Method for producing 1,3-disubstituted 2-nitroguanidines

1. A process for the preparation of a compounds of the Formula (I)

in which

R 1 is hydrogen or C 1 –C 4 -alkyl,

R 2 is hydrogen, C 1 –C 6 -alkyl, C 3 –C 6 -cycloalkyl or a radical —CH 2 R 3 ,

R 3 is C 2 –C 5 -alkenyl, C 2 –C 5 -alkinyl, phenyl, cyanophenyl, nitrophenyl, halogenophenyl having from 1 to 3 halogen atoms; phenyl substituted by C 1 –C 3 -alkyl, C 1 –C 3 -halogenoalkyl having from 1 to 7 halogen atoms, C 1 –C 3 -alkoxy or C 1 –C 3 -halogenoalkoxy having from 1 to 7 halogen atoms; 5-thiazolyl substituted by one to two substituents from the group consisting of C 1 –C 3 -alkyl, C 1 –C 3 -halogenoalkyl having from 1 to 7 halogen atoms, cyclopropyl, halogenocyclopropyl having from 1 to 3 halogen atoms, C 2 –C 3 -alkenyl, C 2 –C 3 -alkinyl, C 1 –C 3 -alkoxy, C 2 –C 3 -halogenoalkenyl having from 1 to 5 halogen atoms, C 2 –C 3 -halogenoalkinyl having from 1 to 3 halogen atoms, C 1 –C 3 -halogenoalkoxy having from 1 to 7 halogen atoms, C 1 –C 3 -alkylthio, C 1 –C 3 -halogenoalkylthio having from 1 to 7 halogen atoms, allyloxy, propargyloxy, allylthio, propargylthio, halogenoallyloxy having from 1 to 5 halogen atoms, halogenoallylthio having from 1 to 5 halogen atoms, halogen, cyano or nitro; or 3-pyridyl substituted by one to four radicals from the group consisting of C 1 –C 3 -halogenoalkyl having from 1 to 7 halogen atoms, cyclopropyl, halogenocyclopropyl having from 1 to 3 halogen atoms, C 2 –C 3 -alkenyl, C 2 –C 3 -alkinyl, C 2 –C 3 -halogenoalkenyl having from 1 to 5 halogen atoms, C 2 –C 3 -halogenoalkinyl having from 1 to 3 halogen atoms, C 1 –C 3 -halogenoalkoxy having from 1 to 7 halogen atoms, C 1 –C 3 -alkylthio, C 1 –C 3 -halogenoalkylthio having from 1 to 7 halogen atoms, allyloxy, propargyloxy, allylthio, propargylthio, halogenoallyloxy having from 1 to 5 halogen atoms, halogenoallylthio having from 1 to 5 halogen atoms, cyano, nitro, C 1 –C 3 -alkyl, C 1 –C 3 -alkoxy or halogen,

Het is an unsubstituted or substituted aromatic or non-aromatic, monocyclic or bicyclic heterocyclic radical selected from the series

which may include one to two substituents from the group consisting of C 1 –C 3 -halogenoalkyl having from 1 to 7 halogen atoms, cyclopropyl, halogenocyclopropyl having from 1 to 3 halogen atoms, C 2 –C 3 -alkenyl, C 2 –C 3 -alkinyl, C 2 –C 3 -halogenoalkenyl having from 1 to 5 halogen atoms, C 2 –C 3 -halogenoalkinyl having from 1 to 3 halogen atoms, C 1 –C 3 -halogenoalkoxy having from 1 to 7 halogen atoms, C 1 –C 3 -alkylthio, C 1 –C 3 -halogenoalkylthio having from 1 to 7 halogen atoms, allyloxy, propargyloxy, allylthio, propargylthio, halogenoallyloxy having from 1 to 5 halogen atoms, halogenoallylthio having from 1 to 5 halogen atoms, cyano, nitro, C 1 –C 3 -alkyl, C 1 –C 3 -alkoxy and halogen,

comprising reacting in the presence of a nitrile having from 3 to 5 carbon atoms, a compound of the Formula (II)

in which

R 1 , R 2 and Het are as defined above, and

R 4 is C 1 –C 10 -alkyl, C 3 –C 6 -cycloalkyl, phenyl, arylalkyl or heterocyclylmethyl, each of which may be unsubstituted or substituted, where heterocyclyl is an unsaturated or saturated 5- or 6-membered heterocycle containing one or more heteroatoms from the series nitrogen, oxygen and sulphur, with an anhydrous hydrogen halide.

