DE19515690A1 - New tetronic and tetramic acid derivs. useful as pesticides - Google Patents

Abstract

Tetronic and tetramic acid derivs. of formula (I) are new: A = H or alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl, alkylthioalkyl, cycloalkyl or heterocycloalkyl (opt. substd. by halo) or aryl, aralkyl or heteroaryl (opt. substd. by halo, alkyl, haloalkyl, alkoxy or NO2); B = H, alkyl or alkoxyalkyl; or A+B = opt. substd. cycloalkyl or heterocycloalkyl; D = O or NZ; Z = H or alkyl or alkoxyalkyl (opt. substd. by halo) or opt. substd. cycloalkyl, phenyl or aralkyl; or A+Z = opt. substd. 5- or 6-membered ring opt. contg. an S atom; G = H, COR<1>, C(L)MR<2>, SO2R<3>, P(L)R<4>R<5>, E, C(L)NR<6>R<7> or X; E = metal or NH4; L, M = O or S; R = opt. substd. cycloalken-1-yl; R<1> = alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl, cycloalkyl or heterocycloalkyl (opt. substd. by halo) or opt. substd. phenyl, phenylalkyl, heteroaryl, phenoxyalkyl or heteroaryloxyalkyl; R<2> = alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl (opt. substd. by halo) or opt. substd. cycloalkyl, phenyl or benzyl; R<3>-R<5> = alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio or cycloalkylthio (opt. substd. by halo) or opt. substd. phenyl, phenoxy or phenylthio; R<6>, R<7> = H; alkyl, cycloalkyl, alkenyl, alkoxy or alkoxyalkyl (opt. substd. by halo) or opt. substd. phenyl or benzyl; or NR<6>R<7> = a ring opt. contg. an O or S atom; X = alkyl, alkenyl, alkynyl or alkoxyalkyl opt. substd. by halogen; or opt. substd. aralkyl.

Description

The invention relates to new tetronic and tetramic acid derivatives, several processes for their production and their use as pesticides, especially as insecticides and acaricides.

3-alkenyl-4-hydroxy-2 (5H) furanones have already been described in the literature and some have pharmaceutical properties (see Tetrahedron Letters 32, 1749-1752 (1991); Liebigs Ann. Chem. 667, 24-35 (1963) and Tetrahedron 44, 7205-12 (1988)).

3- (2-Cycloalken-1-yl) -4-hydroxy-2 (5H) furanones have also already been described (see Tetrahedron 44 7205-12 (1988) and Tetrahedron Letters 29, 581-584 (1988)). Insecticidal or acaricidal effects of these compounds are still not known.

New tetronic and tetramic acid derivatives of the formula (I)

found,
in which
A for hydrogen, for in each case optionally substituted by halogen, alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl, alkylthioalkyl or cycloalkyl, in which one or more methylene groups are optionally replaced by the same number of heteroatoms or for each optionally by halogen, alkyl, haloalkyl, alkoxy or nitro-substituted aryl, arylalkyl or hetaryl,
B represents hydrogen, alkyl or alkoxyalkyl, or
A and B together with the carbon atom to which they are attached represent saturated or unsaturated and optionally substituted cycloalkyl, in which one or more methylene groups may have been replaced by the same number of heteroatoms,
D represents oxygen or the NZ group,
Z stands for hydrogen, for alkyl or alkoxyalkyl optionally substituted by halogen, for optionally substituted cycloalkyl or for optionally substituted phenyl or arylalkyl, or
A and Z together with the atoms to which they are attached represent an optionally substituted 5- or 6-membered ring which may also contain a sulfur atom,
R represents optionally substituted cycloalken-1-yl,
G for hydrogen (a) or for one of the groups

stands, where
E represents a metal ion equivalent or an ammonium ion,
L represents oxygen or sulfur,
M represents oxygen or sulfur,
R¹ is in each case optionally substituted by halogen, alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl or cycloalkyl, in which one or more methylene groups are optionally replaced by the same number of heteroatoms or represents optionally substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryl oxyalkyl ,
R² stands for alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl, optionally substituted by halogen, or for cycloalkyl, 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 or cycloalkylthio or represent optionally substituted phenyl, phenoxy or phenylthio,
R⁶ and R⁷ independently of one another represent hydrogen, each represent optionally substituted by halogen alkyl, cycloalkyl, alkenyl, alkoxy or alkoxyalkyl, represent optionally substituted phenyl or benzyl, or together with the N atom to which they are attached form a ring , which optionally contains a second heteroatom from the series of oxygen and sulfur, and
X represents in each case optionally substituted by halogen alkyl, alkenyl, alkynyl or alkoxyalkyl or for optionally substituted aralkyl.

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

where A, B, D, E, L, M, X, R, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ the above have the meanings given.

Due to one or more centers of chirality, the connections of the Formula (Ia) - (Ih) generally as mixtures of stereoisomers which if necessary, can be separated in the usual way. You can both in the form of their diastereomer mixtures and as pure diastereomers or enantiomers can be used. The following is for the sake of simplicity always spoken of compounds of formula (Ia) to (Ih), although both the pure compounds, as well as the mixtures with different proportions isomeric, enantiomeric and stereomeric compounds are meant.

Furthermore, it was found that the new tetronic and tetramic acid derivatives of formula (I) is obtained by one of the processes described below:

