DE19706399A1 - Process for the preparation of 3- (hydroxyphenyl-1-alkoximinomethyl) dioxazines - Google Patents

Abstract

The invention concerns a plurality of novel processes and novel intermediate products for preparing 3-(1-hydroxyphenyl-1-alkoximinomethyl)dioxazines which are known (WO-A-95/04728) as initial products for preparing compounds having fungicidal properties.

Description

The present invention relates to several new methods and new intermediates products for the production of 3- (1-hydroxyphenyl-1-alkoximinomethyl) dioxazines, which as precursors for the production of compounds with fungicidal properties are known (WO 95-04728).

It has already been known that certain 3- (1-hydroxyphenyl-1-alkox iminomethyl) dioxazines based on the corresponding hydroxyphenylacetic acid have esters synthesized (cf. WO 95-04728). So you get z. B. (5,6-Dihy dro- [1,4,2] dioxazin-3-yl) - (2-hydroxy-phenyl) -methanone-O-methyl-oxime (1) by using Hydroxyphenylacetic acid methyl ester (a) with dihydropyran, ent standing dihydropyranyl ether (b) with t-butyl nitrite in the 2- [2- (tetrahydropyran-2-yl oxy) -phenyl] -2-hydroximino-acetic acid methyl ester (c), this compound with iodomethane to give 2- [2- (tetrahydropyran-2-yloxy) phenyl] -2-methoximino vinegar methyl acid (d) alkylated, this with hydroxylamine to 2- [2- (tetrahydropyran-2-yl oxy) -phenyl] -2-methoximino-N-hydroxyacetamide (e), the latter with dibro methane to 3- {1- [2- (tetrahydropyran-2-yloxy) phenyl] -1-methoximino-methyl} -5,6-di hydro-1,4,2-dioxazin (f) cyclized, and finally the tetrahydropyranyl group acid catalyzed cleaves. This synthesis can be done by the following formula scheme are illustrated:

A crucial disadvantage of this method is that many reak tion steps with sometimes low yields are required, which the economy This process is significantly impaired.

It has now been found that 3- (1-hydroxyphenyl-1-alkoximinomethyl) dioxazine the general formula

in which
A represents alkyl,
R¹, R², R³ and R⁴ are the same or different and each independently represent hydrogen-halogen, cyano, nitro, each optionally substituted by halogen-substituted alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl and
Z¹, Z², Z³ and Z⁴ are the same or different and are independently hydrogen, alkyl, haloalkyl or hydroxyalkyl, or
Z¹ and Z² or Z¹ and Z³ or Z³ and Z⁴ together with the respective carbon atoms to which they are attached form a cycloaliphatic ring,
get when one

• a) O-hydroxyethyl-O'-methyl-benzofurandione dioxime of the formula in which
  A, R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ have the meanings given above,
  optionally rearranged in the presence of a diluent and optionally in the presence of an acid or a base, or if one
• b) hydroxybenzoyldioxazines of the formula in which
  R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ have the meanings given above,
  with an alkoxyamine of the formula A-O-NH₂ (IV) in which
  A has the meaning given above,
  - or an acid addition complex thereof -
  optionally in the presence of a diluent and optionally in the presence of an acid acceptor, or if one
• c) hydroxyphenyl-hydroximinomethyl-dioxazines of the formula in which
  R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ have the meanings given above,
  with an alkylating agent of the formula A-X (VI) in which
  A has the meaning given above and
  X represents halogen, alkylsulfonyloxy, alkoxysulfonyloxy or arylsulfonyloxy,
  if appropriate in the presence of a diluent, and if appropriate in the presence of a base.

In the definitions are the saturated or unsaturated hydrocarbon chains, such as alkyl, also in combination with heteroatoms, such as in alkoxy or alkylthio, each straight or branched.

Compounds of the formula (I) in which
A represents methyl, ethyl, n- or i-propyl,
R¹, R², R³ and R⁴, are the same or different and are each independently hydrogen-halogen, cyano, nitro, each optionally substituted by 1 to 5 halogen atoms, alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms ,
Z¹, Z², Z³ and Z⁴ are the same or different and are independently hydrogen, alkyl or hydroxyalkyl having 1 to 4 carbon atoms or haloalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, or
Z¹ and Z² or Z¹ and Z³ or Z³ and Z⁴ together with the respective carbon atoms to which they are attached form a cycloaliphatic ring with five, six or seven carbon atoms.

Particular preference is given to the preparation of compounds of the formula (I) in which
A represents methyl or ethyl,
R¹, R², R³ and R⁴ are the same or different and are each independently 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, methylsulfinyl , Ethylsulfinyl, methylsulfonyl or ethyl sulfonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, difluorochloromethylthio, trifluoromethylthio, trifluoromifluoromethylsulfonyl
Z¹, Z², Z³ and Z⁴ are the same or different and are independently hydrogen; Are methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, hydroxymethyl, trifluoromethyl or trifluoroethyl, or
Z¹ and Z² or Z¹ and Z³ or Z³ and Z⁴ together with the respective carbon atoms to which they are attached form a cycloaliphatic ring with five, six or seven carbon atoms.

Those used to carry out process a) as starting materials required O-hydroxyethyl-O'-methyl-benzofurandione dioxime are by the formula (II) generally defined. In this formula (II) have A, R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ preferably or in particular those meanings that are already in the Zu connection with the description of the compounds that can be produced according to the invention of the formula (I) as preferred or as particularly preferred for A, R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ were specified.

The starting materials of formula (II) are not yet known and are new substances also the subject of the present application.

The O-hydroxyethyl-O'-methyl-benzofurandione dioxime of the formula (II) are obtained if one
Process d) O-hydroxyethyl-benzofurandione monooximes of the formula

in which
R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ have the meanings given above,
with an alkoxyamine of the formula (IV)
- or an acid addition complex thereof -
optionally in the presence of a diluent and optionally in the presence of an acid acceptor, or if one
Process e) O-alkyl-benzofurandione dioximes of the formula

in which
A, R¹, R², R³ and R⁴ have the meanings given above,
with an ethane derivative of the formula

in which
Y¹ represents halogen, alkylsulfonyloxy, arylsulfonyloxy or alkanoyloxy and
G represents hydrogen, or
Y¹ and G are connected by a single bond, wherein
Y¹ represents oxygen and
G for

stands, or
Y¹ and G together represent a single bond and
Z¹, Z², Z³ and Z⁴ have the meanings given above,
if appropriate in the presence of a diluent, and if appropriate in the presence of a base, or if one
Process f) O-hydroxyethyl-benzofurandione dioxime of the formula

in which
R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ have the meanings given above,
with an alkylating agent of the formula (VI),
if appropriate in the presence of a diluent, and if appropriate in the presence of a base, or if one
Process m) O-oxyethyl-O'-methyl-benzofurandione dioxime of the formula

in which
A, R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ have the meanings given above and
E represents an acyl group or a ketal protective group,
with water or an alcohol, if appropriate in the presence of a diluent and if appropriate in the presence of an acid or a base.

Those used to carry out process d) according to the invention as starting materials required O-hydroxyethyl-benzofurandione monooximes are represented by the formula (VII) generally defined. In this formula (VII), R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ preferably or in particular those meanings that are already together Hang with the description of the compounds of the invention Formula (I) as preferred or as particularly preferred for R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ were specified.

The starting materials of formula (VII) are not yet known and are new substances also the subject of the present application.

The O-hydroxyethyl-benzofurandione monooximes of the formula (VII) are obtained if one
Process g) Benzofurandione monooximes of the formula

in which
R¹, R², R³ and R⁴ have the meanings given above,
with an ethane derivative of the formula (IX),
if appropriate in the presence of a diluent, and if appropriate in the presence of a base, or if one
Process n) O-oxyethyl-benzofurandione monooximes of the formula

in which
E, R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ have the meanings given above,
with water or an alcohol, if appropriate in the presence of a diluent and if appropriate in the presence of an acid or a base.

Those used to carry out process g) according to the invention as starting materials Required benzofurandione monooximes are generally defined by the formula (XI). In this formula (XI), R¹, R², R³ and R⁴ preferably or in particular have those meanings already in connection with the description of the inventions Compounds of the formula (I) which can be prepared according to the invention are preferred or ins particularly preferred for R¹, R², R³ and R⁴ have been given.

The benzofurandione monooximes of the formula (XI) are known and can be based on known processes can be produced (see Beilstein, E (II) 17, 462; Mameli, G. 56, 768; Chem. Ber. 35 (1902), 1640-1646; Proc. Indian Acad. Sci. Sect. A (1976) 83A (6), 238-242)).

Those used to carry out process n) as starting materials required O-oxyethyl-benzofurandione monooximes are represented by the formula (XIV) generally defined. In this formula (XIV), R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ preferably or in particular those meanings that are already together  Hang with the description of the compounds of the invention Formula (I) as preferred or as particularly preferred for R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ were specified. E preferably or in particular has that Be interpretation given below in connection with the description of the invention compounds of the formula (XIII) as preferred or as in particular be is preferably given for E.

The starting materials of the formula (XIV) are not yet known and are new substances also the subject of the present application.

