III) or its hydrochloride between 0.5 and 5 moles, preferably 1
The amount between 3 and 3 moles is used.

The starting materials of formula (II) and (III) and, if appropriate, the diluent are generally combined at room temperature or with slight external cooling, and the reaction mixture is stirred, if appropriate at elevated temperature, until the reaction is complete.

Work-up and isolation of the new compounds of formula (I) are carried out in the customary manner: the solution, if appropriate after cooling and if appropriate after filtration, is diluted with water or evaporated under vacuum to form a residue. is dissolved in water and the solution, after appropriate filtration, is brought to a slightly alkaline pH value, if necessary with one of the acid acceptors mentioned above. The product of formula (I) is obtained in this process in crystalline form and can be isolated by suction filtration.

Process (b) according to the invention in preparing the new compounds of formula (I) is preferably carried out using a diluent.

Suitable diluents are in fact any inert organic solvents, but
However, an aprotic polar injection solvent is preferred. These solvents include optionally propanated hydrocarbons such as methylene chloride, chloroform, toluene and chlorobenzene, nitriles such as acetonitrile and propionitrile, dimethylformamide, dimethylacetamide, dimenal sulfoxide, sulfolane, hexamethylphosphoric triamide, 1,2-dimethoxyethane, pyridine and 2-
Includes methyl-5-ethyl-pyridine.

As acid acceptor in process (b) it is possible to use virtually all commonly used acid binders.

These acid binders are in particular alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal hydrides, organometallic compounds such as butylurium, and also aliphatic, aromatic or heterocyclic amines such as trimethylamine, Triethylamine, N,N-dimethylaniline, N
, N-dimethyl-benzylamine, diazabicyclooctane (DABCO), diazabicycloundecene (DB
U) Includes pyridine and 2-methyl-5-ethyl-pyridine.

In process (b), the reaction temperature can be varied over a relatively wide range. Generally, this reaction takes place between -80°C and +1
It is carried out at a temperature between 00°C and preferably between -30°C and +50°C. Process (b) according to the invention is generally carried out under atmospheric pressure.

To carry out the method (b) according to the invention, generally formula (1)
per mole of guanidine intermediate of formula (IV) or (
Between 0.5 and 5 mol, preferably between 1 and 3 mol of the halogen/sulfur compound of V) is used.

The reaction components are usually combined under room temperature or external cooling, and the reaction mixture is stirred until the reaction is complete.

The work-up and isolation of the new compounds is carried out in the usual manner: the mixture is shaken, if appropriate after distilling off the volatile constituents, with water and a non-hydratable solvent such as methylene chloride, chloroform or toluene, and the organic Wash the phase with water, dry and
Filter and evaporate. Formula (I) remaining as residual liquid
The product is crystallized by disintegration with an organic solvent such as diethyl ether, ethyl acetate, ethanol or isopropanol and, if necessary, purified by recrystallization.

Process according to the invention for producing compounds of formula (I) (
c) is carried out using a diluent. Suitable diluents are especially all inert organic solvents. These solvents include, in particular, optionally chlorinated hydrocarbons, such as chloroform, carbon tetrachloride,
Toluene, xylene, chlorobenzene and 1,2-dichlorobenzene, ethers such as diisopropyl ether and dibutyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane and diglycol dimethyl ether (diglyme), nitriles such as acetonitrile and propionitrile, and dimethyl Includes formamide, dimethylacetamide, dimethylsulfoxide and sulfolane.

As acid acceptor in process (c), an acid binder is used which has nucleophilic properties that are not clearly opposed to the amino compound of formula (III). Examples of acid binders that may be mentioned are alkali metal and alkaline earth metal carbonates, such as potassium carbonate and calcium carbonate, tertiary amines, such as triethylamine,
N,N-dimethylaniline and N,N-dimethylbenzylamine and nitrogen heterocycles such as pyridine, diazabicyclooctane (DABCO) and diazabicycloundecene (DBU).

In process (c), the reaction temperature can be varied within a relatively wide range. Generally, this reaction is carried out between 0 and 200°C.
Preferably it is carried out at a temperature between 20°C and 120°C. Process (c) is generally carried out under atmospheric pressure.

When carrying out the process (c) according to the invention, the formula (VII
) is used between 1 and 5 mol, preferably between 1 and 3 mol of the amino compound of formula (III) per mol of isothiourea.

Generally, the isothiourea of formula (VI) and the diluent are first introduced at room temperature, and the amino compound of formula (III) or its hydrochloride and the acid acceptor are metered in. The reaction mixture is then stirred, generally at elevated temperature, until the reaction is complete.

On cooling, the product of formula (I) is usually obtained in crystalline form;
This can be isolated by suction filtration. If the compound of formula (I) is obtained in the form of an ammonium salt,
The corresponding acids (M=H) can be prepared from this ammonium salt by dissolving it in water and acidifying the solution, for example with hydrochloric acid or sulfuric acid.

Process (d) according to the invention is preferably carried out using a diluent. Suitable diluents are in fact all inert organic solvents and, if appropriate, also water. These solvents include, in particular, alcohols such as methanol, ethanol, n- and isopropanol, ethers such as tetrahydrofuran, dioxane and 1,2-dimethquinethane, esters such as methyl acetate and ethyl acetate, nitriles such as acetonitrile and propionitrile, and Contains dimethylformamide as well as water.

As acid acceptor in process (d) it is possible to use acid binders which have nucleophilic properties that are not clearly opposed to the amino compounds of formula (III).

Acid acceptors that may be mentioned are alkali metal and alkaline earth metal carbonates, such as potassium and calcium carbonate, tertiary amines such as triethylamine, N,N-dimethylaniline and N,N-dimethylbenzylamino, and nitrogen heterocycles. , such as pyridine, diazabicyclooctane (DABCO) and diazabicycloundecene (DBU
).

In process (d), the reaction temperature can be varied within a relatively wide range. Generally this reaction is carried out at a temperature between 0°C and 150°C, preferably between 10°C and 100°C.

Process (d) is generally carried out under atmospheric pressure.

When carrying out process (d) according to the invention, generally between 1 and 10 mol, preferably between 2 and 5 mol of amino compound of formula (III) are used per mole of guanidine intermediate of formula (I).

Generally, the guanisine derivative of formula (I) and the diluent are first introduced at room temperature or with slight cooling, and the guanisine derivative of formula (III) is first introduced at room temperature or with slight cooling.
) or its hydrochloride and a suitable acid acceptor are metered in. The reaction mixture is then generally stirred at room temperature or at elevated temperature until the reaction is complete.

Processing can be carried out in the usual way. If the product of formula (I) is obtained from the reaction mixture in crystalline form, it can be isolated by suction filtration. In other cases, after evaporation if necessary, the mixture is diluted with water and extracted with a solvent that is non-hydratable in nature, such as methylene chloride. By washing the extract with water, drying, filtering, evaporating the filtrate and recrystallizing the residue,
The product of formula (I) is obtained as pure substance.

Process (e) according to the invention is preferably carried out using a diluent. Suitable diluents are virtually all inert organic solvents. These solvents include in particular alcohols such as ethanol, n- and isopropanol, ethers such as tetrahydrofuran, dioxane and 1,2-dimethoxyethane, esters such as methyl acetate and ethyl acetate, and nitriles such as acetonitrile.

In process (e), the reaction temperature can be varied over a relatively wide range. Generally, this reaction takes place between -20°C and +50°C.
It is carried out at a temperature between 0°C and 30°C, preferably between 0°C and 30°C.

