DE4408005A1 - Substituted azadioxacycloalkenes - Google Patents

Description

The invention relates to new substituted azadioxacycloalkenes, a process for their Manufacture and its use as fungicides.

It is known that certain substituted 5,6-dihydro-1,4,2-dioxazines are fungicidal Have properties (cf. JP-A 01221371 - cited in Chem. Abstracts 112: 98566t; JP 02001484 - cited in Chem. Abstracts 113: 6381y). However, these connections have not gained any particular importance.

There have now been the new substituted azadioxacycloalkenes of the general formula (I) found

in which
A represents optionally substituted alkanediyl (alkylene),
Ar represents optionally substituted arylene or heteroarylene,
E represents a 1-alkene-1,1-diyl grouping which contains a radical R 1 in the 2-position, or represents a 2-aza-1-alkene-1,1-diyl grouping which is in 2- Position contains a radical R², or represents a 3-oxa- or 3-thia-1-propene-2,3-diyl group which contains a radical R¹ in the 1-position, or represents a 3-aza-1- propen-2,3-diyl grouping which contains a R group in the 3-position and a R¹ group in the 1-position, or a 1-aza-1-propene-2,3-diyl grouping which contains a radical R² in the 1-position, or represents a 3-oxa- or 3-thia-1-aza-propene-2,3-diyl grouping which contains a radical R² in the 1-position, or represents a 1 , 3-diaza-1-propene-2,3-diyl grouping which contains a R group in the 3-position and a R² group in the 1-position, or for an optionally substituted imino grouping ("Azamethylene", N -R³) stands,
in which
R represents alkyl,
R¹ represents hydrogen, halogen, cyano or optionally substituted alkyl, alkoxy, alkylthio, alkylamino or dialkylamino,
R² stands for hydrogen, amino, cyano or for optionally substituted alkyl, alkoxy, alkylamino or dialkylamino, and
R³ represents hydrogen, cyano or optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkylalkyl,
G represents a single bond, oxygen, alkane diyl, alkenediyl, oxaalkenediyl, alkindiyl or one of the following groups, each optionally substituted by halogen, hydroxy, alkyl, haloalkyl or cycloalkyl

-Q-CQ-, -CQ-Q-, -CH₂-Q-; -Q-CH₂-, -CQ-Q-CH₂-, -CH₂-Q-CQ-, -Q-CQ-CH₂-, -Q-CQ-Q-CH₂-, -N = N-, -S (O ) _n -, -CH₂-S (O) _n -, -CQ-, -S (O) n-CH₂-, -C (R⁴) = NO-, -C (R⁴) = NO-CH₂-, -N (R⁵) -, -CQ-N (R⁵) -, -N (R⁵) -CQ-, -Q-CQ-N (R⁵) -, -N = C (R⁴) -Q-CH₂-, -CH₂- ON = C (R⁴) -, -N (R⁵) -CQ-Q-, -CQ-N (R⁵) -CQ-Q-, -N (R⁵) -CQ-Q-CH₂-, -CQ-CH₂- or -N = NC (R⁴) -NO-,

in which
n represents the numbers 0, 1 or 2,
Q represents oxygen or sulfur,
R⁴ represents hydrogen, cyano or in each case optionally substituted alkyl, alkoxy, alkylthio, alkylamino, dialkylamino or cycloalkyl, and
R⁵ represents hydrogen, hydroxy, cyano or in each case optionally substituted alkyl, alkoxy or cycloalkyl, and
Z represents optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heterocyclyl.

It was also found that the new substituted azadioxacycloalkenes general formula (I) obtained when one

• (a) carboxylic acid derivatives of the general formula (II) in which
  Ar, E, G and Z have the meaning given above, and
  R represents alkyl,
  in a first stage with hydroxylamine or with a hydrogen halide thereof, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, and in situ, ie without intermediate isolation of the product of the first stage, in a second stage with disubstituted alkanes of the general formula (III) XAX (III) in which
  A has the meaning given above and
  X represents halogen, alkylsulfonyloxy or arylsulfonyloxy,
  if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or if
• (b) in the case that in formula (I) G represents oxygen or the group -CH₂-O- and A, Ar, E and Z have the meaning given above, hydroxyaryl compounds of the general formula (IV), in which
  A, Ar and E have the meaning given above,
  with compounds of the general formula (V), Z- (CH₂) _m -X (V) in which
  X and Z have the meaning given above and
  m represents the numbers 0 or 1,
  if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent and if appropriate subsequently carrying out substitution reactions on the group Z by customary methods, or if one
• (c) in the case that in the formula (I) G represents the group -Q-CH₂- and A, Ar, E and Z have the meaning given above, halomethyl compounds of the general formula (VI) in which
  A, Ar and E have the meaning given above and
  X¹ represents halogen,
  with compounds of the general formula (VII) ZQH (VII) in which
  Q and Z have the meaning given above, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or if
• (d) hydroxyalkoxyamides of the general formula (VIII) in which
  A, Ar, E, G and Z have the meaning given above, cyclized with a dehydrating agent, optionally in the presence of a diluent.

Finally, it was found that the new substituted azadioxacycloalkenes general formula (I) show very strong fungicidal activity.  

The compounds according to the invention can optionally be mixed various possible isomeric forms, in particular E and Z isomers, available. There are both the E and the Z isomers as well as any Mixtures of these isomers claimed.

The invention preferably relates to compounds of the formula (I) in which
A represents alkanediyl with 1 to 3 carbon atoms optionally substituted by halogen or by alkyl or haloalkyl each having 1 to 4 carbon atoms,
Ar stands for optionally substituted phenylene or naphthylene or for heteroarylene with 5 or 6 ring members, at least one of which is oxygen, sulfur or nitrogen and optionally one or two more are nitrogen, the possible substituents preferably from the list below are selected:

Halogen, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thio carbamoyl, in each case straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms, in each case ge straight-chain or branched alkenyl, alkenyloxy or alkynyloxy each having 2 to 6 carbon atoms, each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkyl sulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, each straight-chain or branched halogen alkenyl or haloalkenyloxy each having 2 to 6 Carbon atoms and 1 to 13 identical or different halogen atoms, each straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxy carbonyl, alkylsulfonyloxy, hydroximinoalkyl or alkoximinoalkyl, each with 1 to 6 carbon atoms in the individual alkyl parts, in each case optionally singly or multiply, identical or different by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, in each case doubly linked alkylene or Dioxyalkylene with 1 to 6 carbon atoms each,
E represents one of the groupings below

wherein
Y represents oxygen, sulfur, methylene (CH₂) or alkylimino (NR),
R represents alkyl having 1 to 6 carbon atoms,
R¹ represents hydrogen, halogen, cyano or alkyl, alkoxy, alkyl thio, alkylamino or dialkylamino, each of which has 1 to 6 carbon atoms in the alkyl radicals, optionally substituted by halogen, cyano or C₁-C₄alkoxy,
R² stands for hydrogen, amino, cyano or for alkyl, alkoxy, alkyl amino or dialkylamino, each optionally substituted by halogen, cyano or C₁-C Alkalkoxy, each having 1 to 6 carbon atoms in the alkyl radicals, and
R³ for hydrogen, cyano or for alkyl, alkenyl or alkynyl each optionally substituted by halogen, cyano or C₁-C₄alkoxy, each having up to 6 carbon atoms or for each optionally halogen, cyano, carboxy, C₁-C₄alkyl or C₁- C₄-alkoxy-carbonyl substituted cycloalkyl or cycloalkylalkyl having 3 to 6 carbon atoms in the cycloalkyl parts and optionally 1 to 4 carbon atoms in the alkyl part,
G for a single bond, for oxygen, for in each case optionally substituted by halogen, hydroxy, C₁-C₄-alkyl, C₁-C₄-haloalkyl or C₃-C₆-cycloalkyl, alkanediyl, alkenediyl, oxaalkenediyl, alkynediyl each having up to 4 carbon atoms or one of the the following groups

-Q-CQ-, -CQ-Q-, -CH₂-Q-; -Q-CH₂-, -CQ-Q-CH₂-, -CH₂-Q-CQ-, -Q-CQ-CH₂-, -Q-CQ-Q-CH₂-, -N = N-, -S (O ) _n -, -CH₂-S (O) _n -, -CQ-, -S (O) _n -CH₂-, -C (R⁴) = NO-, -C (R⁴) = NO-CH₂-, -N (R⁵) -, -CQ-N (R⁵) -, -N (R⁵) -CQ-, -Q-CQ-N (R⁵) -, -N = C (R⁴) -Q-CH₂-, -CH₂- ON = C (R⁴) -, -N (R⁵) -CQ-Q-, -CQ-N (R⁵) -CQ-Q-, -N (R⁵) -CQ-Q-CH₂-, -CQ-CH₂- or -N = NC (R⁴) = N - = -,

in which
n represents the numbers 0, 1 or 2,
Q represents oxygen or sulfur,
R⁴ for hydrogen, cyano, for alkyl, alkoxy, alkylthio, alkylamino or dialkylamino optionally substituted by halogen, cyano or C₁-C₄alkoxy, each having 1 to 6 carbon atoms in the alkyl groups or for each optionally halogen, cyano, carboxy, C₁- C₄-alkyl or C₁-C₄-alkoxy-carbonyl substituted cycloalkyl having 3 to 6 carbon atoms, and
R⁵ represents hydrogen, hydroxyl, cyano or alkyl which has 1 to 6 carbon atoms and is optionally substituted by halogen, cyano or C₁-C₄alkoxy or represents optionally substituted by halogen, cyano, carboxy, C₁-C₄alkyl or C₁-C₄alkoxy- carbonyl substituted cycloalkyl having 3 to 6 carbon atoms, and
Z for alkyl which is optionally substituted by halogen, cyano, hydroxy, amino, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl or C₁-C₄-alkylsulfonyl (which are each optionally substituted by halogen) and is 1 to 8 Carbon atoms, for each optionally substituted by halogen-substituted alkenyl or alkynyl each having up to 8 carbon atoms for each optionally by halogen, cyano, carboxy, phenyl (which may be replaced by halogen, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or C₁-C₄-haloalkoxy is substituted), C₁-C₄-alkyl or C₁-C₄-alkoxy carbonyl-substituted cycloalkyl with 3 to 6 carbon atoms, for each optionally substituted phenyl, naphthyl or (optionally benz fused) heterocyclyl with 5 or 6 ring members of which at least one is oxygen, sulfur or nitrogen and optionally one or two more are nitrogen, the m possible substituents are preferably selected from the list below:

