DE19540736A1 - 3-aryl-tetronic acid derivatives - Google Patents

Abstract

The invention concerns novel 3-aryl-4-hydroxy- DELTA <3>-dihydrofuranone derivatives of formula (I), wherein: A and B together with the carbon atom to which they are bound form a five to seven member ring which is interrupted by at least one heteroatom and either unsubstituted or substituted; X represents alkyl, halogen or alkoxy; Y represents hydrogen, alkyl, halogen, alkoxy or halogenated alkyl; Z represents alkyl, halogen or alkoxy; n is 0, 1, 2 or 3; G represents hydrogen (a) or one of the groups (b), (c), (d), (e), (f) or (g) shown; E represents a metal ion equivalent or an ammonium ion; L represents oxygen or sulphur; and R<1>, R<2>, R<3>, R<4>, R<5>, R<6> and R<7> have the meanings indicated in the description. The invention also concerns methods of producing the said compounds and the use of the said compounds as anti-parasitic agents, as well as intermediate products of formula (II) in which R<8> represents alkyl.

Description

The present invention relates to new 3-aryl-4-hydroxy-Δ³-dihydro-furanon-De derivatives (3-aryl-tetronic acid derivatives), process for their preparation and their Ver Use as a pesticide.

It is known that certain substituted Δ³-dihydrofuran-2-one derivatives herbizi have properties (cf. DE-A-40 14 420). The synthesis of the starting compounds used tetronic acid derivatives (such as 3 - (2-methylphenyl) -4- Hydroxy-5- (4-fluorophenyl) -Δ³-dihydrofuranon- (2)) is also in DE-A-40 14 420 described. Similar structured compounds without specifying an insecticide and / or acaricidal activity are from the publication Campbell et al., J. Chem. Soc., Perkin Trans. 1, 1985, (8) 1567-76. Furthermore, 3-aryl Δ³-dihydrofuranone derivatives with herbicidal, acaricidal and insecticidal properties known from EP-528 156, but the effect described there is not always sufficient.

New 3-aryl-4-hydroxy-Δ³-dihydrofuranone derivatives of the formula (I)

found in which
A and B together with the carbon atom to which they are attached form an unsubstituted or substituted 5- to 7-membered ring interrupted by at least one heteroatom,
X represents alkyl, halogen or alkoxy,
Y represents hydrogen, alkyl, halogen, alkoxy or haloalkyl,
Z represents alkyl, halogen or alkoxy,
n stands for a number 0, 1, 2 or 3,
G for hydrogen (a) or for one of the groups

stands,
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulfur,
M represents oxygen or sulfur,
R¹ for each optionally substituted by halogen alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl, optionally substituted by halo, alkyl or alkoxy-substituted cycloalkyl, which can be interrupted by at least one heteroatom or in each case optionally substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl stands,
R² represents alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl, optionally substituted by halogen, cycloalkyl optionally substituted by halogen, alkoxy or alkyl, or phenyl or benzyl, optionally substituted,
R³, R⁴ and R⁵ independently of one another each represent optionally substituted by halogen substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio, cycloalkylthio or optionally substituted substituted phenyl, benzyl, phenoxy or phenylthio,
R⁶ and R⁷ independently of one another represent hydrogen, in each case optionally substituted by halogen, alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, in each case optionally substituted phenyl or benzyl, or together for an alkanediyl radical which is optionally interrupted by oxygen or sulfur.

Including the different meanings (a), (b), (c), (d), (e), (f) and (g) of group G, the following main structures (Ia) to (Ig) result:

wherein
A, B, E, L, M, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and n have the meanings given above.

Due to one or more chirality centers, the connections of For meln (Ia) to (Ig) in general as a mixture of stereoisomers. You can  probably in the form of their diastereomer mixtures as well as pure diastereomers or Enantiomers can be used.

It was also found that the new substituted 3-aryl-tetronic acid Derivatives of formula (I) by one of the methods described below receives.

• (A) 3-aryl-tetronic acids of the formula (Ia) in which
  A, B, X, Y, Z and n have the meaning given above if one
  Carboxylic acid esters of formula (II) in which
  A, B, X, Y, Z and n have the meaning given above, and
  R⁸ represents alkyl, preferably C₁-C₈ alkyl,
  intra-molecularly condensed in the presence of a diluent and in the presence of a base;
  and
• (B) compounds of the formula (Ib) are obtained in which
  A, B, X, Y, Z, R¹ and n have the meaning given above,
  if compounds of the formula (Ia), in which
  A, B, X, Y, Z and n have the meaning given above,
  • α) with acid halides of the formula (III) in which
    R¹ has the meaning given above and
    Hal represents halogen, especially chlorine and bromine,
    if appropriate in the presence of a diluent and, if appropriate, in the presence of an acid binder
    or
  • β) with carboxylic anhydrides of the formula (IV) R¹-CO-O-CO-R¹ (IV) in which
    R¹ has the meaning given above,
    optionally in the presence of a diluent and optionally in the presence of an acid binder,
    implements;
    and
• (C) compounds of the formula (Ic-1) are obtained in which
  A, B, X, Y, Z, R² and n have the meaning given above,
  and
  M represents oxygen or sulfur,
  if compounds of the formula (Ia) in which
  A, B, X, Y, Z and n have the meaning given above,
  with chloroformate or chloroformate thiol ester of the formula (V) R²-M-CO-Cl (V) in which
  R² and M have the meaning given above,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder;
  and
• (D) compounds of the formula (Ic-2) are obtained in which
  A, B, R², X, Y, Z and n have the meaning given above
  and
  M represents oxygen or sulfur,
  if compounds of the formula (Ia) in which
  A, B, X, Y, Z and n have the meaning given above,
  • α) with chloromothio formic acid esters or chlorodithio formic acid esters of the formula (VI) in which
    M and R² have the meaning given above,
    if appropriate in the presence of a diluent and, if appropriate, in the presence of an acid binder,
    or
  • β) with carbon disulfide and then with alkyl halides of the formula (VII) R²-Hal (VII) in which
    R² has the meaning given above
    and
    Hal represents chlorine, bromine or iodine,
    optionally in the presence of a diluent and optionally in the presence of a base;
    and
• (E) compounds of the formula (Id) are obtained in which
  A, B, X, Y, Z, R³ and n have the meaning given above,
  if compounds of the formula (Ia) in which
  A, B, X, Y, Z and n have the meaning given above,
  with sulfonic acid chlorides of the formula (VIII) R³-SO₂-Cl (VIII) in which
  R³ has the meaning given above,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
  implements;
  and
• (F) compounds of the formula (Ie) are obtained in which
  A, B, L, X, Y, Z, R⁴, R⁵ and n have the meaning given above,
  if
  Compounds of formula (Ia) in which
  A, B, X, Y, Z and n have the meaning given above,
  with phosphorus compounds of formula (IX) in which
  L, R⁴ and R⁵ have the meaning given above
  and
  Hal represents halogen, especially chlorine and bromine,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder;
  and
• (G) compounds of the formula (If) are obtained in which
  A, B, X, Y, Z and n have the meaning given above,
  and
  E represents a metal ion equivalent or an ammonium ion,
  if compounds of the formula (Ia) in which
  A, B, X, Y, Z and n have the meaning given above,
  with metal compounds or amines of the formulas (X) or (XI) in which
  Me for mono- or divalent metal ions, for example alkali or alkaline earth metal ions such as. B. Li⁺, Na⁺, K⁺, Ca ²⁺ or Mg ²⁺ ,
  t represents the number 1 or 2,
  R¹⁰, R¹¹ and R¹² independently of one another represent hydrogen or alkyl (in particular C₁-C₈-alkyl) and
  R¹³ represents hydrogen, hydroxy or C₁-C₄ alkoxy,
  if appropriate in the presence of a diluent.
• (H) It was also found that compounds of the formula (Ig) in which
  A, B, L, X, Y, Z, R⁶, R⁷ and n have the meaning given above,
  obtained when compounds of the formula (Ia) in which
  A, B, X, Y, Z and n have the meaning given above,
  • α) with compounds of the formula (XII) R⁶-N = C = L (XII) in which
    L and R⁶ have the meaning given above,
    optionally in the presence of a diluent and optionally in the presence of a catalyst
    or
  • β) with carbamic acid chlorides or thiocarbamic acid chlorides of the formula (XIII) in which
    L, R⁶ and R⁷ have the meaning given above,
    optionally in the presence of a diluent and optionally in the presence of an acid binder,
• implements.

It has also been found that the new compounds of the formula (I) are characterized by excellent insecticidal and acaricidal effects. Preferred Substituents or ranges of the formulas mentioned above and below listed residues are explained below.

A and B are preferably single or multiple, the same or differentiated by halogen, C₁-C Alkyl-alkyl, C₃-C₈-cycloalkyl, C₁-C₈- Haloalkyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio or phenyl substituted C₄-C₆-alkanediyl, in which one or two not directly adjacent Koh lenstoffatome by the group

and / or oxygen and / or sulfur are replaced.

A and B are particularly preferably optionally up to four times, identical or different by fluorine, chlorine, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₁-C₆ haloalkyl, C₁-C₄ alkoxy, C₁-C₄ alkylthio or phenyl substitu ized C₄-C₅-alkanediyl in which one or two are not directly adjacent Carbon atoms through the group

or is replaced by oxygen or by sulfur.

A and B very particularly preferably stand for single to triple, if appropriate, identical or different by fluorine, chlorine, methyl, ethyl, n-propyl, i- Propyl, n-butyl, i-butyl, sec.-butyl, tert.-butyl, cyclohexyl, trifluoromethyl,  Methoxy, methylthio or phenyl substituted C₄-C₅-alkanediyl, in wel chem one carbon atom through the group

or is replaced by oxygen or by sulfur.

X preferably represents C₁-C₆-alkyl, halogen or C₁-C₆-alkoxy. X particularly preferably represents C₁-C₄-alkyl, fluorine, chlorine, bromine or C₁-C₄- Alkoxy.

X very particularly preferably represents methyl, ethyl, n-propyl, isopropyl, Fluorine, chlorine, bromine, methoxy or ethoxy.

Y is preferably hydrogen, C₁-C₆-alkyl, halogen, C₁-C₆-alkoxy or C₁-C₃ haloalkyl.

Y particularly preferably represents hydrogen, C₁-C₄-alkyl, fluorine, chlorine, Bromine, C₁-C₄ alkoxy or C₁-C₂ haloalkyl.

Y very particularly preferably represents hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, fluorine, chlorine, bromine, methoxy, ethoxy or trifluoromethyl.

Z preferably represents C₁-C₆-alkyl, halogen or C₁-C₆-alkoxy.

Z particularly preferably represents C₁-C₄-alkyl, fluorine, chlorine, bromine or C₁-C₄- Alkoxy.

Z very particularly preferably represents methyl, ethyl, propyl, i-propyl, n- Butyl, i-butyl, tert-butyl, fluorine, chlorine, bromine, methoxy or ethoxy.

G preferably represents hydrogen (a) or one of the groups

in which
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulfur and
M stands for oxygen or sulfur.

