DE19622353A1 - Pesticide agent comprising new and/or known substituted pyridine compounds - Google Patents

Abstract

An agent for treating pests is claimed,which contains at least one compound of formula (I) or its salts. A = a group of formula (i) - (iv); n = 1 - 3; B = substituted aryl or optionally substituted heteroaryl; R1 = H, halo, OH, NH2, NO2, CN; or alkyl or alkoxy (both optionally substituted by halo); or mono- or dialkylamino, alkylcarbonyl or alkoxycarbonyl. Compounds of formula (Ia) are new. A1 = a group (i) - (iv) in which B = a group B1; and either (A): n = 1 - 3; B1 = optionally substituted aryl or heteroaryl; R1' = halo, OH, NH2, NO2, CN; or alkyl or alkoxy (both optionally substituted by halo); or mono- or dialkylamino, alkylcarbonyl or alkoxycarbonyl (excluding the compound 3-(2,4-dimethoxy-benzylidene)-2-(6-methyl-3-pyridyl)-3,4,5,6-tetrahydr opyrimidine); or (B): n = 1 or 3; B1 = substituted aryl or optionally substituted heteroaryl; R1' = H; or (C): n = 2; B1 = phenyl substituted by F, 2-, 3-, 5- or 6-Cl, Br, I, 3-hydroxy, 5-hydroxy, 2-, 3-, 5- or 6-nitro, 2-, 3-, 5- or 6-methyl, ethyl, n-propyl, isopropyl, n-, iso-, sec.- or tert.-butyl, 5-16C alkyl, haloalkyl, ethoxy, haloalkoxy, tetrahydropyranyloxy, phenylalkoxy, alkylcarbonyloxy, NR2R3, 2-amino, 3,4-dihydroxy, 3-hydroxy-4-methoxy, 4-diethylamino-2-hydroxy, 4-methoxy-2,5-dimethyl, 3,4-dimethoxy, 3,4,5-trimethoxy, 4-N,N-di-(2-acetoxyethyl)amino-2-methoxy, 4-ethoxycarbonylamino-2,5-dimethoxy, 2,5-bis(ethoxycarbonylamino)-4-methoxy, 2-ethoxy-5-dimethylamino, 4-dimethylamino-2-ethoxycarbonylamino, optionally substituted phenyl, triazolyl or pyrazolyl. Or B1 = optionally substituted naphthyl or anthryl (except 4-dimethylamino-2-naphthyl), or optionally substituted and/or benzo-annelated 5- or 6-membered heteroaryl, except unsubstituted 2- or 3-furyl, or B1 = 1,2,3,5,6,7-hexahydropyrido3,2,1-ijquinolinyl; R2, R3 = H, alkyl (optionally substituted by F, Cl, OH, CN, alkylcarbonyloxy or triazolyl) or COR4, provided that R2 and R3 are not both H, methyl or ethyl; R4 = alkyl, alkylamino, alkoxy or optionally substituted phenyl or benzyl; R1' = H.

Description

The present invention relates to the use of partially known sub substituted pyridines to control animal pests.

2- (3-pyridyl) -3,4,5,6-tetrahydropyridine, called anabaseine, comes in certain Seaworms that paralyze their prey with this substance or attackers deter (see Toxicon 9, 23 (1979)). 3-benzylidene-2- (3-pyridyl) -3,4,5,6-tetra hydropyridine and the homologous 3-benzylidene-2- (3-pyridyl) -4,5-dihydro-3H-pyrrole are from JP 4085 (1963) cited in C.A. 59: 11447g with described their insecticidal activity. In addition, the latter are as well as from it 3-benzylidene-2- (3-pyridyl) pyrrolidine obtainable by reduction from Chem. Pharm. Bull 9, 818 (1961). Substituted 3-benzylidene-2- (3-pyridyl) - 3,4,5,6-tetrahydropyridine, 3- (4-dimethylamino-1-naphthyl) -2- (3-pyridyl) -3,4,5,6- tetrahydropyridine and 2- or 3-furyl-linked unsubstituted 3- (2- and 3- Furyl) methylidene-2- (3-pyridyl) -3,4,5,6-tetrahydropyridine are known in the literature as Active substances against neurodegenerative diseases described (see Heterocycles 35, 171 (1993) and WO 94/05288). About their effect against animal However, nothing has been known to pests.

It has now been found that the pyridine derivatives of the formula (I)

in which
A for one of the groups

stands,
wherein
n stands for one of the numbers 1, 2 or 3 and
B represents substituted aryl or optionally substituted hetaryl and
R¹ represents hydrogen, halogen, hydroxy, amino, nitro, cyano, in each case optionally substituted by halogen or alkyl or alkoxy, represents alkylamino, dialkylamino, alkylcarbonyl or alkoxycarbonyl,
and their biologically active salts
are suitable for controlling animal pests, in particular insects, arachnids and nematodes.

The compounds of formula (I) can also, depending on the type of Substituents as geometric and / or optical isomers or isomer mixtures, are present in different compositions, possibly in the usual Way can be separated. The invention relates to both the pure Isomers as well as the isomer mixtures.

Surprisingly, the pyridines used according to the invention show the Formula (I) a significantly better activity against animal pests as the most constitutionally similar known compounds.

The compounds which can be used according to the invention are represented by the formula (I) generally defined.  

Preferred substituents or ranges of those in the above and after The radicals mentioned above formulas are explained below.

Formula (I) preferably represents one of the isomers (I-1) to (I-7)

A preferably represents one of the groups

n preferably represents one of the numbers 1, 2 or 3.

