DE19523087A1 - 1,3-Oxa (thia) tin derivatives - Google Patents

Abstract

The invention pertains to new 1,3-oxa(thia)zine derivatives of formula (I), wherein A is substituted phenyl or in each case substituted naphthyl, pyridyl, thienyl, phenylalkyl or phenylalkenyl; D is hydrogen, alkyl, alkyl halide, alkoxyalkyl, alkylthioalkyl, optionally substituted cycloalkyl or in each case optionally substituted phenyl, naphthyl or pyridyl; E is hydrogen or alkyl; G is hydrogen or alkyl; X is oxygen or sulfur, and Y, together with the two carbon atoms to which it is bonded, is an optionally substituted mono- or bicyclic, saturated or unsaturated ring. The invention also concerns a method for preparing said derivatives and their use for animal pest control.

Description

The invention relates to new 1,3-oxa (thia) zin derivatives, several processes for their Manufacture and its use for controlling animal pests.

It is already known that certain substituted 1,3-oxazines are acaricidal and have insecticidal properties (cf. EP-A-0 635 500 and WO-A 94/1 4783).

The level and / or duration of action of these previously known compounds is however, especially against certain organisms or for low users not entirely satisfactory in all areas of application.

New 1,3-oxa (thia) tin derivatives of the formula (I) have been found

in which
A represents substituted phenyl or optionally substituted naphthyl, pyridyl, thienyl, phenylalkyl or phenylalkenyl,
D stands for hydrogen, alkyl, haloalkyl, alkoxyalkyl, alkylthioalkyl, optionally substituted cycloalkyl or for optionally optionally substituted phenyl, naphthyl or pyridyl,
E represents hydrogen or alkyl,
G represents hydrogen or alkyl,
X represents oxygen or sulfur and
Y together with the two carbon atoms to which it is attached represents an optionally substituted, mono- or bicyclic, saturated or unsaturated cycle.

The compounds of formula (I) can, depending on the nature of the Substi tuenten as geometric and / or optical isomers or isomer mixtures under different composition. The invention relates to both the pure Isomers as well as the isomer mixtures.

Furthermore, it was found that the new 1,3-oxa (thia) zin derivatives of the formula (I) can be obtained if
a) Amide derivatives of the formula (II)

in which
A and D have the meaning given above and
R¹ and R² are the same or different and represent alkyl, or together with the N atom to which they are attached represent an optionally substituted heterocycle,
with olefins of the formula (III)

in which
E, G and Y have the meaning given above,
if appropriate in the presence of hydrogen chloride gas and in the presence of a catalyst and if appropriate in the presence of a diluent;
or
b) amide derivatives of the formula (IV)

A-CX-NH₂ (IV)

in which
A and X have the meaning given above,
with aldehydes of the formula (V)

D-CHO (V)

in which
D has the meaning given above,
and with olefins of formula (III)

in which
E, G and Y have the meaning given above,
if appropriate in the presence of a catalyst and if appropriate in the presence of a diluent;
or
c) 1,3-oxa (thia) tin derivatives of the formulas (Ia) or (Ib)

in which
A, D, E, G, X and Y have the meaning given above,
with boronic acids of the formula (VI)

Ar-B (OH) ₂ (VI)

in which
Ar represents in each case optionally substituted phenyl or pyridyl,
in the presence of a base, optionally in the presence of a catalyst and in the presence of a diluent;
or
d) 1,3-oxazine derivatives of the formula (Ic)

in which
A, D, E, G and Y have the meaning given above,
with a sulfurizing agent, optionally in the presence of a diluent.

Furthermore, it was found that the new 1,3-oxa (thia) zin derivatives of the formula (I) very good for controlling animal pests, especially insects, Arachnids and nematodes found in agriculture, in forests, in and material protection as well as in the hygiene sector are suitable.

Surprisingly, the 1,3-oxa (thia) zin derivatives of the invention Formula (I) a significantly better activity against animal pests than the constitutionally similar known compounds.

The compounds of the invention are generally defined by the formula (I) kidney.

Preferred substituents or ranges mentioned in the above and below Residues listed in formulas are explained below.

A is preferably (preferably) phenyl which is mono- to pentas, identical or differently substituted, or in each case optionally monosubstituted to pentavalent, identical or differently substituted, phenyl-C₁-C₆-alkyl and phenyl-C₂-C₆-alkenyl, where phenyl substituents are suitable
Halogen, nitro, cyano,
C₁-C₁₈ alkyl,
C₁-C₁₈ alkoxy,
C₁-C₁₈ alkylthio,
C₁-C₁₈ haloalkyl,
C₁-C₆ haloalkoxy
C₁-C₆ haloalkylthio,
C₁-C₆-alkoxy-C₁-C₆-alkyl,
3,4-difluoromethylene dioxo,
3,4-tetrafluoroethylene dioxo,
each pyridyl or pyridyloxy, optionally substituted once or twice, identically or differently, by halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl,
and in each case optionally up to five times, identical or different by halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio or C₁-C₄-haloalkylthio substituted phenyl , Benzyl, benzyloxy, phenethyl, phenethenyl, phenethinyl, phenoxy or phenylthio,
for naphthyl which is optionally monosubstituted to trisubstituted, identically or differently, by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy or C₁-C₆-haloalkoxy,
for pyridyl optionally substituted by one to three times, identical or different, by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl, C₁-C₆-haloalkoxy or cyano,
or for thienyl which is optionally monosubstituted to trisubstituted, identically or differently, by halogen or C₁-C₆alkyl.