R¹ preferably represents in each case optionally mono- or polysubstituted by halogen C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₁-C₈-alkoxy-C₁-C₈-alkyl, C₁-C₈-alkylthio-C₁-C₈-alkyl, poly- C₁-C₈-alkoxy-C₂-C₈-alkyl or optionally substituted by halogen, C₁-C₆-alkyl or C₁-C₆-alkoxy-substituted C₃-C₈-cycloalkyl, in which one or two not directly adjacent methylene groups by oxygen and / or Sulfur are replaced,
for phenyl optionally substituted up to five times by halogen, nitro, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl, C₁-C₆-haloalkoxy, C₁-C₆-alkylthio or C₁-C₆-alkylsulfonyl,
for phenyl-C₁-C₆-alkyl optionally substituted up to five times by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl or C₁-C₆-haloalkoxy,
for pyridyl, thienyl, furanyl, pyrazolyl, pyrimidyl or thiazolyl, each of which is optionally mono- or disubstituted by halogen or C₁-C-alkyl,
for phenoxy-C₁-C₆-alkyl which is optionally monosubstituted to trisubstituted by halogen or C₁-C₆-alkyl or
for each optionally mono- or disubstituted by halogen, amino or C₁-C₆-alkyl substituted pyridinyloxy-C₁-C₆-alkyl, pyrimidinyloxy-C₁-C₆-alkyl or thiazolyloxy-C₁-C₆-alkyl.

R² preferably represents in each case optionally mono- or polysubstituted by halogen C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₁-C₈-alkoxy-C₂-C₈-alkyl or poly-C₁-C₈-alkoxy-C₂-C₈-alkyl,
for C₃-C₈-cycloalkyl which is optionally substituted one or more times by halogen, C₁-C oder-alkyl or C₁-C₄-alkoxy or
for phenyl or benzyl which is optionally monosubstituted to trisubstituted by halogen, nitro, C₁-C₆-alkyl, C₁-C₆-alkoxy or C₁-C₆-haloalkyl.

R³ preferably represents optionally one or more times by halogen substituted C₁-C₈ alkyl or for each optionally simple or several times by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-haloalkyl, C₁-C₄ haloalkoxy, cyano or nitro substituted phenyl or benzyl.

R⁴ and R⁵ independently of one another preferably each represent, optionally mono- or polysubstituted by halogen, C₁-C₈-alkyl, C₁-C₈-alkoxy, C₁-C₈-alkylamino, di- (C₁-C₈) -alkylamino, C₁-C₈-alkylthio, C₃- C₆-alkenylthio or C₃-C₇-cycloalkylthio,
for each optionally substituted one or more times by halogen, nitro, cyano, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, C₁-C₄-alkyl or C₁-C₄-haloalkyl nyl, phenoxy or phenylthio.

R⁶ and R⁷ independently of one another preferably represent hydrogen, in each case optionally C₁-C₈alkyl which is monosubstituted or polysubstituted by halogen, C₃-C₈cycloalkyl, C₁-C₈alkoxy, C₃-C₈alkenyl or C₁-C₈alkoxy- C₁-C₈ alkyl,
for phenyl or benzyl which is optionally monosubstituted to trisubstituted by halogen, C₁-C₈-alkyl, C₁-C₈-haloalkyl or C₁-C₈-alkoxy or together for a C₂-C₆-alkanediyl radical which may be interrupted by oxygen or sulfur.

R⁹ preferably represents hydrogen, Q, COQ or CO₂Q,
in which
Q can assume the meanings given above for R² as preferred.

n is preferably 0, 1 or 2.

G particularly preferably represents hydrogen (a) or one of the groups

in which
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulfur and
M stands for oxygen or sulfur.

R¹ particularly preferably represents C₁-C₁₆-alkyl, C₂-C₁₆-alkenyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₁-C₆-alkylthio-C₁-C₆-alkyl optionally optionally substituted up to six times by fluorine or chlorine , Poly-C₁-C₆-alkoxy-C₁-C₆-alkyl or optionally substituted by fluorine, chlorine, C₁-C₅-alkyl or C₁-C₅-alkoxy-substituted C₃-C₇-cycloalkyl, in which one or two not directly adjacent methylene groups by Oxygen and / or sulfur are replaced,
optionally substituted up to three times by fluorine, chlorine, bromine, nitro, C₁-C C-alkyl, C₁-C₄-alkoxy, C₁-C₃-haloalkyl, C₁-C₃-haloalkoxy, C₁-C₄-alkylthio or C₁-C₄-alkylsulfonyl Phenyl,
for phenyl-C₁-C₄-alkyl which is optionally mono- to trisubstituted by fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₃-haloalkyl or C₁-C₃-haloalkoxy,
for pyridyl, thienyl, furanyl, pyrazolyl, pyrimidyl or thiazolyl, each optionally mono- or disubstituted by fluorine, chlorine, bromine or C₁-C₄alkyl,
for phenoxy-C₁-C₅-alkyl which is optionally mono- or disubstituted by fluorine, chlorine, bromine or C₁-C₄-alkyl or
for each optionally mono- or disubstituted by fluorine, chlorine, bromine, amino or C₁-C₄-alkyl substituted pyrimidinyloxy-C₁-C₅-alkyl, pyridinyloxy-C₁-C₅-alkyl or thiazolyloxy-C₁-C₅-alkyl.

R² particularly preferably represents C₁-C₁₆-alkyl, C₂-C₁₆-alkenyl, C₁-C₆-alkoxy-C₂-C₆-alkyl or poly-C₁-C₆-alkoxy-C₂-C₆ which is optionally monosubstituted or disubstituted by fluorine or chlorine -alkyl,
for C₃-C₇-cycloalkyl or optionally substituted up to six times by fluorine, chlorine, C₁-C₃-alkyl or C₁-C₃-alkoxy
for phenyl or benzyl which is optionally mono- or disubstituted by fluorine, chlorine, bromine, nitro, C₁-C₄-alkyl, C₁-C₃-alkoxy or C₁-C₃-haloalkyl.

R³ particularly preferably represents C₁-C₆-alkyl optionally substituted up to six times by fluorine or chlorine or represents in each case optionally mono- or disubstituted by fluorine, chlorine, bromine, C₁-C₅-alkyl, C₁-C₅-alkoxy, C₁-C₃-haloalkyl , C₁-C₃ haloalkoxy, cyano or nitro substituted phenyl or benzyl,
R⁴ and R⁵ independently of one another are particularly preferably in each case optionally C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkylamino, di- (C₁-C₆) alkylamino, C₁-C₆ which is optionally monosubstituted or disubstituted by fluorine or chlorine -Alkyl thio, C₃-C₄-alkenylthio or C₃-C₆-cycloalkylthio,
for each optionally single or double by fluorine, chlorine, bromine, nitro, cyano, C₁-C₃-alkoxy, C₁-C₃-haloalkoxy, C₁-C₃-alkylthio, C₁-C₃-haloalkylthio, C₁-C₃-alkyl or C₁-C₃ -Halogenalkyl substituted phenyl, phenoxy or phenylthio.

R⁶ and R⁷ independently of one another particularly preferably represent hydrogen, each optionally substituted up to six times by fluorine or chlorine, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, C₃-C₆-alkene nyl or C₁-C₆ -Alkoxy-C₁-C₆-alkyl,
for phenyl or benzyl which is optionally mono- or disubstituted by fluorine, chlorine, bromine, C₁-C₅-alkyl, C₁-C₅-haloalkyl or C₁-C₅-alkoxy or together for an optionally interrupted by oxygen or sulfur C₂-C₆-alkanediyl radical.

R⁹ particularly preferably represents hydrogen, Q, COQ or CO₂Q,
in which
Q represents C₁-C₆ alkyl, phenyl or benzyl.

n particularly preferably represents 0 or 1.

G very particularly preferably represents hydrogen (a) or one of the groups

in which
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulfur and
M stands for oxygen or sulfur.

R¹ very particularly preferably represents in each case mono- to trisubstituted by fluorine or chlorine-substituted C₁-C₁₄-alkyl, C₂-C₁₄-alkenyl, C₁-C₄-alkoxy-C₁-C₆-alkyl, C₁-C₄-alkylthio-C₁-C₆ -alkyl, poly-C₁-C₄- alkoxy-C₁-C₄-alkyl or optionally by fluorine, chlorine, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, methoxy, ethoxy, propoxy, i - Propoxy, butoxy, i-butoxy, s-butoxy or t-butoxy substituted C₃-C₆- cycloalkyl, in which a methylene group is optionally replaced by oxygen or sulfur,
for phenyl which is optionally mono- or disubstituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, methylthio, ethylthio, methylsulfonyl, ethylsulfonyl or nitro,
for phenyl-C₁-C₃-alkyl which is optionally mono- or disubstituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy, trifluoromethyl or tri fluoromethoxy,
for thienyl, furanyl or pyridyl which are optionally mono- or disubstituted by fluorine, chlorine, bromine, methyl or ethyl,
for phenoxy-C₁-C₄-alkyl or optionally substituted once or twice by fluorine, chlorine, methyl or ethyl
for each optionally substituted once or twice by fluorine, chlorine, amino, methyl or ethyl pyridyloxy-C₁-C₄-alkyl, pyrimidyloxy-C₁-C gegebenenfalls-alkyl or thiazolyloxy-C₁-C₄-alkyl.

R² very particularly preferably represents in each case mono- to trisubstituted by fluorine or chlorine-substituted C₁-C₁₄-alkyl, C₂-C₁₄-Al kenyl, C₁-C₄-alkoxy-C₂-C₆-alkyl or poly-C₁-C₄-alkoxy-C₂ -C₆ alkyl,
for C₃-C₆-cycloalkyl which is optionally monosubstituted to trisubstituted by fluorine, chlorine, methyl, ethyl, propyl, isopropyl or methoxy,
or for phenyl or benzyl which is optionally mono- or disubstituted by fluorine, chlorine, nitro, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy or trifluoromethyl.

R³ very particularly preferably represents from one to three, if appropriate methyl, ethyl, propyl, isopropyl or fluorine or chlorine substituted each optionally single or double by fluorine, chlorine, bromine, Methyl, ethyl, propyl, isopropyl, tert-butyl, methoxy, ethoxy, Isopropoxy, tert-butoxy, trifluoromethyl, trifluoromethoxy, cyano or Nitro substituted phenyl or benzyl.

R⁴ and R⁵ independently of one another very particularly preferably each represent C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylamino, di- (C₁-C₄) -alkylamino, C₁-C₄-alkylamino, which is optionally mono- to trisubstituted by fluorine or chlorine, C₁- C₄-alkylthio,
for each optionally single or double by fluorine, chlorine, bromine, nitro, cyano, C₁-C₂-alkoxy, C₁-C₂-fluoroalkoxy, C₁-C₂-alkylthio, C₁-C₂- fluoroalkylthio, C₁-C₂-alkyl or C₁-C₂ -Fluoroalkyl substituted phenyl, phenoxy or phenylthio.

R⁶ and R⁷ independently of one another very particularly preferably represent hydrogen,
for each optionally mono- to trisubstituted by fluorine or chlorine substituted C₁-C₄-alkyl, C₃-C₆-cycloalkyl, C₁-C₄-alkoxy, C₃-C₄-alkynyl, C₁-C₄-alkoxy-C₁-C₄-alkyl,
for phenyl or benzyl optionally substituted once or twice by fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-haloalkyl or C₁-C₄-alkoxy, or together for an optionally interrupted by oxygen or sulfur C₂-C₆-alkanediyl radical .