B is preferably halogen, hydroxyl, nitro, cyano, C₁-C₁₆- Alkyl, C₁-C₈ haloalkyl, C₁-C₈ alkoxy, C₁-C₈ haloalkoxy, Tetrahydropyranyloxy, phenyl-C₁-C₈-alkyloxy, C₁-C₈-alkylcarbo nyloxy, a radical -NR²R³ or by optionally by halo  gene, nitro, cyano, C₁-C₁₆ alkyl, C₁-C₄ haloalkyl, C₁-C₈ alk oxy or C₁-C₄-haloalkoxy substituted phenyl or by each because optionally substituted by phenyl triazolyl or Pyrazolyl substituted aryl, especially phenyl, naphthyl or Anthryl or for each optionally by halogen, hydroxy, Nitro, cyano, C₁-C₁₆ alkyl, C₁-C₄ haloalkyl, C₁-C₈ alkoxy, C₁-C₄-haloalkoxy, tetrahydropyranyloxy, phenyl-C₁-C₄-alkoxy, C₁-C₄ alkylcarbonyloxy or a radical -NR²R³ substituted and optionally benzanellated 5- or 6-membered hetaryl with 1 to 3 heteroatoms from the series N, O, S, or for 1,2,3,5,6,7- Hexahydro-pyrido [3,2,1-ÿ] quinolinyl.

R² and R³ are preferably independently of one another hydrogen, Methyl, optionally by fluorine, chlorine, hydroxy, cyano, C₁-C₈- Alkoxy, C₁-C₈-alkylcarbonyloxy or triazolyl substituted C₂- C₈-alkyl or for a residue -COR⁴.

R⁴ is preferably C₁-C₈-alkyl, C₁-C₈-alkylamino, C₁-C₈-alkoxy or in each case optionally by halogen, hydroxy, nitro, cyano, C₁-C₈ alkyl, C₁-C₈ haloalkyl, C₁-C₈ alkoxy or C₁-C₁ halo genalkoxy substituted phenyl or benzyl.

R¹ preferably represents hydrogen, halogen, hydroxy, amino, nitro, cyano, each optionally substituted by halogen C₁-C₆-alkyl or C₁- C₆-alkoxy, for C₁-C₆-alkylamino, di-C₁-C₆-alkylamino, C₁-C₆- Alkylcarbonyl or C₁-C₆ alkoxycarbonyl.

Formula (I) particularly preferably represents one of the isomers (I-1) to (I-4)

A particularly preferably represents one of the groups

n particularly preferably represents one of the numbers 1, 2 or 3.

B particularly preferably represents fluorine, chlorine, bromine, iodine, Hydroxy, nitro, cyano, C₁-C₁₆ alkyl, C₁-C₄ alkyl by fluorine or chlorine is substituted, C₁-C₈ alkoxy, C₁-C₄ alkoxy, by Fluorine or chlorine is substituted, tetrahydropyranyloxy, phenyl-C₁- C₄-alkyloxy, C₁-C₄-alkylcarbonyloxy, a radical -NR²R³, by optionally by fluorine, chlorine, bromine, iodine, nitro, cyano, C₁-C₄- Alkyl which is optionally substituted by fluorine or chlorine, or C₁-C₄ alkoxy, which may be sub-fluorine or chlorine is substituted, substituted phenyl or by in each case optionally triazolyl or pyrazolyl substituted by phenyl Aryl, especially phenyl, naphthyl or anthryl or for each optionally by fluorine, chlorine, bromine, iodine, hydroxy, nitro, Cyano, C₁-C₁₆-alkyl, C₁-C₄-alkyl, which by fluorine or chlorine sub is substituted, C₁-C₈-alkoxy, C₁-C₄-alkoxy by fluorine or Chlorine is substituted, tetrahydropyranyloxy, phenyl-C₁-C₄-alkyloxy, C₁-C₄ alkylcarbonyloxy or a radical -NR²R³ substituted Hetaryl, especially furyl, benzofuryl, thienyl, benzothienyl, Pyrrolyl, indolyl, carbazolyl, pyrazolyl, imidazolyl, triazolyl, Oxazolyl, thiazolyl, pyridyl or pyrimidyl or for 1,2,3,5,6,7- Hexahydro-pyrido [3,2,1-ÿ] quinolinyl.

R² and R³ are particularly preferably independently Hydrogen, methyl, optionally by fluorine, chlorine, hydroxy,  Cyano, C₁-C₄-alkoxy, C₁-C₄-alkylcarbonyloxy or triazolyl sub substituted C₂-C₄ alkyl or for a radical -COR⁴.

R⁴ particularly preferably represents C₁-C₄-alkyl, C₁-C₄-alkylamino, C₁- C₄-alkoxy or in each case optionally by fluorine, chlorine, bromine, Iodine, hydroxy, nitro, cyano, C₁-C₄-alkyl, optionally by Fluorine or chlorine is substituted, or C₁-C₄ alkoxy, the given substituted by fluorine or chlorine, substituted phenyl or benzyl.

R¹ particularly preferably represents hydrogen, fluorine, chlorine, bromine, hydroxy, Amino, nitro, cyano, each optionally by fluorine or chlorine sub substituted methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert-butyl, n-pentyl, n-hexyl or C₁-C₄ alkoxy, for methylamino, ethyl amino, dimethylamino, diethylamino or methylethylamino.

Formula (I) very particularly preferably represents the isomer (I-2)

A very particularly preferably represents one of the groups

n very particularly preferably represents one of the numbers 1 or 2.