D is preferably (preferably) hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₁-C₆-alkylthio-C₁-C₆-alkyl,
for C₃-C₇-cycloalkyl which is optionally mono- to quintuple, identical or different, substituted by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl or C₁-C₆-haloalkoxy,
for pyridyl which is optionally mono- to triple, identical or different, halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl, C₁-C₆-haloalkoxy or cyano,
or for phenyl which is optionally mono- to pentasubstituted by identical or different substituents, suitable substituents
Halogen,
C₁-C₁₈ alkyl,
C₁-C₈-alkoxy-C₁-C₈-alkyl,
C₁-C₈ haloalkoxy,
C₁-C₄ haloalkyl,
C₁-C₁₈ alkoxy, which is optionally interrupted by a further 1 to 3 oxygen atoms,
C₁-C₁₈ alkylthio,
C₁-C₈ haloalkylthio,
Tri-C₁-C₈-alkylsilyl,
Phenyl-di-C₁-C₈-alkylsilyl,
3,4-difluoromethylene dioxo,
3,4-tetrafluoroethylene dioxo,
a fused benzo group,
a fused C₃-C₄ alkanediyl group,
optionally substituted by C₁-C₄-alkyl, C₃-C₆-cycloalkyl or halogen benzyliminooxymethyl,
each optionally substituted by C₁-C₆-alkyl, C₁-C₆-alkoxy, cyclohexyl or phenyl cyclohexyl or cyclohexyloxy,
pyridyloxy optionally substituted once or twice, identically or differently by halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl,
each optionally one to five times, the same or different by C₁-C₁₂-alkyl, halogen, C₁-C₄-haloalkyl, C₁-C₁₂-alkoxy, C₁-C₆-halo genalkoxy, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₁ -C₆-alkoxy-ethyleneoxy, C₁-C₆- alkylthio or C₁-C₆-haloalkylthio substituted phenyl, phenyl-C₁-C₆- alkyl, phenethenyl, phenethynyl, phenoxy, phenylthio, phenyl-C₁-C₆-alkyl oxy or benzylthio.

E is preferably (preferably) hydrogen or methyl.

G is preferably (preferably) hydrogen or methyl.

X is preferably (preferably) oxygen or sulfur.  

Y is preferably (preferably) with the two carbon atoms to which it is bound, for one if necessary up to five times, the same or variously substituted, mono- or bicyclic, saturated or unsung saturated C₅-C₁₈ cycle, which are suitable as substituents C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkyl, and optionally a Phenyl, five to five times, identical or differently substituted, where as Substituents in phenyl substituents mentioned as preferred in D in Question come.

A particularly preferably represents phenyl which is monosubstituted to pentas, identical or different, or in each case optionally monosubstituted to pentas, identical or differently substituted by phenyl-C₁-C₁-alkyl and phenyl-C₂-C₄-alkenyl, phenyl substituents being suitable in each case
F, Cl, Br, Nitro, Cyano,
C₁-C₁₂ alkyl,
C₁-C₁₂ alkoxy,
C₁-C₁₂ alkylthio,
C₁-C₆ haloalkyl,
C₁-C₆ haloalkoxy,
C₁-C₄ haloalkylthio,
C₁-C₆-alkoxy-C₁-C₆-alkyl,
3,4-difluoromethylene dioxo,
3,4-tetrafluoroethylene dioxo,
optionally single or double, identical or different, substituted by F, Cl, CH₃ or CF₃ pyridyloxy,
and in each case optionally single to triple, identical or different by F, Cl, Br, C₁-C₄-alkyl, simple to six-fold, identical or different by F or Cl substituted C₁-C₄-alkyl, C₁-C₄-alkoxy, simple to six times, identically or differently substituted by F or Cl, C₁-C₄-alkoxy, C₁-C₄-alkylthio or simply up to six times, identically or differently substituted by F or Cl, C₁-C₄-alkylthio substituted phenyl, benzyl, benzyloxy, phenoxy or Phenylthio,
for naphthyl which is optionally monosubstituted to trisubstituted identically or differently by F, Cl, C₁-C₆alkyl, C₁-C₆alkoxy or monosubstituted to pentasubstituted by F or Cl and substituted by F or Cl,
for pyridyl optionally substituted once or twice, identically or differently by F, Cl, C₁-C₃-alkyl, C₁-C₃-alkoxy, CF₃, OCF₃ or cyano,
or for thienyl optionally substituted once or twice, identically or differently by Cl, Br, CH₃ or C₂H₅,
D particularly preferably represents hydrogen, C₁-C₄-alkyl, C₁-C₄-halogen alkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkylthio-C₁-C₄-alkyl,
for cyclo propyl, cyclopentyl or cyclohexyl which are optionally monosubstituted to trisubstituted, identically or differently, by C₁-C₃-alkyl, C₁-C₄-alkoxy, CF₃ or OCF₃,
for pyridyl optionally substituted once or twice, identically or differently by F, Cl, C₁-C₃-alkyl, C₁-C₃-alkoxy, CF₃, OCF₃ or cyano,
or for phenyl which is monosubstituted to pentasubstituted by identical or different substituents, suitable substituents
F, Cl, Br,
C₁-C₁₈ alkyl,
C₁-C₆-alkoxy-C₁-C₈-alkyl,
simple to six-fold, the same or different C₁-C₈alkoxy substituted by F or Cl,
single to quintuple, identical or different, C₁-C₂-alkyl substituted by F or Cl,
C₁-C₁₈ alkoxy and - (OC₂H₄) _1-3 -O-C₁-C₆-alkyl,
C₁-C₁₅ alkylthio,
simple to six-fold, the same or different C₁-C Cl-alkylthio substituted by F or Cl,
Tri-C₁-C₆-alkylsilyl,
Phenyl-di-C₁-C₆-alkylsilyl,
3,4-difluoromethylene dioxo,
3,4-tetrafluoroethylene dioxo,
a fused benzo group,
a fused C₄-alkanediyl group,
the groupings

each optionally substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy, cyclohexyl or phenyl cyclohexyl or cyclohexyloxy,
optionally single or double, identical or different, substituted by F, Cl or CF₃ pyridyloxy,
each optionally one to five times, identical or different by C₁-C₁₂-alkyl, F, Cl, Br, simple to six times, identical or different by F or Cl substituted C₁-C₄-alkyl, C₁-C₁₂-alkoxy, simple to six times, the same or different substituted by F or Cl C₁-C₄ alkoxy, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkoxy-ethyleneoxy, C₁-C₄- alkylthio or simple to sixfold, identical or different by F or Cl substituted C₁-C₄-alkylthio substituted phenyl, phenyl-C₁-C₆-alkyl, phenoxy, phenylthio, phenyl-C₁-C₆-alkyloxy or benzylthio.