The O-oxyethyl-benzofurandione monooximes of the formula (XIV) are obtained if one
Process o) Benzofurandione monooxime of the formula (XI) with an ethanol derivative of the formula

in which
E, Z¹, Z², Z³ and Z⁴ have the meanings given above and
Y² represents halogen, alkylsulfonyloxy, arylsulfonyloxy or alkanoyloxy,
if appropriate in the presence of a diluent and if appropriate in the presence of an acid acceptor.

Those for carrying out the process o) as starting materials required Benzofurandionmonooxime of formula (XI) are already in the Description of the inventive method g) has been described.  

Those used to carry out process e) as starting materials required O-alkyl-benzofurandione dioximes are general by the formula (VIII) Are defined. In this formula (VIII), R¹, R², R³ and R⁴ preferably or in particular special those meanings that are already in connection with the description the compounds of the formula (I) which can be prepared according to the invention are preferred or have been given as particularly preferred for R¹, R², R³ and R⁴.

The starting materials of formula (VIII) are not yet known and are new substances also the subject of the present application.

The O-hydroxyethyl-benzofurandione monooximes of the formula (VIII) are obtained if one
Process h) Benzofurandione monooximes of the formula (XI) with an alkoxyamine of the formula (IV),
if appropriate in the presence of a diluent and if appropriate in the presence of an acid acceptor, or if
Process p) Benzofurandione dioximes of the formula

in which
R¹, R², R³ and R⁴ have the meanings given above, with an alkylating agent of the formula (VI),
if appropriate in the presence of a diluent, and if appropriate in the presence of a base.

Those used to carry out process h) according to the invention as starting materials required Benzofurandionmonooxime of formula (XI) are already in the Description of the inventive method g) has been described.

Those used to carry out process p) according to the invention as starting materials Required benzofurandione dioximes are generally defined by the formula (XII). In this formula (XII) have R¹, R², R³ and R⁴ preferably or in particular the those meanings already in connection with the description of the Compounds of the formula (I) which can be prepared according to the invention are preferred or as were particularly preferably indicated for R¹, R², R³ and R⁴.

The Benzofurandiondioxime of formula (XII) are known and can according to known methods are prepared (see Chem. Ber. 42 (1909), 202).

Those used to carry out process f) according to the invention as starting materials required O-hydroxyethyl-benzofurandione dioximes are represented by the formula (X) generally defined. In this formula (X), R¹, R², R³ and R⁴ preferably have or in particular those meanings that are already in connection with the Be writing of the compounds of formula (I) which can be prepared according to the invention as before added or specified as particularly preferred for R¹, R², R³ and R⁴.

The starting materials of formula (X) are not yet known and are new substances also the subject of the present application.

The O-hydroxyethyl-benzofurandione dioximes of the formula (X) are obtained if one
Process i) O-hydroxyethyl-benzofurandione monooximes of the formula (VII),
with hydroxylamine - 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 if
Process q) O-oxyethyl-benzofurandione dioxime of the formula

in which
E, R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ have the meanings given above,
with water or an alcohol, if appropriate in the presence of a diluent and if appropriate in the presence of an acid or a base.

Those used to carry out process i) as starting materials required O-Hydroxyethyl-benzofurandionmonooxime of formula (VII) are already have been described in the description of the method d) according to the invention.

Those used to carry out process q) as starting materials required O-oxyethyl-benzofurandione dioximes are general by the formula (XVI) my defined. In this formula (XVI), R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ have before preferably or especially those meanings that are already related with the description of the compounds of the formula (I) which can be prepared according to the invention  as preferred or as particularly preferred for R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ was specified. E preferably or in particular has the meanings that further below in connection with the description of the Ver Bonds of the formula (XIII) as preferred or as particularly preferred for E. can be specified.

The starting materials of the formula (XVI) are not yet known and are new substances also the subject of the present application.

The O-oxyethyl-benzofurandione dioximes of the formula (XVI) are obtained if one
Process r) O-oxyethyl-benzofurandione monooximes of the formula (XIV) with hydroxylamine - or an acid addition complex thereof -
if appropriate in the presence of a diluent and if appropriate in the presence of an acid acceptor.

To carry out the process r) as starting materials O-oxyethyl-benzofurandione monooximes of the formula (XIV) are already in the Description of the method n) has been described.

Those used to carry out process m) as starting materials required O-oxyethyl-O'-methyl-benzofurandione dioxime of the formula (XIII) are generally defined by formula (III). In this formula (XIII) A, R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ preferably or in particular those meanings, which already produce in connection with the description of the invention ble compounds of formula (I) as preferred or as particularly preferred for R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ were given. E represents an acyl group, preferably for formyl, acetyl or benzoyl, or a ketal protective group, preferably for 2-tetrahydropyranyl, 1-methoxy-1-ethyl, 1-ethoxy-1-ethyl, Methoxymethyl or ethoxymethyl.  

The starting materials of formula (XIII) are not yet known and are new substances also the subject of the present application.

The O-oxyethyl-O'-methyl-benzofurandione dioxime of the formula (XIII) are obtained if one
Process s) O-oxyethyl-benzofurandione monooximes of the formula (XIV) with an alkoxyamine of the formula (IV)
- or an acid addition complex thereof -
optionally in the presence of a diluent and optionally in the presence of an acid acceptor, or if one
Process t) O-oxyethyl-benzofurandione dioximes of the formula (XVI) with an alkylating agent of the formula (VI),
if appropriate in the presence of a diluent, and if appropriate in the presence of a base, or if one
Process u) O-alkyl-benzofurandione dioximes of the formula (VIII) with an ethanol derivative of the formula (XV),
if appropriate in the presence of a diluent and if appropriate in the presence of an acid acceptor.

Those used to carry out process s) as starting materials required O-Oxyethyl-benzofurandionmonooxime of formula (XIV) are already at the description of the method n) has been described.  

Those used to carry out process t) according to the invention as starting materials required O-Oxyethyl-benzofurandiondioxime of formula (XVI) are already in the Description of the inventive method q) has been described.

Those used to carry out process u) as starting materials required O-alkyl-benzofurandione dioximes of formula (VIII) are already in the Description of the inventive method e) has been described.

Those used to carry out process b) according to the invention as starting materials The required hydroxybenzoyldioxazines are generally defined by the formula (III). In this formula (III), R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ preferably or especially those meanings that are already in connection with the Be writing of the compounds of formula (I) which can be prepared according to the invention as before adds or as particularly preferred for R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ were given.

The starting materials of formula (III) are not yet known and are new substances also the subject of the present application.

The hydroxybenzoyldioxazines of formula (III) are obtained if one
Process k) O-hydroxyethyl-benzofurandione monooximes of the formula (VII),
if appropriate in the presence of a diluent and if appropriate in the presence of an acid or a base.

Those used to carry out process k) according to the invention as starting materials required O-Hydroxyethyl-benzofurandionmonooxime of formula (VII) are already have been described in the description of the method d) according to the invention.

Those used to carry out process c) according to the invention as starting materials required hydroxyphenyl-hydroximinomethyl-dioxazines are represented by the formula (V)  generally defined. In this formula (V) R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ have preferably or in particular those meanings that are already together Hang with the description of the compounds of the invention Formula (I) as preferred or as particularly preferred for R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ were specified.

The starting materials of formula (V) are not yet known and are new substances also the subject of the present application.

The hydroxyphenyl-hydroximinomethyl-dioxazines of the formula (V) are obtained if one
Process l) hydroxybenzoyldioxazines of the formula (III)
with hydroxylamine - 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 if
Process v) O-hydroxyethyl-benzofurandione dioximes of the formula (X)
optionally rearranged in the presence of a diluent and optionally in the presence of an acid or a base.

Those used to carry out process l) according to the invention as starting materials required hydroxybenzoyldioxazines of the formula (III) are already in the description Exercise of the method b) has been described.

Those used to carry out process v) according to the invention as starting materials required O-Hydroxyethyl-benzofurandiondioxime of formula (X) are already at the description of the method f) has been described.  

The further to carry out the inventive methods b), d), h) and s) Formula (IV) provides general alkoxyamines required as starting materials Are defined. In this formula (IV), A preferably or in particular has that Be interpretation already in connection with the description of the inventive Compounds of the formula (I) which can be prepared are preferably or in particular be was preferably given for A. Preferred acid addition complexes of the alk Oxyamines of the formula (IV) are their hydrochlorides, sulfates and hydrogen sulfates.

The alkoxyamines of the formula (IV) and their acid addition complexes are known Synthetic chemicals.

The further to carry out the methods c), f), p) and t) as Formula (VI) generalizes the alkylating agents required as starting materials Are defined. In this formula (VI), A preferably or in particular has that Be interpretation already in connection with the description of the invention Compounds of the formula (I) which can be prepared are preferably or in particular be was preferably given for A. X represents halogen, preferably chlorine, bromine or iodine, alkylsulfonyloxy, preferably methylsulfonyloxy, alkoxysulfonyloxy, preferably methoxysulfonyloxy, or arylsulfonyloxy, preferably 4-tolyl sulfonyloxy.

The alkylating agents of the formula (VI) are known synthetic chemicals.