B very particularly preferably represents fluorine, chlorine, bromine, Hydroxy, nitro, cyano, n-C₁-C₁₂ alkyl, isopropyl, isobutyl, sec.-  Butyl, tert-butyl, neo-pentyl, C₁-C₄-alkyl, which can be replaced by fluorine or Chlorine is substituted, C₁-C₄ alkoxy, C₁-C₄ alkoxy by fluorine or chlorine is substituted, tetrahydropyranyloxy, benzyloxy, C₁- C₄-Alkylcarbonyloxy, a radical -NR²R³, by optionally by fluorine, chlorine, bromine, nitro, cyano, methyl, trifluoromethyl, Methoxy, trifluoromethoxy substituted phenyl or by optionally triazolyl or pyrazolyl substituted by phenyl substituted phenyl, naphthyl or anthryl or for each against also by fluorine, chlorine, bromine, hydroxy, nitro, cyano, n-C₁- C₁₂-alkyl, isopropyl, isobutyl, sec-butyl, tert-butyl, neo-pentyl, C₁-C₄-alkyl which is substituted by fluorine or chlorine, C₁-C₄- Alkoxy, C₁-C₄alkoxy which is substituted by fluorine or chlorine, Tetrahydropyranyloxy, benzyloxy, C₁-C₄ alkylcarbonyloxy or a radical -NR²R³ substituted furyl, benzofuryl, thienyl, Benzothienyl, pyrrolyl, indolyl, carbazolyl, thiazolyl or pyridyl or for 1,2,3,5,6,7-hexahydro-pyrido [3,2,1-ÿ] quinolinyl.

R² and R³ are very particularly preferably independently of one another Hydrogen methyl, optionally by fluorine, chlorine, hydroxy, Cyano, methoxy, acetyloxy or triazolyl substituted ethyl or for a rest -COR⁴.

R⁴ very particularly preferably represents methyl, ethyl, methylamino, Ethylamino, methoxy, ethoxy or each optionally by Fluorine, chlorine, bromine, hydroxy, nitro, cyano, methyl, ethyl, Trifluoromethyl, methoxy, ethoxy, trifluoromethoxy substituted Phenyl or benzyl.

R¹ very particularly preferably represents hydrogen, fluorine, chlorine, hydroxy, Amino, nitro, cyano, methyl, trifluoromethyl, methoxy, methylamino or Dimethylamino.

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 using the compounds of the formula (I) in which a combination of the above as preferred (preferred) meanings.

According to the invention, the compounds of Formula (I) in which a combination of the above is particularly preferred listed meanings is present.

According to the invention, the compounds are used with very particular preference of formula (I), in which a combination of the above as very special meanings listed preferably is present.

Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenyl can NEN, also in connection with heteroatoms, such as. B. in alkoxy, if possible, each be straight or branched.

Optionally substituted radicals can be mono- or polysubstituted, in the case of multiple substitutions, the substituents are the same or different can.

Some of the compounds of the formula (I) are known (see, for example, heterocycles 35, 171 (1993)).

The compounds of the formula (I-a) are new

in which
A¹ for one of the residues

and
in which
[A] n represents one of the numbers 1, 2 or 3,
B¹ represents optionally substituted aryl or hetaryl and
R ^{1-1 represents} halogen, hydroxy, amino, nitro, cyano, each optionally substituted by halogen-substituted alkyl or alkoxy, represents alkylamino, dialkylamino, alkylcarbonyl or alkoxycarbonyl,
except for the compound 3- (2,4-dimethoxybenzylidene) -2- (6-methyl-3-pyridyl) -3,4,5,6-tetrahydropyridine,
or in which
[B] n represents the numbers 1 or 3,
B¹ represents substituted aryl or optionally substituted hetaryl and
R ^{1-1 represents} hydrogen,
or in which
[C] n represents 2,
B¹ for fluorine, 2-chlorine, 3-chlorine, 5-chlorine, 6-chlorine, bromine, iodine, 3-hydroxy, 5-hydroxy, 2-nitro, 3-nitro, 5-nitro, 6-nitro, 2 -Methyl, 3-methyl, 5-methyl, 6-methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, C₅-C₁₆ alkyl, haloalkyl, ethoxy, haloalkoxy , Tetrahydropyranyloxy, phenylalkyloxy, alkylcarbonyloxy, a radical -NR²R³, 2-amino, 3,4-dihydroxy, 3-hydroxy-4-methoxy, 4-diethylamino-2-hydroxy, 4-methoxy-2,5-methyl, 3, 4-dimethoxy, 3,4,5-trimethoxy, 4-N, N-di- (2-acetoxy ethyl) amino-2-methoxy, 4-ethoxycarbonylamino-2,5-dimethoxy, 2,5-bis- ( ethoxycarbonylamino) -4-methoxy, 2-ethoxy-5-dimethylamino, 4-dimethylamino-2-ethoxycarbonylamino, in each case optionally substituted phenyl, triazolyl or pyrazolyl substituted phenyl; for each optionally substituted naphthyl or anthryl, except 4-dimethylamino-2-naphthyl; or for optionally substituted and optionally benzanellated 5- or 6-membered hetaryl, with the exception of unsubstituted 2- and 3-furyl; or stands for 1,2,3,5,6,7-hexahydro-pyrido [3,2,1-ÿ] quinolinyl,
R² and R³ independently of one another represent hydrogen, optionally substituted by fluorine, chlorine, hydroxy, cyano, alkylcarbonyloxy or triazolyl alkyl or a radical -COR⁴, but not both at the same time each represent hydrogen, methyl or ethyl,
R⁴ represents alkyl, alkylamino, alkoxy or in each case optionally substituted phenyl or benzyl and
R ^{1-1 represents} hydrogen,
and their salts.