• (A) Tetronic and tetramic acid derivatives of the formula (Ia) are obtained. in which
  A, B, D and R have the meaning given above,
  if
  Tetronic and tetramic acids of formula (II) in which
  A, B and D have the meaning given above,
  with cycloalkanones of the formula (XV) O = R¹ (XV) in which
  R ′ represents optionally substituted cycloalkyl,
  in the presence of a diluent and in the presence of a catalyst;
  and
• (B) compounds of the formula (Ib) are obtained in which
  A, B, D, R and R¹ have the meaning given above,
  if compounds of the formula (Ia) in which
  A, B, D and R 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 or bromine),
    optionally 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, if appropriate, in the presence of an acid binder;
    and
• (C) compounds of the formula (Ic-a) are obtained in which
  A, B, D, R and R² have the meaning given above,
  and
  M represents oxygen or sulfur,
  if compounds of the formula (Ia) in which
  A, B, D and R 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-b) are obtained in which
  A, B, D, R and R² have the meaning given above,
  and
  M represents oxygen or sulfur,
  if compounds of the formula (Ia) in which
  A, B, D and R 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
    implements;
    and
• (E) compounds of the formula (Id) are obtained in which
  A, B, D, R and R³ have the meaning given above,
  if compounds of the formula (Ia) in which
  A, B, D and R 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;
  and
• (F) compounds of the formula (Ie) are obtained in which
  A, B, L, D, R, R⁴ and R⁵ have the meaning given above,
  if compounds of the formula (Ia) in which
  A, B, D and R 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 or bromine),
  optionally in the presence of a diluent and optionally in the presence of a base
  implements;
  or
• (G) compounds of the formula (If) are obtained in which
  A, B, D and R 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, D and R have the meaning given above,
  with metal hydroxides or amines of the formulas (X) or (XI) in which
  Me for mono- or divalent metal ions (especially alkali or alkaline earth metal ions such as lithium, sodium, potassium, magnesium or calcium),
  t for the number 1 or 2 and
  R¹⁰, R¹¹ and R¹² are the same or different and are hydrogen or alkyl (preferably C₁-C₆-alkyl),
  if appropriate in the presence of a diluent;
  and
• (H) compounds of the formula (Ig) are obtained in which
  A, B, L, D, R, R⁶ and R⁷ have the meaning given above,
  if compounds of the formula (Ia) in which
  A, B, D and R have the meaning given above,
  • α) with isocyanates or isothiocyanates of the formula (XII) R⁶-N = C = L (XII) in which
    L and R⁶ have the meaning given above,
    if appropriate in the presence of a diluent and, if appropriate, 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, if appropriate, in the presence of an acid binder;
    and
• (I) compounds of the formula (Ih) are obtained in which
  A, B, D, R and X have the meaning given above,
  if compounds of the formula (Ia) in which
  A, B, D and R have the meaning given above,
  with alkylating agents of the formula (XIV) XQ (XIV) in which
  X has the meaning given above and
  Q for an anionic leaving group, e.g. B. for halogen (preferably chlorine, bromine or iodine), -OSO₂-alkyl (preferably C₁-C₆-alkyl),
  -OSO₂O-alkyl (preferably C₁-C₆-alkyl) or -OSO₂-aryl (preferably phenyl or toluyl),
  if appropriate in the presence of a diluent and if appropriate in the presence of a base.

Furthermore, it was found that the new tetronic and tetramic acid derivatives of formula (I) are characterized by good insecticidal and acaricidal effects.

The compounds of the invention are general by the formula (I) Are defined. Preferred substituents or ranges in the above and after The radicals mentioned above formulas are explained below.

A preferably represents hydrogen or optionally halogen sub substituted C₁-C₁₂-alkyl, C₃-C₈-alkenyl, C₁-C₁₀-alkoxy-C₁-C₈-alkyl, poly- C₁-C₈-alkoxy-C₁-C₈-alkyl, C₁-C₁₀-alkylthio-C₁-C₆-alkyl or C₃-C₈- Cycloalkyl, in which one or two may not be directly neighboring methylene groups by the same number of heteroatoms the series oxygen and sulfur are replaced, or for each optionally by halogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆- Alkoxy or nitro substituted phenyl pyridyl, imidazolyl, pyrazolyl, Triazolyl, indolyl, thiazolyl or phenyl-C₁-C₆-alkyl.

B preferably represents hydrogen, C₁-C₁₂-alkyl or C₁-C₈-alkoxyalkyl or
A, B and the carbon atom to which they are attached are preferably saturated or unsaturated C₃-C₁₀ cycloalkyl, which is optionally substituted by C₁-C₈-alkyl, C₃-C₈-cycloalkyl, C₁-C₆-haloalkyl, C₁-C₈- Alkoxy, C₁-C₈-alkylthio, halogen or phenyl is substituted and in which a methylene group is optionally replaced by oxygen or sulfur or
A, B and the carbon atom to which they are attached are preferably C₃-C₆-cycloalkyl, which may be interrupted by an alkylene diyl or by an alkylenedioxyl or by an alkylenedithioyl group, optionally interrupted by one or two oxygen and / or sulfur atoms is substituted, which forms a further five- to eight-membered ring with the carbon atom to which it is attached or
A, B and the carbon atom to which they are attached are preferably C₃-C₈-cycloalkyl, in which two substituents together give a saturated or unsaturated five-, optionally substituted by C₁-C₈-alkyl, C₁-C₈-alkoxy or halogen to form a seven-membered ring which can contain a heteroatom from the series oxygen and sulfur.

A particularly preferably represents hydrogen, optionally by halogen substituted C₁-C₁₀-alkyl, C₃-C₆-alkenyl, C₁-C₈-alkoxy-C₁-C₆-alkyl, Poly-C₁-C₆-alkoxy-C₁-C₆-alkyl, C₁-C₈-alkylthio-C₁-C₆-alkyl or C₃-C₇- Cycloalkyl, in which optionally a methylene group by acid Substance or sulfur is replaced or for each if necessary by Halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or nitro sub substituted phenyl, pyridyl, imidazolyl, pyrazolyl, triazolyl, indolyl, Thiazolyl or phenyl-C₁-C₄-alkyl.

B particularly preferably represents hydrogen, C₁-C₁₀-alkyl or C₁-C₆-alkoxyalkyl or
A, B and the carbon atom to which they are attached are particularly preferably saturated or unsaturated, C₃-C₉-cycloalkyl, which is optionally by C₁-C₆-alkyl, C₃-C₈-cycloalkyl, C₁-C₃-haloalkyl, C₁ -C₆-alkoxy, C₁-C₆-alkylthio, fluorine, chlorine or phenyl and in which a methylene group is optionally replaced by oxygen or sulfur or
A, B and the carbon atom to which they are attached are particularly preferably C₃-C₆-cycloalkyl, which is substituted by an alkylene diyl group which may be interrupted by one or two oxygen or sulfur atoms or by an alkylene dioxyl or by an alkylene dithiol group which forms a further five- to seven-membered ring with the carbon atom to which it is attached or
A, B and the carbon atom to which they are attached are particularly preferably C₃-C₆-cycloalkyl, in which two substituents together a saturated, optionally substituted by C₁-C₃-alkyl, C₁-C₃-alkoxy or fluorine, chlorine or bromine or form an unsaturated five- or six-membered ring which can contain a heteroatom from the series oxygen or sulfur.

A very particularly preferably represents hydrogen, in each case optionally C₁-C₈-alkyl, C₃-C₄-alkenyl substituted by fluorine, chlorine or bromine, C₁-C₆-alkoxy-C₁-C₄-alkyl, poly-C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₆-alkyl thio-C₁-C₄-alkyl or C₃-C₆-cycloalkyl, in which optionally one Methylene group is replaced by oxygen or, if appropriate, for each by fluorine, chlorine, bromine, methyl, ethyl, n-propyl, iso-propyl, methoxy, Ethoxy, trifluoromethyl or nitro substituted phenyl, pyridyl or Benzyl.