E particularly preferably represents hydrogen or methyl.

G particularly preferably represents hydrogen or methyl.

X particularly preferably represents oxygen or sulfur.

Y particularly preferably with the two carbon atoms to which it is attached represents an optionally mono- to pentasubstituted, identically or differently substituted, mono- or bicyclic, saturated or unsaturated C₅-C₁₂ cycle, suitable substituents
C₁-C₃-alkyl, C₁-C₃-alkoxy, CF₃ and optionally single to triple, the same or different by CH₃, C₂H₅, n- or i-propyl, n-, i-, s- or t-butyl, F, Cl , CF₃, OCH₃, OCF₃, SCH₃, SCF _3, chorphenyl, trifluoromethylphenyl, trifluoromethoxyphenyl or trifluoromethylthiophenyl substituted phenyl.

A very particularly preferably represents phenyl which is monosubstituted to trisubstituted identically or differently, or in each case optionally monosubstituted to trisubstituted, identically or differently, phenyl-C₁-C₄-alkyl or styryl, phenyl substituents being suitable in each case
F, Cl, Br, Nitro, Cyano,
C₁-C₄ alkyl,
C₁-C₂ alkoxy,
C₁-C₂ alkylthio,
single to quintuple, identical or different, C₁-C₂-alkyl substituted by F or Cl,
single to quintuple, identical or different, C₁-C₂ alkoxy substituted by F or Cl,
single to quintuple, identical or different, C₁-C₂-alkylthio substituted by F or Cl,
C₁-C₂-alkoxy-C₁-C₂-alkyl,
3,4-difluoromethylene dioxo,
3,4-tetrafluoroethylene dioxo,
optionally single or double, identical or different, substituted by F, Cl, CH₃ or CF₃ pyridyloxy,
and in each case optionally single or double, identical or different by F, Cl, Br, C₁-C₂-alkyl, simple to fivefold, identical or different C₁-C₂-alkyl, C₁-C₂-alkoxy, simple or fivefold substituted by F or Cl , C₁-C₂-alkoxy, C₁-C₂-alkylthio, identical or differently substituted by F or Cl, or simply to five times, phenyl, benzyl, benzyloxy, phenoxy or phenylthio substituted by C or C₁-C₂-alkylthio substituted by F or Cl,
for naphthyl which is optionally monosubstituted to trisubstituted identically or differently by F, Cl, C₁-C₂alkyl, C₁-C₂alkoxy or monosubstituted to pentasubstituted by F or Cl and substituted by F or Cl,
for pyridyl optionally substituted once or twice, identically or differently by F, Cl, CH₃, C₂H₅, OCH₃, CF₃, OCF₃ or cyano,
or for thienyl optionally substituted once or twice, identically or differently by Cl, Br, CH₃ or C₂H₅.

D very particularly preferably represents hydrogen, C₁-C₄-alkyl, mono- to pentasubstituted, identical or different, C₁-C₂- alkyl substituted by F or Cl, C₁-C₂-alkoxy-C₁-C₄-alkyl, C₁-C₂- Alkylthio-C₁-C₄-alkyl,
for cyclopropyl, cyclopentyl or cyclohexyl which are optionally monosubstituted to trisubstituted, identically or differently, by CH₃, C₂H₅, t-C₄H₉, OCH₃, Ot-C₄H₉, CF₃ or OCF₃,
for pyridyl optionally substituted once or twice, identically or differently by F, Cl, CH₃, C₂H₅, OCH₃, CF₃, OCF₃ or cyano, or for phenyl optionally monosubstituted to triple, identically or differently, where substituents are suitable
F, Cl, Br,
C₁-C₁₈ alkyl,
C₁-C₆-alkoxy-C₁-C₈-alkyl,
simple to six-fold, the same or different C₁-C₈alkoxy substituted by F or Cl,
single to quintuple, identical or different, C₁-C₂-alkyl substituted by F or Cl,
C₁-C₁₈ alkoxy and - (OC₂H₄) _1- ₃-O-C₁-C₆-alkyl,
C₁-C₁₅ alkylthio,
simple to six-fold, the same or different C₁-C Cl-alkylthio substituted by F or Cl,
Tri-C₁-C₆-alkylsilyl,
Phenyl-di-C₁-C₆-alkylsilyl,
3,4-difluoromethylene dioxo,
3,4-tetrafluoroethylene dioxo,
a fused benzo group,
a fused C₄-alkanediyl group,
the groupings

each optionally substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy, cyclohexyl or phenyl cyclohexyl or cyclohexyloxy,
optionally single or double, identical or different, substituted by F, Cl or CF₃ pyridyloxy,
each optionally single to triple, identical or different by C₁-C₁₂-alkyl, F, Cl, Br, single to six times, identical or different by F or Cl substituted C₁-C₄-alkyl, C₁-C₁₂-alkoxy, single to six-fold, the same or different substituted by F or Cl C₁-C₄ alkoxy, C₁-C₄-alkoxy-C₁-C₄-alkyl, C₁-C₄-alkoxy-ethyleneoxy, C₁-C₄- alkylthio or simple to sixfold, identical or different by F or Cl substituted C₁-C₄-alkylthio substituted phenyl, phenyl-C₁-C₆-alkyl, phenoxy, phenylthio, phenyl-C₁-C₆-alkyloxy or benzylthio.

E very particularly preferably represents hydrogen or methyl.

G very particularly preferably represents hydrogen or methyl.

X very particularly preferably represents oxygen or sulfur.

