Preparation of thiazoles

Details Preparation of thiazoles Preparation of thiazoles

1999-06-18

2003-04-15

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

06548676

ABSTRACT:

The invention relates to a process for the preparation of a compound of the formula
and, where applicable, its E/Z-isomers, mixtures of E/Z-isomers and/or tautomers and acid addition products thereof, in each case in free form or in salt form, wherein
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
1
;
R
1
is unsubstituted or substituted C
1
-C
12
alkyl, unsubstituted or substituted C
2
-C
4
alkenyl, unsubstituted or substituted C
2
-C
4
alkenyl, unsubstituted or substituted C
2
-C
4
alkynyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl or unsubstituted or substituted heteroaryl; and
X is a leaving group; which comprises
a) reacting a compound of the formula
 or, where applicable, an E/Z-isomer, a mixture of E/Z-isomers and/or a tautomer thereof, in each case in free form or in salt form, wherein R is as defined for formula (I), with a water-removing reagent; or
b) for the preparation of a compound of formula (I) wherein X is halogen or a sulfonate, reacting a compound of the formula
 and, where applicable, its E/Z-isomers, mixtures of E/Z-isomers and/or tautomers and acid addition products thereof, in each case in free form or in salt form, wherein R is as defined for formula (I), with a halogenating agent or a sulfonylating agent; or
c) for the preparation of a compound of formula (I) wherein X is halogen, reacting a compound of the formula
 and, where applicable, its E/Z-isomers, mixtures of E/Z-isomers and/or tautomers and acid addition products thereof, in each case in free form or in salt form, wherein
R is as defined for formula (I); and
R
2
and R
3
are each independently of the other H, C
1
-C
6
alkyl, C
3
-C
6
cycloalkyl, phenyl or benzyl or, together with the nitrogen atom to which they are bonded, form a five- to seven-membered ring in which a —CH
2
— group has optionally been replaced by a hetero atom selected from the group consisting of O and S, or by NR
9
, and wherein the carbon-chain of the five- to seven-membered ring is unsubstituted or is mono- or di-substituted by C
1
-C
4
alkyl; and
R
9
is an organic radical;
with a compound of the formula halogen-C(═O)—O—C
1
-C
8
alkyl, halogen-C(═O)—O-aryl or halogen-C(═O)—O-benzyl, preferably with ethyl chloroformate;
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 or tautomer and acid addition products thereof, in each case in free form or in salt form, into a different compound of formula (I) or an E/Z-isomer or tautomer and acid addition products 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. However, they are not completely satisfactory and there is therefore the need to make available improved processes for the preparation of those compounds. The compounds of formula (I) are valuable intermediates in the preparation of other compounds that can be used in the preparation of compounds—especially of formula (A) below—having pesticidal activity. Accordingly, the invention relates also to a process for the preparation of a compound of the formula
and, where applicable, their E/Z-isomers, mixtures of E/Z-isomers and/or tautomers and acid addition products 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
6
, O, NR
6
or S,
R
4
and R
5
are either each independently of the other hydrogen or unsubstituted or R
7
-substituted alkyl, or together form an alkylene bridge having two or three carbon atoms, and said alkylene bridge may additionally contain a hetero atom selected from the group consisting of NR
8
, O and S;
R
6
is H or unsubstituted or R
7
-substituted alkyl,
R
7
is unsubstituted or substituted aryl or heteroaryl, and
R
8
is H or C
1
-C
12
alkyl;
which comprises reacting a compound of formula (I), prepared by the process described above, with a compound of the formula
 or, where applicable, an E/Z-isomer, a mixture of E/Z-isomers and/or a tautomer thereof, in each case in free form or in salt form, wherein Q, Y, Z, R
4
and R
5
are as defined above for formula (A), to form a compound of the formula
 or, where applicable, an E/Z-isomer, a mixture of E/Z-isomers and/or a tautomer and acid addition products thereof, in each case in free form or in salt form, wherein R is as defined above for formula (I) and
Q, Y, Z, R
4
and R
5
are as defined above for formula (A), and converting the compound of formula (C) by means of a halogenating agent into a compound of formula (A).
The present invention relates also to a process for the preparation of a compound of formula (C) and, where applicable, its E/Z-isomers, mixtures of E/Z-isomers and/or tautomers and acid addition products thereof, in each case in free form or in salt form, which comprises reacting a compound of the formula (I) with a compound of the formula (B); and a process for the preparation of a compound of formula (A) and, where applicable, its E/Z-isomers, mixtures of E/Z-isomers and/or tautomers and acid addition products thereof, in each case in free form or in salt form, which comprises reacting a compound of the formula (C) with a halogenating agent.
Some compounds of formulae (I) to (VIII) and (A) to (C) defined hereinbefore and hereinafter contain asymmetric carbon atoms, as a result of which the compounds may occur in optically active form. The corresponding formulae are intended to include all those possible isomeric forms as well as mixtures thereof, for example racemates or mixtures of E/Z-isomers.
The general terms used hereinbefore and hereinafter have the meanings given below, unless defined otherwise:
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, more especially 1 or 2, carbon atoms.
Alkyl—both as a group per se and as a structural element of other groups and compounds, such as haloalkyl, arylalkyl or hydroxyalkyl—is preferably, in each case giving due consideration to 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, for example 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, such as haloalkenyl or arylalkenyl—is, in each case giving due consideration to 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, such as haloalkynyl—is, in each case giving due consideration to 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 understood as being a five- to s

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