Process for the preparation of thiazole derivatives

Details Process for the preparation of thiazole derivatives Process for the preparation of thiazole derivatives

1999-07-15

2001-07-24

Gerstl, Robert (Department: 1626)

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

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

Reexamination Certificate

active

06265585

ABSTRACT:

The invention relates to a process for the preparation of a compound of formula
including, where applicable, an E/Z isomer, a mixture of E/Z isomers, an acid addition product and/or a tautomer thereof, in each case in free form or in salt form, wherein X is a leaving group; which process comprises,
a) for the preparation of a compound of formula (I) wherein X is —OS(═O)
2
A and A is C
1
-C
8
alkyl, halo-C
1
-C
8
alkyl, hydroxy-C
1
-C
8
alkyl, C
1
-C
8
alkoxy-C
1
-C
8
alkyl, unsubstituted or halo-substituted C
2
-C
8
alkenyl, C
2
-C
4
alkynyl, C
3
-C
7
cycloalkyl or di-(C
1
-C
4
alkyl)amine; aryl that is unsubstituted or substituted by halogen, C
1
-C
4
alkyl, C
1
-C
4
alkoxy or by dimethylamine; or unsubstituted or halo-substituted benzyl, reacting a compound of formula
including, where applicable, an acid addition product and/or a tautomer thereof, in each case in free form or in salt form, with a sulfonylating agent; or,
b) for the preparation of a compound of formula (I) wherein X is iodine, reacting a compound of formula
including, where applicable, an acid addition product and/or a tautomer thereof, in each case in free form or in salt form, with an iodinating agent, preferably sodium iodide; or,
c) for the preparation of a compound of formula (I) wherein X is bromine, reacting a compound of formula
including, where applicable, an acid addition product and/or a tautomer thereof, in each case in free form or in salt form, with a brominating agent, preferably in the presence of a radical initiator, or,
d) for the preparation of a compound of formula (I) wherein X is chlorine or bromine, reacting with a chlorinating agent a compound of formula
including, where applicable, an E/Z isomer, a mixture of E/Z isomers, an acid addition product and/or a tautomer thereof, in each case in free form or in salt form, wherein X is as defined for formula (I) above, and
R is unsubstituted or substituted C
1
-C
12
alkyl, unsubstituted or substituted C
2
-C
4
alkenyl, unsubstituted or substituted C
2
-C
4
alkynyl, unsubstituted or substituted C
3
-C
6
cycloalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heteroaryl, or —SR
6
, and R
6
is unsubstituted or substituted C
1
-C
12
alkyl, unsubstituted or substituted C
2
-C
4
alkenyl, unsubstituted or substituted C
2
-C
4
alkynyl, unsubstituted or substituted C
1
-C
6
cycloalkyl, unsubstituted or substituted aryl, or unsubstituted or substituted heteroaryl;
and, in each case, if desired, converting a compound of formula (I) obtainable in accordance with the process or by another method, or an E/Z isomer, acid addition product or tautomer thereof, in each case in free form or in salt form, into a different compound of formula (I) or an E/Z isomer, acid addition product or tautomer thereof, in each case in free form or in salt form, separating a mixture of E/Z isomers obtainable in accordance with the process and isolating the desired isomer, and/or converting a free compound of formula (I) obtainable in accordance with the process or by another method, or an E/Z isomer or tautomer thereof, into a salt or converting a salt, obtainable in accordance with the process or by another method, of a compound of formula (I) or of an E/Z isomer or tautomer thereof into the free compound of formula (I) or an E/Z isomer or tautomer thereof or into a different salt.
Methods of synthesis for the compounds of formula (I) are described in the literature but they are not entirely satisfactory. There is therefore a need to make available improved processes for the preparation of those compounds.
The compounds of formula (I) are valuable intermediates which can be used in the preparation of pesticidally active compounds, especially the compounds, known per se, of formula
and, where applicable, the E/Z isomers, mixtures of E/Z isomers, acid addition products and/or tautomers thereof, in each case in free form or in salt form,