Oxygen (as a replacement for two geminal hydrogen atoms), halogen, cyano, Nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl, respectively straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl or Alkylsulfonyl each having 1 to 6 carbon atoms, each straight-chain or branched alkenyl or alkenyloxy each having 2 to 6 carbon atoms, each straight-chain or branched haloalkyl, haloalkoxy, halogen alkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 6 Carbon atoms and 1 to 13 identical or different halogen atoms, each straight-chain or branched haloalkenyl or haloalkenyloxy each having 2 to 6 carbon atoms and 1 to 13 identical or different Halogen atoms, each straight-chain or branched alkylamino, dialkyl amino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylsulfonyloxy, Hydroximinoalkyl or alkoximinoalkyl each having 1 to 6 carbon atoms in the individual alkyl parts, each one or more times if necessary, identical or different by halogen and / or straight-chain or branched Alkyl with 1 to 4 carbon atoms and / or straight-chain or branched Haloalkyl with 1 to 4 carbon atoms and 1 to 9 identical or ver different halogen atoms substituted, each doubly linked alkylene or dioxyalkylene each having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 Carbon atoms, heterocyclyl or heterocyclyl-methyl each with 3 to 7 Ring members, each of which has 1 to 3 identical or different heteroatoms are - especially nitrogen, oxygen and / or sulfur - and each optionally in the phenyl moiety one or more times, the same or different by halogen, cyano, nitro, carboxy, carbamoyl and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or  branched haloalkyl of 1 to 4 carbon atoms and 1 to 9 of the same or various halogen atoms and / or straight-chain or branched Alkoxy with 1 to 4 carbon atoms and / or straight-chain or branched Haloalkoxy with 1 to 4 carbon atoms and 1 to 9 identical or ver different halogen atoms and / or alkylcarbonyl or alkoxycarbonyl up to 5 carbon atoms each substituted phenyl, phenoxy, benzyl, Benzyloxy, phenylethyl or phenylethyloxy.

In the definitions are the saturated or unsaturated hydrocarbon chains, such as alkyl, alkanediyl, alkenyl or alkynyl, also in combination with heteroatoms, as in alkoxy, alkylthio or alkylamino, in each case straight-chain or branched.

Halogen generally represents fluorine, chlorine, bromine or iodine, preferably Fluorine, chlorine or bromine, especially for fluorine or chlorine.

The invention relates in particular to compounds of the formula (I) in which
A represents methylene or dimethylene (ethane-1,2-diyl) which is optionally substituted by fluorine, chlorine, methyl, ethyl or trifluoromethyl
Ar for each optionally substituted ortho-, meta- or para-phenylene, for furandiyl, thiophene diyl, pyrroldiyl, pyrazole diyl, triazole diyl, oxazole diyl, isoxazole diyl, thiazole diyl, isothiazole diyl, oxadiazole diyl, thiadiazole diyl, pyridinedinediyl, pyrimidinediyl, pyrimidinediyl, pyrimidinediyl , 4-triazinediyl or 1,2,3-triazinediyl, the possible substituents being selected in particular from the list below:
Fluorine, chlorine, cyano, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, methyl thio, methylsulfinyl or methylsulfonyl,
E represents one of the groupings below

wherein
Y represents oxygen, sulfur, methylene (CH₂) or alkylimino (NR),
R represents methyl, ethyl, n- or i-propyl, n-, i- or s-butyl,
R¹ represents hydrogen, fluorine, chlorine, bromine, cyano or methyl, ethyl, propyl, methoxy, ethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino, each optionally substituted by fluorine, chlorine, cyano, methoxy or ethoxy,
R² stands for hydrogen, amino, cyano or for methyl, ethyl, methoxy, ethoxy, methylamino, ethylamino or dimethylamino optionally substituted by fluorine, chlorine, cyano, methoxy or ethoxy, and
R³ for hydrogen, cyano or for methyl, ethyl n- or i-propyl, n-, i- or s-butyl, optionally substituted by fluorine, cyano, methoxy or ethoxy, for allyl or propargyl or for in each case optionally by fluorine, chlorine , Cyano, carboxy, methyl, ethyl, n- or i-propyl, methoxycarbonyl or ethoxycarbonyl substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl,
G for a single bond, for oxygen, for methylene, dimethylene (ethane-1,2-diyl) substituted by fluorine, chlorine, hydroxyl, methyl, ethyl, n- or i-propyl, trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl ), Ethene-1,2-diyl, ethyne-1,2-diyl or one of the groupings below

-Q-CQ-, -CQ-Q-, -CH₂-Q-, -Q-CH₂-, -CQ-Q-CH₂-, -CH₂-Q-CQ-, -Q-CQ-CH₂-, -Q -CQ-Q-CH₂-, -N = N-, -S (O) _n -, CH₂-S (O) _n -, -CQ-, -S (O) _n -CH₂-, -C (R⁴) = NO-, -C (R⁴) = NO-CH₂-, -N (R⁵) -, -CQ-N (R⁵) -, -N (R⁵) -CQ-, -Q-CQ-N (R⁵) - , -N = C (R⁴) -Q-CH₂-, -CH₂-ON = (R⁴) -, -N (R⁵) -CQ-Q-, -CQ-N (R⁵) -CQ-Q- or -N (R⁵) -CQ-Q-CH₂- stands,
in which
n represents the numbers 0, 1 or 2,
Q represents oxygen or sulfur,
R⁴ represents hydrogen, cyano, methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, methoxy, ethoxy, propoxy, butoxy, methylthio, optionally substituted by fluorine, chlorine, cyano, methoxy or ethoxy, Ethylthio, propylthio, butylthio, methylamino, ethylamino, propylamino, dimethyl arino or diethylamino or for cyclopropyl, cyclobutyl, in each case optionally substituted by fluorine, chlorine, cyano, carboxy, methyl, ethyl, n- or i-propyl, methoxycarbonyl or ethoxycarbonyl, Cyclopentyl or cyclohexyl, and
R⁵ for hydrogen, hydroxyl, cyano or for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl or optionally substituted by fluorine, chlorine, cyano, methoxy or ethoxy , Chlorine, cyano, carboxy, methyl, ethyl, n- or i-propyl, methoxy carbonyl or ethoxycarbonyl substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, and
Z for methyl, ethyl optionally substituted by fluorine, chlorine, bromine, cyano, hydroxyl, amino, methoxy, ethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl (which are each optionally substituted by fluorine and / or chlorine), n- or i-Propyl, n-, i-, s- or t-butyl, for allyl, crotonyl, 1-methyl-allyl, propargyl or 1-methyl-propargyl optionally substituted by fluorine, chlorine or bromine, for each optionally by fluorine, chlorine, bromine, cyano, carboxy, phenyl (which may be by fluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, Trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy is substituted), methyl, ethyl, n- or i-propyl, methoxy-carbonyl or ethoxy-carbonyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, for each given if substituted phenyl, naphthyl, furyl, tetrahydrofuryl, benzofuryl, Tetra hydropyranyl, thienyl, benzothienyl, pyrrolyl, dihydropyrrolyl, tetrahydro pyrrolyl, benzopyrrolyl, benzodihydropyrrolyl, oxazolyl, benzoxazolyl, isoxazolyl, thiazolyl, benzothiazolyl, isothiazolyl, imidazolyl, oximidiazolyl, oximidiazolyl, benzimidiazolyl, benzimidiazolyl, benzimidiazolyl, 3-triazinyl, 1,2,4-triazinyl or 1,3,5-triazinyl, the possible sub-substituents preferably being selected from the list below:
Oxygen (as a substitute for two geminal hydrogen atoms), fluorine, chlorine, bromine, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarb amoyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylthio, trifluoromifluoromethyl or trifluoromethylsulfonyl, methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, acetyl, propionyl, acetyloxy, methoxycarbonyl, ethoxycarbonyl, methylsulfonyloxy, ethylsulfonyloxy, hydroximinomethyl, hydroximinoethyl, methoximininoethyl, ethoximinoethyl; ethoximinoethyl; each optionally one or more times, identically or differently, by fluorine, chlorine, methyl, ethyl, n- or i-propyl-substituted trimethylene (propane-1,3-diyl), methylenedioxy or ethylenedioxy, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, and in each case optionally in the phenyl moiety one or more times, identically or differently by fluorine, chlorine, bromine, cyano, nitro, carboxy, carbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, Trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, acetyl, methoxycarbonyl or ethoxycarbonyl substituted phenyl, phenoxy, benzyl or benzyloxy.