Process (e) is generally carried out under atmospheric pressure.

When carrying out the process (e) according to the invention, generally 0 metal compounds or amines per mole of guanidine fat body of formula (I) are used.
．． Between 9 and 1.2 mol, preferably between 0.95 and 1.1
Use molar terms.

Generally, the guanidine derivative of formula (I) and the diluent are introduced first and, if appropriate with some external cooling, the metal compound or amine, if appropriate dissolved in the diluent, is metered in. The reaction mixture is stirred until the reaction is complete. Generally, the salt-like products of formula (I) are obtained in crystalline form and can be isolated by suction filtration.

Process (f) according to the invention is preferably carried out using a diluent. Suitable diluents are in fact all common solvents.

These solvents include in particular alcohols such as methanol, ethanol, n- and inpropanol, ethers such as tetrahydrofuran, dioxane and 1,2-dimethoxyethane, and esters such as methyl acetate and ethyl acetate.

If the starting material is used as an aqueous solution, acetic anhydride can also be advantageously used as a diluent.

In process (f), the reaction temperature can be varied within a relatively wide range. Generally, this reaction takes place between -20°C and +50°C.
It is carried out at a temperature between 0°C and 30°C, preferably between 0°C and 30°C.

Process (f) is generally carried out under atmospheric pressure.

When carrying out process (f) according to the invention, generally between 1 and 10 mol, preferably between 1.5 and 5 mol of strong acid are used per mole of guanidine derivative of formula (I).

Generally, the guanidine derivative of formula (I) and the diluent are introduced into the reactor, and the strong acid is metered in, if appropriate with slight external cooling. The reaction mixture is stirred until the reaction is complete. Generally, a 1:1 adduct is obtained in crystalline form, which can be isolated by suction filtration.

The active compounds according to the invention influence plant growth and can therefore be used as defoliants, desiccants, broad-leaved plant eradicators and germination inhibitors, in particular as weed killers, and also as plant growth regulators. Weeds, in a broad sense, refer to all plants that grow where weeds are not desired. Whether the substances according to the invention act as complete herbicides or selective herbicides or as plant growth regulators essentially depend on the mode of use.

The active compounds according to the invention can be used, for example, to combat the following plants: Dicotyledonous plants of the following genera: Sinapis, Lepidium, Galium, Chickweed. (Stellaria)
, Matricaria, Anthemis, Galinsoga
soga), Chenopodium, Urtica, Senacio
), Amaranthus, Portulaca (
Portulaca), Xantium
), Convolvulus, Ipomoea, Polygonum
), Sesbania, Onamia (
Ambro-sia), Cirsium,
Cardus, Sonc
hus), Solanum, Solanum (
Rolippa”), Rotala (Rotala),
Lindernia, Lamium
ium), Veronica, Abutilon, Emex,
Datura (Datura), Viola (V
iola), Galsopsis
, Papaver and Centaurea
ntau-rea).

Dicotyledonous plants of the following genera: Gossypium
), Glycine, Be
ta), carrot genus (Daucus), kidney bean genus (Phaseo-lus), pea genus (Pisum)
, Solanum, Linum,
Sweet potato (Ipomoea), broad bean (Vic)
ia), Nicotiana, Tomato (
Lycopersicon), Arachis (Arac
his), Brassica, Lactuca, Cucumi
s) and Cucurbita.

Monocots of the following genera: Echinochloa
), Setaria, Pa
nicum), Digitaria, Phleum, Phleum (P
oa), Festuca, Elgusine, Bracharia
iaria), Lolium, Bromus, Avena
), Cyparrus, Sorghum, Agropyro
n), Cynodon, Cynodon (
Mono-charia), Fimbis
tylis), Omodakaso (Sagittaria),
Genus Eleocharis, Genus Firefly (S
circus), Paspa-lum
, Platypus (Ischaemum), Spenoclea (Spenoclea), Dactyloctenium (Da
ctyloctenium), Agrost
it), Alopecurus
and Apera.

Monocotyledonous cultivated plants of the following genera: Oryza, Zaa, Triticum
, barley family (Hordeum), oat family (Av
ena), Secale, Sorghum, Ponicum, Saccharum, Ana
nas), Asparagus and Allium.

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

Depending on the temperature, the compounds can be used as complete herbicides of weeds, for example in industrial areas and on railway tracks, on roads and squares with or without trees. Equally, the compounds may be used in perennially cultivated plants, such as silviculture, ornamental trees, orchards, vineyards, citrus groves, walnut orchards, banana plantations, coffee plantations, tea plantations, rubber tree plantations, oil plantations, etc. For complete weed control in palm plantations, cacao plantations, soft fruit plantations and hop cultivation gardens.
and can be used for selective control of weeds in annual crops.

The active compounds according to the invention are related to plant metabolism;
Therefore, it can be used as a growth regulator with certain essential conditions.

Experience to date with the mode of action of plant growth regulators has shown that the active compounds have several different effects on plants. The action of the compounds depends essentially on the time at which they are used, the developmental stage of the plant, and the amount of active compound applied to or around the plant and the method of application of the compound. In each case, the growth regulator influences the cereal seed in a specific desired way.

Plant growth regulating compounds can be used, for example, to stimulate plant growth. Such growth control is due, inter alia, to economic interests in the case of grasses, as it allows them to be used in ornamental gardens, in parks and playgrounds,
This is because it is possible to reduce the number of times of mowing at borders, at ports, or within orchards. It is important to control the growth of grasses and woody plants in areas where significant additional growth of plants is undesirable, such as within boundaries and near pipe lines or overland lines, or quite generally.

It is also important to use it for growth regulation to suppress the growth of grain bamboo. This causes the plants to droop (L) before harvesting.
odgoing) is reduced or completely eliminated. Furthermore, growth regulators can lengthen the grain stalks, which also prevents drooping. The use of growth regulators to shorten and lengthen stems can increase the amount of fertilizer used to increase yield without the risk of grain wilt.

In the case of many cereal plants, suppression of plant growth allows for more dense planting and thus higher yields per area of land. An advantage of the small plants thus created is that the crop can also be more easily handled and harvested.

Suppression of plant growth also results in increased yields, since nutrients and assimilates are available to a greater extent for flowering and fruit formation than for the growing parts of the plant.

Plant growth can also often be promoted with growth regulators. It is highly advantageous if this promotion is the growing part of the plant to be harvested. However, the promotion of plant growth also results in the promotion of reproduction at the same time, since more assimilates are produced and therefore more or larger fruits are obtained.

In some cases, they can act on plant metabolism to increase yield without appreciable changes in plant growth. Furthermore, growth regulators can bring about changes in the composition of the plant that can also lead to better quality of the crop.

Thus, for example, it is possible to increase the sugar content in sugar beet, sugar cane, pineapple and citrus fruits, or to increase the protein content in soybeans or grains. Growth regulators can also be used to prevent degradation of desired components, such as sugars in sugar beet or sugar cane, before or after harvest. It is also possible to advantageously influence the production or effluent of the second plant component. An example of this is the stimulation of latex flow in rubber trees.

Unit-bearing fruits can be produced under the influence of growth regulators. Furthermore, it can influence the sex of the flower. It is also possible to nullify pollen, which is extremely important in the propagation and production of hybrids.

Plant branching can be controlled by growth regulators. On the other hand, by preventing the dominance of the apex, the development of lateral buds can be promoted, which is highly desirable for the cultivation of ornamental plants as it relates to growth inhibition. However, on the other hand, it is also possible to suppress the growth of lateral buds. This effect is extremely important, for example in tobacco cultivation or tomato cultivation.