wherein Q is CH or N, Y is NO
2
or CN, Z is CHR
3
, O, NR
3
or S,
R
1
and R
2
either are, each independently of the other, hydrogen or alkyl that is unsubstituted or substituted by R
4
or together form a two- or three-membered alkylene bridge which may contain a hetero atom from the group consisting of NR
5
, O and S,
R
3
is H or alkyl that is unsubstituted or substituted by R
4
,
R
4
is unsubstituted or substituted aryl or heteroaryl, and
R
5
is H or alkyl.
The invention therefore relates also to a process known per se for the preparation of compounds of formula (A) from a compound of formula (I) prepared in accordance with the process of the invention.
Some compounds of formula (I) contain asymmetric carbon atoms, as a result of which the compounds may occur in optically active forms. Formula (I) is intended to include all those possible isomeric forms, and mixtures thereof, for example race-mates or mixtures of E/Z isomers.
The general terms used hereinbefore and hereinafter have the following meanings, unless defined otherwise:
Carbon-containing groups and compounds each contain from 1 up to and including 8, preferably from 1 up to and including 6, especially from 1 up to and including 4, and more especially 1 or 2, carbon atoms.
Alkyl, both as a group per se and as a structural element of other groups and compounds, for example haloalkyl, alkoxyalkyl and hydroxyalkyl, is, in each case taking due account of the number of carbon atoms contained in the group or compound in question, either straight-chained, i.e. methyl, ethyl, propyl, butyl, pentyl or hexyl, or branched, e.g. isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.
Alkenyl, both as a group per se and as a structural element of other groups and compounds, for example haloalkenyl and arylalkenyl, is, in each case taking due account of the number of carbon atoms contained in the group or compound in question, either straight-chained, for example vinyl, 1-methylvinyl, allyl, 1-butenyl or 2-hexenyl, or branched, for example isopropenyl.
Alkynyl, both as a group per se and as a structural element of other groups and compounds, for example haloalkynyl, is, in each case taking due account of the number of carbon atoms contained in the group or compound in question, either straight-chained, for example propargyl, 2-butynyl or 5-hexynyl, or branched, for example 2-ethynylpropyl or 2-propargylisopropyl.
C
3
-C
6
Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, especially cyclohexyl.
Aryl is phenyl or naphthyl, especially phenyl.
Heteroaryl is to be understood as being a five- to-seven-membered monocyclic aromatic ring having from one to three hetero atoms selected from the group consisting of N, O and S, especially N and S, or a bicyclic heteroaryl that may contain, either in only one ring (as, for example, in quinolinyl, quinoxalinyl, indolinyl, benzothiophenyl or benzofuranyl) or in both rings (as, for example, in pteridinyl or purinyl), one or more hetero atoms, independently of one another, selected from N, O and S. Preference is given to pyridyl, pyrimidinyl, thiazolyl and benzothiazolyl, especially thiazolyl.
Halogen, both as a group per se and as a structural element of other groups and compounds, for example haloalkyl, haloalkenyl and haloalkynyl, is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, more especially chlorine or bromine, and very especially chlorine.
Halo-substituted, carbon-containing groups and compounds, for example haloalkyl, haloalkenyl and haloalkynyl, may be partially halogenated or perhalogenated, the halogen substituents in the case of multiple halogenation being identical or different. Examples of haloalkyl, both as a group per se and as a structural element of other groups and compounds, for example haloalkenyl, are methyl mono- to tri-substituted by fluorine, chlorine and/or by bromine, for example CHF
2
or CF
3
; ethyl mono- to penta-substituted by fluorine, chlorine and/or by bromine, for example CH
2
CF
3
, CF
2
CF
3
, CF
2
CCl
3
, CF
2
CHCl
2
, CF
2
CHF
2
, CF
2
CFCl
2
, CF
2
CHBr
2
, CF
2
CHClF, CF
2
CHBrF or CClFCHClF; propyl or isopropyl

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