2. The process according to claim 1 , wherein in the compound of the Formula (II)

R 1 is hydrogen, methyl, ethyl, n- or i-propyl,

R 2 is hydrogen, methyl, ethyl, n-propyl, i-propyl or n-butyl, cyclopropyl, cyclopentyl, cyclohexyl or a radical —CH 2 R 3 ,

R 3 is C 2 –C 5 -alkenyl, C 2 –C 5 -alkinyl, phenyl, cyanophenyl, nitrophenyl, halogenophenyl having from 1 to 3 halogen atoms; phenyl substituted by C 1 –C 3 -alkyl, C 1 –C 3 -halogenoalkyl having from 1 to 7 halogen atoms, C 1 –C 3 -alkoxy or C 1 –C 3 -halogenoalkoxy having from 1 to 7 halogen atoms; 5-thiazolyl substituted by one to two substituents from the group consisting of C 1 –C 3 -alkyl, C 1 –C 3 -halogenoalkyl having from 1 to 7 halogen atoms, cyclopropyl, halogenocyclopropyl having from 1 to 3 halogen atoms, C 2 –C 3 -alkenyl, C 2 –C 3 -alkinyl, C 1 –C 3 -alkoxy, C 2 –C 3 -halogenoalkenyl having from 1 to 5 halogen atoms, C 2 –C 3 -halogenoalkinyl having from 1 to 3 halogen atoms, C 1 –C 3 -halogenoalkoxy having from 1 to 7 halogen atoms, C 1 –C 3 -alkylthio, C 1 –C 3 -halogenoalkylthio having from 1 to 7 halogen atoms, allyloxy, propargyloxy, allylthio, propargylthio, halogenoallyloxy having from 1 to 5 halogen atoms, halogenoallylthio having from 1 to 5 halogen atoms, halogen, cyano or nitro; or 3-pyridyl substituted by one to two radicals from the group consisting of C 1 –C 3 -halogenoalkyl having from 1 to 7 halogen atoms, cyclopropyl, halogenocyclopropyl having from 1 to 3 halogen atoms, C 2 –C 3 -alkenyl, C 2 –C 3 -alkinyl, C 2 –C 3 -halogenoalkenyl having from 1 to 5 halogen atoms, C 2 –C 3 -halogenoalkinyl having from 1 to 3 halogen atoms, C 1 –C 3 -halogenoalkoxy having from 1 to 7 halogen atoms, C 1 –C 3 -alkylthio, C 1 –C 3 -halogenoalkylthio having from 1 to 7 halogen atoms, allyloxy, propargyloxy, allylthio, propargylthio, halogenoallyloxy having from 1 to 5 halogen atoms, halogenoallylthio having from 1 to 5 halogen atoms, cyano, nitro, C 1 –C 3 -alkyl, C 1 –C 3 -alkoxy or halogen,

R 4 is unsubstituted C 1 –C 10 -alkyl or C 1 –C 10 -alkyl substituted by from 1 to 6 radicals from the group consisting of halogen, hydroxyl, C 1 –C 4 -alkoxy, C 1 –C 4 -halogenoalkoxy having from 1 to 9 halogen atoms, di-(C 1 –C 4 -alkyl)-amino or C 1 –C 5 -alkoxycarbonyl; unsubstituted C 3 –C 6 -cycloalkyl or C 3 –C 6 -cycloalkyl substituted by from 1 to 4 radicals from the series C 1 –C 4 -alkyl or halogen; in each case unsubstituted phenyl, benzyl or heterocyclylmethyl, or phenyl, benzyl or heterocyclylmethyl each substituted by from 1 to 3 ring substituents from the group consisting of halogen, C 1 –C 4 -alkyl, C 1 –C 4 -halogenoalkyl having from 1 to 9 halogen atoms, C 1 –C 4 -alkoxy, C 1 –C 4 -halogenoalkoxy having from 1 to 9 halogen atoms, C 1 –C 4 -alkylthio, nitro or cyano, where heterocyclyl is an unsaturated or saturated 5- or 6-membered heterocycle having one or two heteroatoms from the series nitrogen, oxygen and sulphur,

Het is an unsubstituted or mono- or disubstituted heterocyclic radical from the series

the substituents being chosen from the series fluorine, chlorine, bromine, methyl, ethyl, methoxy and ethoxy.