The amount of leaves in the plants can be regulated under the influence of growth regulators, so that defoliation of the plants can take place at the desired time. Such defoliation is extremely important in mechanical harvesting of cotton, but also for harvest promotion in other crops, such as viticulture. Defoliation of plants can also be done to reduce plant transpiration before transplanting the plants.

In addition, fruit drop can be suppressed using a growth regulator.

On the other hand, it is possible to prevent the fruits from falling prematurely. However, on the other hand, fruit fall or flower fall can be accelerated to a certain extent (sparse) in order to prevent replacement. By alternation, it will be understood that certain variations in fruit are characteristic of producing very different yields from year to year for reasons of intrinsic origin. Finally, the use of growth regulators can reduce the force required to thin the fruit at harvest;
Mechanical harvesting is therefore possible or manual harvesting is facilitated.

Growth regulators can also be used to accelerate or delay ripening of the crop before or after harvest.

This is particularly advantageous since it allows optimal adaptation to market requirements. Additionally, growth regulators can sometimes improve fruit color. In addition, growth regulators can also concentrate maturation within a certain period of time. This provides the prerequisite, for example in the case of tobacco, tomatoes or coffee, that complete mechanical or manual harvesting can be carried out in just one pass.

Growth regulators can be used to influence the incubation period of the seeds or shoots of plants, so that plants such as pineapples or ornamental plants in the nursery germinate, branch or flower at unusually untimely times. Retardation of bud set-off or seed germination by growth regulators is desirable in areas at risk of frost to avoid damage from late frosts.

Finally, tolerance in plants to frost, drought or high salt content in the soil can be induced by growth regulators. It is therefore possible to grow plants in locations not normally suitable for this purpose.

The active compounds can be used in common compositions, such as solutions, emulsions, suspensions, powders, capsules, liniments, granules, aerosols, very fine capsules in polymeric substances for seeds and coating compositions. can be converted into ULV compositions.

These compositions are prepared in a known manner, for example by combining the active compounds with extenders, i.e. liquid solvents, gases liquefied under pressure and/or solid carriers, and optionally surfactants, i.e. emulsifiers and/or dispersants and/or foaming agents. It can be manufactured by mixing it with other agents. Further, when water is used as an extender, for example, an organic solvent can also be used as an auxiliary solvent. As liquid solvents, mainly aromatic hydrocarbons such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane, or paraffins such as mineral oil components are used. , alcohols such as butanol or glycols and their ethers and ester-ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strong organic solvents such as dimethylformamide and dimethyl sulfoxide and water. By liquefied gaseous diluent or carrier is meant a liquid that is a gas at normal temperature and pressure, such as halogenated hydrocarbons and aerosol propellants such as butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are ground natural minerals such as kaolin, clay, talc, chalk, quartz, attapulsite, montmorillonite or diatomaceous earth, as well as synthetic minerals such as highly dispersed silicic acid, alumina and silicates. There is. As solids for the granules, ground and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as inorganic and organic ground synthetic granules and granules of organic substances such as sawdust, coconut shell, corn flour, etc. are used. Cobs and tobacco stalks are suitable. As emulsifiers and/or blowing agents, non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers such as alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, arylsulfonates and albumin hydrides can be used. Decomposition products are suitable. Dispersants include, for example, lignin sulfite waste liquor and methylcellulose.

Extending agents such as carboxymethyl cellulose as well as powders,
Particulate or lattice natural and synthetic polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate can be used in the composition.

Colorants such as inorganic pigments such as iron oxide, titanium oxide and Prussian blue and organic dyes such as alizarin dyes, azo dyes or metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc. can be used.

The preparations generally contain from 0.1 to 9.5% by weight, preferably from 0.5 to 90% by weight of active compound.

The active compounds according to the invention are present in compositions as mixtures with the previous known active compounds, such as fungicides, insecticides, nematicides and herbicides, and also as mixtures with fertilizers and other growth regulators. be able to.

The herbicide for this mixture is a known herbicide, such as 1-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2 for controlling weeds in cereals. ,4(1H,3H)-dione or N-(
2-benzothiazolyl)-N,N'-dimethyl-urea; 4-amino-3- to control weeds in sugar beet
Methyl-6-phenyl-1,2,4-triazine-5 (
4H)-one and 4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one for controlling weeds in soybeans. Surprisingly, some mixtures also have a synergistic effect.

The active compounds may be used as such, or in the form of preparations or seed forms prepared from said preparations, such as ready-made solutions (
ready-to-use solutions), concentrated emulsions, emulsifiers, foams, suspending agents, wettable powders, liniments, wettable powders, powders and granules. These are applied in the customary manner, for example by liquid dispersion, liquid spraying, atomizing, granulation, dusting, foam application, coating, etc. Additionally, active compounds can be prepared using ultra-low volume methods.
-low volume process), or the preparation of the active compound or the active compound itself can be injected into the soil.

The active compounds according to the invention can be applied to the plants both before and after emergence. The present compound is preferably added to the plant before germination. That is, it is applied by the pre-emergence method. The compound can also be incorporated into the soil before sowing seeds.

The amount of active compound applied can vary within a substantial range. This amount essentially depends on the type of effect desired. Generally the applied amounts are between 0.001 and 10 kg of active compound per hectare, preferably between 0.01 and 5 kg/ha.

Regarding the timing of application, the growth regulator is applied at a preferred time, the exact definition of which depends on the weather and growing environment.

The following examples further illustrate the invention.

Production Examples: Example 1 (Method a) O-methylhydroxylamine hydrochloride 109 g (0.6
7 mol), 99 g (0.67 mol) of 2-cyanoamino-4,6-dimethyl-pyrimicine and 600 m of ethanol.
The mixture was heated to boiling under reflux for 7 hours. after that,
The alcohol was distilled off under vacuum using a water temperature pump, the remaining amount was dissolved in hot water, and 100 ml of ammonia was added to this solution. The crystallized product was filtered off with suction and recrystallized from ethanol.

N'-(4,6-dimethyl-
pyrimidin-2-yl)-N″-methoxyguanidine 7
1.8 g (55% of theory) was obtained.

Example 2 (Method a) 7.7 g (0.06 mol) of 4-chloroaniline hydrochloric acid,
2-cyanoamino-4,6-dimethylpyrimidine 7.4
A mixture of g (0.05 mol) and 150 ml of ethanol was heated to boiling under reflux for 15 hours. After cooling, the reaction mixture was diluted with 150 ml of water and made alkaline with 2N sodium hydroxide solution. The crystallized product was filtered off with suction.

8.3 g (60% of theory) of N'-(-4,6-dimethylpyrimidin-2-yl)-N''-(4-chlorophenyl)-guanidine having a melting point of 203 DEG C. were obtained.

Example 3 (Method a) 45 g (0.65 mol) of n-butylamine in 2-cyanoamino-4,6-dimethyl-
It was added dropwise to a solution of 45 g (0.3 mol) of pyrimidine, and the mixture was heated to boiling under reflux for 15 hours. After cooling, the mixture was filtered and about 1.5 liters of water was added to the filtrate. The crystallized product was filtered off with suction.

59.5 g of N'-(4,6-dimethyl-pyrimidin-2-yl)-N''-butyl-guanidine with a melting point of 185°C (
96% of theory) was obtained.