The further to carry out the processes e) and g) as Ethane derivatives required as starting materials are general by the formula (IX) Are defined. In this formula (IX) Z¹, Z², Z³ and Z⁴ preferably or in particular special those meanings that are already in connection with the description the compounds of the formula (I) which can be prepared according to the invention are preferred or have been given as particularly preferred for Z¹, Z², Z³ and Z⁴. Y¹ stands for Halogen, preferably chlorine, bromine or iodine, alkylsulfonyloxy, preferably Methylsulfonyloxy, arylsulfonyloxy, preferably 4-tolylsulfonyloxy, or alkane oyloxy, preferably acetyloxy. G stands for hydrogen or is through one  Single bond connected to Y¹, where Y¹ is oxygen and G is carbonyl stands, or G together with Y¹ also represents a single bond.

The ethane derivatives of the formula (IX) are known synthetic chemicals.

The further to carry out the processes i), l) and r) as Starting material required hydroxylamine, or its acid addition complexes, preferably as its hydrochloride, sulfate and hydrogen sulfate are known synthesis chemicals.

The further to carry out the processes o) and u) as Formula (XV) generalizes ethanol derivatives required as starting materials Are defined. In this formula (XV), Z¹, Z², Z³ and Z⁴ preferably or in particular special those meanings that are already in connection with the description the compounds of the formula (I) which can be prepared according to the invention are preferred or have been given as particularly preferred for Z¹, Z², Z³ and Z⁴. E has preference wise or in particular the meaning already in connection with the Description of the compounds of formula (XIII) according to the invention as preferred or was specified as particularly preferred for E. Y² stands for halogen, preferably chlorine, bromine or iodine, alkylsulfonyloxy, preferably methylsulfonyl oxy, arylsulfonyloxy, preferably 4-tolylsulfonyloxy, or alkanoyloxy, preferred wise acetyloxy.

The ethanol derivatives of the formula (XV) are known and can be prepared according to known ones Methods are produced (compare e.g. Newkome, George R .; Marston, Charles R., J. Org. Chem., 50, 22, 1985, 4238-4245; Henry, Chem. Ber., 7 & <1874 <, 70).

The processes a), k) and v) according to the invention in the presence of an acid performed, all inert organic solvents come as diluents into consideration. These preferably include aliphatic, alicyclic or aromatic Hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, Methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbon  substances such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, Carbon tetrachloride, dichloroethane or trichloroethane; Ethers such as diethyl ether, diiso propyl ether, dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Esters like Methyl acetate or ethyl acetate, or sulfones such as sulfolane and any mixtures of the diluents mentioned. Particularly preferred ver diluents are ethers, such as diethyl ether, 1,2-diethoxyethane or anisole; aromatic hydrocarbons, such as benzene, toluene or xylene.

The processes a), k) and v) according to the invention in the presence of a base water, as well as all organic Solvent. These preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, Cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated Hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, Chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetra hydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Nitriles such as aceto nitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides such as N, N-dimethyl formamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or Hexamethylphosphoric triamide; Esters such as methyl acetate or acetic acid ethyl ester; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane; Alcohols like Methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, Propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, as well as their mixtures with water. Preferred Diluents are water, alcohols, such as methanol, ethanol, n- or i-Pro panol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, Methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; as well as their mixtures with water. Particularly preferred diluents are in in this case water or alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and their Mix with water.  

As a diluent for carrying out processes b), d), h), i), l), r) and s) are all inert organic solvents. For this preferably include aromatic hydrocarbons, such as benzene, Toluene or xylene; halogenated hydrocarbons, such as chlorobenzene, Dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or Trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, Methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or Anisole; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl formanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; organic Acids such as acetic acid; Esters such as methyl acetate or ethyl acetate; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane; Alcohols, such as methanol, Ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, Ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water. Especially before Preferred diluents are amides, such as N, N-dimethylformamide, N, N-dimethyl acetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamid; Alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sek- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol colmonomethyl ether, diethylene glycol monoethyl ether, acids such as acetic acid, the Mix with water or pure water. Are also particularly preferred Two-phase mixtures, such as water / toluene.

As a diluent for carrying out processes c), e), f), g), o), p), t) and u) are all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic coal water substances such as petroleum ether, hexane, heptane, cyclohexane, methylcyclo hexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as for example chlorobenzene, dichlorobenzene, dichloromethane, chloroform, tetra chloromethane, dichloroethane or trichloroethane; Ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2- Dimethoxyethane, 1,2-diethoxyethane or anisole; Ketones such as acetone, butanone, Me  ethyl isobutyl ketone or cyclohexanone; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethyl acetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamid; Esters such as methyl acetate or ethyl acetate; Sulfoxides, such as Dimethyl sulfoxide; Sulfones such as sulfolane; Alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, Methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water. Particularly preferred dilution middle are ketones, such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methyl pyrrolidone or hexamethylphosphoric triamide; Alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, Ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether or diethylene glycol colmonoethyl ether. Two-phase mixtures are also particularly preferred, such as water / toluene.

As a diluent for carrying out the processes m), n) and q) water and all organic solvents come into consideration. For this preferably include ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, Methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxy ethane or anisole; Ketones such as acetone, butanone, methyl isobutyl ketone or cyclo hexanone; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as acetic acid ethyl ester or ethyl acetate, sulfoxides such as dimethyl sulfoxide, sulfones such as Sulfolane, alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sek- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol colmonomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.  

Processes a), k) and v) according to the invention are optionally in the presence an acid or a base. All inorganic and come as acids organic protonic and Lewis acids, as well as all polymeric acids in Question. These include, for example, hydrogen chloride, hydrogen bromide and sulfur acid, formic acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, trifluorme thanesulfonic acid, toluenesulfonic acid, boron trifluoride (also as etherate), boron tribromide, Aluminum trichloride, zinc chloride, ferric chloride, antimony pentachloride, acid Ion exchangers, acidic clays and acidic silica gel. Preferably come Hydrogen chloride or hydrogen bromide in question. All the usual bases arrive organic or organic bases in question. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or bicarbonates, such as sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, Ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, Sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen car bonate or ammonium carbonate, and tertiary amines, such as trimethylamine, triethyl amine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU). Especially preferred bases are sodium methylate, sodium ethylate, potassium tert-butoxide, Sodium hydroxide, potassium hydroxide, ammonium hydroxide, and tertiary amines, such as Trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethyl benzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylamino pyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicyc loundecen (DBU).

Processes b), d), h), i), l), r) and s) according to the invention are, if appropriate, in In the presence of a suitable acid acceptor. As such, everyone comes usual inorganic or organic bases in question. These preferably include Alkaline earth metal or alkali metal hydroxides, alcoholates, acetates, carbonates or bicarbonates, such as sodium methylate, sodium ethylate, Potassium tert-butoxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate,  Potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, Potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate, as well tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-di methylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or Diazabicycloundecene (DBU).

The processes c), e), f), g), o), p), t) and u) are given if carried out in the presence of a suitable acid acceptor. As such come all usual inorganic or organic bases in question. These include preferential as alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, carbonates or bicarbonates, such as sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, Potassium hydroxide, sodium carbonate, potassium carbonate, potassium hydrogen carbonate or Sodium bicarbonate and tertiary amines, such as trimethylamine, triethylamine, Tributylamine, N, N-dimethylaniline, N, N-dimethyl-benzylamine, pyridine, N-methyl pipe ridine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), Diazabicyclonones (DBN) or Diazabicycloundecen (DBU).

The reaction temperatures can be carried out when carrying out the inventive Processes a), k) and v) can be varied over a wide range. In general one works at temperatures from -20 ° C to 100 ° C, preferably at temperatures from -10 ° C to 80 ° C.

The reaction temperatures can be carried out when carrying out the inventive Processes b), d), h), i), l), r and s) can be varied over a wide range. in the generally one works at temperatures from 0 ° C to 200 ° C, preferably at Temperatures from 20 ° C to 150 ° C.

The reaction temperatures can be carried out when carrying out the inventive Processes c), e), f), g), o), p), t) and u) can be varied over a wide range. in the  generally one works at temperatures from -20 ° C to 100 ° C, preferably at Temperatures from 0 ° C to 80 ° C.

Processes a) to v) according to the invention are generally below normal printing done. However, it is also possible to increase or decrease it Pressure - generally between 0.1 bar and 10 bar - to work.

In a preferred process variant (A), a benzofurandione monooxime is used Formula (XI) by reaction with an ethane derivative of the formula (IX) initially, as in Process g) described in an O-hydroxyethyl-benzofurandione monooxime from For mel (VII) convicted. This is then set with one without further cleaning Alkoxyamine of formula (IV) - or an acid addition complex thereof - given otherwise in a buffer system, such as sodium acetate / acetic acid, as in Method d) described to an O-hydroxyethyl-O'-methyl-benzofurandione dioxime of formula (II), which in turn without further purification after treatment with a Acid or a base, according to method a), the desired 3- (1-hydroxyphenyl-1-al koximinomethyl) dioxazine of formula (I) provides.

In a further preferred process variant (B), a benzofuran dione monooxime of the formula (XI) by reaction with an ethane derivative of the formula (IX) first, as described in process g), in an O-hydroxyethyl-benzofurandione monooxime of formula (VII) transferred. This provides after treatment with an acid or a base is a hydroxybenzoyldioxazine of the formula (III), which is subsequently with an alkoxyamine of the formula (IV) - or an acid addition complex thereof - to the desired 3- (1-hydroxyphenyl-1-alkoximinomethyl) dioxazine of the formula (I) implements.