The compounds according to the invention can also be present in the form of their salts. In general, here are salts with organic or inorganic acids called.  

The compounds of formula (I-a) can also, depending on the type of Substituents as geometric and / or optical isomers or isomer mixtures, are present in different compositions, possibly in the usual Way can be separated. The invention relates to both the pure Isomers as well as the isomer mixtures.

It was also found that the new compounds of the formula (I-a) obtained by one of the methods described below.

• A) compounds of the formula (Ib) in which
  B¹ and R ^{1-1 have} the meanings given above,
  can be prepared by iminoheterocyclyl-substituted pyridines of the formula (II) in which
  R ^{1-1 has} the meaning given above,
  with aromatic aldehydes of the formula (III) B¹-CHO (III) in which
  B¹ has the meaning given above
  condensed.
• B) Compounds of the formula (Ic) in which
  B¹ and R ^{1-1 have} the meanings given above,
  can be prepared by hydrogenating pyridines of the formula (Ib).

The new pyridines are generally defined by the formula (I-a).

Compounds of the formula (Ia) in which
[A] the isomers (Ia-1), (Ia-2), (Ia-3) or (Ia-4)

are present in which
A¹ has the meaning given above,
n represents the numbers 1, 2 or 3,
B¹ for by halogen, hydroxy, nitro, cyano, C₁-C₁₆-alkyl, C₁-C₈-haloalkyl, C₁-C₈-alkoxy, C₁-C₈-haloalkoxy, tetrahydro pyranyloxy, phenyl-C₁-C₈-alkyloxy, C₁-C₈- Alkylcarbonyloxy, a radical -NR²R³ or by phenyl optionally substituted by halogen, nitro, cyano, C₁-C₁₆-alkyl, C₁-C₄-haloalkyl, C₁-C₈-alkoxy or C₁-C--haloalkoxy or by triazolyl optionally substituted by phenyl or pyrazolyl-substituted aryl, in particular phenyl, naphthyl or anthryl or for each optionally halogen, hydroxy, nitro, cyano, C₁-C₁₆-alkyl, C₁-C₄-haloalkyl, C₁-C₈-alkoxy, C₁-C₄-haloalkoxy, tetrahydropyranyloxy , Phenyl-C₁-C₄-alkoxy, C₁-C₄- alkylcarbonyloxy or a radical -NR²R³ substituted and optionally benzanellated 5- or 6-membered hetaryl with 1 to 3 heteroatoms from the series N, O, S, or for 1,2,3 , 5,6,7-hexahydro-pyrido [3,2,1-ÿ] quinolinyl stands,
R² and R³ independently of one another represent hydrogen, methyl, optionally substituted by fluorine, chlorine, hydroxy, cyano, C₁-C₈-alkoxy, C₁-C₈- alkylcarbonyloxy or triazolyl, C₂-C₈-alkyl or a radical -COR⁴,
R⁴ for C₁-C₈-alkyl, C₁-C₈-alkylamino, C₁-C₈-alkoxy or in each case optionally by halogen, hydroxy, nitro, cyano, C₁-C₈-alkyl, C₁-C₈-haloalkyl, C₁-C₈-alkoxy or C₁ -C₄-haloalkoxy substituted phenyl or benzyl and
R ^1-1 for halogen, hydroxy, amino, nitro, cyano, each optionally substituted by halogen C₁-C₆-alkyl or C₁-C₆-alkoxy, for C₁-C₆-alkylamino, di-C₁-C₆-alkylamino, C₁-C₆ -Alkylcarbonyl or C₁-C₆-alkoxycarbonyl,
except 3- (2,4-dimethoxy-benzylidene) -2- (6-methyl-3-pyridyl) -3,4,5,6-tetrahydropyridine, or
[B] A¹ has the meaning given above,
n represents the numbers 1 or 3,
B¹ for by halogen, hydroxy, nitro, cyano, C₁-C₁₆-alkyl, C₁-C₈-haloalkyl, C₁-C₈-alkoxy, C₁-C₈-haloalkoxy, tetrahydro pyranyloxy, phenyl-C₁-C₈-alkyloxy, C₁-C₈- Alkylcarbonyloxy, a radical -NR²R³ or by phenyl optionally substituted by halogen, nitro, cyano, C₁-C₁₆-alkyl, C₁-C₄-haloalkyl, C₁-C₈-alkoxy or C₁-C--haloalkoxy or by triazolyl optionally substituted by phenyl or pyrazolyl-substituted aryl, in particular phenyl, naphthyl or anthryl or for each optionally halogen, hydroxy, nitro, cyano, C₁-C₁₆-alkyl, C₁-C₄-haloalkyl, C₁-C₈-alkoxy, C₁-C₄-haloalkoxy, tetrahydropyranyloxy , Phenyl-C₁-C₄-alkoxy, C₁-C₄- alkylcarbonyloxy or a radical -NR²R³ substituted and optionally benzanellated 5- or 6-membered hetaryl with 1 to 3 heteroatoms from the series N, O, S, or for 1,2,3 , 5,6,7-hexahydro-pyrido [3,2,1-ÿ] quinolinyl stands,
R² and R³ independently of one another represent hydrogen, methyl, optionally substituted by fluorine, chlorine, hydroxy, cyano, C₁-C₈-alkoxy, C₁-C₈- alkylcarbonyloxy or triazolyl, C₂-C₈-alkyl or a radical -COR⁴,
R⁴ for C₁-C₈-alkyl, C₁-C₈-alkylamino, C₁-C₈-alkoxy or in each case optionally by halogen, hydroxy, nitro, cyano, C₁-C₈-alkyl, C₁-C₈-haloalkyl, C₁-C₈-alkoxy or C₁ -C₄-haloalkoxy substituted phenyl or benzyl and
R ^1-1 stands for hydrogen, or
[C] A¹ has the meaning given above
n stands for 2,
B¹ for fluorine, 2-chlorine, 3-chlorine, 5-chlorine, 6-chlorine, bromine, iodine, 3-hydroxy, 5-hydroxy, 2-nitro, 3-nitro, 5-nitro, 6-nitro, 2 -Methyl, 3-methyl, 5-methyl, 6-methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, C₅-C₁₆ alkyl, haloalkyl, ethoxy, haloalkoxy , Tetrahydropyranyloxy, phenylalkyloxy, alkylcarbonyloxy, a radical -NR²R³, 2-amino, 3,4-dihydroxy, 3-hydroxy-4-methoxy, 4-diethylamino-2-hydroxy, 4-methoxy-2,5-methyl, 3, 4-dimethoxy, 3,4,5-trimethoxy, 4-N, N-di- (2-acetoxy ethyl) amino-2-methoxy, 4-ethoxycarbonylamino-2,5-dimethoxy, 2,5-bis- ( ethoxycarbonylamino) -4-methoxy, 2-ethoxy-5-dimethylamino, 4-dimethylamino-2-ethoxycarbonylamino, each optionally substituted phenyl, triazolyl or pyrazoline substituted phenyl, for halogen, hydroxy, nitro, cyano, alkyl, haloalkyl, Alkoxy, haloalkoxy, tetrahydropyranyloxy, phenylalkyloxy, alkylcarbonyloxy, a radical -NR²R³ or by optionally substituted Phe nyl, triazolyl or pyrazolyl substituted naphthyl or anthryl, except 4-dimethylamino-2-naphthyl, or for optionally substituted and optionally benzanellated 5- or 6-membered hetaryl, except unsubstituted 2- or 3-furyl, or for 1,2,3,5 , 6,7-hexahydro-pyrido [3,2,1-ÿ] quinolinyl,
R² and R³ are independently hydrogen, methyl, optionally substituted by fluorine, chlorine, hydroxy, cyano, C₁-C₁-alkoxy, C₁-C₈-alkylcarbonyloxy or triazolyl-substituted C₂-C₈-alkyl or a radical -COR⁴, but not both simultaneously for hydrogen, methyl or ethyl,
R⁴ for C₁-C₈-alkyl, C₁-C₈-alkylamino, C₁-C₈-alkoxy or in each case optionally by halogen, hydroxy, nitro, cyano, C₁-C₈-alkyl, C₁-C₈-haloalkyl, C₁-C₈-alkoxy or C₁ -C₄-haloalkoxy substituted phenyl or benzyl and
R ^1-1 stands for hydrogen.