A particularly preferred group of compounds according to the invention are those compounds of the formula (I) in which
A represents dimethylene (ethane-1,2-diyl),
Ar represents ortho-phenylene, pyridine-2,3-diyl or thiophene-2,3-diyl,
E represents one of the groupings below

wherein
R¹ and R² each represent methoxy,
G represents oxygen, methylene or one of the groupings below

-CH₂-O-, -O-CH₂-, -S (O) _n -, -CH₂-S (O) _n -, S (O) _n -CH₂-, -C (R⁴) -NO-, -ON = C (R⁴) -, -C (R⁴) -NO-CH₂-, -N (R⁵) - or -CH₂-ON = C (R⁴) -, where
n represents the numbers 0, 1 or 2,
R⁴ represents hydrogen, methyl or ethyl and
R⁵ represents hydrogen, methyl or ethyl, and
Z represents optionally substituted phenyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl or 1,3,5-triazinyl, the possible substituents preferably being selected from the list below are:
Fluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i- propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylthio, trifluoro-methylthio, trifluoromethylsulphinyl or trifluoromethylsulphonyl, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, ethoximinomethyl, Methox iminoethyl, ethoximinoethyl, in each case optionally monosubstituted or polysubstituted by identical or different Methylenedioxy or ethylenedioxy substituted by fluorine, chlorine, methyl or ethyl, and in each case optionally in the phenyl part singly or repeatedly, identically or differently by fluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl, n-, i- , s- or t-butyl, trifluoromethyl,
Methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy substituted phenyl, phenoxy, benzyl or benzyloxy.

The radicals listed above or specified in preferred ranges definitions apply both to the end products of the formula (I) and correspondingly for the raw materials or intermediate products required for the production.

These residual definitions can be among themselves, that is, between the specified Areas of preferred connections, can be combined as desired.

For example, a-methoximino-a- (2-phenoxy-phenyl) -acetic acid is used methyl ester, hydroxylamine hydrochloride and 1,2-dibromoethane as starting materials, the reaction sequence in the production process (a) according to the invention can be carried out the following formula scheme are outlined:

If, for example, 3- [a-methoximino-a- (2-hydroxyphenyl) methyl] -5,6- is used dihydro-1,4,2-dioxazine and benzyl chloride as starting materials, so the reaction Sequence in the manufacturing process (b) according to the invention by the following formula scheme are outlined:

If, for example, 3- [a-methoximino-a- (2-chloromethylphenyl) methyl] - is used 5,6-dihydro-1,4,2-dioxazine and 2-methylphenol as starting materials, so the Re Action sequence in the method (c) according to the invention by the following formula scheme are outlined:

For example, one uses N- (2-hydroxy-ethoxy) -a-methoximino-a- (2-phenoxy phenyl) -acetamide as the starting compound so the reaction can he Processes according to the invention are outlined by the following formula:

To carry out process (a) according to the invention as starting materials The required carboxylic acid derivatives are generally defined by the formula (II). In this Ar (E), G and Z have formula (II) preferably or in particular that Be interpretations already in connection with the description of the invention ß compounds of formula (I) as preferred or as particularly preferred for Ar, E, G and Z were given; R preferably represents alkyl with 1 to 4 Carbon atoms, especially for methyl or ethyl.

The starting materials of formula (II) are known and / or can be per se known processes can be produced (cf. EP-A 178826, EP-A 242081, EP-A 382375, EP-A 493711).

The ver in the process (a) according to the invention as starting materials Formula (III) provides a general definition of the disubstituted alkanes used. In of the formula (III) A preferably or in particular has the meaning that already in connection with the description of the Ver Bonds of the formula (I) as preferred or as particularly preferred for A. would give; X preferably represents chlorine, bromine, methylsulfonyloxy, phenyl sulfonyloxy or tolylsulfonyloxy.

The starting materials of formula (III) are known organic synthetic chemicals.

The process (b) according to the invention for the preparation of the compounds of all general formula (I) to use as starting materials hydroxyaryl compounds are generally defined by the formula (IV). In formula (IV), A, Ar and E have  preferably or in particular those meanings which have already been mentioned above in Zu in connection with the description of the compounds of formula (I) as preferred or as being particularly preferred for A, Ar and E.

The starting materials of the formula (IV) are not yet known from the literature; she are the subject of the present application as new substances.

The new hydroxyaryl compounds of formula (IV) are obtained when tetra hydropyranyloxy compounds of the general formula (IX)

in which
A, Ar and E have the meaning given above,
with an acid such as B. hydrochloric acid, sulfuric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid or an acidic ion exchanger, optionally in the presence of a diluent, such as. B. water, methanol, ethanol or ethyl acetate at temperatures between 0 ° C and 100 ° C (see. The preparation examples).

The tetrahydropyranyloxy compounds of formula (IX) are not yet out of the Literature known; as new substances, they are the subject of the present application.

The new tetrahydropyranyloxy compounds of the formal (IX) are obtained if Esters of the general formula (X)

in which
Ar, E and R have the meaning given above, with hydroxylamine - or optionally with its hydrochloride - optionally in the presence of an acid acceptor, such as. As potassium hydroxide, and optionally in the presence of diluents, such as. B. methanol and water, and the intermediate formed thereby in situ further with dihaloalkanes of the general formula (III) - above - optionally in the presence of an acid acceptor, such as. As potassium carbonate, at temperatures between 0 ° C and 100 ° C (see. Be the description of the inventive method (a) and the preparation examples).

The esters of formula (X) are not yet known from the literature; they are as new Substances Subject of the present application.

The new esters of formula (X) are obtained when tetrahydropyranyloxy-phenyl acetic acid ester of the general formula (XI)

in which
Ar and R have the meaning given above, derivatized by customary methods (cf. the preparation examples).

The tetrahydropyranyloxy-phenylacetic acid esters of the formula (XI) are not yet out known in literature; as new substances they are the subject of the present An report.

The new tetrahydropyranyloxyphenylacetic acid esters of the formula (XI) are obtained, when hydroxyphenylacetic acid esters of the general formula (XII)

in which
Ar and R have the meaning given above, with dihydropyran, optionally in the presence of a catalyst, such as. B. p-toluene sulfonic acid, and optionally in the presence of a diluent, such as. B. tetrahydrofuran, at temperatures between 0 ° C and 100 ° C (see. Her position examples).

The starting materials of the formula (XII) are known synthetic chemicals.

The process (b) according to the invention for the preparation of the compounds of all general formula (I) are further compounds to be used as starting materials generally defined by formula (V). In formula (V), Z preferably or in particular the meaning already mentioned above in connection with the Be Description of the compounds of formula (I) as preferred or as in particular be was preferably given for Z; X preferably represents chlorine, bromine, methyl sulfonyloxy, phenylsulfonyloxy or tolylsulfonyloxy.

The starting materials of the formula (V) are known synthetic chemicals.

The process (c) according to the invention for the preparation of the compounds of all general formula (I) Halogenmethylver to be used as starting materials Bonds are generally defined by the formula (VI). Have in formula (VI) A, Ar and E preferably or in particular those meanings that already above in connection with the description of the compounds of formula (I) as were given as preferred or as particularly preferred for A, Ar and E; X¹ preferably represents fluorine, chlorine, bromine or iodine, in particular chlorine or Bromine.

The starting materials of the formula (VI) are not yet known from the literature; she are the subject of the present application as new substances.

The new halomethyl compounds of the formula (VI) are obtained if Methyl compounds of the general formula (XIII)

in which
A, Ar and E have the meaning given above, with a halogenating agent, such as. B. N-bromine or N-chloro-succinimide, where appropriate in the presence of a catalyst, such as. B. azoisobutyronitrile, and optionally in the presence of a diluent, such as. B. carbon tetrachloride, at temperatures between 0 ° C and 150 ° C (see. The manufacturing examples).

The methyl compounds of the formula (XIII) required as precursors are still not known from the literature; they are the subject of the present as new substances Registration.

The new methyl compounds of the formula (XIII) are obtained if esters of all common formula (XIV)

in which
Ar, E and R have the meaning given above, with hydroxylamine or hydroxylamine hydrochloride, optionally in the presence of an acid acceptor, such as. As potassium hydroxide, and optionally in the presence of a diluent, such as. B. methanol, and then with a disubstituted alkane of the general formula (III) - above - optionally in the presence of an acid acceptor, such as. B. potassium carbonate, analogous to process (a) according to the invention at temperatures between 0 ° C and 150 ° C (see. The manufacturing games).

The precursors of formula (XIV) are known and / or can be per se known processes can be prepared (cf. EP-A 386561, EP-A 498188, Her position examples).  

The process (c) according to the invention for the preparation of the compounds of all general formula (I) are further compounds to be used as starting materials generally defined by formula (VII). In formula (VII), Q and Z are intended preferably or in particular those meanings that already together in the above hang with the description of the compounds of formula (I) as preferred or as were particularly preferably given for Q and Z.

The starting materials of formula (VII) are known organic synthetic chemicals.

The process (d) according to the invention for the preparation of the compounds of all general formula (I) are hydroxyalkoxyamides to be used as starting materials generally defined by formula (VIII). In formula (VIII), A, Ar, E, G and Z preferably or in particular those meanings which have already been mentioned above in Connection with the description of the compounds of formula (I) as preferred or have been specified as particularly preferred for A, Ar, E, G and Z.

The starting materials of formula (VIII) are not yet known from the literature; she are the subject of the present application as new substances.

The new hydroxyalkoxyamides of the formula (VIII) are obtained when carbon acid derivatives of the general formula (XV)

in which
Ar, E, G and Z have the meaning given above and
Y represents halogen, hydroxy or alkoxy,
with hydroxylamines of the general formula (XVI)

H₂N-O-A-OH (XVI)

in which
A has the meaning given above, optionally in the presence of an acid acceptor, such as. B. triethylamine, pyridine or 4-dimethylamino-pyridine, and optionally in the presence of a diluent, such as. B. methylene chloride, toluene or tetrahydrofuran, at temperatures between 0 ° C and 150 ° C (see. The preparation examples).

The carboxylic acid derivatives of the formula (XV) required as precursors are known and / or can be produced by processes known per se (cf. EP-A 178826, EP-A 242081, EP-A 382375, EP-A493711).

