Organic compounds -- part of the class 532-570 series – Organic compounds – Chalcogen in the nitrogen containing substituent
Patent
1998-11-06
2000-11-21
Raymond, Richard L.
Organic compounds -- part of the class 532-570 series
Organic compounds
Chalcogen in the nitrogen containing substituent
549467, C07D27301, C07D30778
Patent
active
061505218
DESCRIPTION:
BRIEF SUMMARY
The present invention relates to a plurality of novel processes and novel intermediates for preparing 3-(1-hydroxyphenyl-1-alkoximinomethyl)dioxazines, which are known as intermediates for preparing compounds having fungicidal properties (WO 95-04728).
It has already been disclosed that certain 3-(1-hydroxyphenyl-1-alkoximinomethyl)dioxazines can be prepared starting from the corresponding hydroxyphenylacetates (cf. WO 95-04728). Thus, for example (5,6-dihydro-1,4,2-dioxazin-3-yl)-(2-hydroxy-phenyl)-methanone O-methyl-oxime (1) is obtained by reacting methyl hydroxyphenylacetate (a) with dihydropyran, converting the dihydropyranyl ether (b) obtained in this way with t-butyl nitrite into methyl 2-[2-(tetrahydropyran-2-yloxy)-phenyl]-2-hydroximino-acetate (c), alkylating this compound with iodomethane to give methyl 2-[2-(tetrahydropyran-2-yloxy)-phenyl]-2-methoximino-acetate (d), reacting this with hydroxylamine to give 2-[2-(tetrahydropyran-2-yloxy)-phenyl]-2-methoximino-N-hydroxyacetamide (e), cyclizing the latter with dibromoethane to 3-{1-[2-(tetrahydropyran-2-yloxy)-phenyl]-1-methoximino-methyl}-5,6-dihydr o-1,2,4-dioxazine (f), and finally removing the tetrahydropyranyl group using acid catalysis. This synthesis can be illustrated by the following scheme: ##STR1##
A major disadvantage of this process is the fact that it requires a large number of steps, some of which are of low yield, which significantly affects the profitability of this process.
It has now been found that 3-(1-hydroxyphenyl-1-alkoximinomethyl)dioxazines of the general formula ##STR2## in which
A represents alkyl,
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are identical or different and each represent independently of one another hydrogen, halogen, cyano, nitro, respectively optionally halogen-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl, and
Z.sup.1, Z.sup.2, Z.sup.3 and Z.sup.4 are identical or different and each represent independently of one another hydrogen, alkyl, halogenoalkyl or hydroxyalkyl, or
Z.sup.1 and Z.sup.2 or Z.sup.1 and Z.sup.3 or Z.sup.3 and Z.sup.4 form together with the respective carbon atoms that they are attached to a cycloaliphatic ring, are obtained when
a) O-hydroxyethyl-O'-methyl-benzofurandione dioximes of the formula ##STR3## in which
A, R.sup.1, R.sup.2, R.sup.3, R.sup.4, Z.sup.1, Z.sup.2, Z.sup.3 and Z.sup.4 are each as defined above, are rearranged, if appropriate in the presence of a diluent and, if appropriate, in the presence of an acid or a base, or
b) hydroxybenzoyldioxazines of the formula ##STR4## in which
R.sup.1, R.sup.2, R.sup.3, R.sup.4, Z.sup.1, Z.sup.2, Z.sup.3 and Z.sup.4 are each as defined above, are reacted with an alkoxyamine of the formula
A is as defined above--or an acid addition complex thereof--if appropriate in the presence of a diluent and, if appropriate, in the presence of an acid acceptor, or
c) hydroxyphenyl-hydroximinomethyl-dioxazines of the formula ##STR5## in which
R.sup.1, R.sup.2, R.sup.3, R.sup.4, Z.sup.1, Z.sup.2, Z.sup.3 and Z.sup.4 are each as defined above, are reacted with an alkylating agent of the formula
A is as defined above, and
X represents halogen, alkylsulphonyloxy, alkoxysulphonyloxy or arylsulphonyloxy, if appropriate in the presence of a diluent and, if appropriate, in the presence of a base.
In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, also in connection with hetero atoms, such as in alkoxy or alkylthio, are in each case straight-chain or branched.
The methods of the processes a-c) according to the invention are preferably employed for preparing compounds of the formula (I) in which
A represents methyl, ethyl, n- or i-propyl,
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are identical or different and each represent independently of one another hydrogen, halogen, cyano or nitro, or represent alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl, each of which is optionally substituted by 1 to 5 halogen atoms and each of which has 1 to 6 carbon atoms,
Z.sup.1, Z.sup.2, Z.sup.3 and Z.sup.4 are id
REFERENCES:
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Gallenkamp Bernd
Gayer Herbert
Gerdes Peter
Heinemann Ulrich
Kruger Bernd-Wieland
Bayer Aktiengesellschaft
Patel Sudhaker B.
Raymond Richard L.
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