R⁹ very particularly preferably represents hydrogen, Q, COQ or CO₂Q, where
Q represents C₁-C₄ alkyl, phenyl or benzyl.

n very particularly preferably represents 0 or 1.

In the definitions given, saturated or unsaturated coal water residues also in connection with heteroatoms, such as. B. alkoxy or alkyl thio, if possible, be straight or branched.

The optionally multiply substituted radicals can be the same or different be substituted by the substituents mentioned for these radicals.

The radicals listed above or listed in preferred areas Definitions or explanations can be made with each other, i.e. also between the respective areas and preferred areas can be combined as desired. they seem for the end products as well as for the preliminary and intermediate products accordingly.

According to the invention, preference is given to the compounds of the formula (I) in which a combination of the Be listed as preferred (preferred) interpretations are available.  

According to the invention, particular preference is given to the compounds of the formula (I), in which are a combination of those listed as particularly preferred above Meanings exist.

The compounds of the formula are very particularly preferred according to the invention (I) in which a combination of the above is particularly preferred listed meanings is present.

A preferred group of compounds are those of the Formula (I) in which n represents the number 1 and the substituent Z in the 6- Position of the phenyl radical is.

Another preferred group of compounds are those compounds of the formula (I), in which simultaneously n stands for the number 0 and Y not for Hydrogen stands.

Another preferred group of compounds are those Compounds of the formula (I) in which n is simultaneously the number 1 and Y stands for hydrogen.

In particular, except for the verb mentioned in the manufacturing examples the compounds listed in the following Tables 1 to 4 Called formula (Ia):  

Table 1

Table 2 contains the compounds of the formula

in which X, Y and Z have the meanings given in Table 1.

Table 3 contains the compounds of the formula

in which X, Y and Z have the meanings given in Table 1.

Table 4 contains the compounds of the formula

in which X, Y and Z have the meanings given in Table 1.

1- (2,4-dichlorophenylacetyloxy) -4-oxa is used according to process (A) cyclohexane-carboxylic acid ethyl ester, the course of the Ver driving can be represented by the following reaction scheme:

If, according to process (B) (variant α), 3- (2,4,6-trimethylphenyl) - 5,5- (ethyleneoxaethylene) tetronic acid and pivaloyl chloride as starting materials, see above can the course of the method according to the invention by the following reaction Scheme are reproduced:

If 3- (2,4,6-trimethylphenyl) -5,5- is used according to method B (variant β) ethylene oxamethylene tetronic acid and acetic anhydride as starting compounds, so can the course of the method according to the invention by the following reaction Scheme are reproduced:

3- (2,4,6-Trimethylphenyl) -5,5-ethyleneoxa is used according to process (C) methylene tetronic acid and ethyl chloroformate as the starting compound dung, the course of the method according to the invention can by the following Reaction scheme are reproduced:

Is used according to method (Dα) 3- (2,4,6-trimethylphenyl) -5,5-ethylenoxa ethylene tetronic acid and chloromothio formic acid methyl ester as starting pro products, the course of the reaction can be represented as follows:

Is used according to method (Dβ) 3- (2,4,6-trimethylphenyl) -5,5-ethylene thio ethylene tetronic acid, carbon disulfide and methyl iodide as starting components the course of the reaction can be represented as follows:

3- (2,4,6-Trimethylphenyl) -5,5-methylene is used according to process (E) oxa-propylene-tetronic acid and methanesulfonic acid chloride as the starting product, see above the course of the reaction can be reproduced by the following reaction scheme the:

According to method (F), 3- (2,4-dimethylphenyl) -5.5-ethylene-thio is used ethylene tetronic acid and methanthophosphonyl chloride (2,2,2-trifluoroethyl ester) as starting products, the course of the reaction can be carried out by the following reaction Scheme are reproduced:

According to method (G), 3- (2,4,6-trimethylphenyl) -5,5-ethylene-oxa is used methylene tetronic acid and NaOH as components, so the course of the inventions process according to the invention represented by the following reaction scheme the:

Is used according to method (Hα) 3- (2,4,6-trimethylphenyl) -5,5-ethylene oxaethylene tetronic acid and ethyl isocyanate as starting products, so the The course of the reaction can be represented by the following scheme:

Using 3- (2,4,6-trimethylphenyl) -5,5- (ethylene according to method (Hβ) Acetylamino-ethylene tetronic acid and dimethyl carbamic acid chloride as the starting  products, the course of the reaction can be represented by the following scheme will:

The compounds required as starting materials in process (A) above of the formula (II)

in which
A, B, X, Y, Z, n and R⁸ have the meaning given above,
are new.

The compounds of formula (II) are obtained, for example, if
2-hydroxycarboxylic acid derivatives of the formula (XIV),

in which
R⁸ 'represents hydrogen (XIVa) or alkyl (preferably C₁-C₈-alkyl) (XIVb) and
A and B have the meaning given above,
with phenylacetic acid halides of the formula (XV)

in which
X, Y, Z and n have the meaning given above and
Hal represents chlorine or bromine,
acylated (Chem. Reviews 52, 237-416 (1953)); and optionally the compounds of the formula (IIa) formed for R⁸ ′ = hydrogen

in which
A, B, X, Y, Z and n have the meaning given above,
esterified (Chem. Ind. (London) 1568 (1968)).

Some of the compounds of the formula (XIV) are known and / or can be produce by known methods, for example from the cyanohydrins Formula (XVI)

in which
A and B have the meaning given above,
[see eg Nasarow, Unkowskii, Zh. Obshch. Khim. 26, 3486 (1956) or Bennett, Waddington, J. Chem. Soc. 2831 (1929)].

Some of the compounds of the formula (XVI) are known and / or can be Manufacture using known methods (e.g. Eichen, Fritz; Schmidt, Michal; Buchborn, Helga; Arch. Pharm. 320, 348-61, 1987; Sargsyan, M.S; Ukrtumyan, S.A; Gevorkyan A.A; Poor. Khim. Zh 38 494-8, 1985).

The phenylacetic acid halides of the formula (XV) are known and / or not produce themselves by known methods [s. e.g. B. Lutz, Hinkley, J. Amer. Chem. Soc. 72, 4091 (1950), Harispe, Ann. Chim. (Paris) 11, 6, pp. 249, 282, 283 (1936)].

The processes (B), (C), (D), (E), (F), (G) and (H) acid halides of the formula required as starting materials (III), carboxylic anhydrides of the formula (IV), chloroformate or chlorine formic acid thioesters of the formula (V), chloromothio formic acid esters or Chlorodithio formic acid esters of the formula (VI), alkyl halides of the formula (VII), Sulfonic acid chlorides of the formula (VIII), phosphorus compounds of the formula (IX) and Metal compounds or amines of the formulas (X) and (XI) and isocyanates Formula (XII) or carbamic acid chlorides of formula (XIII) are general known compounds of organic or inorganic chemistry.

Process (A) is characterized in that compounds of the formula (II) in which A, B, X, Y, Z, n and R⁸ have the meaning given above, in Presence of bases to intramolecular condensation.  

All of them can be used as diluents in process (A) according to the invention inert organic solvents are used. Are preferably usable Hydrocarbons, such as toluene and xylene, furthermore ethers, such as dibutyl ether, Tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl ether, except the polar solvent, such as dimethyl sulfoxide, sulfolane, dimethylformamide and N-methyl-pyrrolidone, and alcohols such as methanol, ethanol, propanol, iso propanol, butanol, iso-butanol and tert-butanol.

As bases (deprotonating agents) can be in the implementation of the Invention according to method (A) all usual proton acceptors are used. Alkali metal and alkaline earth metal oxides and hydroxides are preferably usable or carbonates, such as sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate, which are also used in counter were from phase transfer catalysts such. B. triethylbenzylammonium chloride, Tetrabutylammonium bromide, ®Adogen 464 (methyltrialkyl (C₈-C₁₀) ammonium chloride) or TDA 1 (tris (methoxyethoxyethyl) amine) can be used.

Alkali metals such as sodium or potassium can also be used. Also alkali metal and alkaline earth metal amides and hydrides such as sodium amide, sodium hydride and calcium hydride, and also alkali metal alcohol latex, such as sodium methylate, sodium ethylate and potassium tert-butoxide can be used.

The reaction temperatures can be carried out when carrying out the process according to the invention Process (A) can be varied within a wide range. In general one works at temperatures between -30 ° C and 250 ° C, preferably between 0 ° C and 150 ° C.

Process (A) according to the invention is generally carried out under atmospheric pressure carried out.

When carrying out process (A) according to the invention, the Re Action component of formula (II) and the deprotonating base in general in molar amounts. However, it is also possible to use one or the other compo nente to use in a larger excess (up to 3 moles).

The process (Bα) is characterized in that compounds of the For mel (Ia) with carboxylic acid halides of the formula (III).  

In the process according to the invention, (Bα) can be used as diluent all solvents which are sufficiently inert towards the acid halides are used will. Hydrocarbons such as gasoline, benzene, Toluene, xylene and tetralin, and also halogenated hydrocarbons, such as methylene chloride rid, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, except the ketones such as acetone and methyl isopropyl ketone, furthermore ethers such as diethyl ether, tetrahydrofuran and dioxane, moreover carboxylic acid esters, such as ethyl acetate, and also strongly polar solvents, such as dimethyl sulfoxide and sulfolane. If the hydrolysis stability of the acid halide permits, the reaction can can also be carried out in the presence of water.

Acid binders used in the reaction according to the invention Process (Bα) all usual acid acceptors into consideration. Preferably used are tertiary amines, such as triethylamine, pyridine, diazabiyclooctane (DABCO), Diazabicycloundecen (DBU), Diazabicyclononen (DBN), Hünig-Base and N, N- Dimethylaniline, also alkaline earth metal oxides, such as magnesium and calcium oxide, also alkali and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate as well as alkali hydroxides such as sodium hydroxide and Potassium hydroxide.

The reaction temperatures can also in the process according to the invention (Bα) can be varied within a wide range. Generally works one at temperatures between -20 ° C and + 150 ° C, preferably between 0 ° C. and 100 ° C.

When performing the method (Bα) according to the invention, the off Starting materials of the formula (Ia) and the carboxylic acid halide of the formula (III) in generally used in approximately equivalent amounts. However, it is also possible, the carboxylic acid halide in a larger excess (up to 5 mol) to use. The processing takes place according to usual methods.

The process (Bβ) is characterized in that compounds of Reacts formula (Ia) with carboxylic anhydrides of formula (IV).

In the method (Bβ) according to the invention can be used as diluents preferably those diluents are used that are also used in the Ver Use of acid halides are preferred. Furthermore  can also use an excess carboxylic anhydride as a diluent act medium.

The reaction temperatures in the process (Bβ) according to the invention can be varied within a wide range. Generally you work at temperatures between -20 ° C and + 150 ° C, preferably between 0 ° C and 100 ° C.

When carrying out the method (Bβ) according to the invention Starting materials of the formula (Ia) and the carboxylic anhydride of the formula (IV) in generally used in approximately equivalent amounts. However, it is also possible, the carboxylic anhydride in a large excess (up to 5 mol) to use. The processing takes place according to usual methods.

The general procedure is to use diluents and in excess existing carboxylic acid anhydride and the resulting carboxylic acid by De stillation or by washing with an organic solvent or with Water removed.

