Substituted thiopyridines

Details Substituted thiopyridines Substituted thiopyridines

2001-02-26

2002-06-18

Aulakh, Charanjit S. (Department: 1625)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C546S303000

Reexamination Certificate

active

06407245

ABSTRACT:

The invention relates to novel thiopyridines of the general formula I
where
n is 1 or 2;
R
1
is chlorine, C
1
-C
3
-fluoroalkyl, nitro or methylsulfonyl;
R
2
is a C
1
-C
10
-alkyl, C
2
-C
10
-alkenyl or C
2
-C
10
-alkynyl radical, in each case unsubstituted or substituted by halogen, C
1
-C
4
-alkoxy, C
1
-C
4
-alkoxycarbonyl, di-(C
1
-C
4
-alkylamino)carbonyl, cyano or nitro, a C
3
-C
8
-cycloalkyl radical, or a C
1
-C
4
-alkylenephenyl, phenyl or naphthyl radical which is unsubstituted or substituted in the phenyl moiety by halogen, C
1
-C
3
-alkyl, C
1
-C
3
-alkoxy, trifluoromethyl, cyano or nitro.
Moreover, the invention relates to processes for their preparation and to their use as intermediates for the preparation of herbicidally active crop protection agents, as they are disclosed in WO-A-95/02580. The invention furthermore relates to the pyridine thioethers of the formula Ia, which are suitable for the preparation of the thiopyridines I, as intermediates.
2-(3-Nitrophenylthio), 2-(2-methyl-4-methoxyphenylthio) and 2-(2-nitrobenzylthio)pyridines which have a further chlorine, or trifluoromethyl or methylsulfonyl radical, in the 5-position and a chlorine substituent in the 3-position have already been disclosed in the literature (EP 320 448, J5 6029-504, EP 498 396) 3-Fluoropyridines which are correspondingly substituted are disclosed in U.S. Pat. No. 4,983,211.
The thiopyridines mentioned in the above publications are used as herbicides or fungicides, or as intermediates for herbicides, the function which is responsible for the herbicidal action in the end molecule being synthesized in each case via the thio substituent, which thus remains in the end molecule.
It is an object of the present invention to provide novel thiopyridine derivatives which are suitable as coupling components for the preparation of substituted phenylpyridines as they are described in WO-A-95/02580. Here, the thio substituent acts as a leaving group.
It is a further object of the present invention to provide a process which makes the desired thiopyridines accessible in high yields.
Accordingly, we have found the thiopyridines defined at the out-set, of the general formula I
where
n is 1 or 2;
R
1
is chlorine, C
1
-C
3
-fluoroalkyl, nitro or methylsulfonyl;
R
2
is a C
1
-C
10
-alkyl, C
2
-C
10
-alkenyl or C
2
-C
10
-alkynyl radical, in each case unsubstituted or substituted by halogen, C
1
-C
4
-alkoxy, C
1
-C
4
-alkoxycarbonyl, di-(C
1
-C
4
-alkylamino)carbonyl, cyano or nitro, a C
3
-C
8
-cycloalkyl radical, or a C
1
-C
4
-alkylenephenyl, phenyl or naphthyl radical which is unsubstituted or substituted in the phenyl moiety by halogen, C
1
-C
3
-alkyl, C
1
-C
3
-alkoxy, trifluoromethyl, cyano or nitro.
The meanings mentioned above for the substituent R
2
in formula I are collective terms for individual enumerations of the individual group members. All carbon chains, ie. all alkyl, alkenyl, alkynyl or alkoxy moieties, can be straight-chain or branched.
Halogenated substituents preferably have attached to them 1-6 identical or different halogen atoms.
Examples of individual meanings are:
halogen fluorine, chlorine, bromine and iodine, preferably fluorine and chlorine;
C
1
-C
3
-alkyl methyl, ethyl, n-propyl, 1-methylethyl;
C
1
-C
10
-alkyl C
l
-C
3
-alkyl as mentioned above, and also n-butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl; n-heptyl, n-octyl, n-nonyl, n-decyl, 1-methylhexyl, 1-ethylhexyl, 1-methylheptyl, 1-methyloctyl, 1-methylnonyl;
C
2
-C
10