Y very particularly preferably, with the two carbon atoms to which it is attached, represents an optionally mono- to pentasubstituted, identically or differently substituted, mono- or bicyclic, saturated or unsaturated C₅-C₁₂ cycle, the substituents being suitable
C₁-C₃-alkyl, C₁-C₃-alkoxy, CF₃, and optionally up to three times, the same or different by CH₃, C₂H₅, F, Cl, CF₃, OCH₃, OCF₃, SCH₃, SCF₃, chlorophenyl, trifluoromethylphenyl, trifluoromethoxyphenyl or trifluoromethylthiophenyl substituted phenyl.

A is particularly emphasized for phenyl, styryl or phenyl-C₁-C₄-alkyl, which are each one to three times, the same or different from fluorine, Chlorine, bromine, C₁-C₄-alkyl, simple to five times, the same or different C₁-C₂-alkyl substituted by fluorine or chlorine, optionally simple up to five times, identical or different, substituted by fluorine or chlorine C₁-C₂ alkoxy, optionally one to five times, the same or different C₁-C₂ alkylthio, 3,4-difluoromethylene substituted by fluorine or chlorine dioxo, 3,4-tetrafluoroethylene dioxo, optionally single or double, identical or different by fluorine, chlorine, methyl or trifluoromethyl substituted pyridyloxy, each optionally single or double, identical or different by fluorine, chlorine, bromine, in each case optionally one to five times, the same or different from fluorine or chlorine substituted C₁-C₂-alkyl, simple to five times, the same or different C₁-C₂-alkoxy substituted phenyl substituted by fluorine or chlorine or benzyloxy are substituted.

D stands out particularly for hydrogen, in each case if appropriate by methyl, ethyl, methoxy, trifluoromethyl or trifluoromethoxy substituted cyclopentyl or cyclohexyl or for phenyl, which optionally substituted up to three times, identically or differently by fluorine, chlorine, bromine, C₁-C₄-alkyl, optionally simply until sixfold, identical or different substituted by fluorine or chlorine C₁-C₄ alkoxy or optionally single to triple, the same or different from fluorine, chlorine, bromine, in each case, if appropriate, simply up to sixfold, identical or different substituted by fluorine or chlorine C₁-C₄ alkyl or C₁-C₄ alkoxy substituted phenyl.

E is particularly highlighted for hydrogen or methyl.

G is particularly highlighted for hydrogen or methyl.

X is particularly highlighted for oxygen or sulfur.  

Y is particularly highlighted with the two carbon atoms to which it is bound, for one if necessary, up to three times, the same or different from C₁-C₃-alkyl, C₁-C₃-alkoxy, trifluoromethyl or phenyl substituted, mono- or bicyclic, saturated or unsaturated C₅- C₈ cycle.

Those mentioned above in the definition of the compounds according to the invention Hydrocarbon residues such as alkyl are - also in connection with heteroatoms like alkoxy - as far as possible, straight or branched.

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.

According to the invention, particular emphasis is given to the compounds of the formula (I) in which a combination of the above is highlighted as being particularly highlighted meanings.  

In addition to the preparation examples, the compounds of following table:

Preferred compounds according to the invention are substances of the formula (IA)

in which
A and Y stand for the abovementioned general, preferred, particularly preferred, very particularly preferred and particularly emphasized meanings and
D¹ represents mono- to pentasubstituted, identical or differently substituted phenyl, the substituents mentioned above under D being preferred, particularly preferred, very particularly preferred and particularly highlighted ge phenyl substituents.

If, for example, N- [morpholin-4-yl- (4-bromo phenyl) methyl] -2,6-difluorobenzamide and cyclopentene as starting materials in The presence of titanium tetrachloride as a catalyst, the course of the invented method according to the invention represented by the following reaction scheme will:

If, for example, 2-chloro-6-fluorobenzamide, 4- tert-Butylbenzaldehyde and cyclohexene as starting materials in the presence of Sulfuric acid as a catalyst, the course of the invention Process can be represented by the following reaction scheme:  

If, for example, 4- (4-bromophenyl) -2- (2,6-di fluorophenyl) -5,6-trimethylene-4H-1,3-oxazine and 4-trifluoromethoxyphenylboron acid as starting materials, the course of the process according to the invention are represented by the following reaction scheme:

If, for example, 2- (2-chloro-6-fluorophenyl) -4- is used according to process (d) (4-tert-butylphenyl) -5,6-trimethylene-4H-1,3-oxazine as starting material and Phos phorpentasulfide as a sulfurizing agent, so the course of the fiction according to the procedure shown in the following reaction scheme:

Those used to carry out process (a) according to the invention as starting materials required amide derivatives are generally defined by the formula (II). In the Formula (II) A and D preferably or particularly preferably have those Meanings already related to the description of the Compounds of formula (I) preferred or particularly preferred for these Substituents were called.

R¹ and R² are the same or different and are preferably C₁-C₄ alkyl, especially for methyl, ethyl, n- or i-propyl or preferably together with the N atom to which they are attached for one optionally one to five times, the same or differently substituted 5- or 6-membered heterocycle, which may contain further heteroatoms, such as O, S or NR can contain, each as a substituent in particular C₁-C₄-alkyl and C₁-C₄-alkoxy may be mentioned and where R for alkyl, preferably C₁-C₄-alkyl or for optionally substituted Aryl, as in particular, represents optionally single or double, the same or different substituted phenyl, with substituents before may also be mentioned: halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁- C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio and C₁-C₄-halogen alkylthio.

Some of the amide derivatives of the formula (II) are known (for D = H see, for example, Liebigs Annalen 343, 207 (1905) and Bull. Soc. Chim. France 1979, II, 409-414); some of them are the subject of a separate, as yet unpublished application (cf. German patent application 19 518 681.8 dated May 22, 1995) or they can be obtained in a known manner by using
Amide derivatives of the formula (IVa)

A-CO-NH₂ (IVa)

in which
A has the meaning given above,
with aldehydes of the formula (V)

D-CHO (V)

in which
D has the meaning given above,
and with secondary amines of the formula (VII)

in which
R¹ and R² have the meaning given above,
optionally in the presence of an inert organic solvent, such as in dichloromethane, at temperatures between 10 and 100 ° C.