Process (C) is characterized in that compounds of the formula (Ia) with chloroformate or chloroformate thiol ester of the formula (V) implements.

Acid binders used in the reaction according to the invention Process (C) all customary acid acceptors into consideration. Preferably used are tertiary amines, such as triethylamine, pyridine, DABCO, DBU, DBA, Hünig- Base and N, N-dimethylaniline, also alkaline earth metal oxides, such as magnesium and Calcium oxide, also alkali and alkaline earth metal carbonates, such as sodium carbo nate, potassium carbonate and calcium carbonate as well as alkali hydroxides such as sodium hy hydroxide and potassium hydroxide.

All of them can be used as diluents in process (C) according to the invention sufficiently inert solvents compared to the compounds of formula (V) be set. Hydrocarbons, such as gasoline, are preferably usable. Benzene, toluene, xylene and tetralin, and also halogenated hydrocarbons, such as methy lene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichloro benzene, also ketones, such as acetone and methyl isopropyl ketone, furthermore ether,  such as diethyl ether, tetrahydrofuran and dioxane, moreover carboxylic acid esters, such as ethyl acetate and also strongly polar solvents, such as dimethyl sulfoxide and Sulfolan.

The reaction temperatures can be carried out when carrying out the process according to the invention Process (C) can be varied within a wide range. You work in the presence of a diluent and an acid binder, so are the Reaction temperatures generally between -20 ° C and + 100 ° C, preferably between 0 ° C and 50 ° C.

Process (C) according to the invention is generally carried out under normal pressure carried out.

When carrying out process (C) according to the invention, the off Starting materials of the formula (Ia) and the chloroformic acid esters or chloric ants acid thiol esters of the formula (V) in general in approximately equivalent amounts used. However, it is also possible to use one or the other component in one use a larger excess (up to 2 moles). The processing takes place after usual methods. In general, the procedure is to use salts which have precipitated out removed and the remaining reaction mixture by withdrawing the diluent confining agent.

In the production process (Dα), the for mel (Ia) in general about 1 mol of chloromothio formic acid ester or chlorodi thioformic acid ester of formula (VI) at 0 to 120 ° C, preferably at 20 to 60 ° C around.

All inert polar come as optionally added diluents organic solvents in question, such as ethers, carboxylic acid esters, halogenated Hydrocarbons amides, alcohols, sulfones or sulfoxides.

Dimethyl sulfoxide, methylene chloride, ethyl acetate, tetrahydro are preferred furan, dimethylformamide or dimethyl sulfide used.

Is made in a preferred embodiment by adding strong Deprotonating agents such. B. sodium hydride or potassium tert-butylate  Enolate salt of the compound of formula (Ia), can on the further addition of Acid binders can be dispensed with.

If acid binders are used, common inorganic or organic compounds are used African bases in question, examples include sodium hydroxide, sodium carbonate, Potassium carbonate, pyridine and triethylamine listed.

The reaction can be carried out at normal pressure or under elevated pressure are, preferably carried out at normal pressure. The processing ge uses standard methods.

In the production process (Dβ), the per mole of starting compound Formula (Ia) the equimolar amount or an excess of carbon disulfide. It is preferably carried out at temperatures from 0 to 50 ° C. and ins especially at 20 to 30 ° C.

All conventional proton acceptors can be used as bases in the process (Dβ) be set. Alkali metal hydrides, alkali metal are preferably usable alcoholates, alkali or alkaline earth metal carbonates or bicarbonates or Nitrogen bases. Examples include sodium hydride, sodium methoxide, Sodium hydroxide, calcium hydroxide, potassium carbonate, sodium hydrogen carbonate, Triethylamine, dibenzylamine, diisopropylamine, pyridine, quinoline, diazabicyclo octane (DABCO), diazabicyclonones (DBN) and diazabicycloundecene (DBU).

All customary solvents can be used as diluents in this process be used.

Aromatic hydrocarbons such as benzene or are preferably usable Toluene, alcohols such as methanol, ethanol, isopropanol or ethylene glycol, nitriles such as acetonitrile, ethers such as tetrahydrofuran or dioxane, amides such as dimethyl formamide or other polar solvents such as dimethyl sulfoxide or sulfolane.

It is often expedient to add the compound of the formula (Ia) first a deprotonating agent (such as potassium tert-butylate or sodium hydride) to produce the appropriate salt. The connection (Ia) is used as long  Carbon disulfide until the formation of the intermediate compound is complete is, e.g. B. after stirring for several hours at room temperature.

The further reaction with the alkyl halide of the formula (VII) takes place preferably at 0 to 70 ° C and in particular at 20 to 50 ° C. Here will at least the equimolar amount of alkyl halide used.

One works at normal pressure or under increased pressure, preferably at Normal pressure.

The processing is again carried out using customary methods.

In production process (E), the per mole of starting compound Formula (Ia) about 1 mol of sulfonic acid chloride (VIII) at 0 to 150 ° C, preferably at 20 to 70 ° C around.

All inert polar come as optionally added diluents organic solvents in question such as ethers, carboxylic acid esters, amides, nitriles, Sulfones, sulfoxides or halogenated hydrocarbons such as methylene chloride.

Dimethyl sulfoxide, ethyl acetate, tetrahydrofuran, dimethyl are preferred formamide, dimethyl sulfide or methylene chloride used.

Is made in a preferred embodiment by adding strong Deprotonating agents (such as sodium hydride or potassium tertiary butoxide) Enolate salt of the compound of formula (Ia), can on the further addition of Acid binders can be dispensed with.

If acid binders are used, the usual inorganic or organic compounds are used bases in question, examples include sodium hydroxide, sodium carbonate, potassium carbonate, triethylamine and pyridine listed.

The reaction can be carried out at normal pressure or under elevated pressure are, preferably carried out at normal pressure. The processing ge uses standard methods.  

The manufacturing process (F) uses to obtain compounds Structure (Ie) for 1 mole of compound (Ia), 1 to 2 moles, preferably 1 to 1.3 Mol of the phosphorus compound of formula (IX) at temperatures between -40 ° C. and 150 ° C, preferably between -10 ° C and 110 ° C.

Any inert, polar diluents that may be added organic solvents in question such as ethers, carboxylic acid esters, halogenated Hydrocarbons, amides, nitriles, sulfides, sulfones, sulfoxides etc.

Acetonitrile, ethyl acetate, methylene chloride, dimethyl sulfoxide, Tetrahydrofuran, dimethylformamide or dimethyl sulfide used.

Conventional inorganic or organic bases in question such as hydroxides, carbonates. Sodium is an example hydroxide, sodium carbonate, potassium carbonate, pyridine listed.

The reaction can be carried out at normal pressure or under elevated pressure are, preferably carried out at normal pressure. The processing ge uses the usual methods of organic chemistry. The cleaning of the falling end products is preferably done by crystallization, chromato graphic cleaning or by so-called "distillation", d. H. Removal of volatile components in a vacuum.

Process (G) is characterized in that compounds of the formula (Ia) with metal compounds of the formula (X) or amines of the formula (XI) puts.

Diluents which can be used in process (G) according to the invention preferably ethers such as tetrahydrofuran, dioxane, diethyl ether or alcohols such as methanol, ethanol, isopropanol, but also water. That he Process (G) according to the invention is generally carried out under normal pressure guided. The reaction temperatures are generally between -20 ° C and 100 ° C, preferably between 0 ° C and 50 ° C.

In the production process (Hα), the per mole of starting compound Formula (Ia) about 1 mol isocyanate of formula (XII) at 0 ° C to 100 ° C, preferably at 20 ° C to 50 ° C.  

All inert organic come as optionally added diluents Solvents in question, such as ethers, aromatic hydrocarbons, carboxylic acids esters, halogenated hydrocarbons, amides, nitriles, sulfones or sulfoxides.

If necessary, catalysts can be added to accelerate the reaction will. Organotin compounds can very advantageously be used as catalysts such as B. Dibutyltin dilaurate can be used. It is preferred at normal pressure worked.

In the production process (Hβ), the per mole of starting compound Formula (Ia) approx. 1 mol of carbamic acid chloride of the formula (XIII) at 0 ° C to 150 ° C, preferably at 20 ° C to 70 ° C.

All inert polar or come as optionally added diluents ganic solvents in question such as ethers, carboxylic acid esters, halogenated Koh Hydrogen oils, amides, alcohols, sulfones or sulfoxides.

Dimethyl sulfoxide, ethyl acetate, tetrahydrofuran, dimethyl are preferred formamide or methylene chloride used.

Is made in a preferred embodiment by adding strong Depro toning agents (such as sodium hydride or potassium tert-butylate) the enolate Salt of the compound of formula (Ia), can on the further addition of acid binders are dispensed with.

If acid binders are used, common inorganic or organic compounds are used African bases in question, examples include sodium hydroxide, sodium carbonate, Potassium carbonate, triethylamine or pyridine called.

The active ingredients are particularly suitable for controlling animal pests insects, arachnids and nematodes, which are used in agriculture, in forests, in storage and material protection as well as in the hygiene sector. she can preferably be used as pesticides. You are against normally sensitive and resistant species as well as against all or individual developments Stages effective. The pests mentioned above include:  

From the order of the Isopoda z. B. Oniscus asellus, Armadillidium vulgare, Por cellio scaber.

From the order of the Diplopoda z. B. Blaniulus guttulatus.

From the order of the Chilopoda z. B. Geophilus carpophagus, Scutigera spec.

From the order of the Symphyla z. B. Scutigerella immaculata.

From the order of the Thysanura z. B. Lepisma saccharina.

From the order of the Collembola z. B. Onychiurus armatus.

From the order of Orthoptera z. B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.

From the order of the Dermaptera z. B. Auricular Forficula.

From the order of the Isoptera z. B. Reticulitermes spp.

From the order of the Anoplura z. B. Pediculus humanus corporis, Haematopinus spp., Linognathus spp.

From the order of the Mallophaga z. B. Trichodectes spp., Damalinea spp.

From the order of the Thysanoptera z. B. Hercinothrips femoralis, Thrips tabaci.

From the order of Heteroptera z. B. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

From the order of Homoptera z. B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix  cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.

From the order of the Lepidoptera z. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Spodoptera litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

From the order of the Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

From the order of the Hymenoptera z. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Diptera z. B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

From the order of the Siphonaptera z. B. Xenopsylla cheopis, Ceratophyllus spp.  

From the order of the Arachnida z. B. Scorpio maurus, Latrodectus mactans.

From the order of Acarina z. B. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.

The compounds of the formula (I) according to the invention are notable for high insecticidal and acaricidal activity. They are also soil insecticidal effective.

They can be used with particularly good success to combat plant damage insects, such as against the larvae of the horseradish leaf beetle (Phaedon cochleariae) or against the larvae of the green leafhopper (Nephotettix cincticeps) or for controlling plant-damaging mites, such as wise against the common spider mite or the bean spider mite (Tetranychus urticae).

The active compounds of the formula (I) also have a certain herbicidal action.

The active ingredients can be converted into the usual formulations, such as Lö solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, sol Liche powder, granules, suspension emulsion concentrates, active ingredient impregnated nated natural and synthetic substances as well as very fine encapsulation in polymers Fabrics.