Compounds of the formula (Ia) in which
[A] structures (Ia-1-1) to (Ia-4-2)

are present in which
n represents the numbers 1, 2 or 3,
B¹ for by fluorine, chlorine, bromine, iodine, hydroxy, nitro, cyano, C₁-C₁₆-alkyl, C₁-C₄-alkyl which is substituted by fluorine or chlorine, C₁- C₈-alkoxy, C₁-C₄-alkoxy, the is substituted by fluorine or chlorine, tetrahydropyranyloxy, phenyl-C₁-C₄-alkyloxy, C₁-C₄-alkylcarbonyloxy, a radical -NR²R³, by optionally by fluorine, chlorine, bromine, iodine, nitro, cyano, C₁-C₄-alkyl, that optionally substituted by fluorine or chlorine, or C₁-C₄-alkoxy, which is optionally substituted by fluorine or chlorine, substituted phenyl or by optionally substituted by phenyl triazolyl or pyrazolyl substituted aryl, in particular phenyl, naphthyl or anthryl or for each optionally by Fluorine, chlorine, bromine, iodine, hydroxy, nitro, cyano, C₁-C₁₆-alkyl, C₁-C₄- alkyl which is substituted by fluorine or chlorine, C₁-C₈-alkoxy, C₁-C₄-alkoxy which is by fluorine or Chlorine substituted, tetra hydropyranyloxy, phenyl C₁-C₄-alkyloxy, C₁-C₄-alkylcarbonyloxy or a radical -NR²R³ substituted hetaryl, especially furyl, benzofuryl, thienyl, benzothienyl, pyrrolyl, indolyl, carbazolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, thiazolyl, pyridyl or pyridyl or pyridyl , 2,3,5,6,7-hexahydro-pyrido [3,2,1-ÿ] quinolinyl,
R² and R³ independently of one another represent hydrogen, methyl, optionally substituted by fluorine, chlorine, hydroxy, cyano, C₁-C₄-alkoxy, C₁-C₄-alkylcarbonyloxy or triazolyl-substituted C₂-C₄-alkyl or a radical -COR⁴,
R⁴ for C₁-C₄-alkyl, C₁-C₄-alkylamino, C₁-C₄-alkoxy or in each case optionally by fluorine, chlorine, bromine, iodine, hydroxy, nitro, cyano, C₁-C₄-alkyl which is optionally substituted by fluorine or chlorine is, or C₁-C₄ alkoxy, which is optionally substituted by fluorine or chlorine, substituted phenyl or benzyl and
R ^1-1 for fluorine, chlorine, bromine, hydroxy, amino, nitro, cyano, each optionally substituted by fluorine or chlorine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.- Butyl, n-pentyl, n-hexyl or C₁-C₄alkoxy, represents methylamino, ethylamino, dimethylamino, diethylamino or methylethylamino,
except 3- (2,4-dimethoxy-benzylidene) -2- (6-methyl-3-pyridyl) -3,4,5,6-tetrahydropyridine,
or
[B] structures (Ia-5-1) and (Ia-5-2)