B very particularly preferably represents hydrogen, C₁-C₈-alkyl or C₁-C₄-alkoxyalkyl or
A, B and the carbon atom to which they are attached are very particularly preferably saturated or monounsaturated C₃-C₈-cycloalkyl, which may be methyl, ethyl, n-propyl, isopropyl, butyl, butyl, so-butyl, sec-butyl , tert-butyl, trifluoromethyl, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, methylthio, ethylthio, fluorine, chlorine or phenyl.

D preferably represents oxygen or the group NZ,
D particularly preferably represents oxygen or the group NZ,
D very particularly preferably represents oxygen or the group NZ,
Z preferably represents hydrogen, each optionally substituted by halogen substituted C₁-C₁₀-alkyl or C₁-C₈-alkoxy-C₂-C₆-alkyl, optionally substituted by halogen or C₁-C₆-alkyl substituted C₃-C₆-cycloalkyl or for each phenyl or phenyl-C₁-C₃-alkyl optionally substituted by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy or C₁-C₄-haloalkyl.

Z particularly preferably represents hydrogen, in each case optionally by Fluorine or chlorine substituted C₁-C₈-alkyl or C₁-C₆-alkoxy-C₁-C₅- alkyl, optionally substituted by fluorine, chlorine or C₁-C₄-alkyl C₃-C₆-cycloalkyl or for optionally by fluorine, chlorine, bromine, C₁- C₄-alkyl, C₁-C₄-alkoxy or C₁-C₂-haloalkyl substituted benzyl.

Z very particularly preferably represents hydrogen, each optionally mono- to trisubstituted, identical or different, C₁-C₁-alkyl or C₁-C₄-alkoxy-C₁-C₄-alkyl substituted by fluorine and / or chlorine, or optionally by fluorine, Chlorine, bromine, methyl, tert-butyl, methoxy or trifluoromethyl substituted benzyl, or
A and Z preferably together represent an optionally substituted by C₁-C₄-alkyl C₃-C₄-alkanediyl, in which a methylene group is optionally replaced by sulfur, or
A and Z are particularly preferably C₃-C₄-alkanediyl optionally substituted by methyl, or
A and Z very particularly preferably represent C₃-C₄-alkanediyl.

R preferably represents C einfach-C₁₂-cycloalken-1-yl which is optionally mono- or polysubstituted by identical or different substituents, the following being mentioned as substituents:
Halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₁-C₆-halogeno alkyl, C₁-C₆-haloalkoxy, C₁-C₆-haloalkylthio, nitro and cyano.

R particularly preferably represents C₅-C₇-cycloalken-1-yl which is optionally mono- to pentasubstituted by identical or different substituents, the following being mentioned as substituents:
Halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, C₁-C₄-haloalkylthio, nitro and cyano.

R very particularly preferably represents C₅-C₇-cycloalken-1-yl which may be monosubstituted to trisubstituted by identical or different substituents, the following being mentioned as substituents:
Fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy and trifluoromethylthio
G preferably represents hydrogen (a) or one of the groups

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

R¹ preferably represents in each case optionally substituted by halogen C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₁-C₈-alkoxy-C₁-C₈-alkyl, C₁-C₈-alkylthio-C₁-C₈-alkyl, poly-C₁-C₈ -alkoxy-C₁-C₈-alkyl or C₃-C₈-cycloalkyl, in which optionally one or two not directly adjacent methylene groups are replaced by the same number of heteroatoms from the series oxygen and sulfur,
for phenyl optionally substituted by halogen, nitro, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl, C₁-C₆-haloalkoxy, C₁-C₆-alkylthio or C₁-C₆-alkyl sulfonyl,
for phenyl-C₁-C₆-alkyl optionally substituted by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl or C₁-C₆-haloalkoxy, for furanyl optionally substituted by halogen or C₁-C₆-alkyl , Thienyl, pyridyl, pyrimidyl, thiazolyl or pyrazolyl,
for optionally substituted by halogen or C₁-C₆-alkyl phenoxy-C₁-C₆-alkyl or
for each optionally substituted by halogen, amino or C₁-C₆-alkyl substituted pyridyloxy-C₁-C₆-alkyl, pyrimidyloxy-C₁-C₆-alkyl or thiazolyloxy-C₁-C₆-alkyl.

R² preferably represents in each case optionally substituted by halogen C₁-C₂₀-alkyl, C₃-C₂₀-alkenyl, C₁-C₈-alkoxy-C₁-C₈-alkyl or poly-C₁-C₈-alkoxy-C₁-C₈-alkyl,
for C₃-C₈-cycloalkyl optionally substituted by halogen, C₁-C₄-alkyl or C₁-C₄-alkoxy, or
for phenyl or benzyl optionally substituted by halogen, nitro, C₁-C₆-alkyl, C₁-C₆-alkoxy or C₁-C₆-haloalkyl.

R³, R⁴ and R⁵ independently of one another are preferably given C₁-C₈-alkyl, C₁-C₈-alkoxy, C₁-C₈- optionally substituted by halogen Alkylamino, di (C₁-C₈) alkylamino, C₁-C₈-alkylthio, C₂-C Al-alkenylthio or C₃-C₇-cycloalkylthio or for each optionally by halogen, Nitro, cyano, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁- C₄-Haloalkylthio, C₁-C₄-alkyl or C₁-C₄-haloalkyl substituted Phenyl, phenoxy or phenylthio.

R⁶ and R⁷ independently of one another preferably represent hydrogen, for each optionally substituted by halogen C₁-C₈-alkyl, C₃-C₈- Cycloalkyl, C₁-C₈-alkoxy, C₃-C₈-alkenyl, C₁-C₈-alkoxy-C₁-C₈-alkyl, for each optionally by halogen, C₁-C₈-alkyl, C₁-C₈-haloalkyl or C₁-C₈ alkoxy substituted phenyl or benzyl or together for C₃-C₆-alkanediyl, in which optionally a methylene group Oxygen or sulfur is replaced.  