These formulations are prepared in a known manner, e.g. B. by Mixing the active ingredients with extenders, i.e. liquid solvents and / or solid carriers, optionally using surfaces active agents, ie emulsifiers and / or dispersants and / or foam generating means.

In the case of the use of water as an extender, e.g. B. also organic Solvents are used as auxiliary solvents. As a liquid solvent essentially come into question: aromatics, such as xylene, toluene, or alkyl naphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons,  such as chlorobenzenes, chlorethylene or methylene chloride, aliphatic coal water serstoffe, such as cyclohexane or paraffins, e.g. B. petroleum fractions, mineral and vegetable oils, 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, such as dimethylformamide and dimethyl sulfoxide, and Water.

The following are suitable as solid carriers:
e.g. B. ammonium salts and natural rock powders such as kaolins, clays, talcum, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, are suitable as solid carriers for granules: 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 from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foam-generating agents come into question: z. B. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as a dispersing agent come into question: z. B. lignin sulfite and methyl cellulose.

In the formulations, adhesives such as carboxymethyl cellulose, natural Liche and synthetic powdery, granular or latex-shaped polymers used such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural Phospholipids such as cephalins and lecithins and synthetic phospholipids. Wei Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azo and metal phthalalo cyanine dyes 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% by weight of active ingredient fabric, preferably between 0.5 and 90%.

The active ingredient according to the invention can be in its commercially available formulations as well as in the use forms prepared from these formulations in  Mix with other active ingredients, such as insecticides, attractants, sterilants, Acaricides, nematicides, fungicides, growth regulators or herbi ziden available. Insecticides include, for example, phosphoric acid esters, Carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms u. a.

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

Fungicides

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ′, 6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoromethyl-1,3-thiazole-5-carboxanide; 2,6-di chloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,
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, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,
Edifenphos, epoxyconazole, ethirimol, etridiazole,
Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanyl, Fuberilafil, Fuberri Furmecyc lox,
Guazatine,
Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodione, Isoprothiolan,
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,
Pefurazoate, penconazole, pencycuron, phosdiphen, phthalide, pimaricin, piperalin, polycarbamate, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,
Quintozen (PCNB),
Sulfur and sulfur preparations,
Tebuconazole, Tecloftalam, Tecnazen, Tetraconazole, Thiabendazole, Thicyofen, Thiophanat-methyl, Thiram, Tolclophos-methyl, Tolylfluanid, Triadimefon, Triadi menol, Triazoxid, Trichlamid, Tricyclazol, Tridemorph, Triforazol, Tri,
Validamycin A, vinclozolin,
Zineb, ziram.

Bactericides

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, Kasugamy cin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, Tecloftalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides

Abamectin, Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,
Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyluthrin, Bifen thrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlor fluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocy thrin, Chrinophhrin, Clophin Cyhalothrin, cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflu benzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,
Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Etho prophos, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenothxatophion, Fufionophon, Fufionophon, Fufionophon, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufon, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufox
HCH, heptenophos, hexaflumuron, hexythiazox,
Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivemectin,
Lamda-cyhalothrin, Lufenuron,
Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,
Naled, NC 184, NI 25, Nitenpyram,
Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,
Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamdon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophhion, Pyrachlophhion, Pyrachlophion, Pyrachlophion, Pyrachlophin, Pyrachlophin, Pyrachlophin, Pyrachlophion Pyridaben, pyrimidifen, pyriproxifen,
Quinalphos,
RH 5992,
Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,
Tebufenozid, Tebufenpyrad, Tebupirimphos, Teflubenzuron, Tefluthrin, Temephos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thio methon, Thionazin, Thuringiensin, Tralomichonon, Triaromenontron, Triaromenontron, Triarathenlarbon, Triarathenltronium, Triarathenltronium, Triarathenltronium, Triarathenltronium, Triarathenltronium, Triarathenltronium, Triaromenontrin, Triarathenltronium, Triaromenontrin, Triarathenltron, Triaromenontron
Vamidothione, XMC, xylylcarb, YI 5301/5302, zetamethrin.

Herbicides

For example anilides, such as. B. Diflufenican and Propanil; Aryl carboxylic acids, such as e.g. B. dichloropicolinic acid, dicamba and picloram; Aryloxyalkanoic acids, such as. B. 2.4 D, 2.4 DB, 2.4 DP, fluroxypyr, MCPA, MCPP and triclopyr; Aryloxy-phenoxy alkanoic acid esters, such as. B. diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, Haloxyfop-methyl and quizalofop-ethyl; Azinones, such as B. Chloridazon and Norflurazon; Carbamates, e.g. B. chlorpropham, desmedipham, phenmedipham and propham; Chloroacetanilides such as e.g. B. Alachlor, Acetochlor, Butachlor, Metaza chlorine, metolachlor, pretilachlor and propachlor; Dinitroanilines such as e.g. B. Oryzalin, Pendimethalin and trifluralin; Diphenyl ether, such as. B. acifluorfen, bifenox, Fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; Ureas, like e.g. B. chlorotoluron, diuron, fluometuron, isoproturon, linuron and methabenz  thiazuron; Hydroxylamines, such as. B. Alloxydim, Clethodim, Cycloxydim, Sethoxy dim and tralkoxydim; Imidazolinones, e.g. B. Imazethapyr, Imazamethabenz, Imazapyr and imazaquin; Nitriles such as B. bromoxynil, dichlobenil and ioxynil; Oxyacetamides such as e.g. B. Mefenacet; Sulfonylureas, such as. B. amidosulfuron, Bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, metsulfuron methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, Triasulfuron and tribenuron-methyl; Thiol carbamates such as e.g. B. butylates, cycloates, Dialallate, EPTC, esprocarb, molinate, prosulfocarb, thiobencarb and triallate; Triazines, e.g. B. Atrazin, Cyanazin, Simazin, Simetryne, Terbutryne and Terbu tylazine; Triazinones such as e.g. B. hexazinone, metamitron and metribuzin; Other, such as B. aminotriazole, benfuresate, bentazone, cinmethylin, clomazone, clopy ralid, difenzoquat, dithiopyr, ethofumesate, fluorochloridone, glufosinate, Glyphosate, Isoxaben, Pyridate, Quinchlorac, Quinmerac, Sulphosate and Tri diphane.

The active compounds according to the invention can also be used in their commercially available form formulations and in the application forms prepared from these formulations in a mixture with synergists. Synergists are connections through which the effect of the active ingredients is increased without the added synergist must be actively active itself.

The active ingredient content of the prepared from the commercially available formulations Application forms can vary widely. The drug concentration the use forms can be from 0.0000001 to 95% by weight of active ingredient, preferably between 0.0001 and 1% by weight.

The application takes place in a customary manner adapted to the application forms Wise.

When used against hygiene and storage pests, the stands out Active ingredient through an excellent residual effect on wood and clay as well due to good stability to alkali on limed substrates.

The active compounds according to the invention act not only against plant and hygiene and storage pests, but also against in the veterinary sector animal parasites (ectoparasites) such as tortoise ticks, leather ticks, mite mites,  Running mites, flies (stinging and licking), parasitic fly larvae, lice, Hair lice, featherlings and fleas. These parasites include:

From the order of the Anoplurida z. B. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.

From the order of the Mallophagida and the subordinates Amblycerina as well Ischnocerina e.g. B. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.

From the order Diptera and the subordinates Nematocerina as well Brachycerina e.g. B. Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp.

From the order of the Siphonapterida z. B. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.

From the order of the Heteropterida z. B. Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.

From the order of the Blattarida z. B. Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp.

From the subclass of Acaria (Acarida) and the orders of the Meta and Mesostigmata e.g. B. Argas spp., Ornithodorus spp., Otabius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemaphysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneu monyssus spp., Sternostoma spp., Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata) z. B. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates  spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp.

For example, they show excellent effectiveness against Boophilus microplus, Lucilia 24309 00070 552 001000280000000200012000285912419800040 0002019540736 00004 24190cuprina and Musca domestica.

The active compounds of the formula (I) according to the invention are also suitable for combating treatment of arthropods, the agricultural livestock, such as. B. cattle, sheep, Goats, horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, Geese, bees, other pets such as B. dogs, cats, house birds, aqua reindeer fish and so-called experimental animals, such as B. hamsters, guinea pigs, Infect rats and mice. By fighting these arthropods are said to Deaths and reduced performance (for meat, milk, wool, skins, eggs, Honey, etc.) can be reduced, so that by using the invention Active ingredients a more economical and easier animal husbandry is possible.

The active compounds according to the invention are used in the veterinary sector in a known manner by enteral administration in the form of, for example, Tab Latvian, capsules, watering, drenching, granules, pastes, boluses, feed-through Method, of suppositories, by parenteral administration, such as by injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), Implan tate, by nasal application, by dermal application in the form, for example of diving or bathing (dipping), spraying (spray), pouring on (pour-on and Spot-on), washing, powdering and with the help of active ingredients Shaped bodies, such as collars, ear tags, tail tags, limb straps, Halters, marking devices etc.

When used for cattle, poultry, pets etc. you can use the active ingredients of the formula (I) as formulations (for example powders, emulsions, flowable Agents), which contain the active ingredients in an amount of 1 to 80 wt .-%, directly or after 100 to 10,000-fold dilution, or as a chemical Use bath.  

It has also been found that the compounds of the formula 1 show a high insecticidal activity against insects, the technical materials to destroy.

The following are examples and preferably - but without limitation - Called insects:

Beetle like
Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearesces, Lyctus pubis linearis, Lyctus pubis linearis, speculum Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus.

Skin wings like
Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur.

Termites like
Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes dar winiensis, Zootermopsis nevadensis, Coptotermes formosanus.

Bristle tails, such as Lepisma sacchanna.

In the present context, technical materials include non-living ones To understand materials, such as preferably plastics, adhesives, glues, Pa paper and cardboard, leather, wood and wood processing products and paints.

It is very particularly preferred to prevent insect attack protective material around wood and wood processing products.

Among wood and wood processing products, which by the invention Agents or mixtures containing them can be protected is exemplary to understand: timber, wooden beams, railway sleepers, bridge parts, jetties, Wooden vehicles, boxes, pallets, containers, telephone poles, wooden panels, Wooden windows and doors, plywood, chipboard, carpentry or wood pro  products that are used in general in house construction or in joinery Find.

The active ingredients can be used as such, in the form of concentrates or in general usual formulations such as powders, granules, solutions, suspensions, emul sions or pastes.

The formulations mentioned can be prepared in a manner known per se be, e.g. B. by mixing the active ingredients with at least one solution or diluent, emulsifier, dispersing and / or binding or fixing agent tels, water repellants, possibly desiccants and UV stabilizers and opp if necessary dyes and pigments and other processing aids.

The insecticidal agents used to protect wood and wood-based materials or concentrates contain the active ingredient according to the invention in a concentra tration from 0.0001 to 95 wt .-%, in particular 0.001 to 60 wt .-%.

The amount of agents or concentrates used depends on the type and type come from insects and depending on the medium. The optimal amount to use can be determined by test series in the application. Generally in my opinion, however, it is sufficient 0.0001 to 20% by weight, preferably 0.001 to 10 wt .-%, of the active ingredient, based on the material to be protected.

An organic chemical solvent serves as the solvent and / or diluent solvent or solvent mixture and / or an oily or oily heavy volatile organic chemical solvent or solvent mixture and / or a polar organic chemical solvent or solvent combination mixed and / or water and optionally an emulsifier and / or wetting agent.