are present in which
n represents the numbers 1 or 3,
B¹ for by fluorine, chlorine, bromine, iodine, hydroxy, nitro, cyano, C₁-C₁₆-alkyl, C₁-C₄-alkyl which is substituted by fluorine or chlorine, C₁- C₈-alkoxy, C₁-C₄-alkoxy, the is substituted by fluorine or chlorine, tetrahydropyranyloxy, phenyl-C₁-C₄-alkyloxy, C₁-C₄-alkyl carbonyloxy, a radical -NR²R³, by optionally by fluorine, chlorine, bromine, iodine, nitro, cyano, C₁-C₄-alkyl, which is optionally substituted by fluorine or chlorine, or C₁-C₄alkoxy, which is optionally substituted by fluorine or chlorine, substituted phenyl or by optionally substituted by phenyl-substituted triazolyl or pyrazolyl-aryl, in particular phenyl) naphthyl or anthryl or for each optionally by Fluorine, chlorine, bromine, iodine, hydroxy, nitro, cyano, C₁-C₁₆-alkyl, C₁-C₄- alkyl which is substituted by fluorine or chlorine, C₁-C₈-alkoxy, C₁-C₄-alkoxy which is by fluorine or Chlorine is substituted, tetra hydropyranyloxy, phenyl-C ₁-C₄-alkyloxy, C₁-C₄-alkylcarbonyloxy or a radical -NR²R³ substituted hetaryl, especially furyl, benzofuryl, thienyl, benzothienyl, pyrrolyl, indolyl, carbazolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, thiazolyl, pyridyl or pyridyl or pyridyl , 2,3,5,6,7-hexahydro-pyrido [3,2,1-ÿ] quinolinyl,
R² and R³ independently of one another are hydrogen, methyl, optionally substituted by fluorine, chlorine, hydroxy, cyano, C₁-C₄-alkoxy, C₁-C₄-alkylcarbonyloxy or triazolyl-substituted C₂-C₄-alkyl or a radical -COR⁴ and
R⁴ for C₁-C₄-alkyl, C₁-C₄-alkylamino, C₁-C₄-alkoxy or in each case optionally by fluorine, chlorine, bromine, iodine, hydroxy, nitro, cyano, C₁-C₄-alkyl which is optionally substituted by fluorine or chlorine is, or C₁-C₄-alkoxy, which is optionally substituted by fluorine or chlorine, substituted phenyl or benzyl, or
[C] structures (Ia-5-1) and (Ia-5-2)

are present in which
n stands for 2,
B¹ for fluorine, 2-chlorine, 3-chlorine, 5-chlorine, 6-chlorine, bromine, iodine, 3-hydroxy, 5-hydroxy, 2-nitro, 3-nitro, 5-nitro, 6-nitro, 2 -Methyl, 3-methyl, 5-methyl, 6-methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, C₅-C₁₆ alkyl, C₁-C₄ alkyl which is substituted by fluorine or chlorine, ethoxy, C₁-C₄-alkoxy which is substituted by fluorine or chlorine, tetrahydropyranyloxy, phenyl-C₁-C₄-alkyloxy, C₁-C₄-alkylcarbonyloxy, a radical -NR²R³, 2-amino, 3,4-dihydroxy, 3-hydroxy-4-methoxy, 4-diethylamino-2-hydroxy, 4-methoxy-2,5-methyl, 3,4-dimethoxy, 3,4,5-trimethoxy, 4-N, N-di- (2-acetoxyethyl) amino-2-methoxy, 4-ethoxycarbonylamino-2,5-dimethoxy, 2,5-bis (ethoxycarbonyl amino) -4-methoxy, 2-ethoxy-5-dimethylamino, 4 -Dimethylamino-2-ethoxycarbonylamino, by optionally by fluorine, chlorine, bromine, iodine, nitro, cyano, C₁-C₄-alkyl, which is optionally substituted by fluorine or chlorine, or C₁-C₄-alkoxy, optionally by F luor or chlorine is substituted, phenyl or substituted by optionally phenyl-substituted triazolyl or pyrazolyl-substituted phenyl, by fluorine, chlorine, bromine, iodine, hydroxy, nitro, cyano, C₁-C₁₆-alkyl, C₁-C₄-alkyl by Fluorine or chlorine is substituted, C₁-C₈-alkoxy, C₁-C Alk-alkoxy which is substituted by fluorine or chlorine, tetrahydropyranyloxy, phenyl-C₁-C₄-alkyloxy, C₁-C₄-alkylcarbonyloxy, a radical -NR²R³, by optionally by Fluorine, chlorine, bromine, iodine, nitro, cyano, C₁-C₄-alkyl, which is optionally substituted by fluorine or chlorine, or C₁-C₄-alkoxy, which is optionally substituted by fluorine or chlorine, substituted by phenyl or by optionally substituted by Phenyl-substituted triazolyl or pyrazolyl-substituted naphthyl or anthryl or for each optionally by fluorine, chlorine, bromine, iodine, hydroxy, nitro, cyano, C₁-C₁₆ alkyl, C₁-C₄- alkyl, which is substituted by fluorine or chlorine is substituted, C₁-C₈-alkoxy, C₁-C₄-alkoxy which is substituted by fluorine or chlorine, tetra hydropyranyloxy, phenyl-C₁-C₄-alkyloxy, C₁-C₄-alkylcarbonyloxy or a radical -NR²R³ substituted hetaryl, especially furyl, Benzofuryl, thienyl, benzothienyl, pyrrolyl, indolyl, carbazolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, thiazolyl, pyridyl or pyrimidyl or for 1,2,3,5,6,7-hexahydro-pyrido [3,2,1-ÿ ] quinolinyl stands,
R² and R³ independently of one another are hydrogen, methyl, if appropriate substituted by fluorine, chlorine, hydroxy, cyano, C₁-C₄alkoxy, C₁-C₄alkylcarbonyloxy or triazolyl, C₂-C₄alkyl or a radical -COR⁴, but not both simultaneously for hydrogen, methyl or ethyl and
R⁴ for C₁-C₄-alkyl, C₁-C₄-alkylamino, C₁-C₄-alkoxy or in each case optionally by fluorine, chlorine, bromine, iodine, hydroxy, nitro, cyano, C₁-C₄-alkyl which is optionally substituted by fluorine or chlorine is, or C₁-C₄ alkoxy, which is optionally substituted by fluorine or chlorine, substituted phenyl or benzyl.

