Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2001-09-26
2002-08-20
Raymond, Richard L. (Department: 1624)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C558S422000, C564S256000
Reexamination Certificate
active
06437153
ABSTRACT:
The present invention relates to a novel process for preparing 3-(1-hydroxyphenyl-1-alkoximinomethyl)dioxazines which are known as intermediates for preparing compounds having fungicidal properties (WO 95-04728). Furthermore, the invention relates to novel 3-(1-hydroxyphenyl-1-alkoximinomethyl)dioxazines, to novel intermediates for their preparation and to a plurality of processes for preparing the novel intermediates.
It has already been disclosed that certain 3-(1-hydroxyphenyl-1-alkoximinomethyl) dioxazines can be prepared starting from the corresponding hydroxyphenyl acetates (cf. WO 95-04728). Thus, for example (5,6-dihydro[1,4,2]dioxazin-3-yl)-(2-hydroxyphenyl)-methanone-O-methyl oxime (1) can be prepared by reacting methyl hydroxyphenylacetate (a) with dihydropyrane, converting the resulting dihydropyranyl ether (b) with t-butyl nitrite into methyl 2-[2-(tetrahydropyran-2-yloxy)-phenyl]-2-hydroximinoacetate (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 give 3-{1-[2-(tetrahydropyran-2-yloxy)-phenyl]-1-methoximino-methyl}-5,6-dihydro-1,4,2-dioxazine (f), and finally removing the tetrahydropyranyl group using acid catalysis. This synthesis can be illustrated by the following scheme:
A major disadvantage of this process is the fact that a large number of steps must be carried out with occasional low yields, which has a decisively adverse effect on cost-efficiency.
It has now been found that novel and known 3-(1-hydroxyphenyl-1-alkoximinomethyl)dioxazines of the general formula (I)
in which
A represents alkyl,
R
1
, R
2
, R
3
and R
4
are identical or different and each represents independently of the others hydrogen, halogen, cyano, nitro, in each case optionally halogen-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl and
Z
1
, Z
2
, Z
3
and Z
4
are identical or different and each represents independently of the others hydrogen, alkyl, halogenoalkyl or hydroxyalkyl, or
Z
1
and Z
2
, or Z
1
and Z
3
, or Z
3
and Z
4
, join with the respective carbon atoms to which they are attached to form a cycloaliphatic ring,
are obtained when (process a) O-hydroxyethyl-O′-alkyl-benzofurandione dioximes of the formula (II)
in which
A, R
1
, R
2
, R
3
, R
4
, Z
1
, Z
2
, Z
3
and Z
4
are each as defined above,
are rearranged, if appropriate in the presence of a diluent and, if appropriate, in the presence of a base or an acid, and the products obtained, which may be present as mixtures of stereoisomers, are, if appropriate, isomerized to give the desired E isomers, if appropriate in the presence of a diluent and, if appropriate, in the presence of an acid.
In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, including in combination with hetero atoms, such as in alkoxy or alkylthio, are in each case straight-chain or branched.
The compounds which are preparable according to the invention and their precursors may, if appropriate, be present as mixtures of various possible isomeric forms, in particular of stereoisomers such as, for example, E and Z isomers, and, if appropriate, also as tautomers. Both the E and Z isomers, and any mixtures of these isomers, and the possible tautomeric forms are claimed.
The method of process a) according to the invention is preferably employed for preparing compounds of the formula (I) in which
A represents methyl, ethyl, n- or i-propyl and
R
1
, R
2
, R
3
and R
4
are identical or different and each represents independently of the others hydrogen, halogen, cyano, nitro, or represents alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms, each of which is optionally substituted by 1 to 5 halogen atoms, and
Z
1
, Z
2
, Z
3
and Z
4
are identical or different and each represents independently of the others hydrogen, alkyl or hydroxyalkyl having in each case 1 to 4 carbon atoms or halogenoalkyl having 1 to 4 carbon atoms and 1 to five identical or different halogen atoms, or
Z
1
and Z
2
, or Z
1
and Z
3
, or Z
3
and Z
4
, join with the respective carbon atoms to which they are attached to form a cycloaliphatic ring of five, six or seven carbon atoms.
Particular preference is given to preparing compounds of the formula (I) in which
A represents methyl or ethyl and
R
1
, R
2
, R
3
and R
4
are identical or different and each represents independently of the others hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl or ethylsulphonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, difluorochloromethylthio, trifluoromethylthio, trifluoromethylsulphinyl or trifluoromethylsulphonyl,
Z
1
, Z
2
, Z
3
and Z
4
are identical or different and each represents independently of the others hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, hydroxymethyl, trifluoromethyl or trifluoroethyl, or
Z
1
and Z
2
, or Z
1
and Z
3
, or Z
3
and Z
4
, join with the respective carbon atoms to which they are attached to form a cycloaliphatic ring of five, six or seven carbon atoms.
The present invention also relates to novel 3-(1-hydroxyphenyl-1-alkoximinomethyl)dioxazines of the formula (I-a)
in which
A, R
1
, R
2
, R
3
, R
4
, Z
1
, Z
2
, Z
3
and Z
4
are each as defined above, but where at least one of the substituents R
1
, R
2
, R
3
, R
4
, Z
1
, Z
2
, Z
3
and Z
4
is different from hydrogen.
The abovementioned general or preferred radical definitions apply both to the compounds of the formula (I) and also, correspondingly, to the starting materials or intermediates required in each case for the preparation.
These radical definitions can be combined with each other at will, i.e. including combinations between the given ranges of preferred compounds.
The formula (II) provides a general definition of the O-hydroxyethyl-O′-alkyl-benzofurandione dioximes required as starting materials for carrying out the process a) according to the invention. In this formula (II), A, R
1
, R
2
, R
3
, R
4
, Z
1
, Z
2
, Z
3
and Z
4
each preferably or in particular have those meanings which have already been mentioned in connection with the description of the compounds of the formula (I) preparable according to the invention as being preferred or as being particularly preferred for A, R
1
, R
2
, R
3
, R
4
, Z
1
, Z
2
, Z
3
and Z
4
.
The starting materials of the formula (II) have not been disclosed before, and as novel compounds they also form part of the subject matter of the present application.
The O-hydroxyethyl-O′-alkyl-benzofurandione dioximes of the formula (II) are obtained when
process b) O-alkyl-benzofurandione dioximes of the formula (III)
in which
A, R
1
, R
2
, R
3
and R
4
are each as defined above
are reacted with an ethane derivative of the formula (IV)
in which
Y
1
represents halogen, alkylsulphonyloxy, arylsulphonyloxy or alkanoyloxy and
G represents hydrogen, or
Y
1
and G are linked by a single bond, where
Y
1
represents oxygen and
G represents
or
Y
1
and G together represent a single bond and
Z
1
, Z
2
, Z
3
and Z
4
are each as defined above,
if appropriate in the presence of a diluent and, if appropriate, in the presence of a base.
The formula (III) provides a general definition of the O-alkyl-benzofurandione dioximes required as starting materials for carrying out the process b) according to the invention. In this formula (III), R
1
, R
2
, R
3
and R
4
each preferably or in particular have those meanings which have already been mentioned in connection with the description of the compounds of the formula (I) preparable according to the invention as being preferred
Gallenkamp Bernd
Gayer Herbert
Gerdes Peter
Rohe Lothar
Bayer Aktiengesellschaft
Norris & McLaughlin & Marcus
Raymond Richard L.
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