In a third preferred process variant (C), a benzofuran dione monooxime of the formula (XI) by reaction with an alkoxyamine of the formula (IV) - or an acid addition complex thereof - first in an O-alkyl-benzofuran dione dioxime of formula (VIII) transferred. You then set this with a Ethane derivative of formula (IX) to an O-hydroxyethyl-O'-methyl-benzofuran  dione dioxime of formula (II), which after treatment with an acid or a base the desired 3- (1-hydroxyphenyl-1-alkoximinomethyl) dioxazine of the formula (I) delivers.

It is extremely surprising that the processes according to the invention in particular in their combination, in high yield and high purity. In Chem. Ber. 1902, 1640, for example, describes that Benzofurandionmono oximes of the formula (XI) both by treatment with acids and by Be treatment with bases to salicylic acid derivatives or hydroxyphenylglyoxylic acid derivatives vaten be split. So it could not be expected that the 3- (1-Hydroxyphenyl-1-alkoximinomethyl) dioxazine in a three-step reaction can be produced without any significant side reactions.

The methods according to the invention have a number of advantages. So enabled lichen the production of a variety of 3- (1-hydroxyphenyl-1-alkoximino methyl) dioxazines in high yield and high purity. It is also favorable that the Benzofurandione monooximes required as starting materials in a simple manner larger quantities are accessible (Beilstein, E (II) 17, 462; Mameli, G. 56, 768).

Process and manufacturing examples example 1 Process variant (A) 1st stage Compound (VII-1) Procedure g)

11.8 g (0.0725 mol) of benzofuran-2,3-dione-2-oxime (XI-1) (Stoermer, Kahlert, B. 35, 1644) are dissolved in 75 ml of dimethylformamide. 3 g (0.075 mol) are added with cooling Add 60% sodium hydride (mineral oil suspension) in portions and stir a temperature of 25 ° C for about an hour until the end of gas evolution. The mixture is then cooled to 0 ° C., 9.3 g (0.0744 mol) are added dropwise at this temperature. Add 2-bromoethanol and stir for a further 24 hours at 25 ° C. You pour the reak tion mixture on water, extracted with ethyl acetate, the organic dries Phase over sodium sulfate and the solvent is distilled off in vacuo. The back is made from a mixture of 150 ml toluene and 100 ml cyclohexane installed. 11.5 g (64% of theory) of benzofuran-2,3-dione-2- [O- (2-hy droxy-ethyl) -oxime] (VII-1) (content according to HPLC analysis: 83.5%). One made from toluene recrystallized sample melts at 110-111 ° C.  

2nd stage Compound (II-1) Procedure d)

11.5 g crude benzofuran-2,3-dione-2- [O- (2-hydroxyethyl) oxime] (VII-1) and 5.15 g (0.0616 mol) of O-methylhydroxylamine hydrochloride are dissolved in 60 ml of dimethyl Dissolved formamide and stirred at 80 ° C for 30 minutes. The reaction mixture is poured on water and extracted with ethyl acetate. The organic is dried Phase over sodium sulfate and the solvent is distilled off in vacuo. You get 14.1 g of an oil containing 40.5% benzofuran-2,3-dione-2- [O- (2-hydroxyethyl) oxime] -3- (O-me ethyl oxime) (II-1) and 14% (5,6-dihydro- [1,4,2] dioxazin-3-yl) - (2-hydroxy phenyl) -methanone-O-methyl-oxime (1) contains.

3rd stage Connection (1) Procedure a)

14.1 g of the oil obtained from the second stage of process A, which contains the compounds (II-1) and (1), are dissolved in 200 ml of diethyl ether, which was previously saturated at 0 ° C. with hydrogen chloride gas. The mixture is stirred for 30 minutes without further cooling and the mixture is poured onto a sodium hydrogen carbonate solution cooled to 0.degree. The organic phase is separated off and the aqueous phase is extracted several times with diethyl ether. The combined organic phases are dried over sodium sulfate and concentrated under reduced pressure. The residue is stirred with tert-butyl methyl ether, the product crystallizing. 5.4 g (28% of theory, based on benzofuran-2,3-dione-2-oxime) of crystalline (5,6-dihydro- [1,4,2] dioxazin-3-yl) - (2nd -hydroxy-phenyl) -methanone-O-met-hyl-oxime (1) (content according to HPLC analysis: 88.8%).
1 H NMR Spectrum (CDCl₃ / TMS): δ = 4.10 (3H); 4.19 / 4.20 / 4.21 / 4.22 (2H); 4.47 / 4.48 / 4.4914.50 (2H); 6.26 (1H); 6.95-7.0 (2H); 7.21 / 7.23 (1H); 7.31-7.36 (2H) ppm.

Example 2 Process variant B 1st stage Compound (VII-1)

This stage is already in process 1) in stage 1 of process variant (A) have been described.

2nd stage Compound (III-1) Procedure k)

The mixture is passed at 20 ° C. into the mixture of 19 g (0.0917 mol) of benzofuran-2,3-dione-2- [O- (2-hydroxyethyl) oxime] (VII-1) and 439 ml of diethyl ether dry, gaseous hydrogen chloride, the mixture warms to 35 ° C. After 7 hours, decant from undissolved material and the solvent is distilled off in vacuo. The residue is taken up in ethyl acetate and washed first with 50 ml of water, then with 20 ml of a saturated, aqueous sodium hydrogen carbonate solution. The organic phase is separated off, dried over sodium sulfate, the solvent is distilled off in vacuo and 17 g of crude product are obtained. This is chromatographed on silica gel with dichloromethane. 10 g (51.9% of theory based on compound (VII-1) (5,6-dihydro- [1,4,2] dioxazin-3-yl) - (2-hydroxyphenyl) methanone are obtained (III-1) in a purity of 98.7% (HPLC).
1 H-NMR (CDCl₃, TMS): δ = 4.28 / 4.29 / 4.30 / 4.31 (2H); 4.55 / 4.56 / 4.57 / 4.58 (2H); 6.90 / 6.92 / 6.93 / 6.95 / 6.99 / 7.02 (2H); 7.50 / 7.51 / 7.53 / 7.54 / 7.55 / 7.56 (1H); 8.27 / 8.29 / 8.30 (1H); 11.52 (1H) ppm.

3rd stage Connection (1) Procedure b)

4.4 g (0.021 mol) (5,6-dihydro- [1,4,2] dioxazin-3-yl) - (2-hydroxyphenyl) methanone (III-1) are mixed with 1.87 g ( 0.022 mol) of O-methylhydroxylamine hydrochloride in 22 ml of dimethylformamide heated to 100 ° C. for 2 hours. The reaction mixture is poured onto water, extracted with ethyl acetate, the organic phase is dried over sodium sulfate and the solvent is distilled off in vacuo. 5.7 g of crude (5,6-dihydro- [1,4,2] dioxazin-3-yl) - (2-hydroxyphenyl) methanone-O-methyl-oxime (1) are obtained HPLC consists of 17.5% E isomer and 38% Z isomer. This crude product is chromatographed on silica gel in a mixture of petroleum ether / tert-butyl methyl ether (1: 1). 1.55 g of Z- (5,6-dihydro- [1,4,2] dioxazin-3-yl) - (2-hydroxyphenyl) methanone-O-methyl-oxime (1) are obtained in a purity of 91.5% (HPLC) = 28.27% of theory.
1 H NMR Spectrum (CDCl₃ / TMS): δ = 4.08 (3H); 4.30 / 4.32 / 4.33 (2H); 4.53 / 4.54 / 4.55 (2H); 6.89 / 6.92 / 6.94 / 6.98 / 7.01 (2H); 7.28 / 7.31 / 7.33 / 7.34 / 7.35 / 7.37 (2H); 10.11 (1H) ppm.

0.9 g of E-3 (5,6-dihydro- [1,4,2] dioxazin-3-yl) - (2-hydroxyphenyl) methanone-O-methyl-oxime (1) are also obtained. in a purity of 93.7% (HPLC) = 16.8% of theory.
1 H NMR Spectrum (CDCl₃ / TMS): δ = 4.09 (3H); 4.18 / 4.19 / 4.20 / 4.21 (2H); 4.47 / 4.48 / 4.50 (2H); 6.28 (1H: OH); 6.94 / 6.95 / 6.97 (2H); 7.20-7.36 (2H) ppm.

Example 3 Process variant C 1st stage Compound (VIII-1) Procedure h)

3.26 g (0.02 mol) of benzofuran-2,3-dione-2-oxime (XI-1) in 20 ml of dimethylformamide with 3.36 g (0.04 mol) of O-methylhydroxylamine hydrochloride for 20 minutes 20 ° C and then stirred at 80 ° C for 45 minutes. It is poured into a mixture of aqueous sodium bicarbonate solution and ethyl acetate. The organic phase is separated off, dried over sodium sulfate and the solvent is distilled off under reduced pressure. The residue is stirred with diethyl ether. 1.4 g of crystalline benzofuran-2,3-dione-3- (O-methyl-oxime) -2-oxime (VIII-1) are obtained which, according to HPLC analysis, contains 70.7% of the stereoisomers A and 8.5 % of stereoisomer B contains.
1 H NMR Spectrum (CDCl₃ / TMS): δ = 4.09 (3H, isomer B); 4.11 (3H, isomer A); 7.21-7.35 (2H); 7.51-7.65 (1H, isomer A and 2H, isomer B); 8.02 / 8.04 / 8.05 (1H, isomer A); 11.35 (1H, isomer A); 11.74 (1H, isomer B) ppm.