X preferably represents C₁-C₁₂-alkyl, C₂-C₆-haloalkyl, C₃-C₈-alkenyl, C₃- C₈-alkynyl, C₃-C₈-haloalkenyl, C₃-C₈-haloalkynyl, C₁-C₆-alkoxy- C₁-C₆- alkyl, C₁-C₆-haloalkoxy-C₁-C₆-alkyl or for phenyl-C₁-C substitu substituted by halogen, nitro, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl or C₁-C₆-haloalkoxy -alkyl,
G particularly preferably represents hydrogen (a) or one of the groups

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

R¹ particularly preferably represents in each case optionally substituted by fluorine, chlorine or bromine C₁-C₁₆-alkyl, C₂-C₁₆-alkenyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₁-C₆-alkylthio-C₁-C₆-alkyl or C₃-C₇-cycloalkyl, in which a methylene group is optionally replaced by oxygen or sulfur,
for phenyl optionally substituted by halogen, nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₃-haloalkyl, C₁-C₃-haloalkoxy, C₁-C₄-alkylthio or C₁-C₄-alkyl sulfonyl,
for phenyl-C₁-C₄-alkyl optionally substituted by halogen, C₁-C₄-alkyl, C₁-C--alkoxy, C₁-C₃-haloalkyl or C₁-C₃-haloalkoxy, or
for optionally substituted by fluorine, chlorine, bromine or C₁-C₄-alkyl phenoxy-C₁-C₅-alkyl.

R² particularly preferably represents C₁-C₁₆-alkyl, C₃-C₁₆-alkenyl, C₁-C₆-alkoxy-C₁-C₆-alkyl or poly-C₁-C₆-alkoxy-C₁-C₆- each optionally substituted by fluorine, chlorine or bromine alkyl,
for C₃-C₇-cycloalkyl optionally substituted by halogen, C₁-C₃-alkyl or C₁-C₃-alkoxy, or
for phenyl or benzyl optionally substituted by halogen, nitro, C₁-C₄-alkyl, C₁-C₃- alkoxy or C₁-C₃-haloalkyl.

R 3, R⁴ and R⁵ independently of one another are particularly preferably each C₁-C₆-alkyl optionally substituted by fluorine, chlorine or bromine, C₁-C₆-alkoxy, C₁-C₆-alkylamino, di- (C₁-C₆) -alkylamino, C₁-C₆-alkylthio, C₃-C₄-alkenylthio or C₃-C₆-cycloalkylthio or for each given if by fluorine, chlorine, bromine, nitro, cyano, C₁-C₃-alkoxy, C₁-C₃- Halogenalkoxy, C₁-C₃-alkylthio, C₁-C₃-haloalkylthio, C₁-C₃-alkyl or C₁-C₃-haloalkyl substituted phenyl, phenoxy or phenylthio.

R⁶ and R⁷ independently of one another particularly preferably represent hydrogen, for each C₁- optionally substituted by fluorine, chlorine or bromine C₆-alkyl, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, C₃-C₆-alkenyl or C₁-C₆- Alkoxy-C₁-C₆-alkyl, each optionally by halogen, C₁- C₅-alkyl, C₁-C₅-haloalkyl or C₁-C₅-alkoxy substituted phenyl or benzyl, or together for C₃-C₆ alkanediyl, in which given if a methylene group is replaced by oxygen or sulfur.

X particularly preferably represents C₁-C₈-alkyl, C₂-C₄-haloalkyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl, C₃-C₆-haloalkenyl, C₃-C₆-haloalkynyl, C₁-C₄-alkoxy-C₁-C₄ -alkyl, C₁-C₄-haloalkoxy-C₁-C₄-alkyl or, if appropriate, by fluorine, chlorine, bromine, nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁- C₄-haloalkyl or C₁-C₄-haloalkoxy substituted phenyl-C₁-C₄ alkyl,
G very particularly preferably represents hydrogen (a) or one of the groups

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

R¹ very particularly preferably represents C₁-C₁₄-alkyl, C₂-C₁₄-alkenyl, C₁-C₄-alkoxy-C₁-C₆-alkyl, C₁-C₄-alkylthio-C₁-C₆-alkyl or C₃, each optionally substituted by fluorine or chlorine -C₆ cycloalkyl,
for phenyl optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, methylthio, ethylthio, methylsulfonyl, ethylsulfonyl or nitro,
for optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy-substituted phenyl-C₁-C₃-alkyl, or
for optionally substituted by fluorine, chlorine, methyl or ethyl phenoxy-C₁-C₄-alkyl.

R² very particularly preferably represents C₁-C₁₄-alkyl, C₃-C₁₄-alkenyl, C₁-C₄-alkoxy-C₁-C₆-alkyl or poly-C₁-C₄-alkoxy-C₁-C₆-alkyl, each optionally substituted by fluorine or chlorine ,
for C₃-C₆-cycloalkyl optionally substituted by fluorine, chlorine, methyl, ethyl, propyl, isopropyl or methoxy,
or for phenyl or benzyl optionally substituted by fluorine, chlorine, nitro, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy or trifluoromethyl.

R³, R⁴ and R⁵ independently of one another very particularly preferably represent each C₁-C₄-alkyl optionally substituted by fluorine or chlorine, C₁-C₄ alkoxy, C₁-C₄ alkylamino, di- (C₁-C-) alkylamino or C₁-C₄- Alkylthio or for each optionally by fluorine, chlorine, bromine, nitro, Cyano, C₁-C₂-alkoxy, C₁-C₃-fluoroalkoxy, C₁-C₂-alkylthio, C₁-C₂-fluorine alkylthio or C₁-C₃-alkyl substituted phenyl, phenoxy or phenylthio.

R⁶ and R⁷ independently of one another very particularly preferably represent water substance, for each optionally by fluorine, chlorine or bromine substituted C₁-C₄-alkyl, C₃-C₆-cycloalkyl, C₁-C₄-alkoxy, C₃-C₄- Alkenyl or C₁-C₄-alkoxy-C₁-C₄-alkyl, each optionally by Fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-haloalkyl or C₁-C₄-alkoxy substituted phenyl or benzyl, or together for C₄-C₆-alkanediyl, in which is optionally a methylene group by oxygen or Sulfur is replaced.

X very particularly preferably represents C₁-C₆-alkyl, C₂-C₃-haloalkyl, C₃- C₄-alkenyl, C₃-C₄-alkynyl, C₃-C₄-haloalkenyl, C₃-C₄-haloalkynyl, C₁-C₃-alkoxy-C₁-C₃-alkyl or C₁-C₃-haloalkoxy-C₁-C₃-alkyl or for optionally substituted phenyl-C₁-C₂-alkyl, the phenyl ring being a can be substituted by three to three, the same or different Fluorine, chlorine, nitro, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy, Trifluoromethyl or trifluoromethoxy.