The amide derivatives of the formula (IVa), the aldehydes of the formula (V) and the secondary amines of the formula (VII) are generally known or in general known way available.

Which also to carry out the processes (a) and (b) as Formula (III) provides a general definition of olefins required as starting materials. In formula (III), E, G and Y have preferred or particularly preferred those meanings that are already related to the description above of the compounds of formula (I) as preferred or particularly preferred for them Substituents were called.

The olefins of the formula (III) are generally known or more generally known and known way available.

Those used to carry out process (b) according to the invention as starting materials Formula (IV) provides a general definition of the amide derivatives required. In the Formula (IV) A and X preferably or particularly preferably have those Meanings already related to the description of the  Compounds of formula (I) preferred or particularly preferred for these Substituents were called.

The also to carry out the method (b) as off Formula (V) generally defines the aldehydes required. In of the formula (V), D preferably or particularly preferably has those meanings which have already been described above in connection with the description of the connection gene of formula (I) preferred or particularly preferred for this substituent were called.

The amide derivatives of formula (IV) and the aldehydes of formula (V) are generally known or available in a generally known manner.

Those used to carry out process (c) according to the invention as starting materials required 1,3-oxa (thia) zin derivatives are represented by the formulas (Ia) and (Ib) generally defined. In these formulas, A, D, E, G, X and Y preferably have or particularly preferably those meanings that already together in the above preferred with the description of the compounds of formula (I) or were particularly preferred for these substituents.

The 1,3-oxa (thia) tin derivatives of the formulas (Ia) and (Ib) are according to the invention Compounds and according to processes (a), (b) or (d) according to the invention true.

Which also for performing the method (c) according to the invention as Formula (VI) generalizes the boronic acids required as starting materials Are defined. In the formula (VI), Ar stands for in each case simply until triple, identical or different by C₁-C₄-alkyl, halogen, C₁-C₄-halo genalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio and C₁-C₄-halo genalkylthio substituted phenyl or pyridyl, preferably for optionally single to triple, the same or different by C₁-C₄-alkyl, F, Cl, Br, simple up to six times substituted by F and / or Cl C₁-C₄-alkyl, C₁-C₄-alkoxy, a times to six times substituted by F and / or Cl alkoxy, C₁-C₄-alkylthio so such as simple to sixfold substituted by F and / or Cl C₁-C₄-alkylthio sub substituted phenyl and preferably for optionally single to triple, Identically or differently substituted pyridyl, being mentioned as a substituent  be: Halogen and, if necessary, simply up to sixfold by F substituted C₁-C₄ alkyl, C₁-C₄ alkoxy or C₁-C₄ alkylthio.

The boronic acids of the formula (VI) are generally known compounds of organic chemistry or can be obtained by generally known methods will.

Those used to carry out process (d) according to the invention as starting materials The 1,3-oxazine derivatives required are generally defined by the formula (Ic). In of this formula, A, D, E, G and Y have preferred or particularly preferred those meanings that are already related to the description above of the compounds of formula (I) preferred or particularly preferred for this Substituents were called.

The 1,3-oxazine derivatives of the formula (Ic) are compounds according to the invention and obtainable according to processes (a) to (c) according to the invention.

Process (a) according to the invention is optionally in the presence of chlorine hydrogen gas and carried out in the presence of a catalyst. As a kata Analyzers come in Lewis acids, such as preferably transition metal halides Question such as in particular titanium tetrachloride, tin tetrachloride and zinc dichloride.

As a diluent for carrying out process (a) according to the invention usual organic solvents come into consideration. These include, for example as chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, Chloroform and carbon tetrachloride.

The reaction temperatures can be carried out when carrying out the process according to the invention Process (a) can be varied over a wide range. Generally works one at temperatures between 0 ° C and 120 ° C, preferably at temperatures between 0 ° C and 100 ° C.

The process (a) according to the invention is carried out per mole Amide derivative of formula (II) generally between 1 and 5 mol, preferably between 1 to 3 mol of olefin of the formula (III) and between 1 and 5 mol, preferably between 1 to 4 mol of catalyst and optionally between 1 and 5 moles, preferably between 1 to 3 moles of hydrogen chloride gas.  

The workup can be carried out in the usual way; is preferred the reaction mixture is made alkaline with cooling between 0 ° C and 10 ° C and isolating the end product in a conventional manner.

Process (b) according to the invention is optionally carried out in the presence of a Catalyst carried out. In principle, inorganic or organic come for this Acids in question. For example, sulfuric acid, fluorine are preferably used hydrogen, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid or p-toluenesulfonic acid.

As a diluent for carrying out process (b) according to the invention acetic acid and dichloromethane are preferred.

The reaction temperatures can be carried out when carrying out the process according to the invention Process (b) can be varied over a wide range. Generally works one at temperatures between 0 ° C and 100 ° C, preferably at temperatures between 10 ° C and 80 ° C.

The process (b) according to the invention is carried out per mole Amide derivative of the formula (IV) in general between 1 and 1.5 mol preferably between 1 and 1.2 mol of aldehyde of the formula (V) and between 1 and 2 Mol, preferably between 1 and 1.5 mol of olefin of the formula (III) and optionally between 1 and 5 mol, preferably between 1 and 3 mol, of catalyze sator one.

The processing takes place in the usual way; preferably the reaction mix with cooling between 0 ° C and 10 ° C and the end product isolated in the usual way.

Suitable diluents for carrying out the inventive Process (c) all organic under the given reaction conditions Solvent in question. If necessary, they can be mixed with water be applied. Hydrocarbons such as toluene are preferably used, Xylene, tetralin, hexane, cyclohexane, halogenated hydrocarbons such as methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, alcohols such as methanol, etha nol, glycol, the isomeric propanols, butanols, pentanols, ethers, such as diethyl ether,  Diisopropyl ether, dimethoxyethane, tetrahydrofuran, dioxane, nitriles such as aceto nitrile or butyronitrile, amides such as dimethylformamide, sulfoxides such as dimethyl sulfide, also sulfolane.