The hydroxylamines of the formula (XVI) which are also required as precursors are flat if known and / or can be prepared by methods known per se (see J. Chem. Soc. Perkin Trans. I 1987, 2829-2832).

Processes (a), (b) and (c) according to the invention are preferably carried out in the presence a suitable acid acceptor. As such, all the usual anors come ganic or organic bases in question. These include, for example, 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 carbonate or ammonium carbonate, and tertiary amines, such as trimethylamine, tri ethylamine, tributylamine, N, N-dimethylanine, N, N-dimethylbenzylamine, pyridine, N- Methylpiperidine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabi cyclonones (DBN) or diazabicycloundecene (DBU).

As a diluent for carrying out processes (a), (b) according to the invention and (c) water and organic solvents are suitable. This includes in particular aliphatic, alicyclic or aromatic, optionally halogenated Hydrocarbons, such as gasoline, benzene, toluene, xylene, chlorobenzene, Dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetra chloromethane, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones such as acetone, butanone or  Methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or benzonitrile; Amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methyl pyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate, sulfoxides, such as dimethyl sulfoxide, alcohols, such as methanol, Ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol mono ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the Mix with water or pure water.

Process (d) according to the invention is preferably carried out in the presence of a De hydrating agent performed. The dehydrating agents here are customary dehydrating chemicals, especially acid anhydrides, such as. B. Phosphorus (V) oxide (phosphorus pentoxide) suitable.

As a diluent for carrying out process (d) according to the invention the usual inert organic solvents come into consideration. This includes in particular aliphatic, alicyclic or aromatic, optionally halogenated Hydrocarbons, such as gasoline, benzene, toluene, xylene, chlorobenzene, Dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, tetra chloromethane; Ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones such as acetone, butanone or Methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or benzonitrile; Amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methyl pyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate, sulfoxides such as dimethyl sulfoxide.

The reaction temperatures can be carried out when carrying out the inventive Processes (a), (b), (c) and (d) can be varied over a wide range. Generally mine work at temperatures between -20 ° C and + 200 ° C, preferably at Temperatures between 0 ° C and 150 ° C.

The process (a) according to the invention is carried out per mole Carboxylic acid derivative of the formula (II) in general 1 to 5 mol, preferably 1.0 to 2.5 moles of hydroxylamine or hydroxylamine hydrogen halide and in general  1 to 10 moles, preferably 1.0 to 5.0 moles, of a disubstituted alkane of the formula (III) a.

The process (b) according to the invention is carried out per mole Hydroxyaryl compound of formula (IV) in general 0.5 to 2.0 mol, preferably example, 0.9 to 1.2 moles of a compound of formula (V).

To carry out process (c) according to the invention, halo is employed per mole Gene compound of formula (VI) generally 1 to 5 mol, preferably 1.5 to 3 Mol of a compound of formula (VII).

The process (d) according to the invention is carried out per mole Hydroxyalkoxyamide of the formula (VIII) in general 1 to 5 mol, preferably 1.5 to 4 moles of a dehydrating agent.

Carrying out the reaction, working up and isolating the reaction products takes place in each case according to known methods (cf. the production examples).

The active compounds according to the invention have a strong microbicidal action and can be used to combat unwanted microorganisms become. The active ingredients are for use as crop protection agents, in particular suitable as fungicides.

Fungicides in crop protection are used to combat plasmo diophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basi diomycetes, Deuteromycetes.

Some pathogens causing fungal diseases are exemplary but not limiting fall under the generic terms listed above, called:

Pythium species, such as, for example, Pylhium ultimum;
Phytophthora species, such as, for example, Phytophthora infestans;
Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseu doperonospora cubense;
Plasmopara species, such as, for example, Plasmopara viticola;
Peronospora species, such as, for example, Peronospora pisi or Peronospora brassicae;
Erysiphe species, such as, for example, Erysiphe graminis;
Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;
Podosphaera species, such as, for example, Podosphaera leucotricha;
Venturia species, such as, for example, Venturia inaequalis;
Pyrenophora species, such as, for example, Pyrenophora teres or Pyrenophora grarninea (conidial form: Drechslera, synonym: Helminthosporium);
Cochliobolus species, such as, for example, Cochliobolus sativus (conidial form: Drechs lera, synonym: Helminthosporium);
Uromyces species, such as, for example, Uromyces appendiculatus;
Puccinia species, such as, for example, Puccinia recondita;
Tilletia species, such as, for example, Tilletia caries;
Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;
Pellicularia species, such as, for example, Pellicularia sasakii;
Pyricularia species, such as, for example, Pyricularia oryzae;
Fusarium species, such as, for example, Fusarium culmorum;
Botrytis species, such as, for example, Botrytis cinerea;
Septoria species, such as, for example, Septoria nodorum;
Leptosphaeria species, such as, for example, Leptosphaeria nodorum;
Cercospora species, such as, for example, Cercospora canescens;
Altemaria species, such as, for example, Alternaria brassicae;
Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.

The good plant tolerance of the active ingredients in the control of plants Concentrations necessary for diseases allow treatment above ground Parts of plants, of seedlings and soil.

The active compounds according to the invention can be used with particularly good success fighting diseases in fruit and vegetable growing, such as against Phytophthora species, or for combating cereal diseases such as against Pyrenophora species.

In addition, the active compounds according to the invention have a good effect, for example against Erisyphe graminis, Cochliobolus sativus, Leptosphaeria nodorum, pseudo cercosporella herpotrichoides and fusaria on cereals, against Pyricularia oryzae and Pellicularia sasakii on rice and a broad in vitro activity.

The active ingredients can depend on their respective physical and / or chemical properties are converted into conventional formulations, such as solutions genes, emulsions, suspensions, powders, foams, pastes, granules, aerosols, Fine encapsulation in polymeric substances and in coating compositions for seeds, as well ULV cold and warm fog formulations.

These formulations are prepared in a known manner, e.g. B. by mixing of the active ingredients are under pressure with extenders, i.e. liquid solvents the liquefied gases and / or solid carriers, if necessary with use formation of surface-active agents, i.e. emulsifiers and / or dispersants and / or foam-generating agents. In case of using water as Extenders can e.g. B. also ver organic solvents as auxiliary solvents be applied. The following are essentially suitable as liquid solvents: aroma ten such as xylene, toluene, alkylnaphthalenes, chlorinated aromatics or chlorinated aliphati cal hydrocarbons, such as chlorobenzenes, chlorethylenes, or methylene chloride, ahphatic hydrocarbons, such as cyclohexane or paraffins, e.g. B. petroleum fractions, Alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone,  Methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents tel, such as dimethylformamide or dimethyl sulfoxide, and water; with liquefied gaseous extenders or carriers are meant such liquids, wel che are gaseous at normal temperature and pressure, e.g. B. Aerosol Propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and Carbon dioxide; as solid carriers come into question: B. natural stone powder, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or Diatomaceous earth and synthetic rock powder, such as highly disperse silica, aluminum minium oxide and silicates; as solid carriers for granules come into question: z. B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, Dolomite and synthetic granules from inorganic and organic flours as well as granules of organic material such as sawdust, coconut shells, corn pistons and tobacco stems; come as emulsifying and / or foam-generating agents in question: e.g. B. non-ionic and anionic emulsifiers, such as polyoxyethylene fat acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as a dispersant come into question: z. B. Ligninsulfitablaugen and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural, can be used in the formulations and synthetic, powdery, granular or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholi pide, such as cephalins and lecithins and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, ferrocy blue and organic dyes such as alizarin, azo and metal phthalocyanine substances and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, Molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such or in their formulations also in a mixture with known fungicides, bactericides, acartzides, nematicides  or insecticides can be used, e.g. B. the spectrum of activity too broaden or prevent the development of resistance. In many cases you get thereby synergistic effects, d. H. the effectiveness of the mixture is greater than that Effectiveness of the individual components.

Particularly cheap mixing partners are e.g. B. the following connections:

Fungicides

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-1,3-thiazole-5-carboxanilide; - 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyanophenoxy) py rimidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyl oxy) -o-tolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, aza conazol,
Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S,
Bromuconazole, Bupirimate, Buthiobate,
Calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate (quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb,
Cymoxanil, cyproconazole, cyprofuram,
Dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylalnine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,
Edifenphos, epoxyconazole, ethirimol, etridiazole,
Fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropi morph, fentinacetate, fentinhydroxyd, ferbam, ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanyl, futolanil, futinoletil Furmecyclox,
Guazatine,
Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodione, Isoprotmolan,
Kasugamycin, copper preparations, such as copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,
Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,
Ofurace, oxadixyl, oxamocarb, oxycarboxin,
Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Polyoxin, Pro benazol, Prochloraz, Procymidon, Propamocarb, Propiconazole, Propineb, Pyrazophos, Pyrifenox, Pyrimethanil, Pyroquilon,
Quintozen (PCNB),
Sulfur and sulfur preparations,
Tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, Thicyofen, thiophanate-methyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
Validamycin A, vinclozolin,
Zineb, ziram

Bactericides:

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin,
Octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, teclofta lam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides

Abamectin, Abamectin, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclo tin,
Bacillus thuringiensis, 4-bromo-2- (4-chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, bendiocarb, benfuracarb, bensultap, betacyluthrin, bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chloethocarb, Chlorethoxyfos, Chloretoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, N - [(6-Chloro-3-pyridmyl) -methyl] -N'-cyano-N-methyl-ethanimamide , Chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin, clofentezin, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,
Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethoprophos, Etofenprox, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil,
Fluazinam, Fluazuron, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenprox, Fluvalinate, Fonophos, Formothion, Fosthiazat, Fubfenprox, Furathiocarb,
HCH, heptenophos, hexaflumuron, hexythiazox,
Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivemectin,
Lamda-cyhalothrin, Lufenuron,
Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos, Metha midophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Mono crotophos, Moxidectin,
Naled, NC 184, Nitenpyram
Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,
Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phos phamdon, Phoxim, Pirimicarb, Pirimiphos M, Primiphos A, Profenofos, Profenophos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothiophos, Prothroosra, Pothroosra, Pothroos, Pothroos , Pyraclophos, Pyradaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen,
Quinalphos,
Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,
Tebufenozide, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiome thon, Thionazin, Thuringiensin, Tralomenhrononium, Triaromenhriazonium, Triaromenhriazonium, Tri
Vamidothione, XMC, xylylcarb, YI 5301/5302, zetamethrin.