The organic chemical solvents used are preferably oily or oily ones Solvents with an evaporation number above 35 and a flash point above half 30 ° C, preferably above 45 ° C, used. As such volatile, water-insoluble, oily and oily solvents become corresponding mine ralöle or their aromatic fractions or mineral oil-containing solvent mixtures cal, preferably white spirit, petroleum and / or alkylbenzene used.  

Mineral oils with a boiling range of 170 ° C to 220 ° C are advantageous, test petrol with a boiling range of 170 ° C to 220 ° C, spindle oil with a boiling point range from 250 ° C to 350 ° C, petroleum or aromatics with a boiling range of 160 ° C up to 280 ° C, turpentine oil and the like.

In a preferred embodiment, liquid aliphatic hydrocarbons substances with a boiling range of 180 ° C to 210 ° C or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range from 180 ° C to 220 ° C and / or locker oil and / or monochloronaphthalene, preferably two se α-monochloronaphthalene used.

The organic non-volatile oily or oily solvents with a Evaporation rate above 35 ° C and a flash point above 30 ° C, preferably above 45 ° C, can be partly due to slightly or medium-volatile organic chemistry cal solvents are replaced, with the proviso that the solvent mixture also has an evaporation number above 35 ° C and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide fungicide Mixture is soluble or emulsifiable in this solvent mixture.

According to a preferred embodiment, part of the organic chemical Solvent or solvent mixture or an aliphatic polar orga niche chemical solvent or solvent mixture replaced. Preferably come alipha containing hydroxyl and / or ester and / or ether groups organic chemical solvents such as glycol ether, esters or the like for use.

As an organic chemical binder in the present Er finding the known water-dilutable and / or in the used organic chemical solvents soluble or dispersing or emul gable synthetic resins and / or binding drying oils, especially binders consisting of or containing an acrylic resin, a vinyl resin, e.g. B. polyvinyl acetate, Polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene Coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a natural and / or Resin used.  

The synthetic resin used as a binder can be in the form of an emulsion, disper sion or solution. Bitumen or bituminous substances up to 10 wt .-%, are used. In addition, you can dyes, pigments, water-repellants, odor correctors known per se tien and inhibitors or corrosion protection agents and the like. Be used.

According to the invention, preference is given to organic chemical binders least an alkyd resin or modified alkyd resin and / or a drying one vegetable oil contained in the medium or in the concentrate. According to the invention alkyd resins with an oil content of more than 45 wt .-%, preferably as 50 to 68 wt .-%, used.

The binder mentioned can be wholly or partly by a fixation medium (mixture) or a plasticizer (mixture) can be replaced. These additions should volatilize the active ingredients and crystallize or from prevent falling. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).

The plasticizers come from the chemical classes of phthalic acid esters such as Dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, glycerol ether or higher molecular weight Gly kolether, glycerol ester and p-toluenesulfonic acid ester.

Fixing agents are chemically based on polyvinyl alkyl ethers such as. B. Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone.

Water is also particularly suitable as a solvent or diluent, optionally in a mixture with one or more of the above organic chemical solvents or diluents, emulsifiers and dispersers gators.

A particularly effective wood protection is provided by industrial impregnation drive, e.g. B. vacuum, double vacuum or printing process.

The ready-to-use agents can optionally also be other insecticides and optionally contain one or more fungicides.  

The additional mixing partners are preferably those in WO 94/29 268 Insecticides and fungicides mentioned in question. The ones mentioned in this document Connections are an integral part of this application.

Insecticides such as chlorine pyriphos, phoxime, silafluofin, alphamethrin, cyfluthrin, cypermethrin, delta methrin, permethrin, iniidacloprid, M-25, flufenoxuron, hexaflumuron and tri-flumuron can be used as very particularly preferred mixing partners.
as well as fungicides such as epoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole, metconazole, imazalil, dichlorofluoride, tolylfluanid, 3-iodo-2-propynylbutylcarbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro - octylisothiazolin-3-one.

The manufacture and use of the active compounds according to the invention start out the following examples.

Manufacturing examples Example (Ia-1)

67.3 g (0.60 mol) of potassium tert-butoxide in 400 ml of abs. Dimethylformamide (DMF), at 0 ° C to 10 ° C a solution of 133.6 g (0.40 mol) 1- (2,4,6- Trimethylphenylacetyl-oxy) -4-oxa-cyclohexane-carboxylic acid ethyl ester was added dropwise and stirred overnight at room temperature.

For working up, the reaction mixture is slowly dripped into 2 l of ice-cooled 1N Hydrochloric acid, sucks off the precipitate, washes well with water and dries the product in a vacuum drying cabinet.

For cleaning, the crude product is boiled out with n-hexane and suctioned off again and dried.

Yield: 91.6 g (79% of theory) of a solid; Mp .: 224-226 ° C.

The following compounds of the formula (Ia) are obtained analogously or according to the general information on the preparation:
(The following abbreviations are used in the tables:
Me = methyl, Et = ethyl, Pr = propyl, Bu = butyl, Ph = phenyl).

Table 5

Example (Ib-1)

28.8 g (0.10 mol) of 3 - (2,4,6-trimethylphenyl) -5,5-ethylene-oxa-ethylene tetronic acid according to Ex. (Ia-1) in 400 ml abs. Submitted methylene chloride, with 15.2 g (0.15 mol) triethylamine added, at 0 ° C to 10 ° C a solution of 15.7 g (0.13 mol) pivaloyl chloride was added dropwise and a few hours at room temperature touched.

For working up, the reaction mixture is washed successively with 10% strength Citric acid, sodium bicarbonate solution and water dry the organi cal phase over sodium sulfate and evaporated.

For cleaning, the crude product is stirred with petroleum ether and suction filtered.

Yield: 29.4 g (78% of theory) of a solid; Mp .: 119-120 ° C.

Analogously or in accordance with the general information on the manufacture, the fol the following compounds of the formulas (Ib) to (Ig):  

Table 6

Table 7

Table 8

Example of the preparation of an intermediate of formula (II) Example (II-1)

31.3 g (0.18 mol) of 1-hydroxy-4-oxa-cyclohexanecarboxylic acid ethyl ester are dissolved in 150 ml of methylene chloride were introduced, 21.9 g (0.216 mol) of triethylamine were added, a solution of 38.9 g (0.20 mol) of mesitylacetic acid chloride in 50 ml of methylene chloride added dropwise at 0 ° C to 10 ° C and stirred overnight at room temperature.

For working up, the reaction mixture is washed successively with 10% strength Citric acid, sodium bicarbonate solution and water dry the orga African phase over magnesium sulfate and evaporated.

Yield: 60.6 g of an oil (quantitative).

Analogously or according to the general information on the manufacture, the following will follow the compounds of the formula (II):  

Table 9

Example (XIV-1)

A mixture of 130 g (approx. 1 mol) of 4-hydroxy-tetrahydropyran-4-carbonitrile and 1050 ml of dry ethanol is saturated with hydrochloric acid at -20 ° C to 0 ° C. The mixture is allowed to come to room temperature, excess HCl is removed, the mixture is concentrated in vacuo, 1.5 l of water are added and the mixture is stirred at room temperature for 3 hours. It is filtered and extracted twice with methylene chloride. After removing the solvent, 118 g (61% of theory) of 4-hydroxy-tetrahydropyran-4-carboxylic acid ethyl ester of KP _0.1 65 ° C. are obtained.

In the application examples, the following were from the prior art known comparison compounds used:

(all known from EP-528 156)  

Example A Myzus test

Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified amount of emulsifier and dilute the concentrate with water to the wanted concentration.

Cabbage leaves (Brassica oleracea), heavily from the peach aphid (Myzus persicae) are infested by dipping into the active ingredient preparation desired concentration treated.

After the desired time, the kill is determined in%. 100 means % that all aphids were killed; 0% means that no aphid comes off was killed.

In this test z. B. the connections according to the manufacturing example len Ia-1, Ib-1, Ib-12, Ib-15 and Ic-1 at an exemplary active ingredient concentration of 0.1% a kill of at least 95% after 6 days while out Compound (B) known in the prior art at an active ingredient concentration of 0.1% caused a kill of only 70%.  

Example B Limit concentration test / root systemic effect

Test insect: Aphis fabae
Solvent: 4 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified amount of emulsifier and dilute the concentrate with water to the wanted concentration.

The active ingredient preparation is intimately mixed with the soil. The plays Concentration of the active ingredient in the preparation practically no role, ent the only decisive factor is the weight of active substance per unit volume of soil, which che in ppm (= mg / l) is given. The treated soil is filled into pots and planted them with broad beans (Vicia faba). The active ingredient can be from the plant roots from the soil and transported into the leaves will.

To demonstrate the root systemic effect, the Leaves populated with the above test animals. After another 6 days the evaluation by counting or estimating the dead animals. From the killings the root systemic effect of the active ingredient is derived. she is 100% if all test animals are killed and 0% if exactly as many Test insects live like in the untreated control.

In this test, e.g. B. the compounds according to the preparation examples Ia-1, Ib-2, Ib-5, Ib-7, Ib-8, Ib-12, Ib-15, Ib-16, Ib-17 and Ic-2 in one case playful active ingredient concentration of 200 ppm an effect of 100%.  

Example C Nephotettix test

Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified amount of emulsifier and dilute the concentrate with emulsifier Water to the desired concentration.

Rice seedlings (Oryza sativa) are dipped into the active ingredient preparation the desired concentration and treated with green rice leafhopper larvae (Nephotettix cincticeps) occupied while the seedlings are still moist.

After the desired time, the kill is determined in%. Here means 100% that all cicadas have been killed; 0% means that no cicada is released was killed.

In this test z. B. the connections according to the manufacturing example len Ia-1, Ib-1, Ib-16, Ic-1 and 1c-3 at an exemplary active ingredient concentration of 0.01% a killing of 100% after 6 days, while the known Compound (A) did not kill.  

Example D Tetranychus test (OP-resistant)

Solvent: 3 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified amount of emulsifier and dilute the concentrate with water to the wanted concentration.

Bean plants (Phaseolus vulgaris), strongly affected by all stages of development common spider mite (Tetranychus urticae) are infected with a Active ingredient preparation of the desired concentration injected.

After the desired time, the effect is determined in%. Here means 100% that all spider mites have been killed; 0% means that no spinning mite was killed.

In this test z. B. the connections according to the manufacturing example len Ia-1, Ia-24, Ib-1, Ib-2, Ib-16, Ib-31 and Ic-1 in an exemplary active ingredient concentration of 0.02% a killing of at least 95% after 7 days and the compounds according to the preparation examples Ib-5, Ib-7, Ib-11 and Ib-22 at an exemplary active ingredient concentration of 0.1%, a kill of min at least 98% after 7 days.  

Example E Panonychus test

Solvent: 3 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified amount of emulsifier and dilute the concentrate with emulsifier Water to the desired concentrations.

Approx. 30 cm high plum trees (Prunus domestica), which are strong from all Ent development stages of the fruit tree spider mite (Panonychus ulmi) are infected, are injected with an active ingredient preparation of the desired concentration.

After the desired time, the effect is determined in%. Here means 100% that all spider mites have been killed; 0% means that no spinning mite was killed.