3. The process according to claim 1 , wherein in the compound of the Formula (II)

R 1 is hydrogen, methyl or ethyl,

R 2 is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, cyclopropyl, cyclopentyl, cyclohexyl or a radical —CH 2 R 3 ,

R 3 is C 2 –C 3 -alkenyl, C 2 –C 3 -alkinyl, phenyl, cyanophenyl, nitrophenyl, halogenophenyl having from 1 to 3 halogen atoms; phenyl substituted by C 1 –C 3 -alkyl, C 1 –C 3 -halogenoalkyl having from 1 to 7 halogen atoms, C 1 –C 3 -alkoxy or C 1 –C 3 -halogenoalkoxy having from 1 to 7 halogen atoms; 5-thiazolyl or 3-pyridyl each substituted by one or two substituents from the group consisting of C 1 –C 3 -alkyl, C 1 –C 3 -halogenoalkyl having from 1 to 7 halogen atoms, C 1 –C 3 -alkoxy, C–C 3 -halogenoalkoxy having from 1 to 7 halogen atoms, C 1 –C 3 -alkylthio, C 1 –C 3 -halogenoalkylthio having from 1 to 7 halogen atoms, halogen, cyano or nitro,

R 4 is C 1 –C 10 -alkyl; C 1 –C 8 -alkyl, substituted by from 1 to 6 radicals from the group consisting of halogen, C 1 –C 4 -alkoxy and C 1 –C 4 -halogenoalkoxy having from 1 to 9 halogen atoms; unsubstituted C 3 –C 6 -cycloalkyl or C 3 –C 6 -cycloalkyl substituted by 1 or 2 radicals from the series methyl, ethyl, fluorine and chlorine; unsubstituted phenyl, benzyl or heterocyclylmethyl, or phenyl, benzyl or heterocyclylmethyl each substituted by from 1 to 3 ring substituents from the group consisting of halogen, C 1 –C 4 -alkyl, C 1 –C 4 -halogenoalkyl having from 1 to 9 halogen atoms, C 1 –C 4 -alkoxy, C 1 –C 4 -halogenoalkoxy having from 1 to 9 halogen atoms, C 1 –C 4 -alkylthio, nitro or cyano, where heterocyclyl is an unsaturated or saturated 5- or 6-membered heterocycle containing one heteroatom from the series nitrogen, oxygen and sulphur,

Het is thiazolyl, pyridyl or tetrahydrofuranyl, each of which may be unsubstituted or mono- or disubstituted the substituents being chosen from the series fluorine, chlorine, methyl and methoxy.

4. The process according to claim 1 , wherein in the compound of the Formula (II)

R 1 is hydrogen, methyl or ethyl,

R 2 is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, cyclopropyl, cyclopentyl, allyl, propargyl, benzyl, p-chlorobenzyl, 3-pyridylmethyl or 6-chloro-3-pyridylmethyl,

R 4 is methyl, ethyl, n-propyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, benzyl or furfuryl,

Het is one of the radicals.

5. The process according to claim 1 , wherein in the compound of the Formula II is a compound of the Formula (IIa)

in which

R 4 is as defined in claim 1 .

6. The process according to claim 1 , wherein in the compound of the Formula II is a compound of the Formula (IIb)

in which

R 4 is as defined in claim 1 .

7. The process according to claim 1 , wherein the compound of the Formula II is a compound of the Formula (IIc)

in which

R 4 is as defined in claim 1 .

8. The process according to claim 1 , wherein the reaction is carried out in the presence of an aliphatic mono- or dinitrile having 3 to 5 carbon atoms.

9. The process according to claim 8 , wherein the nitrile is selected from the group consisting of propionitrile, butyronitrile, valeronitrile, malononitrile, succinonitrile and glutaronitrile.

10. The process according to claim 9 , wherein the nitrile is propionitrile or butyronitrile.

11. The process according to claim 10 , wherein the nitrile is butyronitrile.

12. The process according to claim 1 , wherein the anhydrous hydrogen halide is selected from the group consisting of hydrogen chloride, hydrogen bromide hydrogen iodide.

13. The process according to claim 12 , wherein the anhydrous halogen halide is hydrogen chloride or hydrogen bromide.

14. The process according to claim 13 , wherein the anhydrous hydrogen halide is hydrogen chloride.

15. The process according to claim 1 , wherein said process is carried out at a temperature between −10° C. and 200° C.