Compounds of the formula (I) in which
A for hydrogen, for each optionally substituted by fluorine or chlorine C₁-C₈-alkyl, C₃-C₄-alkenyl, C₁-C₆-alkoxy-C₁-C₄-alkyl or C₃-C₆-cycloalkyl, or for each optionally by fluorine, chlorine , Bromine, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, trifluoromethyl or nitro substituted phenyl or benzyl,
B represents hydrogen, C₁-C₈-alkyl or C₁-C₄-alkoxyalkyl or
A, B and the carbon atom to which they are attached represent saturated or monounsaturated C₃-C₈-cycloalkyl, which is optionally substituted by methyl, ethyl, n-propyl, isopropyl, butyl, iso-butyl, sec-butyl, tert- Butyl, trifluoromethyl, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, methylthio, ethylthio, fluorine, chlorine or phenyl,
D represents oxygen or the NZ group,
R represents optionally mono- to triple, identical or differently substituted C₅-C gegebenenfalls-cycloalken-1-yl, where the following may be mentioned as substituents: fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i -, s- or t-butyl or methoxy,
G for hydrogen (a) or for one of the groups

stands,
in which
E stands for a metal ion equivalent or for an ammonium ion and
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 or C₃-C₆-cycloalkyl, each optionally substituted by fluorine or chlorine or
represents phenyl optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, methylthio, ethylthio, methylsulfonyl, ethylsulfonyl or nitro,
R² for C₁-C₁₄-alkyl, C₃-C₁₄-alkenyl or C₁-C₄-alkoxy-C₁-C₆-alkyl, each optionally substituted by fluorine or chlorine,
for C₃-C₆-cycloalkyl optionally substituted by fluorine, chlorine, methyl, ethyl, propyl, isopropyl or methoxy,
or represents phenyl or benzyl optionally substituted by fluorine, chlorine, nitro, methyl, ethyl, propyl, i-propyl, methoxy, ethoxy or trifluoromethyl,
R³, R⁴ and R⁵ independently of one another each optionally substituted by fluorine or chlorine substituted C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylamino, di- (C₁-C₄) alkylamino or C₁-C₄-alkylthio or for each optionally substituted by fluorine, chlorine, bromine, nitro, cyano, C₁-C₂-alkoxy, C₁-C₃-fluoro alkoxy, C₁-C₂-alkylthio, C₁-C₂-fluoroalkylthio or C₁-C₃-alkyl phenyl, phenoxy or Phenylthio,
R⁶ and R⁷ independently of one another for hydrogen, for in each case optionally substituted by fluorine or chlorine C₁-C₄-alkyl, C₃-C₆-cycloalkyl, C₁- C₄-alkoxy, C₃-C₄-alkenyl or C₁-C₄-alkoxy-C₁-C₄- alkyl, for each optionally substituted by fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-haloalkyl or C₁-C₄-alkoxy-substituted phenyl or benzyl, or together represent C₄-C₆-alkanediyl, in which a methylene group is optionally by Oxygen or sulfur is used and
X for C₁-C₆-alkyl, C₂-C₃-haloalkyl, C₃-C₄-alkenyl, C₃-C₄-alkynyl, C₃-C₄-haloalkenyl, C₃-C₄-haloalkynyl, C₁-C₃-alkoxy-C₁-C₃-alkyl or C₁-C₃-haloalkoxy-C₁-C₃-alkyl or optionally substituted benzyl, where the phenyl ring can be monosubstituted to trisubstituted, identically or differently, by fluorine, chlorine, nitro, methyl, ethyl, propyl, i-propyl, methoxy, Ethoxy, trifluoromethyl or trifluoromethoxy.

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 those listed as preferred (preferred) above Meanings exist.

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.

According to the invention, the compounds of Formula (I) in which a combination of these above is very special meanings listed preferably is present.

The compounds of the formulas according to the invention are of particular interest (Ia), (Ib), (Ic), (Ig) and (Ih).

According to process (A), 5,5-dimethyl-4-hydroxy-dihydrofuran-2-one is used and 2-methylcyclohexanone as starting materials, so the course of the Invention according to the process can be represented by the following reaction scheme:

If 3- (2-methyl-cyclohexen-1-yl) -5,5- is used according to process (Bα) dimethyl-pyrrolidine-2,4-dione and pivaloyl chloride as starting materials, so the Course of the process according to the invention by the following reaction scheme are reproduced:

Is used according to method (Bβ 3-cyclohexen-1-yl-5-isopropyl-5-methyl pyrrolidine-2,4-dione and acetic anhydride as starting compounds, so the Course of the process according to the invention by the following reaction scheme are reproduced:

According to method (C), 3- (2-methyl-cyclohexen-1-yl) -5,5-diethyl is used pyrrolidine-2,4-dione 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:

According to method (Dα), 3-cyclohexen-1-yl-5,5-pentamethylene is used pyrrolidin-2,4-dione 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-methyl-cyclohexen-1-yl) -5,5-ethyl mercaptoethyl-pyrrolidine-2,4-dione, carbon disulphide and methyl iodide as the end products, the course of the reaction can be represented as follows:

If 3- (2-methyl-cyclohexen-1-yl) -5,5- (2- methyl) -pentamethylene-pyrrolidine-2,4-dione and methanesulfonic acid chloride as the out products, the course of the reaction can be represented as follows:

According to process (F), 3- (2-methyl-cyclohexen-1-yl) -5-isobutyl-5-methyl-pyrrolidin-2,4-dione and methanethio-phosphonic acid chloride (2,2,2-trifluoro - ethyl ester) as starting products, the course of the invention Process can be represented by the following reaction scheme:

If, according to process (G), 3- (2-methyl-cyclohexen-1-yl) -5-cyclopropyl- 5-methyl-pyrrolidine-2,4-dione and NaOH as starting products, so the Course of the process according to the invention by the following reaction scheme are reproduced:

If 3- (2-methyl-cyclohexen-1-yl) -5,5-hexamethylene-pyrrolidin-2,4-dione and ethyl isocyanate are used as starting products according to process (Hα), the The course of the reaction can be represented by the following scheme:

If, according to process (Hβ), 3- (2-methyl-cyclohexen-1-yl) -5-methyl-pyrrolidin-2,4-dione and dimethyl carbamic acid chloride are used as starting products, then the course of the reaction can be represented by the following scheme:

According to method (I), 5,5-dimethyl-4-hydroxy-3- (2,4,6-trimethyl) is used cyclohexen-1-yl) dihydrofuran-2-one and toluenesulfonic acid methyl ester as Aus materials, so the course of the method according to the invention can the following reaction scheme can be reproduced:

Those required as starting materials in process (A) according to the invention Tetronic and tetramic acids of the formula (H) are known (cf., for example, J. Chem. Soc. Chem. Commun. 1973, 328; Tetrahedron Letters 1979, 4517; Heterocycles 1986, 25, 1429 or J. Org. Chem. 1984, 49, 927) or in a generally known manner and Available in this way (see e.g. the above-mentioned references).