In this test z. B. the connections according to the manufacturing example len Ia-1, Ia-24, Ib-1, Ib-2, Ib-16, Ib-31 and Ic-1 in an exemplary action concentration of 0.02%, a death of at least 95% after 7 days.  

Example F Test with fly larvae / development-inhibiting effect

Test animals: All larval stages of Lucilia cuprina (OP-resistant) [Dolls and adults (without contact to the active ingredient)]

Solvent: 35 parts by weight of ethylene glycol monomethyl ether
35 parts by weight of nonylphenol glycol ether

Three weights are mixed to prepare a suitable formulation parts of active ingredient with seven parts of the solvent emulsifier specified above Mix and dilute the emulsion concentrate thus obtained with water to desired concentration.

30 to 50 larvae per concentration are on horses in glass tubes deflected (1 cm³), to which 500 µl of the dilution to be tested pi be petted. The glass tubes are placed in plastic cups Floor is covered with sea sand, and in an air-conditioned room (26 ° C ± 15 ° C, 70% rel. Humidity ± 10%). The effects are checked after 24 hours and 48 hours (larvicidal activity). After the larvae migrate (approx. 72 h) the glass tubes are removed and perforated plastic lids on the beakers set. After 1½ times the development time (hatching of the control flies) the hatched flies and the dolls / doll covers counted.

The criterion for the effect is the occurrence of death in the treated Larvae after 48 h (larcidal effect), or the inhibition of adult hatching from the Dolls or the inhibition of doll formation. As a criterion for the in vitro we The inhibition of flea development or development applies cessation of activity before the adult stage. 100% larvicidal means we that all larvae have died after 48 hours. 100% development inhibitory effect means that no adult flies have hatched.

In this test, e.g. B. the compounds according to the preparation examples Ia-2, Ia-24, Ib-4, Ib-15, Ib-22, Ib-24 and Ib-30 in an exemplary Active ingredient concentration of 1000 ppm an effect of 100% each.

Claims (17)

1. Compounds of formula (I) in which
A and B together with the carbon atom to which they are attached form an unsubstituted or substituted 5- to 7-membered ring interrupted by at least one heteroatom,
X represents alkyl, halogen or alkoxy,
Y represents hydrogen, alkyl, halogen, alkoxy or haloalkyl,
Z represents alkyl, halogen or alkoxy,
n stands for a number 0, 1, 2 or 3,
G for hydrogen (a) or for one of the groups stands,
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulfur,
M represents oxygen or sulfur,
R¹ represents in each case optionally substituted by halogen, alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl, optionally substituted by halogen, alkyl or alkoxy, cycloalkyl, which can be interrupted by at least one heteroatom or in each case optionally substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl ,
R² represents alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl, optionally substituted by halogen, cycloalkyl optionally substituted by halo, alkoxy or alkyl, or phenyl or benzyl, optionally substituted,
R³, R⁴ and R⁵ independently of one another each represent optionally substituted by halogen alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio, cycloalkylthio or optionally substituted phenyl, benzyl, phenoxy or phenylthio,
R⁶ and R⁷ independently of one another represent hydrogen, in each case optionally substituted by halogen alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, in each case optionally substituted phenyl or benzyl, or together for an alkanediyl radical which may be interrupted by oxygen or sulfur. 2. Compounds of the formula (I) according to Claim 1, which, with inclusion of the different meanings (a), (b), (c), (d), (e) and (f) of the group G, have the following structures (Ia) to (Ig) have: wherein
A, B, E, L, M, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and n have the meanings given above. 3. Compounds of formula (I) according to claim 1, in which
A and B are optionally mono- or polysubstituted, identically or differently, by halogen, C₁-C₈-alkyl, C₃-C₈-cycloalkyl, C₁-C₈-halo alkyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio or phenyl-substituted C₄- C₆-Alkanediyl, in which one or two not directly adjacent carbon atoms through the group and / or oxygen and / or sulfur are replaced,
X represents C₁-C₆-alkyl, halogen or C₁-C₆-alkoxy,
Y represents hydrogen, C₁-C₆-alkyl, halogen, C₁-C₆-alkoxy or C₁-C₃- haloalkyl,
Z represents C₁-C₆-alkyl, halogen or C₁-C₆-alkoxy,
G for hydrogen (a) or for one of the groups stands in which
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulfur and
M represents oxygen or sulfur,
R¹ for C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₁-C₈-alkoxy-C₁-C₈- alkyl, C₁-C₈-alkylthio-C₁-C₈-alkyl, poly-C₁-, each optionally mono- or polysubstituted by halogen C₈-alkoxy-C₂-C₈-alkyl or C₃-C₈-cycloalkyl optionally substituted by halogen, C₁-C₆-alkyl or C₁-C₆-alkoxy, in which one or two not directly adjacent methylene groups are optionally replaced by oxygen and / or sulfur ,
for phenyl optionally substituted up to five times by halogen, nitro, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl, C₁-C₆-haloalkoxy, C₁-C₆-alkylthio or C₁-C₆-alkylsulfonyl,
for phenyl-C₁-C₆-alkyl optionally substituted up to five times by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl or C₁-C₆-haloalkoxy,
for pyridyl, thienyl, furanyl, pyrazolyl, pyrimidyl or thiazolyl optionally substituted once or twice by halogen or C₁-C₆alkyl,
for phenoxy-C₁-C₆-alkyl which is optionally monosubstituted to trisubstituted by halogen or C₁-C₆-alkyl or
represents pyridinyloxy-C₁-C₆-alkyl, pyrimidinyloxy-C₁-C₆-alkyl or thiazolyloxy-C₁-C₆-alkyl which is optionally mono- or disubstituted by halogen, amino or C₁-C₆-alkyl,
R² for C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₁-C₈-alkoxy-C₂-C₈-alkyl or poly-C₁-C₈-alkoxy-C₂-C₈-alkyl, each optionally mono- or polysubstituted by halogen,
for C₃-C₈-cycloalkyl which is optionally mono- or polysubstituted by halogen, C₁-C₄-alkyl or C₁-C₄-alkoxy or for in each case optionally up to three times by halogen, nitro, C₁-C₆-alkyl, C₁-C₆-alkoxy or C₁ -C₆-haloalkyl substituted phenyl or benzyl,
R³ for C₁-C₈-alkyl optionally substituted one or more times by halogen or for each optionally optionally single or multiple by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-halo genalkyl, C₁-C₄-haloalkoxy, Cyano or nitro substituted phenyl or benzyl,
R⁴ and R⁵ independently of one another, each optionally mono- or polysubstituted by halogen, C₁-C₈-alkyl, C₁-C₈-alkoxy, C₁-C₈-alkylamino, di- (C₁-C₈) -alkylamino, C₁-C₈-alkylthio, C₃- C₆- alkenylthio or C₃-C₇-cycloalkylthio,
for each optionally mono- or polysubstituted by halogen, nitro, cyano, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkyl thio, C₁-C₄-haloalkylthio, C₁-C₄-alkyl or C₁-C₄-haloalkyl Are phenyl, phenoxy or phenylthio,
R⁶ and R⁷ independently of one another for hydrogen,
for in each case optionally mono- or polysubstituted by halogen C₁-C₈-alkyl, C₃-C₈-cycloalkyl, C₁-C₈-alkoxy, C₃-C₈-alkenyl or C₁-C₈-alkoxy-C₁-C₈-alkyl,
each represent phenyl or benzyl which is optionally mono- to trisubstituted by halogen, C₁-C₈-alkyl, C₁-C₈-haloalkyl or C₁-C₈-alkoxy or together represents a C₂-C₆-alkanediyl radical which may be interrupted by oxygen or sulfur,
R⁹ represents hydrogen, Q, COQ or CO₂Q,
in which

• Q can take on the meanings mentioned above for R² as preferred and

n stands for 0, 1 or 2. 4. Compounds of formula (I) according to claim 1, in which
A and B for optionally monosubstituted to tetrasubstituted, identically or differently, by fluorine, chlorine, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₁-C Hal-halo alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio or phenyl C₄-C₅-alkanediyl, in which one or two not directly adjacent carbon atoms through the group or is replaced by oxygen or by sulfur.
X represents C₁-C₄-alkyl, fluorine, chlorine, bromine or C₁-C₄-alkoxy,
Y represents hydrogen, C₁-C₄-alkyl, fluorine, chlorine, bromine, C₁-C₄-alkoxy or C₁-C₂-haloalkyl,
Z represents C₁-C₄-alkyl, fluorine, chlorine, bromine or C₁-C₄-alkoxy,
G for hydrogen (a) or for one of the groups stands in which

• E represents a metal ion equivalent or an ammonium ion,
  L represents oxygen or sulfur and
  M represents oxygen or sulfur,

R¹ for C₁-C₁₆-alkyl, C₂-C₁₆-alkenyl, C₁-C₆-alkoxy- C₁-C₆-alkyl, C₁-C₆-alkylthio-C₁-C₆-alkyl, poly- each optionally monosubstituted or disubstituted by fluorine or chlorine, C₁-C₆-alkoxy-C₁-C₆-alkyl or optionally substituted by fluorine, chlorine, C₁-C₅-alkyl or C₁-C₅-alkoxy-substituted C₃-C₇-cycloalkyl, in which one or two not directly adjacent methylene groups are optionally substituted by oxygen and / or sulfur is replaced,
for optionally single to triple by fluorine, chlorine, bromine, nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₃-haloalkyl, C₁-C₃- haloalkoxy, C₁-C₄-alkylthio or C₁-C₄-alkylsulfonyl substi tuated phenyl,
for phenyl-C₁-C₄-alkyl which is optionally mono- to trisubstituted by fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₃-haloalkyl or C₁-C₃-haloalkoxy,
for pyridyl, thienyl, furanyl, pyrazolyl, pyrimidyl or thiazolyl, each optionally mono- or disubstituted by fluorine, chlorine, bromine or C₁-C₄alkyl,
for phenoxy-C₁-C₅-alkyl which is optionally mono- or disubstituted by fluorine, chlorine, bromine or C₁-C₄-alkyl or
represents pyrimidinyloxy-C₁-C₅-alkyl, pyridinyloxy-C₁-C₅-alkyl or thiazolyloxy-C₁-C₅-alkyl optionally substituted once or twice by fluorine, chlorine, bromine, amino or C₁-C₄-alkyl,
R² for C₁-C₁₆-alkyl, C₂-C₁₆-alkenyl, C₁-C₆-alkoxy-C₂-C₆-alkyl or poly-C₁-C₆-alkoxy-C₂-C₆-alkyl, each optionally monosubstituted or disubstituted by fluorine or chlorine,
for C₃-C₇-cycloalkyl or optionally substituted up to six times by fluorine, chlorine, C₁-C₃-alkyl or C₁-C₃-alkoxy
represents phenyl or benzyl optionally substituted once or twice by fluorine, chlorine, bromine, nitro, C₁-C₄-alkyl, C₁-C₃-alkoxy or C₁-C₃-haloalkyl,
R³ for C₁-C₆-alkyl optionally substituted up to six times by fluorine or chlorine or for each optionally mono- or disubstituted by fluorine, chlorine, bromine, C₁-C₅-alkyl, C₁-C₅-alkoxy, C₁-C₃-haloalkyl, C₁ -C₃-haloalkoxy, cyano or nitro substituted phenyl or benzyl,
R⁴ and R⁵ independently of one another, in each case optionally up to six times substituted by fluorine or chlorine, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkylamino, di- (C₁-C₆) alkylamino, C₁-C₆-alkyl thio , C₃-C₄-alkenylthio or C₃-C₆-cycloalkylthio,
for each optionally single or double by fluorine, chlorine, bromine, nitro, cyano, C₁-C₃-alkoxy, C₁-C₃-haloalkoxy, C₁-C₃- alkylthio, C₁-C₃-haloalkylthio, C₁-C₃-alkyl or C₁-C₃ -Halo genalkyl substituted phenyl, phenoxy or phenylthio,
R⁶ and R⁷ independently of one another for hydrogen,
for each C₁-C bis-alkyl, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, C₃-C₆-alkenyl or C₁-C₆-alkoxy-C₁-C₆-alkyl optionally substituted up to six times by fluorine or chlorine,
for phenyl or benzyl optionally substituted once or twice by fluorine, chlorine, bromine, C₁-C₅-alkyl, C₁-C₅-haloalkyl or C₁-C₅-alkoxy or together for a C₂-C₆- optionally interrupted by oxygen or sulfur Alkanediyl radical,
R⁹ represents hydrogen, Q, COQ or CO₂Q,
in which