2nd stage Compound (II-1) Procedure e)

4.49 g (0.0234 mol) of benzofuran-2,3-dione-3- (O-methyl-oxime) -2-oxime (VIII-1) are dissolved in 25 ml of dimethylformamide. 1 g (0.025 mol) of 60% sodium hydride are added to the solution and the mixture is stirred for one hour at room temperature. 3.1 g (0.0248 mol) of 2-bromoethanol are added and the mixture is stirred at 25 ° C. for 12 hours. After adding a further 0.5 g of sodium methylate and 1.22 g of 2-bromoethanol, the mixture is stirred at room temperature for 2 hours. Another 0.5 g of sodium methylate and 1.22 g of 2-bromoethanol are added and the mixture is stirred for a further 2 hours at room temperature. The reaction mixture is poured onto water, extracted with ethyl acetate, the organic phase is washed with 3 times 20 ml of 2N sodium hydroxide solution. The solvent is distilled off in vacuo and the residue is chromatographed in diethyl ether / petroleum ether (1: 1) on silica gel. The eluent is distilled off in vacuo and 2.26 g (39.6% of theory) of benzofuran-2,3-dione-2- [O- (2-hydroxyethyl) oxime] -3- (O- methyl-oxime) (II-1), which consists of 84.29% stereoisomer A and 12.58% stereoisomer B according to HPLC.
1 H-NMR spectrum (CDCl₃ / TMS):
δ = 3.95-4.03 (2H); 4.20 (3H, isomer B); 4.21 (3H, isomer A); 4.37-4.40 (2H); 7.14-7.21 (2H); 7.40-7.49 (1H), 7.63 / 7.64 / 7.66 (1H, isomer B); 8.04 / 8.06 / 8.07 (1H, isomer A) ppm.

3rd stage Connection (1) Procedure a)

2 g benzofuran-2,3-dione-2- [O- (2-hydroxyethyl) oxime] -3- (O-methyloxime) (II-1) (content according to HPLC analysis 96.88% , 0.0082 mol), which was prepared by method e), are dissolved in 50 ml of diethyl ether, which was previously saturated at 0 ° C. with hydrogen chloride gas. The mixture is stirred for 30 minutes without further cooling, then the solvent is distilled off in vacuo and the residue is mixed again with diethyl ether. Part of the product crystallizes out and is filtered off. The mother liquor is concentrated in vacuo and the residue is dissolved in 25 ml in diethyl ether saturated at 0 ° C. with hydrogen chloride gas. The mixture is stirred again for 30 minutes without further cooling, the solvent is distilled off in vacuo and the residue is again mixed with diethyl ether. Another part of the product crystallizes, which is also filtered off. A total of 1.37 g (69% of theory) (5,6-dihydro- [1,4,2] dioxazin-3-yl) - (2-hydroxyphenyl) methanone-O-methyl-oxime is obtained (1) (content according to HPLC analysis: 97.59%).
1 H-NMR spectrum (CDCl₃ / TMS):
δ = 4.09 (3H); 4.18 / 4.19 / 4.20 / 4.21 (2H); 4.47 / 4.48 / 4.50 (2H); 6.94 / 6.95 / 6.97 (2H); 7.20-7.36 (2H) ppm.

Example 4 Process variant (D) 1st stage Connection (XIV-1) Procedure o)

1.63 g (0.01 mol) of benzofuran-2,3-dione-2-oxime (XI-1) are dissolved in 5 ml of N-methyl-2-pyrrolidinone with 1.14 g (0.0108 mol) of sodium carbonate Stirred at 20 ° C for 30 minutes. After adding 1.7 g (0.0102 mol) of 2-bromoethyl acetate, the mixture is stirred for 2 hours at 70.degree. The mixture is poured onto 30 ml of water and the product is filtered off. It is dried and 1.57 g (63% of theory) of crystalline acetic acid are re-2- (3-oxo-3H-benzofuran-2-ylidenaminooxy) ethyl ester (XIV-1).
1 H NMR Spectrum (CDCl₃ / TMS): δ = 2.11 (3H); 4.43 / 4.44 / 4.45 / 4.46 / 4.47 (2H); 4.52 / 4.54 / 4.55 / 4.57 (2H); 7.28 / 7.30 / 7.33 (2H); 7.72 / 7.74 / 7.76 / 7.78 / 7.80 (2H) ppm.

2nd stage Compound (XIII-1) Procedure s)

10 g (0.04 mol) of acetic acid 2- (3-oxo-3H-benzofuran-2-ylidenaminooxy) ethyl ester (XIV-1) and 4, 18 g (0.05 mol) of O-methylhydroxylamine hydrochloride are in 40 ml of N-methyl-2-pyrrolidinone dissolved and stirred at 80 ° C for 1 hour. The reaction mixture is poured onto water and extracted with ethyl acetate. The organic phase is dried over sodium sulfate and the solvent is distilled off in vacuo. 10.6 g of crude product are obtained, which is chromatographed on silica gel using tert-butyl methyl ether / petroleum ether (1: 1). 6.9 g (59.1% of theory) of acetic acid 2- (3-methoxyimino-3H-benzofuran-2-ylidenaminooxy) ethyl ester (XIII-1) with a content of 82.15% isomer A are obtained and 13.38% isomer B (HPLC).
1 H NMR Spectrum (CDCl₃ / TMS): δ = 2.10 (3H); 4.21 (3H, isomer B); 4.22 (3H, isomer A); 4.41-4.48 (4H); 7.15 / 7.17 / 7.20 (2H); 7.44-7.50 (1H); 7.63-7.66 (1H, isomer B); 8.05-8.09 (1H, isomer A) ppm.

3rd stage Compound (II-1) Procedure m)

2 g (0.00718 mol) of acetic acid 2- (3-methoxyimino-3H-benzofuran-2-ylidenaminooxy) ethyl esters (XIII-1) are dissolved in 8 ml dimethylformamide at 20 ° C with 7.2 ml (0.0144 mol) 2N sodium hydroxide solution was added and the mixture was stirred at 20 ° C. for 16 hours. You pour the reak  tion mixture on water and extracted with ethyl acetate. You dry them organic phase over sodium sulfate and the solvent is distilled off in vacuo. 1.7 g (67.6% of theory) of benzofuran-2,3-dione-2- [O- (2-hydroxyethyl) oxime] -3- (O-me thyl-oxime) (II-1), which according to HPLC 56.8% of the stereoisomer A and contains 10.7% of stereoisomer B.

Data from GC / MS analysis (the substance was silylated with N-methyl-N-trimethylsilyltrifluoroacetamide before analysis):
Stereoisomer A:
Retention index = 2062
M⁺ = 309, 308, 293, 249, 233, 192, 176, 145, 132, 89, 73, 45, 26.
Stereoisomer B:
Retention index = 2000
M⁺ = 309, 308,293,249,218,192,176, 145, 132, 90, 73, 45.

4th stage Connection (1)

This stage is as process a) in the 3rd stage of process variant (A) and in 3rd stage of process variant (C) has already been described.

More examples of individual processes Example 5 Connection (1) Procedure c)

1.2 g (0.0054 mol) of Z- (5,6-dihydro- [1,4,2] dioxazin-3-yl) - (2-hydroxyphenyl) methanone oxime (V-1) are initially stirred for 30 minutes at 20 ° C. in 5 ml of dimethylformamide with 0.66 g (0.0062 mol) of sodium carbonate. Then 0.83 g (0.00658 mol) of dimethyl sulfate are added and the mixture is stirred at 20 ° C. for a further 16 hours. The reaction mixture is made weakly acidic with 2 N aqueous hydrochloric acid and extracted with ethyl acetate. The organic phase is dried over sodium sulfate and the solvent is distilled off in vacuo. 0.8 g (50.35% of theory) of Z- (5,6-dihydro- [1,4,2] dioxazin-3-yl) - (2-hydroxyphenyl) methanone omethyl is obtained -oxime (1) in a purity of 80.3% (HPLC).
1 H NMR Spectrum (CDCl₃ / TMS): δ = 4.08 (3H); 4.30 / 4.32 / 4.33 (2H); 4.53 / 4.54 / 4.55 (2H); 6.89 / 6.92 / 6.94 / 6.98 / 7.01 (2H); 7.28 / 7.31 / 7.33 / 7.34 / 7.35 / 7.37 (2H); 10.11 (1H) ppm.