The also as starting materials in process (A) according to the invention required cycloalkanones of the formula (XV) are generally known compounds of organic chemistry.

The processes (B), (C), (D), (E), (F), (G), (H) and (I) also require acid halides as starting materials Formula (III), carboxylic anhydrides of the formula (IV), chloroformate or Chloroformic 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 hydroxides or amines of the formula (X) and (XI) and isocyanates or Carbamic acid chloride of the formula (XIII) and alkylating agent of the formula (XIV) are generally known compounds of organic or inorganic Chemistry.

All of them can be used as diluents in process (A) according to the invention organic solvents which are inert to the reactants will. Aromatic hydrocarbons, such as Toluene and xylene; halogenated hydrocarbons such as chloroform and Methylene chloride; and ethers such as dibutyl ether, tetrahydrofuran or dioxane.

As catalysts in the implementation of the invention Process (A) amines, preferably secondary amines and their salts as in for example piperidine, piperidinium acetate or chloride, and also pyridine, pyridinium chloride as well as ammonium acetate, sodium acetate and ethylenediammonium diacetate used.

The reaction temperature can be carried out when the invention is carried out Process (A) can be varied within a wide range. In general one works at temperatures between 0 ° C and 150 ° C, preferably between 50 ° C and 120 ° C.

The process (A) according to the invention is carried out preferably in equimolar amounts or with a small excess Cycloalkanone of formula (XV). Per mol of the compound of formula (II) is used generally between 0.2 and 0.001 mol of catalyst.

The process (Bα) is characterized in that compounds of Formula (Ia) with carboxylic acid halides of the formula (III) optionally in counter were a diluent and possibly in the presence of an acid binder implemented by means.

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 Formula (Ia) with carboxylic anhydrides of the formula (IV) optionally in counter waited for a diluent and, if necessary, an acid binder puts.

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) if appropriate in the presence of a diluent and if appropriate in In the presence of an acid binder.

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.

The process (Dα) is characterized in that compounds of Formula (Ia) with compounds of formula (VI) optionally in the presence of a Diluent and optionally in the presence of an acid binder puts.

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, amides, alcohols, sulfones, Sulfoxides and halogenated hydrocarbons.

Dimethyl sulfoxide, tetrahydrofuran, dimethylformamide or Methylene chloride 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.

The process (Dβ) is characterized in that compounds of Formula (Ia) with carbon disulfide and then with alkyl halides Formula (VII) optionally in the presence of a diluent and if appropriate in the presence of a base.

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.

Process (E) is characterized in that compounds of the formula (Ia) with sulfonic acid chlorides of the formula (VIII), if appropriate in the presence of a Diluent and optionally in the presence of an acid binder puts.

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, amides, nitriles, alcohols, sulfones, Sulfoxides or halogenated hydrocarbons such as methylene chloride.

Dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, di methyl 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 and 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.

Process (F) is characterized in that compounds of the formula (Ia) with phosphorus compounds of formula (IX) optionally in the presence of a Diluent and optionally in the presence of a base.

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 and 110 ° C.

Any inert, polar diluents that may be added organic solvents in question such as (halogen) hydrocarbons, ethers, Amides, nitriles, alcohols, sulfides, sulfones, sulfoxides etc.

Acetonitrile, dimethyl sulfoxide, tetrahydrofuran, dimethyl are preferred formamide or methylene chloride used.

Conventional inorganic or organic bases in question such as hydroxides, carbonates. Sodium is an example 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 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 (M) if appropriate in the presence of a diluent.

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.

The process (Hα) is characterized in that compounds of Formula (Ia) with compounds of formula (XII) optionally in the presence of a Diluent and optionally in the presence of a catalyst.

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

All inert organic come as optionally added diluents Solvents in question, such as ethers, 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.

The process (Hβ) is characterized in that compounds of Formula (Ia) with compounds of the formula (XIII), if appropriate in the presence a diluent and optionally in the presence of an acid binder implemented by means.

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 to 150 ° C, preferably at 20 to 70 ° C.  

All inert polar or come as optionally added diluents ganic solvents in question such as ethers, amides, alcohols, sulfones or Sulfoxides or halogenated hydrocarbons.

Dimethyl sulfoxide, tetrahydrofuran, dimethylformamide or Methylene chloride used.

Is made in a preferred embodiment by adding strong Deprotonating agents (such as sodium hydride or potassium tertiary butoxide) Enol salt of compound (Ia), can be added to the further addition of acid binding be dispensed with by means.

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

The reaction can be carried out at normal pressure or under elevated pressure are, preferably carried out at normal pressure. The workup happens according to usual methods.

The process (I) is characterized in that compounds of Formula (Ia) with compounds of the formula (XIV), if appropriate in the presence a diluent and optionally in the presence of a base.

To carry out process (I) according to the invention, Ver fertilizer sufficiently inert to the reaction partners Solvent in question. It is preferred to use aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as Petrol, benzene, toluene, xylene, pentane, hexane, heptane, cyclohexane, petroleum ether, Ligroin, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene or Dichlorobenzene, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol diethyl ether or dimethyl ether, ketones such as acetone, butanone, Methyl isopropyl ketone or methyl isobutyl ketone, esters, such as ethyl acetate, Acids such as acetic acid, nitriles such as acetonitrile or propionitrile, amides such as Dimethylformamide, dimethylacetamide, N-methyl-pyrrolidone or hexamethyl phosphoric triamide. If one uses compounds of the  Formula (XIV) in liquid form, it is also possible to use this in the corresponding Use excess as a diluent at the same time.

All commonly used inorganic and organic bases in question. Alkali metal hydrides are preferably used, hydroxides, amides, carbonates or bicarbonates, such as Sodium hydride, sodium amide, sodium hydroxide, sodium carbonate or sodium hydrogen carbonate, or also tertiary amines, such as triethylamine, N, N-dimethylaniline, pyridine, 4- (N, N-dimethylamino) pyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).

The reaction temperatures can be carried out in a larger one Range can be varied. Generally one works between -20 ° C and + 150 ° C, preferably between 0 ° C and + 100 ° C.

The process (I) according to the invention is carried out per mole Compounds of the formula (Ia) in general in each case 1 to 20 mol, preferably in each case 1 to 15 mol, alkylating agent of the formula (XIV) and optionally 1 to 3 moles, preferably 1 to 2 moles, of acid binder. The reaction implementation, processing and isolation of the reaction products of the formula (Ia) takes place according to the methods usual in organic chemistry.