The base used when carrying out process (c) according to the invention all usual acid acceptors in question. Tertiary are preferably used Amines such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicyclo undecene (DBU), diazabicyclonones (DBN), N, N-dimethylaniline, also earth alkali metal oxides such as magnesium or carcium oxide, also alkali and earth alkali metal carbonates and alkali metal bicarbonates, such as sodium carbonate, Potassium carbonate, calcium carbonate and sodium hydrogen carbonate, alkali hydroxides such as sodium or potassium hydroxide, furthermore alcoholates such as sodium ethanolate or Potassium tert-butoxide.

Process (c) according to the invention is optionally carried out in the presence of a Catalyst carried out. Examples of suitable catalysts are in Question: tetrakis (triphenylphosphine) palladium; Palladium II acetate / tri (o-tolyl) phos phin; Palladium-II-chloride, -II-acetate / triphenylphosphine; Bis (triphenylphosphine) palladium II chloride; and Pd / C / triphenylphosphine.

The reaction temperatures can be carried out when carrying out the process according to the invention Process (c) can be varied over a wide range. Generally works one at temperatures between 0 ° C and 150 ° C, preferably between 0 ° C and 100 ° C or at the boiling point of the solvent used.

When carrying out process (c) according to the invention, the reaction is carried out per mole 1,3-oxa (thia) tin derivative of the formulas (Ia) or (Ib) in general between 1 and 3 moles, preferably between 1 and 1.5 moles of boronic acid of the formula (VI) and optionally between 0.01 and 0.2 mol, preferably between 0.05 and 0.1 mol of catalyst, preferably the catalyst and the 1,3-oxa (thia) tin derivative under an inert gas stream, such as. B. an argon flow, will be added. The processing takes place according to usual methods.

The sulfurizing agents used in carrying out the invention Process (d) preferably in question: phosphorus pentasulfide or Lawesson's Reagent [2,4-bis (4-methoxyphenyl) -1,3,2,4-dithiadiphosphetane-2,4-dithione].  

Suitable diluents for carrying out the inventive Process (d) preferably hydrocarbons, such as toluene, xylene, tetralin, Hexane or cyclohexane in question.

The reaction temperatures can be carried out when carrying out the process according to the invention Process (d) can be varied over a wide range. Generally works one at temperatures between 0 ° C and 200 ° C, preferably between 20 ° C and 150 ° C.

When carrying out process (d) according to the invention, the reaction is carried out per mole 1,3-oxazine derivative of the formula (Ic) generally between 1 and 3 mol preferably between 1 and 2 moles of sulfurizing agent. The processing takes place according to usual methods.

The active ingredients are suitable for good plant tolerance and cheaper Warmblood toxicity to control animal pests, in particular 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, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus amndinis, 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, Phyllocoptmta oleivora, Boophilus spp., Rhipicephalus spp., Alnblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.

The plant parasitic nematodes include z. B. Pratylenchus spp., Radopho lus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp.  

The compounds of the formula (I) according to the invention are particularly noteworthy with excellent insecticidal and acaricidal activity. You let yourself with particularly good success in combating plant-damaging insects and use mites. They show strong effects, for example against Horseradish leaf beetle larvae (Phaedon cochleariae), caterpillars of the cabbage cockroach (Plu tella maculipennis), caterpillars of the owl butterfly (Spodoptera frugiperda) and against the green rice leafhopper (Nephotettix cincticeps) and the common spider mite (Tetra nychus urticae).

The active compounds according to the invention show not only protective, but also leaf systemic and root systemic properties.

The active compounds of the formula (I) also have one fungicidal activity, for example against Pyricularia oryzea on rice.

The active ingredients can be converted into the usual formulations, such as Solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, 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, chlorethylenes or methylene chloride, aliphatic carbons Hydrogen, 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 cyclo hexanone, 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, talc, 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 stems; 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 dispersing agents come into question: z. B. lignin sulfite and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural, can be used in the formulations 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. 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 phthalocyanine 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 Active ingredient, 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, B actericides, acaricides, nematicides, fungicides, growth-regulating substances fen or herbicides. Insecticides include, for example, phosphorus acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenyl ureas, 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-trifluofomethylbenzyl) 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, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alpha methrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,
Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyfluthrin, Bifen thrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlorfiuazu ron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocythrinhrinotin, Clyanophinhrinothrinothrinothrinothrinothrinothrinothrinothrinflin, Clyanophinhrinotin, Clyanothrinothrin, Clyanothrinothrin, Cythrinothrinotin, Clyanothrinotin, Cychrenthrin, Cychrenthrin, Cychrenthrin, Clocytenthrin, Cychrenthrin, Clocythrinotin, Cychrenthrin, Cythrinothrin, Clocythrinotin, Cythrinothrin, Cythrinophyne , Cyhexatin, cyper methrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Di azinon, 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, Ivermec tin, Lambda-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, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothoat, Pymetrozin, Pyrachlophhine, Pyrachlophhion, Pyrachlophion, Pyrachlophin, Pyrachlophin, Pyrachlophin, 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.

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

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. For example, they show an excellent ent anti-winding effect against against fly larvae of Lucilia cuprina.

The active compounds of the formula (I) according to the invention are also suitable for loading fighting arthropods that farm 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, aquarium fish and so-called experimental animals, such as B. hamsters, Infest guinea pigs, rats and mice. By fighting this Arthropods are said to cause deaths and reduced performance (in meat, milk, Wool, skins, eggs, honey, etc.) can be reduced, so that through the use the active ingredients according to the invention a more economical and simple animal neck tion 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, the feed-through Method, of suppositories, by parenteral administration, such as by injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), Implants, by nasal application, by dermal application in the form for example diving or bathing (dipping), spraying (spray), pouring on (Pour-on and spot-on), washing, powdering and with the help of molded articles containing active ingredients, such as collars, ear tags, tail tags, Limb straps, holsters, 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.