Example 6 Compound (II-1) Procedure e)

3.19 g (0.0166 mol) benzofuran-2,3-dione-3- (O-methyl-oxime) -2-oxime (VIII-1) (mixture of 2 stereoisomers A: B = 13: 86) are suspended in 20 ml of methanol and 8.3 g of a 2 molar sodium methylate solution are added dropwise at 20 ° C. After the mixture has become homogeneous, the methanol is distilled off in vacuo and the crystalline residue is dried for 12 hours in a desiccator. 3.55 g of the sodium salt of benzofuran-2,3-dione-3- (O-methyl-oxime) -2-oxime (VIII-1) are obtained. This is suspended at 20 ° C. in 16 ml of N-methyl-2-pyrrolidinone and 2.1 g (0.0168 mol) of 2-bromoethanol are added. The mixture is stirred at 20 ° C. for 48 hours. The reaction mixture is poured onto water, extracted with ethyl acetate and the organic phase is washed with 3 times 20 ml of 2N sodium hydroxide solution. The solvent is distilled off in vacuo and the residue is chromatographed on silica gel using diethyl ether / petroleum ether (1: 1). The eluent is distilled off in vacuo and 2.91 g (73.8% of theory) of benzofuran-2,3-dione-2- [O- (2-hydroxyethyl) oxime] -3- (O- methyl-oxime) (II-1), consisting of 88.6% stereoisomer B, 7.7% stereoisomer A and 3.2% stereoisomer C (HPLC).
1 H NMR Spectrum (CDCl₃ / TMS): δ = 3.43 (1H, broad); 4.0-4.03 (2H); 4.20 (3H); 4.38-4.41 (2H); 7.14-7.21 (2H); 7.40 / 7.42 / 7.43 / 7.445 (1H); 7.63 / 7.64 / 7.66 (1H) ppm.

Example 7 Compound (II-1) Procedure f)

0.44 g (0.002 mol) benzofuran-2,3-dione-2- [O- (2-hydroxyethyl) oxime] -3-oxime (X-1) are at 20 ° C in 5 ml of dimethylformamide for 20 minutes with 0.08 g (0.002 mol) 60% sodium hydride stirred. After the evolution of gas has ended, 0.28 g is added (0.002 mol) of methyl iodide and stirred at 20 ° C. for 16 hours. You pour the reak tion mixture on water, extracted with ethyl acetate, the organic dries Phase over sodium sulfate, the solvent is distilled off in vacuo and receives 0.5 g (35% of theory) crude product. According to the HPLC analysis, this contains 23% of the Stereoisomers A and 10.1% of the stereoisomers B of benzofuran-2,3-dione-2- [O- (2-hy doxy-ethyl) -oxime] -3- (O-methyl-oxime) (II-1).

Data from GC / MS analysis (the substance was silylated with N-methyl-N-trimethylsilyltrifluoroacetamide before analysis):
Retention index = 2053 (isomer A)
M⁺ = 309, 308, 293, 249, 233, 192, 176, 145, 132, 89, 73, 45, 26.
Retention index = 1997 (isomer B)
M⁺ = 309, 308, 293, 249, 218, 192, 176, 145, 132, 90, 73, 45.

After 20.5% (HPLC), the crude product also contains N- [2- (2-hydroxy-ethoxyimino) -benzofuran-3-ylidenes] -N-methylamine-N-oxide.
GC / MS analysis (silylated sample):
Retention index = 2234
M⁺ = 310, 308, 233, 192, 175, 159, 132, 102, 73, 45, 26).

Example 8 Connection (X-1) Procedure i)

10.1 g (0.05 mol) of benzofuran-2,3-dione-2- [O- (2-hydroxyethyl) oxime] (VII-1) who in 50 ml of N-methyl-2-pyrrolidinone stirred with 3.5 g of hydroxylamine hydrochloride at 80 ° C for 2 hours. The reaction mixture is poured onto water, extracted with ethyl acetate, the organic phase is dried over sodium sulfate and the solvent is distilled off in vacuo. Then the residue was chromatographed in tert-butyl methyl ether / petroleum ether (1: 1) on silica gel. The mobile solvent is distilled off in vacuo and 4.2 g (29.6% of theory) of benzofuran-2,3-di on-2- [O- (2-hydroxyethyl) oxime] -3-oxime are obtained. consisting of 62.4% isomer A and 15.8% isomer B (HPLC).
1 H NMR Spectrum (DMSO-d₆ / TMS): δ = 3.64-3.71 (2H); 4.10-4.26 (2H); 4.78-4.87 (1H); 7.2-7.3 (1H); 7.3-7.4 (1H); 7.5-7.7 (1H); 8.11-8.14 (1H); 12.82 (1H, isomer A); 12.91 (1H, isomer B) ppm.

Example 9 Connection (V-1) Procedure l)

4.14 g (0.02 mol) (5,6-dihydro- [1,4,2] dioxazin-3-yl) - (2-hydroxyphenyl) methanone (III-1) are dissolved in 20 ml dimethylformamide Stirred for 2 hours at 80 ° C. with 2.1 g (0.03 mol) of hydroxylamine hydrochloride. The reaction mixture is poured onto water, extracted with ethyl acetate, the organic phase is dried over sodium sulfate and concentrated in vacuo. 4.7 g of crude product, consisting of 15% E and 57.5% Z isomer (HPLC), are obtained. This is chromatographed on silica gel using a mixture of diethyl ether and petroleum ether (1: 1). 2.7 g (60.8% of theory) (5,6-dihydro- [1,4,2] dioxazin-3-yl) - (2-hydroxyphenyl) methaneone oxime (V- 1) (content according to HPLC analysis: 93.4%).
1 H-NMR spectrum (DMSO-d₆ / TMS): δ = 4.19 / 4.20 / 4.21 (2H); 4.45 / 4.46 / 4.47 (2H); 6.89-6.92 (2H); 7.22-7.32 (1H); 7.33 - 7.40 (1H); 10.30 (1H); 12.16 (1H) ppm.

Example 10 Compound (VII-1) Procedure n)

2.07 g (0.01 mol) of benzofuran-2,3-dione-2- {O- [2- (tetrahydropyran-2-yloxy) ethyl] oxime} (XIV-2) are dissolved in 12 ml of methanol and stirred with 100 mg of acidic ion exchange resin for 16 hours at room temperature. The reaction mixture is mixed with 40 ml of methanol, heated until the crystals are dissolved and filtered off from the acidic ion exchange resin. The filtrate is concentrated and the residue is recrystallized from 10 ml of toluene. 1.69 g (81.5% of theory) of crystalline benzofuran-2,3-dione-2- [O- (2-hydroxyethyl) oxime] (VII-1) with a melting point of 110-111 ° C. are obtained .
1 H NMR Spectrum (CDCl₃ / TMS): δ = 2.33 (1H, broad), 4.00-4.03 (2H); 4.47-4.50 (2H); 7.27-7.32 (2H); 7.70-7.78 (2H) ppm.

Example 11 Compound (XIV-2) Procedure o)

5 g (0.03 mol) of benzofuran-2,3-dione-2-oxime (XI-1) are dissolved in 30 ml of methanol and 15 ml of 2 molar sodium methylate solution in methanol are added dropwise at 20 ° C. The solvent is distilled off in vacuo. The crystalline residue is dissolved in 30 ml of N-methyl-2-pyrrolidinone and 6.27 g (0.03 mol) of 2- (2-bromoethoxy) tetrahydropyran are added at 20 ° C. The mixture is stirred at 20 ° C. for 16 hours, poured onto 100 ml of water and extracted twice with 100 ml of dichloromethane each time. After the solvent has been distilled off in vacuo, the residue is chromatographed in a mixture of diethyl ether / dichloromethane / petroleum ether (1: 1: 2) on silica gel. 5.55 g (62.1% of theory) of benzofuran-2,3-dione-2- {O- [2- (tetrahydropyran-2-yloxy) ethyl] oxime (XIV-2) are obtained.
1 H NMR Spectrum (CDCl₃ / TMS): δ = 1.50-1.86 (6H); 3.49-3.53 (1H); 3.81-3.88 (2H); 4.02-4.09 (1H); 4.52-4.55 (2H); 4.66-4.69 (1H); 7.26-7.31 (2H); 7.69-7.80 (2H) ppm.

Example 12 Compound (VIII-1) Procedure p)

To a suspension of 2.4 g (0.06 mol) of 60% sodium hydride in 25 ml Dimethylformamide is added dropwise to a solution of 11 g (0.0617 mol) of benzofurandi on-2,3-dioxime in 50 ml of dimethylformamide and stirred for one hour at 20 ° C. Then drips 7.55 g (0.06 mol) of dimethyl sulfate are added and the mixture is stirred at 20 ° C. for a further 16 hours. Man pour the reaction mixture onto water and extract with ethyl acetate, dries the organic phase over sodium sulfate and concentrates in vacuo. Of the The residue is chromatographed on silica gel using hexane / acetone (7: 3). After this Stirring the residue with diethyl ether gives 0.7 g of benzofuran-2,3-dione-3- (O-me thyl-oxime) -2-oxime (VIII-1) as a mixture of stereoisomers, consisting of 90.6% Isomer A and 9% isomer B (HPLC).  