Compounds of the formula (Ia) in which
[A] structures (Ia-1-1) to (Ia-4-2)

are present in which
n represents the numbers 1, 2 or 3,
B¹ for by fluorine, chlorine, bromine, hydroxy, nitro, cyano, n-C₁-C₁₂- alkyl, isopropyl, isobutyl, sec-butyl, tert-butyl, neo-pentyl, C₁-C₄- alkyl, which by fluorine or chlorine is substituted, C₁-C₄-alkoxy, C₁-C₄-alkoxy which is substituted by fluorine or chlorine, tetra hydropyranyloxy, benzyloxy, C₁-C₄-alkylcarbonyloxy, a radical -NR²R³, by optionally by fluorine, chlorine, bromine, Nitro, cyano, methyl, trifluoromethyl, methoxy, trifluoromethoxy-substituted phenyl or phenyl, naphthyl or anthryl which is optionally substituted by phenyl-substituted triazolyl or pyrazolyl or each in each case by fluorine, chlorine, bromine, hydroxy, nitro, cyano, n-C₁- C₁₂-alkyl, isopropyl, isobutyl, sec.-butyl, tert-butyl, neo-pentyl, C₁-C₄-alkyl, which is substituted by fluorine or chlorine, C₁-C₄-alkoxy, C₁-C₄-alkoxy, by Fluorine or chlorine is substituted, tetrahydropyranyloxy, benzyloxy, C₁-C₄-alkylcarbonyloxy or one Radical -NR²R³ substituted furyl, benzofuryl, thienyl, benzothienyl, pyrrolyl, indolyl, carbazolyl, thiazolyl or pyridyl or stands for 1,2,3,5,6,7-hexahydro-pyrido- [3,2,1-ÿ] quinolinyl ,
R² and R³ independently of one another are hydrogen, methyl, optionally substituted by fluorine, chlorine, hydroxyl, cyano, methoxy, acetyloxy or triazolyl or represent a radical -COR⁴,
R⁴ represents methyl, ethyl, methylamino, ethylamino, methoxy, ethoxy or in each case optionally substituted by fluorine, chlorine, bromine, hydroxy, nitro, cyano, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, trifluoromethoxy and phenyl or benzyl and
R ^{1-1 represents} fluorine, chlorine, hydroxy, amino, nitro, cyano, methyl, trifluoromethyl, methoxy, methylamino or dimethylamino,
except 3- (2,4-dimethoxy-benzylidene) -2- (6-methyl-3-pyridyl) -3,4,5,6-tetrahydropyridine, or
[B] structures (Ia-5-1) and (Ia-5-2)

are present in which
n represents the numbers 1 or 3,
B¹ for by fluorine, chlorine, bromine, hydroxy, nitro, cyano, n-C₁-C₁₂- alkyl, isopropyl, isobutyl, sec-butyl, tert-butyl, neo-pentyl, C₁-C₄- alkyl, which by fluorine or chlorine is substituted, C₁-C₄-alkoxy, C₁-C₄-alkoxy which is substituted by fluorine or chlorine, tetrahydropyranyloxy, benzyloxy, C, -C₄-alkylcarbonyloxy, a radical -NR²R³, by optionally by fluorine, chlorine, bromine, Nitro, cyano, methyl, trifluoromethyl, methoxy, trifluoromethoxy-substituted phenyl or phenyl, naphthyl or anthryl optionally substituted by triazolyl or pyrazolyl or optionally by fluorine, chlorine, bromine,
Hydroxy, nitro, cyano, n-C₁-C₁₂-alkyl, isopropyl, isobutyl, sec.-butyl, tert.-butyl, neo-pentyl, C₁-C₄-alkyl which is substituted by fluorine or chlorine, C₁-C₄- Alkoxy, C₁-C₄-alkoxy which is substituted by fluorine or chlorine, tetrahydropyranyloxy, benzyloxy, C₁-C₄-alkylcarbonyloxy or a radical -NR²R³ substituted furyl, benzofuryl, thienyl, benzothienyl, pyrrolyl, indolyl, carbazolyl, thiazolyl or pyridyl or for 1,2,3,5,6,7-hexahydro-pyrido [3,2,1-ÿ] quinolinyl,
R² and R³ independently of one another are hydrogen, methyl, optionally substituted by fluorine, chlorine, hydroxyl, cyano, methoxy, acetyloxy or triazolyl or represent a radical -COR⁴,
R⁴ represents methyl, ethyl, methylamino, ethylamino, methoxy, ethoxy or in each case optionally substituted by fluorine, chlorine, bromine, hydroxy, nitro, cyano, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, trifluoromethoxy and phenyl or benzyl and
R ^{1-1 stands} for hydrogen, fluorine, chlorine, hydroxy, amino, nitro, cyano, methyl, trifluoromethyl, methoxy, methylamino or dimethylamino, or
[C] structures (Ia-5-1) and (Ia-5-2)