A mixture with other known active ingredients, such as herbicides or with Fertilizers and growth regulators are possible.  

The active substances can be used as such, in the form of their formulations or in the form thereof rode application forms, such as ready-made solutions, suspensions, spray powders, pastes, soluble powders, dusts and granules can be used. The Application happens in the usual way, e.g. B. by pouring, spraying, spraying, Scattering, dusting, foaming, brushing, etc. It is also possible to use the Apply active ingredients according to the ultra-low-volume process or the active ingredient preparation or inject the active substance yourself into the soil. It can also do that Seeds of the plants are treated.

In the treatment of parts of plants, the drug concentrations in the Application forms can be varied in a larger area:

They are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.

In the seed treatment, amounts of active ingredient are generally from 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g.

When treating the soil, active ingredient concentrations are from 0.00001 to 0.1 % By weight, preferably from 0.0001 to 0.02% by weight, is required at the site of action.

Manufacturing examples example 1

1.8 g (25 mmol) of hydroxylamine hydrochloride are at 20 ° C in 20 ml of methanol submitted and slowly with a solution of 3.3 g of potassium hydroxide (86%) in 20 ml Methanol added. Then 4.0 g (12.8 mmol) of a-methoximino-a- [2- (2- methyl-phenoxy-methyl) -phenyl] -acetic acid methyl ester added in portions and the reaction mixture is then until the end of the reaction (thin layer chromatographic control) stirred at 40 ° C. Then 1.7 g (12.8 mmol) potassium carbonate and then 10.8 g (59 mmol) 1,2-dibromoethane for Given reaction mixture. The mixture is then stirred at 65 ° C. for 12 hours, then cooled to 20 ° C and filtered. The filtrate is in the water jet vacuum concentrated and the residue by column chromatography on silica gel (toluene / acetone, vol .: 9: 1) cleaned.

1.4 g (33% of theory) of 3- {a-methoximino-a- [2- (2-methylphenoxy methyl) phenyl] methyl} -5,6-dihydro-1,4,2 are obtained -dioxazin.
Refractive index n _D ²⁰ = 1.5705.

Analogous to Example 1 and according to the general description of the Invention Production processes according to the invention can, for example, also be those in the following Compounds of formula (I) listed in Table 1 are prepared.

The ¹H-NMR spectra were recorded in CDCl₃ with tetramethylsilane as the internal standard. Are in the Rule the chemical shifts as δ values.

For example, the compound listed in Table 1 as Example 60 may be like are produced as follows:

To a mixture of 1.5 g (6 mmol) of 3- [α-methoximino-4a- (2-hydroxy-phenyl) - methyl] -5,6-dihydro-1,4,2-dioxazine, 0.9 g (6 mmol) of 4,6-dichloropyrimidine and 30 ml N, N-dimethylformamide are 0.3 g (6 mmol) of a 60% pure with ice cooling Sodium hydride suspension in white oil. After removing the ice bath that will Reaction mixture stirred at 20 ° C for 15 hours. Then in an oil pump vacuum concentrated, the residue taken up in ethyl acetate, washed with water, dried with sodium sulfate and filtered. The solvent is removed from the filtrate Water jet vacuum carefully distilled off.

1.9 g (86% of theory) of 3- {α-methoximino-α- [2- (6-chloro-pyrimidin-4-yl- oxy) -phenyl] -methyl} -5,6-dihydro-1,4,2-dioxazine as an oily residue.  

For example, the compound listed in Table 1 as Example 61 may be like are produced as follows:

A mixture of 0.3 g (0.9 mmol) of 3- {α-methoximino-α- [2- (6-chloro-pyrimidine-4- yl-oxy) -phenyl] -methyl} -5,6-dihydro-1,4,2-dioxazine (see 1 step), 0.1 g (0.9 mmol) 2-hydroxy-benzonitrile, 0.1 g (0.9 mmol) potassium carbonate, a spatula tip Copper (I) chloride and 5 ml of N, N-dimethylformamide is at 100 ° C for 15 hours touched. The mixture is then concentrated in an oil pump vacuum, the residue in acetic acid taken up ethyl ester, washed with water, dried with sodium sulfate and filtered. The filtrate is concentrated and the residue by column chromatography on silica gel (with hexane / acetone, vol .: 7: 3).

0.3 g (81% of theory) of 3- {α-methoximino-α- [2- (6- (2-cyano-phenoxy) - pyrimidin-4-yl-oxy) phenyl] methyl} -5,6-dihydro-1,4,2-dioxazine from the melting point 82 ° C.  

For example, the compound listed in Table I as Example 58 may be like are produced as follows:

A mixture of 0.5 g (2 mmol) of 3- [α-methoximino-α- (2-hydroxy-phenyl) methyl] - 5,6-dihydro-1,4,2-dioxazine, 0.3 g (2.2 mmol) 2-methyl-benzyl chloride, 0.4 g (2.5 mmol) of potassium carbonate and 10 ml of acetonitrile is heated under reflux for 15 hours. Then it is concentrated, the residue is taken up in methylene chloride, with water washed, dried with sodium sulfate and filtered. The solution becomes from the filtrate medium carefully distilled off in a water jet vacuum.

0.4 g (59% of theory) of 3- {α-methoximino-α- [2- (2-methyl-benzyloxy) phenyl] -methyl} -5,6-dihydro-1,4,2-dioxazine with a melting point of 142 ° C.  

The compound obtainable according to Example 1 can also be as follows, for example getting produced:

0.75 g (2.4 mmol) of 3- [4a-methoximino-α- (2-bromomethyl-phenyl) methyl] -5,6-dihydro-1,4,2-dioxazine and 0.70 g (6 , 4 mmol) 2-methylphenol in 15 ml of dimethyl Formamide dissolved and after cooling the mixture to -10 ° C, 0.21 g (7.0 mmol) of sodium hydride (80%) slowly added. After removing the cooling bath the reaction mixture is stirred for 14 hours at a maximum of 25 ° C. and then poured into about twice the volume of water. After shaking with The organic phase is separated off with ethyl acetate, using 2N sodium hydroxide solution washed, dried with sodium sulfate and filtered. The filtrate will The solvent is carefully distilled off under reduced pressure.

0.40 g (49% of theory) of 3 - {- α-methoximino-α- [2- (2-methyl-penoxymethyl) phenyl] methyl} -5,6-dihydro-1,4 are obtained , 2-dioxazine (refractive index: n _D ²⁰ = 1.5705).

For example, the compound listed in Table 1 as Example 19 may be like are produced as follows:

0.20 g (0.56 mmol) of N- (2-hydroxy-ethoxy) -α-methoximino-α- [2- (2,4-dimethyl-phen oxy-methyl) -phenyl] -acetamide are dissolved in 3 ml of chloroform and at 0 ° C with 0.25 g (1.76 mmol) of phosphorus (V) oxide added. The reaction mixture becomes a Hour at 20 ° C and then 4 hours under reflux, then to about poured twice the volume of water and shaken. After disconnecting the organic phase, the aqueous phase is extracted three times with chloroform. The combined organic extracts are dried with magnesium sulfate, then concentrated and by column chromatography (silica gel; toluene / acetone, 10: 1) cleaned.

84 mg (42% of theory) of 3- {α-methoximino-α- [2- (2,4-dimethyl- phenoxy-methyl) phenyl] methyl} -5,6-dihydro-1,4,2-dioxazine.

1 H NMR (D₆-DMSO, δ): 4.87; 3.84; 4.38; 4.10 ppm.  

Starting materials of formula (IV) Example (IV-1)

9.0 g (28 mmol) 3- [α-methoximino-α- (2-tetrahydropyran-2-yl-oxy) benzyl] -5,6- dihydro-1,4,2-dioxazine are mixed in with 1.8 g of "Lewatit SPC 108" ion exchanger 90 ml of methanol stirred at 20 ° C for 15 hours. The mixture is then in the water jet vacuum concentrated, the residue taken up in methylene chloride and filtered. The filtrate is concentrated in a water jet vacuum and the residue through columns Chromatography on silica gel (with hexane / acetone, vol .: 7: 3) purified.

0.6 g (9% of theory) of Z- {3- [α-methoximino-α- (2- hydroxy-phenyl) -methyl] -5,6-dihydro-1,4,2-dioxazin} as an amorphous product and as 2nd fraction 3.3 g (50% of theory) E- {3- [α-methoximino-α- (2-hydroxyphenyl) methyl] -5,6-dihydro-1,4,2-dioxazin} melting at 153 ° C.  

Starting materials of formula (IX) Example (IX-1)

13.9 g are added to 6.8 g (98 mmol) of hydroxylamine hydrochloride in 290 ml of methanol (211 mmol) of an 85% aqueous potassium hydroxide solution and 17 g (58 mmol) Given α-methoximino-α- (2-tetrahydropyran-2-yl-oxy-phenyl) -acetic acid methyl ester and the mixture is stirred at 40 ° C for one hour. Then 7.7 g (56 mmol) Potassium carbonate was added and 42.5 g (226 mmol) of 1,2-dibromoethane was added dropwise. The mixture is then refluxed for 15 hours and then in Water jet vacuum concentrated. The residue is dissolved in methylene chloride taken, washed with water, dried with sodium sulfate and filtered. The The filtrate is concentrated and the residue is purified by column chromatography on silica gel (with hexane / acetone, vol .: 7: 3).