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

Manufacturing examples example 1 (Method a)

0.9 g (2.2 mmol) of N- [morpholin-4-yl- (4-bromophenyl) methyl] -2,6-difluorobenzamide and 0.4 g (5.8 mmol) of cyclopentene are mixed in 20 ml of dry dichloromethane 8 ml (8 mmol) of titanium IV chloride (1 molar solution in dichloromethane) are added and Stirred at 50 ° C for 18 hours. After cooling, the reaction mixture is mixed with Ammonia solution made alkaline and extracted several times with dichloromethane. The combined organic phases are dried over magnesium sulfate, in Concentrated vacuum and cleaned by column chromatography.

0.32 g (38% of theory) of 4- (4-bromophenyl) -2- (2,6-difluorophenyl) -5.6- trimethylene-4H-1,3-oxazine as a cis / trans isomer mixture (ratio 2: 1).

1 H-NMR (δ in ppm in CDCl₃): 7.51-6.91 (m, aromatics-H); 5.01 (d, H-4, cis Isomer); 4.7 (d, H-4, trans isomer); 4.86 (t, H-6, cis isomer); 4.45 (t, H-6, trans Isomer).  

Example 2 (Method b)

To a solution of 3.4 g (0) 0196 mol) of 2-chloro-6-fluorobenzamide, 3.3 g (0.02 Mol) of 4-tert-butylbenzaldehyde and 1.9 g (0.023 mol) of cyclohexene in 30 ml A solution of 5.2 g (0.051 mol) is concentrated in acetic acid with ice cooling trated sulfuric acid in 20 ml of acetic acid within 10 minutes. On the reaction mixture is then stirred at room temperature for 18 hours. After The reaction mixture is removed by distillation of the acetic acid with 50 ml Ice water added, made alkaline at 0 ° C with sodium hydroxide solution and with dichlor extracted methane. The organic phase is dried over magnesium sulfate and concentrated in vacuo.

1.4 g (18% of theory) of 4- (4-tert-butylphenyl) -2- (2-chloro-6-fluorine) are obtained phenyl) -5,6-tetramethylene-4H-1,3-oxazine, melting point 56 ° C.  

Example 3 (Method b)

To a solution of 5 g (0.026 mol) of 4-tert-butylthiobenzamide, 5 g (0.027 mol) 4-bromobenzaldehyde and 3.6 g (0.053 mol) of cyclopentene in 40 ml of acetic acid a solution of 8.2 g (0.081 mol) of concentrated weld is cooled with ice rock acid in 30 ml of acetic acid within 10 minutes. Then stir the reaction mixture for 18 hours at room temperature. After distillative Removal of acetic acid, the reaction mixture is mixed with 70 ml of ice water sets, made alkaline at 0 ° C with sodium hydroxide solution and extracted with dichloromethane. The organic phase is dried over magnesium sulfate and in a vacuum narrowed.

8.9 g (80% of theory) of 4- (4-bromophenyl) -2- (4-tert-butylphenyl) -5,6- trimethylene-4H-1,3-thiazine, melting point 101 ° C.  

Example 4 (Method c)

To a solution of 0.24 g (0.21 mol) of tetrakis (triphenylphosphine) palladium in 12 ml of toluene are introduced under a stream of argon into 1.3 g (3.3 mol) of 4- (4-bromophenyl) 2- (2,6-difluorophenyl) -5,6-trimethylene-4H-1,3-oxazine as a cis / trans isomer mixture (Ratio 2: 1; see Example 1). For this purpose, 6 ml of 2 molar sodium carbonate solution and then, with vigorous stirring, a solution of 0.88 g (4.3 mmol) of 4-trifluoromethoxyphenylboronic acid dropped in 6 ml of ethanol. You leave the reaction mixture is stirred under reflux for 3 hours, then cooled, gives up Water and extracted three times with 20 ml of diethyl ether. The united organi phases are washed with saturated sodium chloride solution, over Mag dried sodium sulfate and concentrated in vacuo. The residue becomes pebble chromatographed gel with methylene chloride as the eluent.

0.52 g (33% of theory) of cis-4- [4- (4-trifluoromethoxyphenyl) phenyl] -2- (2,6-difluorophenyl) -5,6-trimethylene-4H-1,3- oxazine melting point 66 ° C-67 ° C and 0.25 g (16% of theory) trans-4- [4- (4-trifluoromethoxyphenyl) phenyl] -2- (2,6-difluorophenyl) -5.6 -trimethylene-4H-1,3-oxazine with
1 H-NMR (δ in ppm in CDCl₃: 1.6-2.1; 4.51; 4.80; 6.9-7.0; 7.2-7.6.

Example 53 (Method d)

11.6 g (0.03 mol) of 4- (4-tert-butylphenyl) -2- (2-chloro-6-fluorophenyl) -5,6-trimethylene- 4H-1,3-oxazine and 23 g (0.052 mol) of phosphorus pentasulfide are added for 18 hours Stirred 140 ° C. After cooling, the reaction mixture with 100 ml Ice water added and after the addition of 30 ml of 45% sodium hydroxide solution for 1 hour touched. The mixture is then extracted several times with 200 ml of dichloromethane. The combined organic phases are washed several times with water until one clear solution is formed, then dried over magnesium sulfate and in Vacuum concentrated.

4.1 g (34% of theory) of 4- (4-tert-butylphenyl) -2- (2-chloro-6-fluorophenyl) -5,6-trimethylene-4H-1,3-thiazine are obtained.
1 H-NMR (δ in ppm in CDCl₃): 7.39-6.98 (m, aromatics-H); 4.62 (d, H-4); 3.52 (m, H-6); 1.31 (tert-butyl); 2.3-1.76 (m, H-5 and trimethylene).