Example 13 Connection (X-1) Procedure q)

5.28 g (0.02 mol) of ethyl acetic acid 2- (3-hydroxyimino-3H-benzofuran-2-ylideneamino oxy) (XVI-1) are dissolved in 20 ml of dimethylformamide with 4.24 g (0.048 mol) 45 % sodium hydroxide solution stirred at 20 ° C for 3 hours. It is acidified with 2N hydrochloric acid, extracted with ethyl acetate, the organic phase is dried over sodium sulfate and the solvent is distilled off in vacuo. According to HPLC analysis, the crude product contains 23.4% stereoisomer A and 4.1% of stereoisomer B of benzofuran-2,3-di on-2- [O- (2-hydroxy-ethyl) -oxime] -3- oxime (X-1). After stirring with diethyl ether, 1.4 g (28.5% of theory) of crystalline benzofuran-2,3-dione-2- [O- (2-hydroxyethyl) oxime] -3-oxime ( X-1), consisting of 84.7% stereoisomer A and 6% stereoisomer B (HPLC).
1 H NMR Spectrum (DMSO-d₆ / TMS): δ = 3.64-3.71 (2H); 4.10-4.26 (2H); 4.78-4.87 (1H); 7.2-7.3 (1H); 7.3-7.4 (1H); 7.5-7.7 (1H); 8.11-8.14 (1H); 12.82 (1H, stereoisomer A); 12.91 (1H, stereoisomer B) ppm.

Example 14 Compound (XVI-1) Procedure r)

5 g (0.02 mol) of acetic acid 2- (3-oxo-3H-benzofuran-2-ylidenaminooxy) ethyl ester (XIV-1) and 1.74 g (0.025 mol) of hydroxylamine hydrochloride are dissolved in 20 ml of dimethylformamide and stirred at 100 ° C for 2 hours. The reaction mixture is poured onto water and extracted with ethyl acetate. The organic phase is dried over sodium sulfate and the solvent is distilled off in vacuo. The residue is chromatographed on silica gel using tert-butyl methyl ether / petroleum ether (1: 1). 2.7 g (38.5% of theory) of ethyl acetate (XVI-1) consisting of 64.23% of stereoisomer A and 14 are obtained (2- (3-hydroxyimino-3H-ben zofuran-2-ylideneaminooxy)) , 9% stereoisomer B (HPLC).
1 H NMR Spectrum (CDCl₃ / TMS): δ = 2.11 (3H, stereoisomer A); 2.12 (3H, stereoisomer B); 4.43-4.46 (4H); 7.19-7.23 (2H); 7.46-7.52 (1H); 7.65-7.8 (1H, stereoisomer B); 8.16 / 8.17 / 8.19 (1H, stereoisomer A); 8.9 (1H) ppm.

Example 15 Compound (XIII-1) Procedure s)

10 g (0.04 mol) of acetic acid 2- (3-oxo-3H-benzofuran-2-ylidenaminooxy) ethyl ester (XIV-1) and 4.18 g (0.05 mol) of O-methylhydroxylamine hydrochloride are added 40 ml of N-methyl-2-pyrrolidinone dissolved and stirred at 80 ° C for 1 hour. The reaction mixture is poured onto water and extracted with ethyl acetate. The organic phase is dried over sodium sulfate and the solvent is distilled off in vacuo. 10.6 g of crude acetic acid 2- (3-methoxyimino-3H-benzofuran-2-ylidene aminooxy) ethyl ester (XIII-1) are obtained, which is mixed with a mixture of tert-butyl methyl ether and petroleum ether (1: 1) Silica gel is chromatographed. 6.9 g (59.1% of theory) of acetic acid 2- (3-methoxyimino-3H-benzofuran-2-ylidenaminooxy) ethyl ester (XIII-1) containing 82.15% of stereoisomer A and 13.38% stereoisomer B.
1 H NMR Spectrum (CDCl₃ / TMS): δ = 2.10 (3H); 4.21 (3H, stereoisomer B); 4.22 (3H, stereoisomer A); 4.41-4.48 (4H); 7.15 / 7.17 / 7.20 (2H); 7.44-7.50 (1H); 8.05-8.09 (1H) ppm.

Example 16 Compound (XIII-1) Procedure t)

0.26 g (0.001 mol) of acetic acid 2- (3-hydroxyimino-3H-benzofuran-2-ylidenamino oxy) ethyl ester (XVI-1) are dissolved in 2 ml of dimethylformamide. 0.04 g is added (0.001 mol) of 60% sodium hydride at 20 ° C and stirred until the end of Gas evolution. Then 0.05 g (0.0005 mol) of sodium carbonate and 0.13 g are added (0.001 mol) of dimethyl sulfate to the reaction mixture and leave it at 20 ° C. for 2 days stand. The reaction mixture is poured onto water and extracted with acetic acid ethyl ester. The organic phase is dried over sodium sulfate and the product is distilled Solvent in a vacuum. 0.24 g (42.5% of theory) of raw vinegar are obtained 2- (3-methoxyimino-3H-benzofuran-2-ylidenaminooxy) ethyl acid (XIII-1), the according to HPLC analysis contains 33.9% stereoisomer A and 15.4% stereoisomer B.

Data from the GC / MS analysis:
Retention index = 2097 (stereoisomer A)
M⁺ = 279, 278, 218, 187, 160, 144, 130, 87, 75, 43, 26.
Retention index = 2036 (stereoisomer B)
M⁺ = 279, 278, 218, 187, 160, 144, 130, 87, 63, 43, 26.

Example 17 Compound (XIII-1) Procedure u)

1.92 g (0.01 mol) of benzofuran-2,3-dione-3- (O-methyl-oxime) -2-oxime (VIII-1) dissolved in 10 ml of dimethylformamide at 20 ° C. 0.4 g (0.01 mol) is added to this solution 60% sodium hydride and stirred at 20 ° C for 1 hour. Now give 1.67 g (0.01 mol) of 2-bromoethyl acetate and stirred for 16 hours at 20 ° C. The The reaction mixture is poured onto water and extracted with ethyl acetate. The organic phase is dried over sodium sulfate and concentrated in vacuo. 2.3 g (52.6% of theory) of acetic acid 2- (3-methoxyimino-3H-benzo) are obtained furan-2-ylidenaminooxy) ethyl ester (XIII-1), consisting of 51.17% stereoisomer A. and 12.49% stereoisomer B (HPLC).

Data from GC / MS analysis (the substance was silylated with N-methyl-N-trimethylsilyltrifluoroacetamide before analysis):
Retention index = 2097 (stereoisomer A)
M⁺ = 279, 278, 218, 187, 160, 144, 130, 87, 75, 43, 26.
Retention index = 2035 (stereoisomer B)
M⁺ = 279, 278, 218, 187, 160, 144, 130, 87, 75, 43, 26.

Example 18 Connection (V-1) Procedure v)

1.11 g (0.005 mol) benzofuran-2,3-dione-2- [O- (2-hydroxyethyl) oxime] -3-oxime (X-1) are dissolved in 20 ml of diethyl ether, which was previously at 0 ° C with hydrogen chloride gas was saturated. The mixture is stirred for 3 hours without further cooling and the mixture is poured on a sodium hydrogen carbonate solution cooled to 0 ° C. You separate the organi cal phase and the aqueous phase extracted several times with ethyl acetate ester. The combined organic phases are dried over sodium sulfate and concentrated under reduced pressure. 0.8 g (29.9% of theory) of crude is obtained (5,6-Dihydro- [1,4,2] dioxazin-3-yl) - (2-hydroxyphenyl) methanone oxime (V-1) from 19.7% E isomer and 21.8% Z isomer (HPLC).

Data from GC / MS analysis (the substance was silylated with N-methyl-N-trimethylsilyltrifluoroacetamide before analysis):
Retention index = 1980 (E-isomer)
M⁺ = 368, 351, 307, 292, 250, 235, 203, 176, 147, 117, 100, 73, 45.
Retention index = 2036 (Z-isomer)
M⁺ = 367, 351, 306, 292, 250, 235, 203, 176, 147, 117, 100, 73, 45.

Claims (30)

1. Process for the preparation of compounds of formula (I) in which
A represents alkyl,
R¹, R², R³ and R⁴ are the same or different and are each independently hydrogen; Halogen, cyano, nitro, in each case optionally substituted by halogen, alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl and
Z¹, Z², Z³ and Z⁴ are the same or different and are independently hydrogen; Are alkyl, haloalkyl or hydroxyalkyl, or
Z¹ and Z² or Z¹ and Z³ or Z³ and Z⁴ together with the respective carbon atoms to which they are attached form a cycloaliphatic ring,
characterized in that

• a) O-hydroxyethyl-O'-methyl-benzofurandione dioxime of the formula in which
  A, R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ have the meanings given above,
  optionally rearranged in the presence of a diluent and optionally in the presence of an acid or a base, or that one
• b) hydroxybenzoyldioxazines of the formula in which
  R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ have the meanings given above,
  with an alkoxyamine of the formula A-O-NH₂ (IV), in which
  A has the meaning given above,
  - or an acid addition complex thereof -
  optionally in the presence of a diluent and, if appropriate, in the presence of an acid acceptor, or that
• c) hydroxyphenyl-hydroximinomethyl-dioxazines of the formula in which
  R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ have the meanings given above,
  with an alkylating agent of formula A-X (VI), in which
  A has the meaning given above and
  X represents halogen, alkylsulfonyloxy, alkoxysulfonyloxy or arylsulfonyloxy,
  if appropriate in the presence of a diluent, and if appropriate in the presence of a base.