Example 4 (Method b) N'-(4,6-dimethyl-pyrimidin-2-yl)-
29.4 g (0.15 mol) of N''-methoxy-guanidine, 63.2 g of 2-chloro-benzenesulfonyl chloride.
A mixture of 6 g (0.3 mol) and 150 ml of pyridine was stirred at 20° C. for 2 days. After the pyridine had been substantially distilled off under a water jet vacuum, 200 ml of water were added to the residue and the mixture was extracted with 200 ml of methylene chloride.

The organic phase was separated, dried and evaporated. The residue was triturated with ethanol to crystallize.

N'-(4,6-dimethyl-
pyrimidin-2-yl)-N″-methoxy-N″,N″
41.2 g (51% of theory) of '-bis(2-chloro-benzenesulfonyl)-guanidine were obtained.

The above structural formula was applied to the crystalline state, which was confirmed by X-ray structural analysis. Other spectroscopic data (IR, 3H- and 13C-NMR) and elemental analysis confirmed this structural formula.

Example 5 (Method b) 113 g (0.48 mol) of 2-methoxycarbonyl-benzenesulfonyl chloride was mixed with 35.1 g (4,6-dimethyl-pyrimidin-2-yl)-N''-methoxy-guanidine ( 0.18 mol) and pyridine 160 m
1 of the mixture cooled to 10° C. and the reaction mixture was stirred at 20° C. for 2 days.

After the pyridine has been substantially distilled off under a water pump vacuum, 200 ml of water are added to the residue and the mixture is extracted with 200 ml of methylene chloride. The organic phase was separated, dried over sodium sulphate, filtered and evaporated. The residue was triturated with isopropanol to crystallize.

N′-(4,6-dimethyl-pyrimidin-2-yl)-N″-methoxy-N″,N″′-bis(
59 g (55% of theory) of 2-methoxycarbonyl-benzenesulfonyl)-guanidine were obtained.

The above structural formula fits the crystalline state, which was confirmed by X-ray structural analysis. Other spectroscopic data (IR, 1H- and 13C-NMR) and elemental analysis confirmed this structure.

Example 6 (Method b) 21.2 g of 2-chloro-benzenesulfonyl chloride
(0.1 mol) to N'-(4,6-dimethyl-pyrimidin-2-yl)-N''-phenyl-guanidine 12.1
g (0.05 mol), triethylamine 10.5 g (0
, 1 mol) and 100 ml of chloroform.
C. and the reaction mixture was stirred at 20.degree. C. for 15 hours.

Afterwards, the reaction mixture was shaken with water, the organic phase was separated and evaporated. The residue was suspended in ethanol, the suspension was filtered, the filtrate was evaporated and the residue was triturated with ethyl acetate to crystallize.

N′-(4,6-dimethyl-pyrimidin-2-yl)-N″-phenyl-N″,N″′-bis(
2-Chloro-benzenesulfonyl)-guanidine 6.6
g (22% of theory) was obtained.

Example 7a and Example 7b (Method b) 2,5-dichloro-benzenesulfonyl chloride 12
．． 2g (0.05 mol) of N'-(4,
12.1 g (0.05 mol) of 6-dimethyl-pyrimidin-2-yl)-N''-phenyl-guanidine, 5.1 g (0.05 mol) of triethylamine, and 1 g of chloroform.
50 ml of the mixture and the reaction mixture was heated at 20°C for 1 hour.
Stirred for 5 hours. Then, add 5% hydrochloric acid to 100% of the reaction mixture.
ml, evaporated, the residue was triturated with ethanol and the product was filtered off with suction.

N′-(4,6-dimethyl-pyrimidin-2-yl)-N″-phenyl-N″-(2,5-dichloro-benzenesulfonyl)-guanidine with melting point 188°C (Example 7a)
) 3.5 g (16% of theory) were obtained.

The product, which gradually crystallized from the mother liquor, was isolated after a few days by suction filtration. N′-(4,6-dimethyl-pyrimidin-2-yl)-N″-phenyl-N″- with melting point 153°C
1.8 g (8% of theory) of (2,5-dichloro-benzenesulfonyl)-guanidine (Example 7b) were obtained.

Example 8 (Method b) 1.6 g (0.055 mol) of 80% sodium hydride was dissolved in N'-(4,6-
14.3 g (0.05 mol) of dimethyl-pyrimidin-2-yl)-N″-(4-nitrophenyl)-guanidine
portions at 20°C to 30°C and the mixture was stirred at 20°C for 15 hours.

Then, 2-chlorobenzenesulfonyl chloride 10
．． 6 g (0.05 mol) was added dropwise, and the reaction mixture was heated to 20°C.
The mixture was stirred for 15 hours. Then, 500 ml of 5% hydrochloric acid was added. The product obtained in crystalline form was filtered off with suction.

N'-(4,6-dimethyl-pyrimidin-2-yl)-N''-(4-nitrophenyl)-N''' with melting point 220°C
-(2-chloro-benzenesulfonyl)-guanidine 9
．． 4 g (41% of theory) were obtained.

Example 9 (Method b) 5.3 g of 2-chloro-benzenesulfonyl chloride (
0.025 mol), 7.3 g (0.025 mol) of N'-(4,6-dimethyl-pyrimidin-2-yl)-N'',N'''-dibutyl-guanidine and 5 mol of triethylamine.
．． It was added dropwise to 3 g (0.05 mol) of the mixture at 20°C.

The reaction mixture was stirred at 20°C for 15 hours, then 5% hydrochloric acid 1
00ml and evaporated. The residue was triturated with ethanol to crystallize.

N'-(4,6-dimethyl-pyrimidin-2-yl)-N'',N'''-dibutyl-N''-(2
-chloro-benzenesulfonyl)-guanidine 1.8g
(16% of theory) was obtained.

Example 10a and Example 10b (Method c) 4.5 g (0.1 mol) of dimethylamine was added to N'-(4,
6-dimethoxy-s-triazin-2-yl)-N″-
Passed into a mixture of 15 g (0.037 mol) of (2-chloro-benzenesulfonyl)-S-methyl-isothiourea and 100 ml of dithioxane at 25°C to 35°C. The reaction mixture was then stirred at 80°C for 1 hour. After cooling the reaction mixture, the product obtained in crystalline form was filtered off with suction.

N'-(4,6-dimethoxy-s-triazin-2-yl)-N'',N'''-dimethyl-N''' with melting point 162°C
12.1 g (73% of the amount of hydrochloric acid) of the dimethylammonium salt of -(2-chloro-benzenesulfonyl)-guanidine (10a) was obtained.

The ammonium salt (10a) was dissolved in 20 ml of water and the solution was made acidic with concentrated hydrochloric acid. The product obtained in this way in crystalline form was isolated by filtration with suction.

N'-(4,6-dimethoxy-s-triazin-2-yl)-N'',N'''-dimethyl-N''', melting point 185°C
-(2-chloro-benzenesulfonyl)-guanidine (
10b) 4 g (28% of theory) were obtained.

Example 11 (Method d) N'-(4,6-dimethyl-pyrimidin-2-yl)-
N″-methoxy-N″,N″′-bis(2-chloro-benzenesulfonyl)-guanidine (4) 5.5 g (0.
01 mol) -N,N-dimethylhydrazine 1.5 g (0
．． 025 mol) - A mixture of 20 ml of ethanol and 10 ml of water was heated to boiling under reflux for 15 minutes. After the mixture had cooled, the product obtained in crystalline form was isolated by filtration with suction.

N′-(4,6-dimethyl-pyrimidin-2-yl)-N″-dimethylamino-N″′-(2-
2.5 g of chloro-benzenesulfonyl)-guanidine (
65% of theory) was obtained.