9.0 g (49% of theory) of 3- [α-methoximino-α- (2-tetrahydropyran-2-yl- oxy) benzyl] -5,6-dihydro-1,4,2-dioxazine as an oily product.  

Starting materials of formula (X) Example (X-1)

203 g (1.81 mol) of potassium t-butoxide are placed in 2 liters of t-butanol and added to it Solution become 564 g (4.93 mol) of t-butyl nitrite and 411 g (1.64 mol) of 2-tetrahydro methyl pyranyloxy-phenylacetate - dissolved in 500 ml t-butanol - dropwise given. After 90 minutes, 350 g (2.47 mol) of methyl iodide are added dropwise and the Mixture is stirred at 20 ° C for 15 hours. Then a in a water jet vacuum concentrated, the residue taken up in methyl t-butyl ether with sodium sulfate dries and filtered. The residue is made up by digestion with diethyl ether Bring crystallization and the product is isolated by suction.

69.3 g (15% of theory) of α-methoximino-α- (2-tetrahydropyran-2-yl-oxy- phenyl) acetic acid methyl ester of melting point 79 ° C.  

Starting materials of the formula (XI) Example (XI-1)

A mixture of 500 g (3.0 mol) of 2-hydroxy-phenylacetic acid, methyl ester, 506 g (6.0 mol) of 3,4-dihydropyran, a spatula tip of p-toluenesulfonic acid and 2.5 liters Tetrahydrofuran is stirred for 15 hours at 20 ° C, then with ice-cold 10% aqueous potassium hydroxide solution stirred, mixed with sodium sulfate and filtered. The solvent is carefully distilled off from the filtrate in a water jet vacuum.

698 g (99% of theory) of 2-tetrahydropyranyloxyphenylacetic acid are obtained. methyl ester as an oily residue.  

Starting materials of the formula (VI) Example (VI-1)

0.50 g (2.13 mmol) of 3- [α-methoximino-α- (2-methylphenyl) methyl] -5,6-dihydro- 1,4,2-dioxazine and 0.57 g (3.2 mmol) of N-bromosuccinimide are dissolved in 10 ml Tetrachloromethane submitted and after adding 200 mg of azoisobutyronitrile 4 Heated under reflux for hours. After adding a further 0.57 g (3.2 mmol) of N- Bromosuccinimide, the mixture is heated under reflux for a further hour. It is then cooled, filtered, the filtrate concentrated and the residue chromatographed (silica gel; toluene / acetone, 10: 1).

20 mg (30% of theory) of 3- [α-methoximino-α- (2-bromomethyl-phenyl) methyl] -5,6-dihydro-1,4,2-dioxazine are obtained.
1 H-NMR (CDCl₃, 6): 4.4 ppm.

Starting materials of the formula (XIII) Example (XIII-1)

19.6 g (0.283 mol) of hydroxylamine hydrochloride are placed in 150 ml of methanol and slowly with a solution of 36.9 g (0.565 mol) of potassium hydroxide (86%) in 150 ml of methanol were added. Then 30 g (0.145 mol) of α-metlioximino-α- (2- methyl-phenyl) -acetic acid methyl ester was added in portions. The mixture will Stirred at 50 ° C for 3 hours. Then 20 g (0.145 mol) at 20 ° C Potassium carbonate and 122 g (0.65 mol) of 1,2-dibromoethane added and the Reaction mixture stirred at 65 ° C for 17 hours. After cooling down suction filtered, the filtrate concentrated and the residue chromatographed (silica gel; Toluene / acetone, 15: 1).

15.2 g (45% of theory) of 3- [α-methoximino-α- (2-methyl-pbenyl) methyl] -5,6-dihydro-1,4,2-dioxazine are obtained.
1 H-NMR (CDCl₃, δ): 2.2 ppm.

Starting materials of the formula (XIV) Example (XIV-1)

187.5 g (1.673 mol) of potassium t-butoxide are dissolved in 1875 ml of t-butanol. For this 471.5 g (4.57 mol) of t-butyl nitrite and 250 g (1.525 mol) of 2-methylphenylacetic acid Acid methyl ester - dissolved in 500 ml of t-butanol - dosed in such a way that the inside temperature does not exceed 50 ° C. The mixture is ge at 90 ° C to 30 ° C for 90 minutes stirs. Then 326.5 g (2.3 mol) of methyl iodide are added dropwise and the The reaction mixture is stirred at 20 ° C. for 14 hours. Then that will Solvent was distilled off in a water jet vacuum, the residue in 2 liters of water added and extracted three times with ethyl acetate. The united orga African phases are dried over sodium sulfate and filtered. The filtrate is concentrated, the residue taken up in 250 ml of isopropanol and at reflux to mixed with water for cloudiness.

After cooling to 0 ° C. and stirring for 60 minutes, the crystalline product is obtained Product isolated by suction.

84.5 g (27% of theory) of α-methoximino-α- (2-methylphenyl) acetic acid methyl ester of melting point 53 ° C. are obtained.
1 H-NMR (CDCl₃, δ): 2.19 ppm.

Starting materials of formula (VIII) Example (VIII-1)

0.8 g (2.36 mmol) of α-methoximino-α- [2- (2,4-dimethylpbenoxymethyl) phenyl] - acetic acid chloride are dissolved in 10 ml of tetrahydrofuran and 0.26 g (2.6 mmol) Triethylamine added. Then 0.25 g (2.6 mmol) of O- (2-hydroxy-ethyl) - at 0 ° C hydroxylamine, dissolved in 10 ml of tetrahydrofuran, was added dropwise. The reaction mixture is stirred for 2 hours at 20 ° C, then poured onto water and with Extracted ethyl acetate. The extraction solution is mixed with Magne 04940 00070 552 001000280000000200012000285910482900040 0002004408005 00004 04821sulfate dried, concentrated and chromatographed (silica gel; toluene / acetone, 10: 1).

0.4 g (50% of theory) of N- (2-hydroxy-ethoxy) -α-methoximino-α- [2- (2,4-dimethyl-phenoxy-methyl) -phenyl] -acetamide is obtained.
1 H NMR (CDCl₃, δ): 3.65; 3.90; 9.15 ppm.

Starting materials of formula (XV) Example (XV-1)

0.93 g (2.95 mmol) of α-methoximino-α- [2- (2,4-dimethyl-phenoxymethyl) phenyl] acetic acid with 4.0 g (2.9 mmol) of thionyl chloride and 50 mg of dimethylformamide mixed and the mixture is stirred under reflux for 30 minutes. Then be the more volatile components carefully under reduced pressure distilled off.

0.95 g of α-methoximino-α- [2- (2,4-dimethyl-phenoxy-methyl) -phenyl] - is obtained acetic acid chloride as an oily residue.  

Example (XV-2)

2.0 g (6.1 mmol) of α-methoximino-α- {2- (2,4-dimethyl-phenoxy-methyl) -phenyl) - methyl acetate are dissolved in 20 ml of isopropanol and mixed with 30 ml of 1N Sodium hydroxide solution added. The mixture is stirred at 40 ° C for 14 hours and then on Poured water. Then it is adjusted to pH 6 with 2N hydrochloric acid and the crystalline accrued product isolated by suction.

1.5 g (78% of theory) of α-methoximino-α- [2- (2,4-dimethyl-phenoxy-methyl) -phenyl] -acetic acid are obtained.
1 H NMR (CDCl₃, δ): 3.9; 4.85 ppm.

Examples of use Example A

Pyrenophora teres test (barley) / protective
Solvent: 10 parts by weight of N-methyl-pyrrolidone
Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are sprayed with the active ingredient dew wet fabric preparation. After the spray coating has dried, the plants sprayed with a conidia suspension of Pyrenophora teres. The plants remain in one for 48 hours at 20 ° C and 100% relative humidity Incubation cabin.

The plants are grown in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of approx. 80%.

Evaluation is carried out 7 days after the inoculation.

In this test, for example, showed the compound according to Preparation Example 1 an application rate of 400 g / ha an efficiency of 100%.  

Example B

Phytophthora test (tomato) / systemic
Solvent: 4.7 parts by weight of acetone
Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

The active ingredient preparation is used to test for systemic properties Poured uniform earth in which there are young plants ready for testing. 3 days after the treatment, the plants are treated with an aqueous spore suspension of Phytophthora infestans inoculated.

The plants are grown in an incubation cabin with 100% relative humidity and set up at about 20 ° C.

Evaluation is carried out 3 days after the inoculation.

In this test, for example, showed the compound according to Preparation Example 1 an active ingredient concentration of 100 ppm an efficiency of 58%.  

Example C

Pyricularia test (rice) / systemic
Solvent: 12.5 parts by weight of acetone
Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amounts of solvent and dilutes this Concentrate with water and the specified amount of emulsifier to the desired Concentration.

To test for systemic properties, 40 ml of the active ingredient preparation poured on uniform earth in which young rice plants were grown. 7 days after the plants are treated with an aqueous spore suspension of Pyricularia oryzae inoculated. The plants then remain in a greenhouse a temperature of 25 ° C and a rel. Humidity from 100% to Evaluation.

The disease infestation is evaluated 4 days after the inoculation.

In this test, for example, showed the compound according to Preparation Example 1 an application rate of 100 mg / 100 ml an efficiency of 80%.