Analogous to the preparation examples 1 to 5 and according to the general The following compounds of the formula (I) are used for preparation hold:

(Isomer A and B stand for one of the two possible geometric cis / trans isomers; no indication means that one of the two possible isomers is present lies.)

Examples of use

The following application examples list the following Compounds used as reference substances:

Compounds (A) to (H) known from EP-A 0 635 500.

Compound (I) known from WO-A 94/14783  

Example A Phaedon larval 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) are dipped into the active ingredient preparation the desired concentration and treated with horseradish leaf beetle larvae Phaedon cochleariae occupied while the leaves are still moist.

After the desired time, the kill is determined in%. Here means 100% that all beetle larvae have been killed; 0% means that no beetles Larvae were killed.

In this test z. B. the connections according to the manufacturing play 4a, 10 and 37 at an exemplary drug concentration of 0.1% a mortality of at least 80% after 7 days, while standing Compounds (A), (B) and (C) known in the art do not kill caused.  

Example B Plutella 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) are dipped into the active ingredient preparation the desired concentration and treated with caterpillars Plutella macuhpennis occupied while the leaves are still moist.

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

In this test z. B. the connections according to the manufacturing example len 4a, 32, 43, 46, 55, 62, 63 and 64 at an exemplary active ingredient concentration tration of 0.1% a kill of at least 80% after 3 days, while the Compounds (A), (B), (D) and (G) known from the prior art caused a maximum kill of 5%.  

Example C Spodoptera Frugiperda 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) are dipped into the active ingredient preparation the desired concentration and treated with caterpillars of the owl butterfly Spodoptera frugiperda occupied while the leaves are still moist.

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

In this test, z. B. the connection according to preparation example 4a an exemplary active ingredient concentration of 0.1% a kill of 100% after 7 days, while the compounds known from the prior art (A), (E) and (F) did not kill.  

Example D 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 water to the wanted concentration.

Rice seedlings (Oryza sativa) are dipped into the active ingredient preparation the desired concentration and treated with green rice leafhopper larvae Nephotettix cincticeps populates 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 cicadas are removed were killed.

In this test z. B. the connections according to the manufacturing example len 9, 10, 24, 25, 26, 36, 41 and 43 at an exemplary active ingredient concentration tration of 0.1% a kill of 100% after 6 days, while that from the Compounds (A), (B), (C) and (G) known in the art none caused killing.  

Example E Tetranychus test (OP-resistant / immersion treatment)

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 concentrations.

Bean plants (Phaseolus vulgaris), strongly affected by all stages of development common spider mite Tetranychus urticae are infested in a Drug preparation of the desired concentration dipped.

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 connections according to the manufacturing examples 2, 21, 38 and 71 at an exemplary active ingredient concentration of 0.1% a kill of 95% after 13 days, while from the prior Technically known compounds (B), (G) and (H) a maximum of one kill of 45%.  

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 polyglycol 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 placed in glass tubes Horse meat (1 cm²) brought on which 500 µ of the dilution to be tested be pipetted. The glass tubes are placed in plastic cups Floor is covered with sea sand, and in an air-conditioned room (26 ° C ± 1.5 ° C, 70% relative humidity ± 10%). The effects are checked after 24 Hours and 48 hours (larvicidal activity). After the larvae emigrate (approx. 72 hours) the glass tubes are removed and perforated plastic lids put on the mug. After 1½ times the development period (hatching of the control flies), the hatched flies and the dolls / doll covers are counted.

The criterion for the effect is the occurrence of death in the treated Larvae after 48 hours (larvicidal effect), or the inhibition of the adult hatching from the dolls or the inhibition of doll formation. As a criterion the inhibition of flea development applies to the in vitro effect of a substance, or a development standstill before the adult stage. 100% means Larvicidal effect that all larvae have died after 48 hours. 100% development-inhibitory effect means that no adult flies hatch are.

In this test, e.g. B. the compounds of the invention Production Examples 10 and 55 at an exemplary active ingredient concentration from 1000 ppm a 100% effect.

Claims (7)

1. Compounds of formula (I) in which
A stands for substituted phenyl or for optionally optionally substituted naphthyl, pyridyl, thienyl, phenylalkyl or phenylalkenyl,
D stands for hydrogen, alkyl, haloalkyl, alkoxyalkyl, alkylthioalkyl, optionally substituted cycloalkyl or for optionally substituted phenyl, naphthyl or pyridyl,
E represents hydrogen or alkyl,
G represents hydrogen or alkyl,
X represents oxygen or sulfur and
Y together with the two carbon atoms to which it is attached represents an optionally substituted, mono- or bicyclic, saturated or unsaturated cycle. 2. A process for the preparation of compounds of formula (I) according to claim 1, characterized in that

• a) Amide derivatives of the formula (II) in which
  A and D have the meaning given above and
  R¹ and R² are identical or different and stand for alkyl, or together with the N atom to which they are bound represent an optionally substituted heterocycle,
  with olefins of the formula (III) in which
  E, G and Y have the meaning given above,
  if appropriate in the presence of hydrogen chloride gas and in the presence of a catalyst and if appropriate in the presence of a diluent;
  or
• b) compounds of the formula (IV) A-CX-NH₂ (IV) in which
  A and X have the meaning given above,
  with aldehydes of the formula (V) D-CHO (V) in which
  D has the meaning given above,
  and with olefins of formula (III) in which
  E, G and Y have the meaning given above,
  if appropriate in the presence of a catalyst and if appropriate in the presence of a diluent;
  or
• c) compounds of the formulas (Ia) or (Ib) in which
  A, D, E, G, X and Y have the meaning given above,
  with boronic acids of the formula (VI) Ar-B (OH) ₂ (VI) in which
  Ar represents in each case optionally substituted phenyl or pyridyl,
  in the presence of a base, optionally in the presence of a catalyst and in the presence of a diluent;
  or
• d) 1,3-oxazine derivatives of the formula (Ic) in which
  A, D, E, G and Y have the meaning given above,
  with a sulfurizing agent, optionally in the presence of a diluent.

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.