Example 12 (Method d) N'-(4,6-dimethyl-pyrimidin-2-yl)-
N″-methoxy-N″,N″′-bis(2-chloro-benzenesulfonyl)-guanidine (4) 5.5 g (0.
01 mol), hydroxylamine hydrochloride 2.1 g (0.01 mol), hydroxylamine hydrochloride 2.1 g (0.01 mol)
03 mol), a mixture of 30 ml of ethanol and 5 ml of water, and 3.0 g (0.03 mol) of triethylamine were added to 2
Stirred at 0°C for 6 hours. The product obtained in crystalline form was isolated by suction filtration.

2.7 g (76% of theory) of N′-(4,6-dimethyl-pyrimidin-2-yl)-N″-hydroxy-N″′-(2-chloro-benzenesulfonyl)-guanidine, melting point 139°C. was gotten.

Example 13 (Method e) 0.9 g of potassium ethylate in 15 ml of ethanol (
0.01 mol) of N′-(4,6-dimethyl-pyrimidin-2-yl)-N″-methyl-N″′-(2-
3.5 g (chloro-benzenesulfonyl)-guanidine (
0.01 mol) and 15 ml of ethanol, and the reaction mixture was stirred at 20° C. for 3 hours. The product obtained in crystalline form was isolated by filtration with suction.

N′-(4,6-dimethyl-pyrimidin-2-yl)-N″-methyl-N″′-(2-chloro-
Potassium salt of benzenesulfonyl)-guanidine 3.8
g (96% of theory) was obtained.

Example 14 (Method f) 5 ml (0.05 mol) of concentrated hydrochloric acid was dissolved in N'-(4,6-dimethyl-pyrimidin-2-yl)-N''-methoxy-N''
, N″′-bis(2-chloro-benzenesulfonyl)-
Guanidine 5.5g (0.01 mol) and acetic anhydride 2
Added to 5 ml of the mixture at 20° C. (exothermic reaction) and stirred the reaction mixture for 2 hours. The product obtained in crystalline form was isolated by suction filtration.

N′-(4,6-dimethyl-pyrimidin-2-yl)-N″-methoxy-N″,N″′-bis(
4.3 g (74% of theory) of 2-chloro-benzenesulfonyl)-guanidine hydrochloride were obtained.

Example 15 (Method f) N'-(4,6-dimethyl-pyrimidin-2-yl)-
A mixture of 3.5 g (0.01 mol) of N''-methyl-N''-(2-chloro-benzenesulfonyl)-guanidine, 25 ml of isopropanol and 4.9 g (0.05 mol) of concentrated sulfuric acid was heated at 20°C for 6 hours. Stir for hours. The product obtained in crystalline form was isolated by filtration with suction.

N′-(4,6-dimethyl-pyrimidin-2-yl)-N″-methyl-N″′-(2-chloro-
benzenesulfonyl)-guanidine dihydrogen sulfate 3.1
g (64% of theory) was obtained.

By the method described by way of example in the above embodiment, the following first
Shown in the table. A compound of formula (I) could be prepared.

Table 1: Example No. R1 R2 R3 R4
M Melting point (°C) 1
6 H H -OC
2H5 H 6617
H H
H 7718 H
H
H19 H H
-CH3H2
4020 H H
-C2H5H 1842
1 H H -CH
(CH3)2 H 21322
H H H
H24023
H n-C4H9 n-C4H9
H 8824 H
H
H 19725 H H
-N(CH3)2H
14926 H H
H
20727 H H
H 1
8228 H H
H 1382
9 H H
H23230
HCH3
H 19731
H H
-CH3 20832H
H
H 20533 H
H
H34 H H -
OCH3-CH335
H
H 19636
H
H37 H
H38
H
H39 H
H40
H
H21241
H
H20842
H
H25543H

H 10344 H
H
21245H
H
24846H
H 178
47H
H23148
H
H 16549
H
H 18850
H
H 13951
H
H 13952 H
H
19153H
H
16854H
H 15
055 H n
-C4H9 H 10356
H n-C4
H9 H57
-C4H9n n-C4H9
H 15058 H
-C2H5H
11259H
-CH3H
16060-CH3
H 200
61-CH3
H 17162
H
H 18563
H
H22164
H
H23565
H
H 16266 H
H
20467H
H
22068H
H21
869H
H70
H-OCH3
H 9771 H
-OCH3H
9172
-OCH3H
15473
-OCH3 H 14
974-
OCH3 H 14275
-OCH
3 H 13576
-OC2H5
H 12977
-OC2H5
H 17078
-OCH3
H12979
-OCH3H
17180
-OC2H5H
17481
-OC2H5 H 1
5882
-OCH3H 1508
3-OC
H3 H 12184
-OCH3
H 14785
-OCH3
H 16686
-OCH3
H 19687

H 17588
H
8589H
-CH(CH3)2H1
3690H
H H 1769
1H-CH
2CH(CH3)2H 10592
H-CH2CH
2Cl H 15293
H
H22594
H H
H 16795
H-C2H5
H 14396 H
-CH2COOC2H5 H
12397H
-CH2CH=CH2H
10898-CH3
-CH3H 160
99 -CH(CH3)2 -C
H(CH3)2 H 189100
-CH(CH3)2 -CH(C
H3)2 H 88101

H 122102
H-C(CH3)3
H 113103
H-OCH3
H 142104 H
-CH3H
157105H
H
162106H
-CH2CH2OH H 841
07 H-N(
CH3)2H 150108
H-CH3
H 134109
H-OCH3
H 132110
H-C3H7n
H 100111
-C2H5 -C2H5
H 134112 H
-CH2CH2OH H
136113-C2H5
-C2H5H
145114H
H 171
115H-C
H2-CH2-OCH3 H 118116
H-N(CH
3) 2H 128117
H-NHCOCH3
H 185118
H-NHCOCH■
H 143119
H-NHCOCH3
H 150120-C
H2CH2-O-CH2CH2- H
192121H
-OCH3H
114122H
-NHCOOCH3 H 18
7123H
H 20312
4H
H 153125
H-OCH3
H 166126
H-OCH3
H 160127
H
H 210128 H
H
188129
H
100130
-OCH3 Na 1
82131
-OCH3 K 1651
32-OC
H3 1/2Ca 165133
-CH3 -OH
H 161134
H
H 121135 H
H
H 179136 H
H
H 171137 H
i-C3H7H
185138H
n-C4H9H
103139H
-OCH3H 901
40H
H 170141
H
CH3 204142
H
H 135143
H-CH2-CH=CH2
H 117144
HCH3
H 153145 H
i-C3H7H
108146H
-N(CH3)2H
140147H
-OCH3H 901
48-OC
2H5 H 139149
H
H 205150
H-NHCOOCH3
H 142151
H
H251152
H-CH2-CH(OCH3)2
H 129153 H
-OCH3H
163154
-OCH3K
170155H
H H 135
156 CH3 CH
3 H 136157
-OCH2
CH2CH3 H 110158
-OCH3
H 112159
H-OCH3
H 135160
H-OCH3
H 126161
-OCH3H
159162H
H
118163
-OCH3 H 15
0164-
OCH3 H 15716
5-OCH
3 H 150166
H -C4H9-n
H90167H
H
CH3 267168
H
H205169
H
95170H
H H171
H-OCH3
H 138172
H-N(CH3)2
H 169173
H H
H 155174 H
CH3H
153175H
H
184176 CH3
CH3 H1
70177H
CH3 H 1661
78 CH3 CH3
H88179
H-CH2-CH
=CH2H 115180
H-CH(CH3)2
H75181
H-OCH3
H91182H
-N(CH3)2H
134183H
H
113184H
CH3 H 152
185 CH3 CH
3 H 203186
H-CH2C
H=CH2H 105187
H-CH(CH3)
2 H 85188
H-OCH3
H 105189
H-N(CH3)2
H 108190 H
H
176 The preparation of several further derivatives of process (b) according to the invention is mentioned below by way of example: Preparation of the compound shown above as example (147): 2-
Chloro-benzenesulfonyl chloride 10.6 (0.
05 mol) to N'-(4,6-dimethyl-pyrimidine-
2-yl)-N″-methoxy-guanidine 4.9 g (0
．． 025 mol) and pyridine (50 ml) cooled to -7°C.