2. The method according to claim 1, wherein in the formula (I)
A represents methyl, ethyl, n- or i-propyl,
R¹, R², R³ and R⁴, are the same or different and are each independently hydrogen; Halogen, cyano, nitro, each optionally substituted by 1 to 5 halogen atoms, alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms,
Z¹, Z², Z³ and Z⁴ are the same or different and are independently hydrogen; Alkyl or hydroxyalkyl having 1 to 4 carbon atoms or haloalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, or
Z¹ and Z² or Z¹ and Z³ or Z³ and Z⁴ together with the respective carbon atoms to which they are attached form a cycloaliphatic ring with five, six or seven carbon atoms. 3. The method according to claim 1, wherein in the formula (I)
A represents methyl or ethyl,
R¹, R², R³ and R⁴ are the same or different and are each independently 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, methylsulfinyl , Ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluoroethyl, di fluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, difluorochloromethylthio, trifluoromethylthio, trifluoromethylluoromethyl or trifluoromethylmethylsulfinyl
Z¹, Z², Z³ and Z⁴ are the same or different and are independently hydrogen; Are methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, hydroxymethyl, trifluoromethyl or trifluoroethyl, or
Z¹ and Z² or Z¹ and Z³ or Z³ and Z⁴ together with the respective carbon atoms to which they are attached form a cycloaliphatic ring with five, six or seven carbon atoms. 4. Compounds of formula (II) in which
A, R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ have the meanings given in Claim 1. 5. A process for the preparation of compounds of formula (II) as defined in claim 4, characterized in that

• d) O-hydroxyethyl-benzofurandione monooximes of the formula in which
  R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ have the meanings given above,
  with an alkoxyamine of the formula (IV)
  - 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 that
• e) O-alkyl-benzofurandione dioximes of the formula in which
  A, R¹, R², R³ and R⁴ have the meanings given above, with an ethane derivative of the formula in which
  Y¹ is halogen, alkylsulfonyloxy, arylsulfonyloxy or alkanoyl oxy and
  G stands for hydrogen, or
  Y¹ and G are connected by a single bond, wherein
  Y¹ represents oxygen or
  G for stands, or
  Y¹ and G together represent a single bond and
  Z¹, Z², Z³ and Z⁴ have the meanings given above,
  optionally in the presence of a diluent, and if appropriate in the presence of a base, or that
• f) O-hydroxyethyl-benzofurandione dioximes of the formula in which
  R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ have the meanings given above,
  with an alkylating agent of the formula (VI),
  optionally in the presence of a diluent, and if appropriate in the presence of a base, or that
• m) O-oxyethyl-O'-methyl-benzofurandione dioxime of the formula in which
  A, R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ have the meanings given above and
  E represents an acyl group or a ketal protective group,
  with water or an alcohol, if appropriate in the presence of a diluent and if appropriate in the presence of an acid or a base.

6. Compounds of formula (VII) in which
R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ have the meanings given in Claim 1. 7. A process for the preparation of compounds of formula (VII) as defined in claim 6, characterized in that

• g) Benzofurandione monooximes of the formula in which
  R¹, R², R³ and R⁴ have the meanings given above,
  with an ethane derivative of the formula (IX),
  optionally in the presence of a diluent, and if appropriate in the presence of a base, or that
• n) O-oxyethyl-benzofurandione monooximes of the formula in which
  E, R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ have the meanings given above,
  with water or an alcohol, if appropriate in the presence of a diluent and if appropriate in the presence of an acid or a base.

8. Compounds of the formula (XIV) in which
R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ have the meanings given in Claim 1 and
E represents an acyl group or a ketal protective group. 9. A process for the preparation of compounds of formula (XIV) as defined in claim 8, characterized in that

• o) Benzofurandione monooxime of the formula (XI) with an ethanol derivative of the formula in which
  E, Z¹, Z², Z³ and Z⁴ have the meanings given above and
  Y² represents halogen, alkylsulfonyloxy, arylsulfonyloxy or alkanoyl oxy,
  optionally in the presence of a diluent and, if appropriate, in the presence of an acid acceptor.

10. Compounds of formula (VIII) in which
A, R¹, R², R³ and R⁴ have the meanings given in claim 1. 11. A process for the preparation of compounds of formula (VIII) as defined in claim 10, characterized in that

• h) benzofuranedione monooximes of the formula (XI) with an alkoxyamine of the formula (IV),
  optionally in the presence of a diluent and if appropriate in the presence of an acid acceptor, or that
• p) Benzofurandione dioximes of the formula in which
  R¹, R², R³ and R⁴ have the meanings given above,
  with an alkylating agent of the formula (VI),
  if appropriate in the presence of a diluent, and if appropriate in the presence of a base.

12. Compounds of the formula (X) in which
R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ have the meanings given in Claim 1. 13. A process for the preparation of compounds of formula (X) as defined in claim 12, characterized in that

• i) O-hydroxyethyl-benzofurandione monooximes of the formula (VII),
  with hydroxylamine - or an acid addition complex thereof -
  optionally in the presence of a diluent and if appropriate in the presence of an acid acceptor, or that
• q) O-oxyethyl-benzofurandione dioxime of the formula in which
  E, R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ have the meanings given above,
  with water or an alcohol, if appropriate in the presence of a diluent and if appropriate in the presence of an acid or a base.

14. Compounds of the formula (XVI) in which
R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ have the meanings given in Claim 1 and
E represents an acyl group or a ketal protective group. 15. A process for the preparation of compounds of formula (XVI) as defined in claim 14, characterized in that

• r) O-oxyethylbenzofurandione monooximes of the formula (XIV),
  with hydroxylamine - or an acid addition complex thereof -
  optionally in the presence of a diluent and, if appropriate, in the presence of an acid acceptor.

16. Compounds of the formula (XIII) in which
A, R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ have the meanings given in Claim 1 and
E represents an acyl group or a ketal protective group. 17. A process for the preparation of compounds of formula (XIII) as defined in claim 16, characterized in that

• s) O-oxyethyl-benzofurandione monooximes of the formula (XIV) with an alkoxyamine of the formula (IV),
  - or an acid addition complex thereof -
  optionally in the presence of a diluent and, if appropriate, in the presence of an acid acceptor, or that
• t) O-oxyethyl-benzofurandione dioximes of the formula (XVI) with an alky lating agent of the formula (VI),
  optionally in the presence of a diluent, and if appropriate in the presence of a base, or that
• u) O-alkyl-benzofurandione dioximes of the formula (VIII) with an ethanol derivative of the formula (XV),
  optionally in the presence of a diluent and, if appropriate, in the presence of an acid acceptor.

18. Compounds of the formula (III) in which
R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ have the meanings given in Claim 1. 19. A process for the preparation of compounds of formula (III) as defined in claim 18, characterized in that

• k) O-hydroxyethyl-benzofurandione monooximes of the formula (VII),
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid.

20. Compounds of formula (V) in which
R¹, R², R³, R⁴, Z¹, Z², Z³ and Z⁴ have the meanings given in Claim 1. 21. A process for the preparation of compounds of formula (V) as defined in claim 20, characterized in that

• l) hydroxybenzoyldioxazines of the formula (III),
  with hydroxylamine - or an acid addition complex thereof -
  optionally in the presence of a diluent and if appropriate in the presence of an acid acceptor, or that
• v) O-hydroxyethyl-benzofurandione dioximes of the formula (X),
  optionally rearranged in the presence of a diluent and optionally in the presence of an acid.

22. Use of the compounds of the formulas (II), (VII), (XIV), (VIII), (X), (XVI), (XIII), (III) and (V) as intermediates or precursors for Preparation of compounds with fungicidal properties. 23. Process for the preparation of compounds of formula (I) in which
A represents alkyl,
R¹, R², R³ and R⁴ are the same or different and are each independently hydrogen; Halogen, cyano, nitro, in each case optionally substituted by halogen, alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl and
Z¹, Z², Z³ and Z⁴ are the same or different and are independently hydrogen; Are alkyl, haloalkyl or hydroxyalkyl, or
Z¹ and Z² or Z¹ and Z³ or Z³ and Z⁴ together with the respective carbon atoms to which they are attached form a cycloaliphatic ring,
characterized in that these compounds of the formula (I), starting from the compound (XI), are prepared via process steps o), n) or g) and d), a) or h), e) and a). 24. The method according to claim 23, characterized in that one ver compounds of the formula (I), starting from the compounds of the formula (XII), about the process steps p), e) and a). 25. The method according to claim 23, characterized in that one Ver compounds of the formula (I), starting from compounds of the formula (XIV), about the process steps n), d) and a) or r), q), f) and a) or t), m) and a) produces. 26. The method according to claim 23, characterized in that this Ver compounds of the formula (I), starting from compounds of the formula (VII), via process steps d) and a) or i), f) and c) or k) and b). 27. The method according to claim 23, characterized in that one Ver compounds of the formula (I), starting from compounds of the formula (XVI), about the process steps q), f) and a) or s), m) and a). 28. The method according to claim 23, characterized in that Ver compounds of the formula (I), starting from compounds of the formula (VIII), about the process steps e) and a) or u), m) and a). 29. The method according to claim 23, characterized in that this Ver compounds of formula (I), starting from compounds of formula (III), on process steps l) and c). 30. The method according to claim 23, characterized in that one Ver compounds of formula (I), starting from compounds of formula (X), on process steps f) and a) or v) and c).