The active ingredients are suitable for controlling animal pests, preferably arthropods and nematodes, especially insects and spiders animals in agriculture, in forestry, in the protection of stocks and materials as well occur in the hygiene sector. They are normally sensitive and resistant Species as well as against all or individual stages of development. To the above Pests mentioned include:

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

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

From the order of the Chilopoda e.g. 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. Forficula auricuiaria.

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

From the order of the Anoplura z. B. Phylioxera vastatrix, Pemphlgus spp., 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, Aphls gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Sais setia 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, Piutella 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, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chiio spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Chonstoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.  

From the order of the Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Acanthoscelides obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemiineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varive stis, Atomaria spp., Oryzaephilus surinamensis, Antho nomus 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., Cono derus spp., Melolontha melolontha, Amphimallon solsti tialis, 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, Oscinelia 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 active compounds according to the invention are particularly notable for a high insecticidal and acaricidal activity.

They can be used with particularly good success to combat plant damage insects, such as the caterpillar caterpillars (Plutella maculipeunis) or to control plant-damaging mites, such as  for example against the common spider mite or the bean spider mite (Tetranychus urticae).

They show a general good leaf insecticidal activity and can be in appropriate application rates also to control Pyricularia oxyzae on Use rice.

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 Ver mixing the active ingredients with extenders, i.e. liquid solvents and / or solid carriers, optionally using surface-active agents Agents, that is emulsifiers and / or dispersants and / or foam generators resources.

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, Biasticidin-S, Bromuconazole, Bupirimate, Buthiobate,
Calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate (quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,
Dichlorophene, diclobutrazole, diciofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenyamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolone,
Edifenphos, epoxyconazole, ethirimol, etridiazole,
Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fiuazinam, Fludioxonil, Fiuoromide, Fluquinconazole, Fusilazole, Flusulfamide, Futoafolid, Fuzinolid, Fuzinolid, Futinazilid, Fuzinylid, Fuzinyl 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, Metaxam, Myclulfam, Mobulfam
Nickel dimethyldithiocarbamate, nitrothal isopropyl, nuanmol,
Ofurace, oxadixyl, oxamocarb, oxycarboxin,
Pefurazoate, penconazole, pencycuron, phosdiphen, phthalide, pimancin, piperalin, polycarbamate, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pynmethanil, 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, Tecloftälam, 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, Butyipyridaben,
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, Flucy cloxuron, Flucythrinat, Flufenoxuron, Fufionproxophon, Fufionproxophon, Fufonproxophon, Fufonproxophon, Fufonproxophon, Fufonfox, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufon
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, M 25, Nitenpyram,
Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,
Parathion A, parathion M, permethrin, phenthoate, phorate, phosalone, phosmet, Phosphamdon, phoxim, pirimicarb, pirimiphos M, Primiphos A, profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate, pymetrozine, Pyrachlophos, Pyradaphenthion, Pyresmethrin, pyrethrum, 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, Fiuroxypyr, MCPA, MCPP and Triclopyr; Aryloxy-phenoxy alkanoic acid esters, such as. B. diclofop-methyl, fenoxaprop-ethyl, fiuazifop-butyl, Haloxyfop-methyl and quizalofop-ethyl; Azinones, such as B. Chloridazon and Norfiurazone; 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, fiuometuron, isoproturon, linuron and methabenz thiazuron, hydroxylamines, such as. B. Alloxydim, Clethodim, Cycloxydim, Sethoxy dim and tralkoxydim, imidazolinones, such as. B. Imazethapyr, Imazamethabenz, Imazapyr and Imazaquin, Nitnle, such as. B. bromoxynil, dichlobenil and ioxyml, Oxyacetamides such as e.g. B. Mefenacet, sulfonylureas, such as. B. amidosulfuron, Bensulfuron-methyl, chlonmuron-ethyl, chlorsulfuron, cinosulfuron, metsulfuron methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, Triasulfuron and Tribenuron-methyl, thiol carbamates, such as. 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 ingredient according to the invention can also be in its 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 active substances can be used as such, in the form of their formulations or in the form thereof application forms prepared by further dilution, such as ready-to-use Solutions, suspensions, emulsions, powders, pastes and granules are used will. The application is done in the usual way, e.g. B. by pouring, spraying, Spray, sprinkle.

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

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

Manufacturing examples example 1 (Method A)

A solution of 6.40 g (0.05 mol) of 5,5-dimethyl-4-hydroxy-dihydrofuran-2-one and 5.61 g (0.05 mol) of 2-methylcyclohexanone in 100 ml of chloroform is mixed with 0.90 g (0.005 mol) of ethylenediammonium diacetate (EDDA) were added and initially stirred overnight at 60 ° C and then at 80 ° C for 24 hours. After this When the precipitate has cooled, it is suctioned off. The solid so obtained is stirred several times at room temperature with diethyl ether. From the rest The residue is filtered off and the ethereal solution is evaporated to dryness.

7.90 g (71% of theory) of 5,5-dimethyl-4-hydroxy-3- (2-methylcyclo hexen-1-yl) -Δ³-dihydrofuran-2-one as a yellow solid.  

Example 2 (Method Bα)

To a solution of 1.11 g (0.005 mol) of 5,5-dimethyl-4-hydroxy-3- (2-methyl cyclohexen-1-yl) -Δ³-dihydrofuran-2-one according to Example 1, 0.51 g (0.005 mol) Triethylamine and a spatula tip of diazabicyclo [2.2.2] octane (DABCO) in 20 ml Tetrahydrofuran are 0.39 g (0.005 mol) acetyl chloride at room temperature dripped. The mixture is stirred at room temperature for 2 hours and left to stand overnight. hydrolyzed with water and extracted several times with diethyl ether. The United organic phases are dried over MgSO₄, filtered and to dryness constricted.

1.24 g (94% of theory) of 4-acetoxy-5,5-dimethyl-3- (2-methylcyclohexen-1-yl) -Δ³-dihydrofuran-2-one are obtained as a red oil.
1 H-NMR (CDCl₃): δ = 1.50, 1.52, 1.61, 2.25 ppm.

Example 3 (Method A)

A solution of 9.05 g (0.05 mol) of 4-hydroxy-5,5- (2-methyl) pentamethylene pyrrolin-2-one and 4.90 g (0.05 mol) of cyclohexanone in 200 ml of chloroform in the presence of 0.2 g (0.001 mol) of ethylene diammonium diacetate (EDDA) 15 Cooked for hours on a water separator. Then the solvent distilled off and the residue thus obtained on silica gel 60 with dichloro methane / ethyl acetate 2: 1 chromatographed.