After stirring the reaction mixture at -7°C for 10 minutes, it was added 4 ml of water.
00ml was added. The product obtained in crystalline form was isolated by filtration with suction.

N'-(4,6-dimethyl-pyrimidine-) with a melting point of 90°C
2-yl)-N″-(2-chloro-benzenesulfonyl)-N″-methoxy-guanidine (5.2 g of theoretical
6%) was obtained. Preparation of the compounds shown above as Examples (35) and (6): and 10.6 g of 2-chloro-benzenesulfonyl chloride.
(0.05 mol) and 9.3 g (0.0 mol) of tributylamine.
5 mol), N'-(4,6-dimethyl-pyrimidine-2
-yl)-N''-phenyl-guanidine 6.1 g (0.
025 mol) and 60 ml of cyclohexane.
It was added dropwise at 0°C. After the mixture was stirred at 25° C. for 15 hours, it was evaporated and the residue was triturated with 50 ml of ethanol. The product obtained in crystalline form was isolated by filtration with suction.

1.4 g of N′-(4,6-dimethyl-pyrimidin-2-yl)-N″-phenyl-N″′-(2-chloro-benzenesulfonyl)-guanidine (35), melting point 196°C
(13% of theory) was obtained.

400 ml of water and 10 ml of concentrated hydrochloric acid were added to the mother liquor.

The crystalline product formed during this step was isolated by suction filtration.

N′-(4,6-dimethyl-pyrimidin-2-yl)-N″-phenyl-N″,N″′-bis(
2-Chloro-benzenesulfonyl)-guanidine (6)
5.0 g (34% of theory) was obtained. Example (10
9) Preparation of the compound shown above as - 4.9 g (0.025 mol) of guanidine and 40 m of pyridine
1 of the mixture was cooled to -7°C. After stirring the reaction mixture for 30 minutes, 200 ml of water was added to it. The product obtained in crystalline form was isolated by filtration with suction.

N′-(4,6-dimethyl-pyrimidin-2-yl)-N″-methoxy-N″′-(2-methoxycarbonyl-benzenesulfonyl)-guanidine with melting point 115°C7.
9 g (71% of theory) were obtained.

Furthermore, the following acid adducts of the compound of formula (1) were prepared in the same manner as in Example 15: (5a) 1:1 adduct of Example (5) with sulfuric acid (4a)
1:1 adduct of Example (4) with p-toluenesulfonic acid (103a) 1:1 adduct of Example (103) with sulfuric acid [Method (a1)] 2-chloro-4,6-dimethoxy -s-triazine 52
．． 7 g (0.3 mol) are added to a solution of 30 g (0.3 mol) of disodium cyanamide in 600 ml of acetone,
The reaction mixture was heated to boiling under reflux for 6 hours. After distilling off the solvent, the crystalline residue was dissolved in 250 ml of water,
This solution was made acidic with concentrated hydrochloric acid. The product obtained in crystalline form was isolated by filtration with suction.

33 g (61% of theory) of 2-cyanoamino-4,6-dimethyl-s-triazine having a melting point of 300 DEG C. or higher was obtained.

[Method (a2)] Cyanoguanison (“dicyanodiamide”) 42 g (0
．． A mixture of 50 g (0.5 mol) of 2,4-pentanedione ("acetylacetone") and 2,4-pentanedione ("acetylacetone") was heated to 120 DEG C. for 15 hours. The reaction mixture is then cooled and then
500 ml of water was added and the solution was acidified with hydrochloric acid at 0°C to 10°C.

The product obtained in crystalline form during this step was isolated by filtration with suction. 2-cyanoamino-4,6 with melting point 205°C
-dimethyl-pyrimidine 51.8 g (70% of theory)
was gotten.

In a similar manner, the following compounds of formula (II) could be prepared: 2-(allyl-cyano-amino)-pyrimidine of formula (II) could be prepared, for example, as follows: Result: 12.6 g (0.1 mol) of dimethyl sulfate in 60 ml of water 15 g (0.1 mol) of 2-cyanoamino-4-hydroxy-6-methyl-pyrimidine - prepared by method (a2) - and Sodium hydroxide 4.1g (0.1
mol) solution, and the reaction temperature rose from 20°C to 40°C. After stirring the mixture for 2 hours at 20° C., the product obtained in crystalline form was isolated by filtration with suction.

2-(methyl-cyano-amino)-4- with melting point 290°C
11.1 g (68% of theory) of hydroxy-6-methyl-pyrimidine were obtained.

The following compounds were obtained in a similar manner: Melting point: 215°C to 220°C.

127.5 g (1 mol) of dimethyl sulfate in 750 ml of water, 75 g (0.5 mol) of 2-cyanoamino-4-hydroxy-6-methyl-pyrimidine prepared by process (a2) and 44 g of sodium hydroxide. (1.1 mol) was added dropwise to the bath liquid, and the reaction sensitivity increased from 20°C to 40°C. After stirring the mixture for 12 hours at 20°C, the pH value was brought to 9-10 by addition of sodium hydroxide solution.
The product obtained in crystalline form was isolated by filtration with suction.

2-(methyl-cyano-amino)-4- with acid point 123°C
13 g of methoxy-6-methyl-pyrimidine (theoretical amount of 1
5%) was obtained.

In a similar manner the following compounds were obtained: Example for the preparation of starting materials of formulas (IV) and (V): [Method (b1)] Phosphoryl chloride ("phosphorus oxychloride") 295m
1 was added dropwise at 20°C to 30°C to a mixture of 172g (0.8 mol) of sodium 2-chloro-benzenesulfonate, 300ml of acetonitrile and 300ml of sulfolane. The reaction mixture was stirred at 70°C for 4 hours, then cooled to 5°C and diluted with ice water.

The mixture was extracted with petroleum ether, the extract was washed with water,
After drying, filtration and evaporation, the product remaining in the bottom solution was purified by high vacuum distillation.

117 g (70% of theory) of 2-chloro-benzenesulfonyl chloride with a boiling point of 110 DEG C./0.8 mm Hg were obtained.

By the same method, the following compound of formula (IV) could be produced: [Method (b2)] 75.5 g (0.5 mol) of methyl 2-aminobenzoate was mixed with 176 ml of concentrated hydrochloric acid and acetic acid. It was dissolved in 100ml.

To this solution at 0°C, add 3 ml of sodium nitrite in 70 ml of water.
4.4 g of solution was added dropwise. After stirring the reaction mixture for a further 15 minutes, it was added slowly to a solution saturated with sulfur dioxide in 450 ml of acetic acid and cooled to 0°C. After removing the cooling bath, the mixture was stirred until gas evolution had ceased and 10 g of copper(II) chloride were introduced in portions. After the mixture was diluted with ice water and extracted with methylene chloride, the extract was washed with water, dried, filtered and evaporated, the product remaining in the residue was purified by high vacuum distillation.