Claims (9)

1. found azadioxacycloalkenes of the general formula (I), in which
A represents optionally substituted alkanediyl (alkylene),
Ar represents optionally substituted arylene or heteroarylene,
E represents a 1-alkene-1,1-diyl grouping which contains a radical R 1 in the 2-position, or represents a 2-aza-1-alkene-1,1-diyl grouping which is in 2- Position contains a radical R², or represents a 3-oxa- or 3-thia-1-propene-2,3-diyl group which contains a radical R¹ in the 1-position, or represents a 3-aza-1- propen-2,3-diyl grouping which contains a R radical in the 3-position and a R¹ radical in the 1-position, or a 1-aza-1-propene-2,3-diyl grouping which contains a radical R² in the 1-position, or represents a 3-oxa- or 3-thia-1-aza-propene-2,3-diyl group which contains a radical R² in the 1-position, or represents a 1 , 3-diaza-1-propene-2,3-diyl grouping which contains a R group in the 3-position and a R² group in the 1-position, or for an optionally substituted imino grouping ("Azamethylene", N -R³) stands, whereby
R represents alkyl,
R¹ represents hydrogen, halogen, cyano or any optionally substituted alkyl, alkoxy, alkylthio, alkylamino or dialkyl amino,
R² stands for hydrogen, amino, cyano or for optionally substituted alkyl, alkoxy, alkylamino or dialkylamino, and
R³ represents hydrogen, cyano or optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkylalkyl,
G stands for a single bond, for oxygen, for alkanediyl, alkenediyl, oxaalkenediyl, alkindiyl or one of the following groupings, which is optionally substituted by halogen, hydroxyl, alkyl, haloalkyl or cycloalkyl, or one of the following groups -Q-CQ-, -CQ-Q-, -CH₂- Q-; -Q-CH₂-, -CQ-Q-CH₂-, -CH₂-Q-CQ-, -Q-CQ-CH₂-, -Q-CQ-Q-CH₂-, -N = N-, S (O) _n -, CH₂-S (O) _n -, -CQ-, S (O) _n -CH₂-, -C (R⁴) = NO-, -C (R⁴) = NO-CH₂-, -N (R⁵) -, -CQ-N (R⁵) -, -N (R⁵) -CQ-, -Q-CQ-N (R⁵) -, -N = C (R⁴) -Q-CH₂-, -CH₂- ON = C (R⁴) -, -N (R⁵) -CQ-Q-, -CQ-N (R⁵) -CQ-Q-, -N (R⁵) -CQ-Q-CH₂-, -CQ-CH₂- or -N = NC (R⁴) = NO-, where
n represents the numbers 0, 1 or 2,
Q represents oxygen or sulfur,
R⁴ represents hydrogen, cyano or in each case optionally substituted alkyl, alkoxy, alkylthio, alkylamino, dialkylamino or cycloalkyl, and
R⁵ represents hydrogen, hydroxy, cyano or in each case optionally substituted alkyl, alkoxy or cycloalkyl, and
Z represents optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heterocyclyl. 2. The invention preferably relates to compounds of the formula (I) in which
A represents alkanediyl having 1 to 3 carbon atoms which is optionally substituted by halogen or by alkyl or haloalkyl, each having 1 to 4 carbon atoms,
Ar stands for optionally substituted phenylene or naphthylene or for heteroarylene with 5 or 6 ring members, at least one of which is oxygen, sulfur or nitrogen and optionally one or two more are nitrogen, the possible substituents being preferably from the list below are selected:
Halogen, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl, each straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms, each straight-chain or branched alkenyl, alkenyloxy or alkynyloxy each 2 to 6 carbon atoms, each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, each straight-chain or branched haloalkenyl or haloalkenyloxy each having 2 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, in each case straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylsulfonyloxy, hydroximinoalkyl or alkoximinoalkyl, each having 1 to 6 carbon atoms in the individual alkyl parts, in each case optionally egg n times or more, identical or different, halogen-substituted and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, each having a doubly linked alkylene or dioxyalkylene 1 to 6 carbon atoms each,
E represents one of the groupings below wherein
Y represents oxygen, sulfur, methylene (CH₂) or alkylimino (NR),
R represents alkyl having 1 to 6 carbon atoms,
R¹ stands for hydrogen, halogen, cyano or for alkyl, alkoxy, alkylthio, alkylamino or dialkylamino, each optionally substituted by halogen, cyano or C₁-C jeweilsalkoxy, each having 1 to 6 carbon atoms in the alkyl radicals,
R² represents hydrogen, amino, cyano or alkyl, alkoxy, alkylamino or dialkylamino, each of which has 1 to 6 carbon atoms in the alkyl radicals and is optionally substituted by halogen, cyano or C₁-C₄alkoxy, and
R³ for hydrogen, cyano or for alkyl, alkenyl or alkynyl each optionally substituted by halogen, cyano or C₁-C₄alkoxy, each having up to 6 carbon atoms or for each optionally halogen, cyano, carboxy, C₁-C₄alkyl or C₁- C₄-alkoxy-carbonyl substituted cycloalkyl or cycloalkyl alkyl having 3 to 6 carbon atoms in the cycloalkyl moieties and optionally 1 to 4 carbon atoms in the alkyl moiety,
G for a single bond, for oxygen, for in each case optionally substituted by halogen, hydroxy, C₁-C₄-alkyl, C₁-C₄-haloalkyl or C₃-C₆-cycloalkyl, alkanediyl, alkenediyl, oxaalkenediyl, alkynediyl each having up to 4 carbon atoms or one of the the following groups are -Q-CQ-, -CQ-Q-, -CH₂-Q-; -Q-CH₂-, -CQ-Q-CH₂-, -CH₂-Q- CQ-, -Q-CQ-CH₂-, -Q-CQ-Q-CH₂-, -N = N-, -S (O ) _n -, -CH₂-S (O) _n -, CQ, S (O) _n -CH ₂ , C (R⁴) = NO-, -C (R⁴) = NO-CH₂-, -N (R⁵) - , -CQ-N (R⁵) -, -N (R⁵) -CQ-, -Q-CQ-N (R⁵) -, -N = C (R⁴) -Q-CH₂-, -CH₂-ON = C ( R⁴) -, -N (R⁵) -CQ-Q-, -CQ-N (R⁵) -CQ-Q-, -N (R⁵) -CQ-Q- CH₂-, -CQ-CH₂- or -N = NC (R⁴) = N - = -, where
n represents the numbers 0, 1 or 2,
Q represents oxygen or sulfur,
R⁴ for hydrogen, cyano, optionally substituted by halogen, cyano or C₁-C₄alkoxy alkyl, alkoxy, alkylthio, alkyl amino or dialkylamino each having 1 to 6 carbon atoms in the alkyl groups or for each optionally by halogen, cyano, carboxy, C₁ -C₄-alkyl or C₁-C₄-alkoxy-carbonyl substituted cycloalkyl having 3 to 6 carbon atoms, and
R⁵ for hydrogen, hydroxy, cyano or for optionally substituted by halogen, cyano or C₁-C₄-alkoxy-substituted alkyl having 1 to 6 carbon atoms or for optionally by halogen, cyano, carboxy, C₁-C₄-alkyl or C₁-C₄-alkoxy-carbonyl substituted cycloalkyl having 3 to 6 carbon atoms, and
Z for alkyl which is optionally substituted by halogen, cyano, hydroxy, amino, C₁-C₄alkoxy, C₁-C₄alkylthio, C₁-C₄alkylsulfinyl or C₁-C₄alkylsulfonyl (which are each optionally substituted by halogen) and is substituted by 1 to 8 carbon atoms, each for alkenyl or alkynyl optionally substituted by halogen, each having up to 8 carbon atoms, each for optionally optionally halogen, cyano, carboxy, phenyl (which may optionally be halogen. Cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or C₁-C₄-haloalkoxy is substituted), C₁-C₄-alkyl or C₁-C₄-alkoxy-carbonyl-substituted cycloalkyl having 3 to 6 carbon atoms, for each optionally substituted phenyl, naphthyl or (optionally benzyl-fused) heterocyclyl with 5 or 6 ring members, of which at least one is oxygen, sulfur or nitrogen and optionally one or two more are nitrogen, the possible substituents are preferably selected from the list below:
Oxygen (as a substitute for two geminal hydrogen atoms), halogen, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarb amoyl, each straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl, each with 1 to 6 carbon atoms, each straight-chain or branched alkenyl or alkenyloxy each having 2 to 6 carbon atoms, each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, each straight-chain or branched haloalkenyl or haloalkenyloxy 2 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, each straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkyl sulfonyloxy, hydroximinoalkyl or alkoximinoalkyl each having 1 to 6 carbon atoms in the one individual alkyl parts, each optionally mono- or polysubstituted, identically or differently, by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, each contain two-linked alkylene or dioxyalkylene, each with 1 to 6 carbon atoms, cycloalkyl with 3 to 6 carbon atoms, heterocyclyl or heterocyclyl-methyl, each with 3 to 7 rings, of which 1 to 3 are identical or different heteroatoms - in particular nitrogen, oxygen and / or sulfur -, and in each case optionally in the phenyl moiety one or more times, identically or differently, by halogen, cyano, nitro, carboxy, carbamoyl and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 same or ve different halogen atoms and / or straight-chain or branched alkoxy with 1 to 4 carbon atoms and / or straight-chain or branched haloalkoxy with 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms and / or alkylcarbonyl or alkoxycarbonyl with up to 5 carbon atoms each substituted phenyl , Phenoxy, benzyl, benzyloxy, phenylethyl or phenylethyloxy. 3. The invention particularly relates to compounds of formula (I) according to claim 1, in which
A represents methylene or dimethylene (ethane-1,2-diyl) which is optionally substituted by fluorine, chlorine, methyl, ethyl or trifluoromethyl
Ar represents respectively optionally substituted ortho-, meta- or para-phenylene, furandiyl for, thiophenediyl, pyrrolediyl, pyrazolediyl, triazolediyl, oxazole diyl, Isoxazoldiyl, thiazolediyl, Isothiazoldiyl, oxadiazolediyl, thiadiazole diyl, pyridinediyl, pyrimidinediyl, pyridazinediyl, pyrazinediyl, 1, 3,4-triazine diyl or 1,2,3-triazinediyl, the possible substituents being selected in particular from the list below:
Fluorine, chlorine, cyano, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, methylthio, methylsulfinyl or methylsulfonyl,
E represents one of the groupings below wherein
Y represents oxygen, sulfur, methylene (CH₂) or alkylimino (NR),
R represents methyl, ethyl, n- or i-propyl, n-, i- or s-butyl,
R1 represents hydrogen, fluorine, chlorine, bromine, cyano or methyl, ethyl, propyl, methoxy, ethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino, each optionally substituted by fluorine, chlorine, cyano, methoxy or ethoxy,
R² stands for hydrogen, amino, cyano or for methyl, ethyl, methoxy, ethoxy, methylamino, ethylamino or dimethylamino optionally substituted by fluorine, chlorine, cyano, methoxy or ethoxy, and
R³ for hydrogen, cyano or for methyl ethyl n- or i-propyl, n-, i- or s-butyl, optionally substituted by fluorine, cyano, methoxy or ethoxy, for allyl or propargyl or for in each case optionally by fluorine, chlorine, Cyano, carboxy, methyl, ethyl, n- or i-propyl, methoxycarbonyl or ethoxycarbonyl substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl,
G for a single bond, for oxygen, for each optionally by fluorine, chlorine, hydroxyl, methyl, ethyl, n- or i-propyl. Trifluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl substituted methylene, dimethylene (ethane-1,2-diyl), ethene-1,2-diyl. Ethyne-1,2-diyl or one of the following groupings -Q-CQ-, -CQ-Q-, -CH₂-Q-, -Q-CH₂-, -CQ-Q-CH₂-, -CH₂-Q-CQ -, -Q-CQ-CH₂-, -Q-CQ-Q-CH₂-, -N = N-, -S (O) _n -, -CH₂-S (O) _n -, -CQ-, -S (O) _n -CH₂-, -C (R⁴) = NO-, -C (R⁴) = NO-CH₂-, -N (R⁵) -, -CQ-N (R⁵) -, -N (R⁵) - CQ-, -Q-CQ-N (R⁵) -, -NC (R⁴) -Q-CH₂-, CH₂-ON = C (R⁴) -, -N (R⁵) -CQ-Q-, -CQ-N (R⁵) -CQ-Q- or -N (R⁵) - CQ-Q-CH₂-, where
n represents the numbers 0, 1 or 2,
Q represents oxygen or sulfur,
R⁴ represents hydrogen, cyano, methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, methoxy, ethoxy, propoxy, butoxy, methylthio, optionally substituted by fluorine, chlorine, cyano, methoxy or ethoxy, Ethylthio, propylthio, butylthio, methylamino, ethyl amino, propylamino, dimethylamino or diethylamino or for cyclopropyl, cyclobutyl, optionally substituted by fluorine, chlorine, cyano, carboxy, methyl, ethyl, n- or i-propyl, methoxycarbonyl or ethoxycarbonyl, Cyclopentyl or cyclohexyl, and
R⁵ for hydrogen, hydroxy, cyano or for each optionally substituted by fluorine, chlorine, cyano, methoxy or ethoxy substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl or for if necessary by Fluorine, chlorine, cyano, carboxy, methyl, ethyl, n- or i-propyl, methoxy-carbonyl or ethoxy-carbonyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, and
Z for methyl, ethyl, n. Optionally substituted by fluorine, chlorine, bromine, cyano, hydroxy, amino, methoxy, ethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl (which are each optionally substituted by fluorine and / or chlorine) - or i-Propyl, n-, i-, s- or t-butyl, for allyl, crotonyl, 1-methyl-allyl, propargyl or 1-methyl-propargyl, each optionally substituted by fluorine, chlorine or bromine, for each optionally by fluorine, chlorine, bromine, cyano, carboxy, phenyl (which may be by fluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, Methoxy, ethoxy, n- or i-propoxy, difluoromoxy or trifluoromethoxy is substituted), methyl, ethyl, n- or i-propyl, methoxy-carbonyl or ethoxy-carbonyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, for each given if substituted phenyl, naphthyl, furyl, tetrahydrofuryl, benzofur yl, tetrahydropyranyl, thienyl, benzothienyl, pyrrolyl, dihydropyrrolyl, tetrahydropyrrolyl, benzopyrrolyl, benzodihydropyrrolyl, oxazolyl, benzoxazolyl, isoxazolyl, thiazolyl, benzthiazolyl, isothiazolyl, imidazolyl, pyridylazidyl, pyridyl 3-triazinyl, 1,2,4-triazinyl or 1,3,5-triazinyl, where the possible substituents are preferably selected from the list below:
Oxygen (as a replacement for two geminal hydrogen atoms), fluorine, chlorine, bromine, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s - or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylthio, trifluoromethylthio Trifluoromethyl sulfonyl, methylamino, ethylamino, n- or i-propylamino, dimethyl amino, diethylamino, acetyl, propionyl, acetyloxy, methoxycarbonyl, ethoxycarbonyl, methylsulfonyloxy, ethylsulfonyloxy. Hydroximino methyl, hydroximinoethyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl or ethoximinoethyl; trimethyl (propane-1,3-diyl), methylene dioxy or ethylenedioxy, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, as well as, in each case, single or multiple, the same or different, substituted by fluorine, chlorine, methyl, ethyl, n- or i-propyl in each case optionally in the phenyl moiety one or more times, identically or differently by fluorine, chlorine. Bromine, cyano, nitro, carboxy, carbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, Trifluoromethoxy, acetyl, methoxycarbonyl or ethoxy carbonyl substituted phenyl, phenoxy, benzyl or benzyloxy. 4. Compounds of formula (I) according to claim 1, in which
A represents dimethylene (ethane-1,2-diyl),
Ar represents ortho-phenylene, pyridine-2,3-diyl or thiophene-2,3-diyl,
E represents one of the groupings below wherein
R¹ and R² each represent methoxy,
G represents oxygen, methylene or one of the following groups -CH₂-O-, -O-CH₂-, S (O) _n -, CH₂-S (O) _n -, -S (O) _n -CH₂-, -C (R⁴) = N- O-, ON- (R⁴) -, -C (R⁴) = NO-CH₂-, -N (R⁵) - or -CH₂-ON- (R⁴) -, where
n represents the numbers 0, 1 or 2,
R⁴ represents hydrogen, methyl or ethyl and
R⁵ represents hydrogen, methyl or ethyl, and
Z stands for optionally substituted phenyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl or 1,3,5-triazinyl, the possible substituents preferably from the list below are selected:
Fluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i -Propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, difluoromethylthio, trifluoromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl, methoxycarbonyl, ethoxyomethyl, methoxim, methyloxym, methyloximethyl, methoximine, or methyloxymethyl, methoximine, simple or methyloxymethyl, methoximethyl, methoximethyl, methoximethyl, methoximethyl, methoximethyl, methyloximethyl, methoximine, or methyloxymethyl, methoximine, simple or methyloxymethyl, methoximethyl, methoximethyl, methoximethyl or methyloxymethyl, methoximine or methyloxymethyl, methoximethyl or methoximino Fluorine, chlorine, methyl or ethyl substituted methylenedioxy or ethylenedioxy, and in each case optionally in the phenyl part singly or repeatedly, identically or differently by fluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy substituted phenyl, phenoxy, benzyl or benzyloxy. 5. Fungicidal agents, characterized by a content of at least one A compound of formula (I) according to claim 1. 6. A method for controlling unwanted fungi, characterized in that that compounds of formula (I) according to claim 1 on fungi and / or lets their living space take effect. 7. A process for the preparation of azadioxacycloalkenes of the general formula (I) according to claim 1, characterized in that