9.40 g (72% of theory) of 3- (cyclohexen-1-yl) -4-hydroxy-5,5- (2- methyl) -pentamethylene-pyrrolin-2-one with a melting point of 175-77 ° C.

In a corresponding manner and in accordance with the general information on the manufacture the following compounds are listed in Table 1:  

Table 1

Examples of use Example A Tetranychus test (OP-resistant / immersion treatment)

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

To produce a suitable preparation of active compound, it is mixed 1 part by weight of active ingredient with the specified amount of solvent and specified amount of emulsifier and dilute the concentrate with emulsifier containing water to the desired concentrations.

Bean plants (Phaseolus vulgaris), strongly affected by all stages of development Common spider mite Tetranychus urticae are infested in an active ingredient preparation of the desired concentration submerged.

After the desired time, the effect is determined in%. Here means 100% that all spider mites have been killed; 0% means that none Spider mites have been killed.

In this test z. B. the connection according to preparation example 19 an exemplary active ingredient concentration of 0.1% and a kill rate of 98% after 7 days.  

Example B Plutella test

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

To produce a suitable preparation of active compound, it is mixed 1 part by weight of active ingredient with the specified amount of solvent and specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with caterpillars Plutella maculipennis occupied while the leaves are still moist.

After the desired time, the kill is determined in%. 100 means % that all caterpillars have been killed; 0% means that no caterpillars are killed were.

In this test z. B. the connection according to Production Example 2 an exemplary active ingredient concentration of 0.1% a kill of 100% after 7 days.

Claims (7)

1. Compounds of formula (I) in which
A for hydrogen, for each alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl, alkyl thioalkyl or cycloalkyl optionally substituted by halogen, in which one or more methylene groups are optionally replaced by the same number of heteroatoms or for each optionally by halogen, alkyl, haloalkyl, Alkoxy or nitro substituted aryl, arylalkyl or hetaryl,
B represents hydrogen, alkyl or alkoxyalkyl, or
A and B together with the carbon atom to which they are attached represent saturated or unsaturated and optionally substituted cycloalkyl, in which one or more methylene groups may have been replaced by the same number of heteroatoms,
D represents oxygen or the NZ group,
Z stands for hydrogen, for alkyl or alkoxyalkyl optionally substituted by halogen, for optionally substituted cycloalkyl or for optionally substituted phenyl or arylalkyl, or
A and Z together with the atoms to which they are attached represent an optionally substituted 5- or 6-membered ring which may contain a sulfur atom,
R represents optionally substituted cycloalken-1-yl,
G for hydrogen (a) or for one of the groups stands, where
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 or cycloalkyl, in which one or more methylene groups are optionally replaced by the same number of heteroatoms or for each optionally substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl stands,
R² represents in each case optionally substituted by halogen alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl or represents in each case optionally substituted cycloalkyl, phenyl or benzyl,
R³, R⁴ and R⁵ independently of one another each represent optionally substituted by halogen substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio or cycloalkylthio or each optionally substituted phenyl, phenoxy or phenylthio,
R⁶ and R⁷ independently of one another represent hydrogen, each optionally substituted by halogen-substituted alkyl, cycloalkyl, alkenyl, alkoxy or alkoxyalkyl, each optionally substituted phenyl or benzyl, or together with the N atom to which they are attached, a ring form, which optionally contains a second heteroatom from the series of oxygen and sulfur, and
X represents in each case optionally substituted by halogen alkyl, alkenyl, alkynyl or alkoxyalkyl or for optionally substituted aralkyl. 2. 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, D and R have the meaning given in claim 1,
  Tetronic and tetramic acids of formula (II) in which
  A, B and D have the meaning given above,
  with cycloalkanones of the formula (XV) O = R ′ (XV) in which
  R ′ represents optionally substituted cycloalkyl,
  in the presence of a diluent and in the presence of a catalyst;
• (B) to obtain compounds of the formula (Ib) in which
  A, B, D, R and R¹ have the meaning given in claim 1,
  Compounds of formula (Ia) in which
  A, B, D and R 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;
• (C) to obtain compounds of the formula (Ic-a) in which
  A, B, D, R and R² have the meaning given in claim 1,
  and
  M represents oxygen or sulfur,
  Compounds of formula (Ia) in which
  A, B, D and R 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;
• (D) to obtain compounds of the formula (Ic-b) in which
  A, B, D, R and R² have the meaning given above,
  and
  M represents oxygen or sulfur,
  Compounds of formula (Ia) in which
  A, B, D and R 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 geniden 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
    implements;
• (E) to obtain compounds of the formula (Id) in which
  A, B, D, R and R³ have the meaning given in claim 1,
  Compounds of formula (Ia) in which
  A, B, D and R 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;
• (F) to obtain compounds of the formula (Ie) in which
  A, B, L, D, R, R⁴ and R⁵ have the meaning given in claim 1,
  Compounds of formula (Ia) in which
  A, B, D and R 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 optionally in the presence of a base
  implements;
• (G) to obtain compounds of the formula (If) in which
  A, B, D and R have the meaning given above,
  and
  E represents a metal ion equivalent or an ammonium ion,
  Compounds of formula (Ia) in which
  A, B, D and R have the meaning given above,
  with metal hydroxides or amines of the formulas (X) or (XI) in which
  Me for mono- or divalent metal ions,
  t for the number 1 or 2 and
  R¹⁰, R¹¹ and R¹² are the same or different and represent hydrogen or alkyl,
  if appropriate in the presence of a diluent;
• (H) to obtain compounds of the formula (Ig) in which
  A, B, L, D, R, R⁶ and R⁷ have the meaning given in claim 1,
  Compounds of formula (Ia) in which
  A, B, D and R have the meaning given above,
  • α) with isocyanates or isothiocyanates of the formula (XII) R⁶-N = C = L (XII) in which
    L and R⁶ have the meaning given above,
    if appropriate in the presence of a diluent and if appropriate 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;
• (I) to obtain compounds of the formula (Ih) in which
  A, B, D, R and X have the meaning given above,
  Compounds of formula (Ia) in which
  A, B, D and R have the meaning given above,
  with alkylating agents of the formula (XIV) XQ (XIV) in which
  X has the meaning given above and
  Q represents an anionic leaving group,
  optionally in the presence of a diluent and optionally in the presence of a base.

3. pesticide, characterized by a content of at least one compound of formula (I) according to claim 1. 4. Use of compounds of formula (I) according to claim 1 for Pest control. 5. 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. 6. 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.   7. Use of compounds of formula (I) according to claim 1 for Manufacture of pesticides.