-alkenyl ethenyl, prop-1-en-1-yl, prop-2-en-1-yl, 1-methylethenyl, n-buten-1-yl, n-buten-2-yl, n-buten-3-yl, 1-methylprop-1-en-1-yl, 2-methylprop-1-en-1-yl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, n-penten-1-yl, n-penten-2-yl, n-penten-3-yl, n-penten-4-yl, 1-methylbut-1-en-1-yl, 2-methylbut-1-en-1-yl, 3-methylbut-1-en-1-yl, 1-methylbut-2-en-1-yl, 2-methylbut-2-en-1-yl, 3-methylbut-2-en-1-yl, 1-methylbut-3-en-1-yl, 2-methylbut-3-en-1-yl, 3-methylbut-3-en-1-yl, 1,1-dimethylprop-2-en-1-yl, 1,2-dimethylprop-1-en-1-yl, 1,2-dimethylprop-2-en-1-yl, 1-ethylprop-1-en-2-yl, 1-ethylprop-2-en-1-yl, n-hex-1-en-1-yl, n-hex-2-en-1-yl, n-hex-3-en-1-yl, n-hex-4-en-1-yl, n-hex-5-en-1-yl, 1-methylpent-1-en-1-yl, 2-methylpent-1-en-1-yl, 3-methylpent-1-en-1-yl, 4-methylpent-1-en-1-yl, 1-methylpent-2-en-1-yl, 2-methylpent-2-en-1-yl, 3-methylpent-2-en-1-yl, 4-methylpent-2-en-1-yl, 1-methylpent-3-en-1-yl, 2-methylpent-3-en-1-yl, 3-methylpent-3-en-1-yl, 4-methylpent-3-en-1-yl, 1-methylpent-4-en-1-yl, 2-methylpent-4-en-1-yl, 3-methylpent-4-en-1-yl, 4-methylpent-4-en-1-yl, 1,1-dimethylbut-2-en-1-yl, 1,1-dimethylbut-3-en-1-yl, 1,2-dimethylbut-1-en-1-yl, 1,2-dimethylbut-2-en-1-yl, 1,2-dimethylbut-3-en-1-yl, 1,3-dimethylbut-1-en-1-yl, 1,3-dimethylbut-2-en-1-yl, 1,3-dimethylbut-3-en-1-yl, 2,2-dimethylbut-3-en-1-yl, 2,3-dimethylbut-1-en-1-yl, 2,3-dimethylbut-2-en-1-yl, 2,3-dimethylbut-3-en-1-yl, 3,3-dimethylbut-1-en-1-yl, 3,3-dimethylbut-2-en-1-yl, 1-ethylbut-1-en-1-yl, 1-ethylbut-2-en-1-yl, 1-ethylbut-3-en-1-yl, 2-ethylbut-1-en-1-yl, 2-ethylbut-2-en-1-yl, 2-ethylbut-3-en-1-yl, 1,1,2-trimethylprop-2-en-1-yl, 1-ethyl-1-methylprop-2-en-1-yl, 1-ethyl-2-methylprop-1-en-1-yl and 1-ethyl-2-methylprop-2-en-1-yl, hept-2-en-1-yl, oct-2-en-1-yl, non-2-en-1-yl, dec-2-en-1-yl, preferably ethenyl and prop-2-en-1-yl;
C
2
-C
10
-alkynyl ethynyl and C
3
-C
6
-alkynyl such as prop-1-yn-1-yl, prop-2-yn-3-yl, n-but-1-yn-1-yl, n-but-1-yn-4-yl, n-but-2-yn-1-yl, n-pent-1-yn-1-yl, n-pent-1-yn-3-yl, n-pent-1-yn-4-yl, n-pent-1-yn-5-yl, n-pent-2-yn-1-yl, n-pent-2-yn-4-yl, n-pent-2-yn-5-yl, 3-methylbut-1-yn-1-yl, 3-methylbut-1-yn-3-yl, 3-methylbut-1-yn-4-yl, n-hex-1-yn-1-yl, n-hex-1-yn-3-yl, n-hex-1-yn-4-yl, n-hex-1-yn-5-yl, n-hex-1-yn-6-yl, n-hex-2-yn-1-yl, n-hex-2-yn-4-yl, n-hex-2-yn-5-yl, n-hex-2-yn-6-yl, n-hex-3-yn-1-yl, n-hex-3-yn-2-yl, 3-methylpent-1-yn-1-yl, 3-methylpent-1-yn-3-yl, 3-methylpent-1-yn-4-yl, 3-methylpent-1-yn-5-yl, 4-methylpent-1-yn-1-yl, 4-methylpent-2-yn-4-yl and 4-methylpent-2-yn-5-yl, hept-2-yn-1-yl, oct-2-yn-1-yl, non-2-yn-1-yl, dec-2-yn-1-yl, preferably prop-2-yn-1-yl, 1-methylprop-2-yn-1-yl;
C
1
-C
3
-fluoroalkyl C
1
-C
3
-alkyl as mentioned above, where in each case 1-5 hydrogen atoms are replaced by fluorine, eg. fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 3,3,3-trifluoropropyl, preference is given to difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 3,3,3-trifluoropropyl, special preference is given to trifluoromethyl;
C
1
-C
10
-haloalkyl C
1
-C
10
-alkyl as mentioned above, where in each case 1-6 hydrogen atoms are replaced by fluorine, chlorine and/or bromine, ie., for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl and 3-chloropropyl, preferably trifluoromethyl;
C
2
-C
10
-haloalkenyl C
2
-C
10
-alkenyl as mentioned above, where in each case 1-6 hydrogen atoms are replaced by fluorine, chlorine and/or bromine;
C
2
-C
10
-haloalkynyl C
2
-C
10
-alkynyl as mentioned above, where in each case one to six hydrogen atoms are replaced by fluorine, chlorine and/or bromine;
C
3
-C
8
-cycloalkyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, preferably cyclopropyl, cyclopentyl and cyclohexyl;
cyano-(C
1
-C
10
)-alkyl C
1
-C
10
-alkyl as mentioned above, where in each case one hydrogen atom is repla

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