45 g of 2-methoxy-carbonylbenzenesulfonyl chloride (38% of theory) with a boiling point of 150°C/1 mmHg
)was gotten.

In a similar manner, the following compounds of formula (IV) could be prepared: Example of Preparation of Starting Material of Formula (VI) 11 g (0.4 mol) of sodium hydride (80%) were dissolved in tetrahydrofuran. 2-Amino-4,6- in 200ml
It was added in portions at 20 DEG C. to a suspension of 31.2 g (0.2 mol) of dimethyl-s-triazine.

After stirring the mixture for 12 hours, N-(2-chloro-
60 g (0.2 mol) of benzenesulfonyl)-S',S''-dimethylisoduthiocarpamate were added and the reaction temperature rose to 60°C. The reaction mixture was stirred at 20°C for 5 hours and diluted with 800 ml of water. After acidification with concentrated hydrochloric acid, the product crystallized and was isolated by suction filtration.

42 g (48% of theory) of N'-(4,6-dimethoxy-s-triazin-2-yl)-N''-(2-chloro-benzenesulfonyl)-S-methyl-isothiourea with a melting point of 176°C Obtained.

In a similar manner, the following compounds of formula (VI) could be prepared: Example for the preparation of starting material of formula (VIII): 8 g (0.2 mol) of sodium hydroxide - dissolved in 15 ml of water What I did-
and 6 ml (0.11 mol) of carbon disulfide were simultaneously added dropwise (from different addition funnels) to a solution of 20 g (0.1 mol) of 2-chloro-benzenesulfonamide in 80 ml of total dimethylformamide at 20°C. After stirring the mixture for 1 hour, 13 ml of methyl iodide were added dropwise and the reaction mixture was stirred for a further hour at 20°. , the product in 500 m of water
A precipitate was produced by addition of 1.1 ml of chloride, which was isolated by filtration with suction.

N-(2-chloro-benzenesulfonyl)S',S''-dimethylisodithiocarbamate with melting point 112°C 22.
1 g (75% of theory) was obtained.

In a similar manner, the following compounds of formula (VIII) could be prepared: Use Examples Example A Pre-emergence Test Solvent: 5 parts by weight of acetone Emulsifier: Alkylaryl polyglycol ether Suitable preparation of active compounds To prepare 1 part by weight of the active compound is mixed with the above amount of solvent, the above amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Seeds of the test plants were sown in standard soil and 24 hours later sprayed with a preparation of the active compound. It is advantageous to keep the amount of water per unit area constant. The concentration of active compound in the preparation is not critical, only the amount applied per unit area is decisive. After 3 weeks, the degree of damage to the plants was evaluated as % damage compared to the development of the untreated control: % = no effect (same as untreated control) 100% = total eradication In this test, for example the manufacturing example ( 4), (5),
Compounds according to (5A), (132) and (154) showed excellent activity. The results are shown in Table A.

Table A Pre-emergence test active compounds Amount of active compound applied kg
/hectare Cotton (Cotton) Pigweed (Che
nopodium) Mustard (Sinapis) Hekumugi (Lolium) Enopodium (Setaria)
) (A) (known compound) 0.5
0 0
10
10 50 (4)
0.5 0
100
60 80
90(5) 0.5
40 100
80
100 100 (5A)
0.5
70 100
60 80
100 (132) 0.5
0
100 50
60 100 (154
) 0.5
0 100
40 90
100 Example B Soybean Growth Inhibition Solvent: 30 parts by weight of dimethylformamide Emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate To prepare a suitable preparation of the active compound, 1 part by weight of the active compound is mixed with the above amount of solvent. and an emulsifier, and the mixture was brought to the desired concentration with water.

Soybean plants were grown in a greenhouse until the first second leaf fully opened. At this stage the plants were sprayed with the active compound preparation until dripping wet.

After 3 weeks, additional growth was measured for all plants and growth inhibition was calculated as a percentage of additional growth of control plants. 100% growth inhibition means that growth has stopped.
0% represents growth corresponding to the growth of control plants.

In this test, for example, the compound according to Preparation Example (4) showed excellent activity. The results are shown in Table B below.

Table B Soybean Growth Inhibition Active Compounds Concentration % Growth Inhibition % Control ・
... 0 (4) 0.005 60* 0.0005 27 *=Example C in which the leaves turned dark green Barley growth inhibition Solvent: 30 parts by weight of dimethylformamide Emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate To prepare suitable preparations of the active compound, 1 part by weight of the active compound is mixed with the above amounts of solvent and emulsifier and the mixture is brought to the desired concentration with water.

Barley plants were grown to the two-leaf stage in a greenhouse. At this stage the plants were sprayed with the active compound preparation until dripping wet. After 3 weeks, additional growth was measured for all plants and growth inhibition was calculated as a percentage of additional growth of control plants. 100% inhibition of growth means growth has stopped, 0% represents growth corresponding to the growth of the control plants.

In this test, for example, the following compounds according to the Preparation Examples showed excellent activity: (4), (16), (72)
, (73), (74), (75), (77), (78)
, (79) and (80). The results are shown in Table C below.

Table C Compounds active in barley growth inhibition Concentration % Growth inhibition % control ・
... 0 (4) 0.05 100 0.0005 40 (16) 0.05 89 (72) 0.05 95 (73) 0.05 100 (74) 0.05 100 (75) 0.05 89 ( 77) 0.05 100 (78) 0.05 100 (79) 0.05 50 (80) 0.05 50 All compounds caused an increase in barley fly on barley plants;
The leaves turned dark green.

Example D Cotton Growth Inhibition Solvent: 30 parts by weight of dimethylformamide Emulsifier: 1 part by weight of polyoxyenalene sorbitan monolaurate To prepare a suitable preparation of the active compound, 1 part by weight of the active compound is mixed with the above amount of solvent. and an emulsifier, and the mixture was brought to the desired concentration with water.

Cotton plants were grown in a greenhouse until the fifth two leaves were fully opened. At this stage the plants were sprayed with the active compound preparation until dripping wet. After 3 weeks, additional growth of the plants was measured and growth inhibition was calculated as a percentage of additional growth of the control. 100% inhibition of growth means growth has stopped, 0% represents growth corresponding to the growth of the control plants.

In this test, for example, the compound according to Preparation Example (4) showed excellent activity. The results are shown in Table D below.

Table D Cotton growth inhibiting active compound Concentration % Growth inhibiting control ... 0 (4) 0.05 58 0.0005 35 Patent applicant Bayer Akchenkuselschaft (DE)■P3334455.8 ゛@Inventor 5600 Butzpeltal 1 Inderbeek 92 0 Inventor Ludwig Oie 5090 Leverkusen 1 Paul Kle 11 Strasse 36 Inventor Robert Earl Schmidt 5060 Belgium Schüdlerbach 2 Im Waldwinkel 110 0 Inventor Klaus Lürsesj ♂ Federal Republic of Germany Day 5060 Bergitzschüldbach 2 Alagust-Kielspel-Strasse 89-6 [

Claims (7)