• (a) carboxylic acid derivatives of the general formula (II) in which
  Ar, E, G and Z have the meaning given above, and
  R represents alkyl,
  in a first stage with hydroxylamine or with a hydrogen halide thereof, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, and in situ, ie without intermediate isolation of the product of the first stage, in a second stage with disubstituted alkanes of the general formula (III) XAX (III) in which
  A has the meaning given above and
  X represents halogen, alkylsulfonyloxy or arylsulfonyloxy,
  if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or if
• (b) in the case that in formula (I) G represents oxygen or the group -CH₂-O- and A, Ar, E and Z have the meaning given in claim 1,
  Hydroxyaryl compounds of the general formula (W), in which
  A, Ar and E have the meaning given above,
  with compounds of the general formula (V), Z- (CH₂) _m -X (V) in which
  X and Z have the meaning given above and
  m represents the numbers 0 or 1,
  if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent and if appropriate subsequently carrying out substitution reactions on the group Z by customary methods, or if one
• (c) in the case that in the formula (I) G represents the group -Q-CH₂- and A, Ar, E and Z have the meaning given above, halomethyl compounds of the general formula (VI) in which
  A, Ar and E have the meaning given above and
  X¹ represents halogen,
  with compounds of the general formula (VII) ZQH (VII) in which
  Q and Z have the meaning given above, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or if
• (d) hydroxyalkoxyamides of the general formula (VIII) in which
  A, Ar, E, G and Z have the meaning given above, cyclized with a dehydrating agent, optionally in the presence of a diluent.

8. Use of compounds of formula (I) according to claim 1 as Fungicides. 9. A process for the preparation of fungicidal compositions, characterized in that compounds of formula (I) according to claim 1 with extenders and / or surface-active substances mixed.