• Q represents C₁-C₆ alkyl, phenyl or benzyl and

n stands for 0 or 1. 5. Compounds of formula (I) according to claim 1, in which
A and B for optionally single to triple, identical or different by fluorine, chlorine, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, cyclohexyl, trifluoromethyl , Methoxy, methylthio or phenyl substituted C₄-C₅-alkanediyl, in which a carbon atom through the group or is replaced by oxygen or by sulfur,
X represents methyl, ethyl, n-propyl, isopropyl, fluorine, chlorine, bromine, methoxy or ethoxy,
Y represents hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, fluorine, chlorine, bromine, methoxy, ethoxy or trifluoromethyl,
Z represents methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, tert-butyl, fluorine, chlorine, bromine, methoxy or ethoxy,
G for hydrogen (a) or for one of the groups stands in which

• E represents a metal ion equivalent or an ammonium ion,
  L represents oxygen or sulfur and
  M represents oxygen or sulfur,

R¹ for C₁-C₁₄-alkyl, C₂-C₁₄-alkenyl, C₁-C₄-alkoxy-C₁-C₆-alkyl, C₁-C₄-alkylthio-C₁-C₆-alkyl, poly- each optionally monosubstituted to trisubstituted by fluorine or chlorine, C₁-C₄-alkoxy-C₁- C₄-alkyl or optionally by fluorine, chlorine, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, methoxy, ethoxy, propoxy, i-propoxy, butoxy, i-butoxy, s-butoxy or t-butoxy substituted C₃-C₆-cycloalkyl, in which a methylene group is optionally replaced by oxygen or sulfur,
for phenyl which is optionally mono- or disubstituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, methylthio, ethylthio, methylsulfonyl, ethylsulfonyl or nitro,
for phenyl-C₁-C₃-alkyl which is optionally mono- or disubstituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy,
for thienyl, furanyl or pyridyl which are optionally mono- or disubstituted by fluorine, chlorine, bromine, methyl or ethyl,
for phenoxy-C₁-C₄-alkyl or optionally substituted once or twice by fluorine, chlorine, methyl or ethyl
represents in each case optionally mono- or disubstituted by fluorine, chlorine, amino, methyl or ethyl pyridyloxy-C₁-C₄-alkyl, pyrimidyloxy-C₁-C₄-alkyl or thiazolyloxy-C₁-C₄-alkyl,
R² for C₁-C₁₄-alkyl, C₂-C₁₄-alkenyl, C₁-C₄-alkoxy- C₂-C₆-alkyl or poly-C₁-C₄-alkoxy-C₂-C₆-alkyl, each optionally monosubstituted to trisubstituted by fluorine or chlorine,
for C₃-C₆-cycloalkyl which is optionally monosubstituted to trisubstituted by fluorine, chlorine, methyl, ethyl, propyl, isopropyl or methoxy,
or represents phenyl or benzyl which is optionally mono- or disubstituted by fluorine, chlorine, nitro, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy or trifluoromethyl,
R³ for methyl, ethyl, propyl, isopropyl which is optionally monosubstituted to trisubstituted by fluorine or chlorine or in each case optionally mono- or trisubstituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, tert-butyl, methoxy, ethoxy, Isopropoxy, tert-butoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro substituted phenyl or benzyl,
R⁴ and R⁵ independently of one another each optionally mono- to trisubstituted by fluorine or chlorine-substituted C₁-C₄-alkyl, C₁-C₄- alkoxy, C₁-C₄-alkylamino, di- (C₁-C₄) alkylamino, C₁-C₄-alkyl thio ,
for each optionally single or double by fluorine, chlorine, bromine, nitro, cyano, C₁-C₂-alkoxy, C₁-C₂-fluoroalkoxy, C₁-C₂- alkylthio, C₁-C₂-fluoroalkylthio, C₁-C₂-alkyl or C₁-C₂ Fluoroalkyl substituted phenyl, phenoxy or phenylthio,
R⁶ and R⁷ independently of one another for hydrogen,
for C₁-C₄-alkyl, C₃-C₆-cycloalkyl, C₁-C₄-alkoxy, C₃-C₄-alkenyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, each optionally monosubstituted to trisubstituted by fluorine or chlorine,
for phenyl or benzyl optionally substituted once or twice by fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-haloalkyl or C₁-C gegebenenfalls-alkoxy, or together for a C₂-C₆ optionally interrupted by oxygen or sulfur - Alkanediyl radical stand,
R⁹ represents hydrogen, Q, COQ or CO₂Q, where

• Q represents C₁-C₄ alkyl, phenyl or benzyl and

n stands for 0 or 1. 6. A process for the preparation of compounds of formula (I) according to claim 1, characterized in that

• (A) to obtain compounds of the formula (Ia) in which
  A, B, X, Y, Z and n have the meaning given in claim 1,
  Carboxylic acid esters of formula (II) in which
  A, B, X, Y, Z and n have the meaning given above, and
  R⁸ represents alkyl,
  intramolecularly condensed in the presence of a diluent and in the presence of a base;
  or
• (B) to obtain compounds of the formula (Ib) in which
  A, B, X, Y, Z, R¹ and n have the meaning given in claim 1,
  Compounds of the formula (Ia), in which
  A, B, X, Y, Z and n have the meaning given above,
  • α) with acid halides of the formula (III) in which
    R¹ has the meaning given above and
    Hal stands for halogen,
    if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder
    or
  • β) with carboxylic anhydrides of the formula (IV) R¹-CO-O-CO-R¹ (IV) in which
    R¹ has the meaning given above,
    if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
    implements;
    or
• (C) to obtain compounds of the formula (Ic-1) in which
  A, B, X, Y, Z, R² and n have the meaning given in claim 1,
  and
  M represents oxygen or sulfur,
  Compounds of formula (Ia) in which
  A, B, X, Y, Z and n have the meaning given above,
  with chloroformate or chloroformate thiol ester of the formula (V) R²-M-CO-Cl (V) in which
  R² and M have the meaning given above,
  optionally in the presence of a diluent and, if appropriate, in the presence of an acid binder;
  or
• (D) to obtain compounds of the formula (Ic-2) in which
  A, B, R², X, Y, Z and n have the meaning given in claim 1
  and
  M represents oxygen or sulfur,
  Compounds of formula (Ia) in which
  A, B, X, Y, Z and n have the meaning given above,
  • α) with chloromothio formic acid esters or chlorodithio formic acid esters of the formula (VI) in which
    M and R² have the meaning given above,
    if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
    or
  • β) with carbon disulfide and then with alkyl halides of the formula (VII) R²-Hal (VII) in which
    R² has the meaning given above
    and
    Hal represents chlorine, bromine or iodine,
    if appropriate in the presence of a diluent and if appropriate in the presence of a base;
    or
• (E) to obtain compounds of the formula (Id) in which
  A, B, X, Y, Z, R³ and n have the meaning given in claim 1,
  Compounds of formula (Ia) in which
  A, B, X, Y, Z and n have the meaning given above,
  with sulfonic acid chlorides of the formula (VIII) R³-SO₂-Cl (VIII) in which
  R³ has the meaning given above,
  optionally in the presence of a diluent and optionally in the presence of an acid binder,
  implements;
  or
• (F) to obtain compounds of the formula (Ie) in which
  A, B, L, X, Y, Z, R⁴, R⁵ and n have the meaning given in claim 1,
  Compounds of formula (Ia) in which
  A, B, X, Y, Z and n have the meaning given above,
  with phosphorus compounds of formula (IX) in which
  L, R⁴ and R⁵ have the meaning given above
  and
  Hal stands for halogen,
  optionally in the presence of a diluent and, if appropriate, in the presence of an acid binder;
  or
• (G) to obtain compounds of the formula (If) in which
  A, B, X, Y, Z and n have the meaning given above,
  and
  E represents a metal ion equivalent or an ammonium ion,
  Compounds of formula (Ia) in which
  A, B, X, Y, Z and n have the meaning given above,
  with metal compounds or amines of the formulas (X) or (XI) in which
  Me stands for mono- or divalent metal ions,
  t represents the number 1 or 2,
  R¹⁰, R¹¹ and R¹² independently represent hydrogen or alkyl and
  R¹³ represents hydrogen, hydroxy or C₁-C₄ alkoxy,
  if appropriate in the presence of a diluent;
  or
• (H) to obtain compounds of the formula (Ig) in which
  A, B, L, X, Y, Z, R⁶, R⁷ and n have the meaning given in claim 1,
  Compounds of formula (Ia) in which
  A, B, X, Y, Z and n have the meaning given above,
  • α) with compounds of the formula (XII) R⁶-N = C = L (XII) in which
    L and R⁶ have the meaning given above,
    optionally in the presence of a diluent and optionally in the presence of a catalyst
    or
  • β) with carbamic acid chlorides or thiocarbamic acid chlorides of the formula (XIII) in which
    L, R⁶ and R⁷ have the meaning given above,
    if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
• implements.

7. Compounds of the formula (II) in which
A, B, X, Y, Z and n have the meaning given in claim 1 and
R⁸ represents alkyl. 8. A process for the preparation of compounds of formula (II) according to claim 4, characterized in that
2-hydroxycarboxylic acid derivatives of the formula (XIV), in which
R⁸ 'represents hydrogen or alkyl and
A and B have the meaning given in claim 1,
with phenylacetic acid halides of the formula (XV) in which
X, Y, Z and n have the meaning given in claim 1 and
Hal represents chlorine or bromine,
acylated (Chem. Reviews 52, 237-416 (1953)); and optionally the compounds of the formula (IIa) formed for R⁸ ′ = hydrogen in which
A, B, X, Y, Z and n have the meaning given above,
esterified. 9. pesticide, characterized by a content of min at least one compound of formula (I) according to claim 1. 10. Use of compounds of formula (I) according to claim 1 for Pest control. 11. A method for controlling pests, characterized in that compounds of formula (I) according to claim 1 on pests and / or let their living space take effect. 12. Process for the preparation of pesticides, thereby characterized in that compounds of the formula (I) according to Claim 1 mixed with extenders and / or surfactants.