[Claims] 1. General formula (I) in which R1 represents hydrogen or the group -S(O)m-R5, where m is the number 0, 1 or 2, and R5 is selected from alkyl, aralkyl, aryl and heteroaryl. R represents a 6-membered aromatic heterocyclic structural formula selected from the group consisting of: halogen, amino, cyano or formyl; and/or optionally substituted with an optionally substituted group selected from the group consisting of alkyl, alkoxy, alkylamino, dialkylamino, alkylcarbonyl and alkoxycarbonyl, and/or optionally fused. , R3 represents hydrogen, an optionally substituted group selected from the group consisting of alkyl, cycloalkyl, alkenyl, alkynyl, and aralkyl, or a group -S(O)n-R6, where n is a number. 0, 1 or 2, and R6 represents an optionally substituted group selected from the group consisting of alkyl, aralkyl, aryl and heteroaryl, and R4 represents hydrogen or hydroxyl, with the proviso that
At least one of the groups R1 and/or R3 shall not be hydrogen; and furthermore if -R5 is not hydrogen -
R4 represents an optionally substituted group selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl and aryl, or R3 and R4 together represent alkanediyl;
The group optionally contains an intermediate oxygen atom or a bridge >N-R7, where R7 represents an optionally substituted alkyl, alkylcarbonyl or aryl; and R4 represents a group -X-R8, where Oxygen, sulfur,
-SO- or -SO2, and R8 represents an optionally substituted group selected from the group consisting of C1-C6-alkyl, alkenyl, alkynyl, cycloalkyl, phenylalkyl and aryl; and R4 represents a group where R9 represents hydrogen or optionally substituted alkyl, and R10 represents alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl, aryl, heteroaryl, alkyl- or alkoxycarbonyl and alkyl- or represents an optionally directly substituted group selected from the group consisting of arylsulfonyl, or R9 and R10 together represent alkanediyl, which group may optionally contain an intermediate oxygen atom: Furthermore, R4 represents a group, where R11 represents hydrogen or optionally substituted alkyl, and R12 is an optionally substituted group selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl and aryl. or R11 and R12 together represent alkanediyl; further R4 represents trialkylsilyl or a group, where q represents the number 0 or 1, and Y represents oxygen or sulfur; , and R13 and R14 are the same or different,
Any individual selected from the group consisting of alkyl, alkenyl, aralkyl, alkynyl, aryl, alkoxy, alkenoxy, alkynoxy, aralkoxy, aryloxy, alkylthio, alkenylthio, aralkylthio, alkynylthio, arylthio, amino, alkylamino and dialkylamino. represents an optionally substituted group, or R13 and R14 together represent alkanedioxy, oxyalkyleneamino or alkanediamino; further R4 represents an optionally directly substituted heterocyclic group; ,
Furthermore, M represents hydrogen, one equivalent of metal or an ammonium group optionally substituted with alkyl, alkenyl, alkynyl and/or aralkyl, or -M represents R2
- also represents an optionally substituted group selected from the group consisting of alkyl, alkenyl, alkynyl and aralkyl, when bonded to the same nitrogen atom such as guanidine derivatives and 2 (1), where M is hydrogen 1:1 adduct of a compound of and a strong acid, and R1, R2, R3 and R4 have the meanings given above. 2. (a) R1 represents hydrogen, R3 represents hydrogen or an optionally substituted group selected from the group consisting of alkyl, cycloalkyl, alkenylalkynyl, and aralkyl, and M represents hydrogen or alkyl, alkenyl, alkynyl, and aralkyl; represents an optionally substituted group selected from the group consisting of
I) where M1 represents water or an optionally substituted group selected from the group consisting of alkyl, alkenyl, alkynyl and aralkyl, and R2 has the above meaning, if appropriate. In the presence of a diluent, the formula (III) is obtained: wherein R3 represents hydrogen or an optionally substituted group selected from the group consisting of alkyl, cycloalkyl, alkenyl, alkynyl and aralkyl, and R4 has the meaning defined above. or the hydrochloride of an amino compound of formula (III) having: and optionally treating the reaction product with an acid acceptor: (b) R1 is a group -S(0) m-R5, where m
and R5 have the meanings given in claim 1, and M represents hydrogen or an optionally substituted group selected from the group consisting of alkyl, alkenyl, alkynyl and aralkyl, and R2, R3 and R4 has the above meaning, or R3 is a group -S(O)n-R6
, where n and R6 have the meanings given in claim 1, and M represents hydrogen or an optionally substituted group selected from the group consisting of alkyl, alkenyl, alkynyl and aralkyl. and further R1, R
2 and R4 have the above meanings, when R1 is obtained by the above production method (a) and R1 represents hydrogen, R3
is hydrogen or alkyl, cycloalkyl, alkenyl,
represents an optionally substituted group selected from the group consisting of alkyl and aralkyl, M represents hydrogen or an optionally substituted group selected from the group consisting of alkyl, alkenyl, alkynyl and aralkyl, and A guanidine derivative of formula (I) in which R2 and R4 have the abovementioned meanings, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, is converted into a compound of formula (IV) R5-S(O)m -X1 (IV) where X1 represents fluorine, chlorine or bromine, and m and R5 have the above meanings, and/or a halogen/sulfur compound of formula (V) R6-5
(O)n-X2(V) in which X2 represents fluorine, chlorine or bromine and n and R6 have the meanings given above; (c) R3 is hydrogen or containing an optionally substituted group selected from the group consisting of alkyl, cycloalkyl, alkenyl, alkynyl and aralkyl, and when the radicals R1, R2 and R4 have the abovementioned meanings, the formula (VI) R13 represents optionally substituted alkyl or aralkyl, and M and the groups R1 and R2
has the abovementioned meaning, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, an isothiourea of the formula (II
I) An amino compound or an amino compound of the formula wherein R3 represents hydrogen or an optionally substituted group selected from the group consisting of alkyl, cycloalkyl, alkenyl, alkynyl and aralkyl, and R4 has the above meanings or (d) R3 is hydrogen or is selected from the group consisting of alkyl, cycloalkyl, alkenyl, alkynyl and aralkyl. represents a selected optionally substituted radical, and M and the radicals R1, R2 and R4 have the abovementioned meaning,
Formula (I) in which R3 represents the group -S(0)n-R6, where n and R6 have the abovementioned meaning, and M and the group R1
, R2 and R4 have the abovementioned meanings, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent.
II) wherein R3 represents hydrogen or an optionally substituted group selected from the group consisting of alkyl, cycloalkyl, alkenyl, alkynyl and aralkyl, and R4 has the above meaning, an amino compound of the formula or (III) with the hydrochloride of the amino compound; (e) M represents one equivalent of the metal, or alkyl,
represents an ammonium group optionally substituted with alkenyl, alkynyl and/or aralkyl, and the groups R1, R
2, when R3 and R4 have the above meanings, formula (I)
, in which M represents hydrogen and the radicals R1, R2, R3 and R4 have the meanings given above, are combined with metal hydroxides, hydrides or alkanolates, if appropriate in the presence of diluents. or with an organometallic compound or ammonia or a suitable amine, or (f) a guanidine derivative of formula (I) with a strong acid:
1 adduct, the formula (I), with M and the radicals R1, R2, R3 and R4 having the abovementioned meaning,
A process for preparing guanidine derivatives of the formula (I) according to claim 1, characterized in that the guanidine derivatives of formula (I) are reacted with a strong acid, if appropriate using an inert diluent. 3. A herbicide containing at least one guanidine derivative of formula (I) according to claim 1. 4. Use of a guanidine derivative of general formula (I) according to claim 1 for controlling weeds. 5. A plant growth regulator containing at least one guanidine derivative of general formula (I) according to claim 1. 6. Use of a guanidine derivative of general formula (I) according to claim 1 as a plant growth regulator. 7. A method for producing a herbicide or a plant growth regulator, which comprises mixing the guanidine derivative of general formula (I) according to claim 1 with an extender and/or a surfactant.