are present in which
n stands for 2,
B¹ for by fluorine, 2-chlorine, 3-chlorine, 5-chlorine, 6-chlorine, bromine, 3-hydroxy, 5-hydroxy, 2-nitro, 3-nitro, 5-nitro, 6-nitro, 2-methyl , 3-methyl, 5-methyl, 6-methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neo-pentyl, n-C₅-C₁₂-alkyl, C₁ -C₄- alkyl, which is substituted by fluorine or chlorine, ethoxy, C₁-C₄- alkoxy, which is substituted by fluorine or chlorine, tetrahydro pyranyloxy, benzyloxy, C₁-C₄-alkylcarbonyloxy, a radical -NR²R³, 2-amino, 3rd , 4-dihydroxy, 3-hydroxy-4-methoxy, 4-diethylamino-2-hydroxy, 4-methoxy-2,5-methyl, 3,4-dimethoxy, 3,4,5-trimethoxy, 4-N, N -Di- (2-acetoxyethyl) amino-2-methoxy, 4-ethoxycarbonylamino-2,5-dimethoxy, 2,5-bis (ethoxycarbonyl amino) -4-methoxy, 2-ethoxy-5-dimethylamino, 4- Dimethylamino-2-ethoxycarbonylamino, by phenyl optionally substituted by fluorine, chlorine, bromine, nitro, cyano, methyl, trifluoromethyl, methoxy, trifluoromethoxy or by triazolyl or optionally substituted by phenyl the pyrazolyl substituted phenyl for fluorine, chlorine, bromine, hydroxy, nitro, cyano, n-C₁-C₁₂-alkyl, isopropyl, isobutyl, sec-butyl, tert-butyl, neo-pentyl, C₁-C₄-alkyl , which is substituted by fluorine or chlorine, C₁-C₄- alkoxy, C₁-C₄-alkoxy which is substituted by fluorine or chlorine, tetrahydropyranyloxy, benzyloxy, C₁-C₄-alkylcarbonyloxy, a radical -NR²R³, optionally by fluorine, chlorine , Bromine, nitro, cyano, methyl, trifluoromethyl, methoxy, trifluoromethoxy substituted phenyl or naphthyl or anthryl optionally substituted by triazolyl or pyrazolyl or optionally substituted by fluorine, chlorine, bromine, hydroxy, nitro, cyano, n-C₁ -C₁₂-alkyl, isopropyl, isobutyl, sec-butyl, tert-butyl, neo-pentyl, C₁-C--alkyl which is substituted by fluorine or chlorine, C₁-C₄-alkoxy, C₁-C--alkoxy, which is substituted by fluorine or chlorine, tetrahydropyranyloxy, benzyloxy, C₁-C₄- Al kylcarbonyloxy or a radical -NR²R³ substituted furyl, benzofuryl, thienyl, benzothienyl, pyrrolyl, indolyl, carbazolyl, thiazolyl or pyridyl or for 1,2,3,5,6,7-hexahydro-pyrido- [3,2,1-ÿ ] quinolinyl stands,
R² and R³ independently of one another are hydrogen, methyl, optionally substituted by fluorine, chlorine, hydroxyl, cyano, methoxy, acetyloxy or triazolyl, or a radical -COR⁴, but not both at the same time each for hydrogen, methyl or ethyl,
R⁴ represents methyl, ethyl, methylamino, ethylamino, methoxy, ethoxy or in each case optionally substituted by fluorine, chlorine, bromine, hydroxy, nitro, cyano, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, trifluoromethoxy-substituted phenyl or benzyl.

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-a), in which a combination of those listed above as preferred (preferred) meanings.

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

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

Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenyl can NEN, also in connection with heteroatoms, such as. B. in alkoxy, if possible, each be straight or branched.

Optionally substituted radicals can be mono- or polysubstituted, in the case of multiple substitutions, the substituents are the same or different can.

For example, 2- (3-pyridyl) -3,4,5,6-tetrahydropyridine dihydro is used chloride and 4-propylbenzaldehyde as starting materials, so the reaction can process (A) according to the invention using the following formula are given:

For example, if 3- (4-trifluoromethoxybenzylidene) -2- (5-methyl-3- pyridyl) -4,5-dihydro-3H-pyrrole as starting material and sodium borohydride as Reducing agent, the reaction sequence of the process according to the invention (B) can be represented by the following formula scheme:

The imino required to carry out process (A) according to the invention Formula (II) generally defines heterocyclyl-substituted pyridines.

The compounds of formula (II) are known in part or can be, for. B. produce by known methods (cf., for example, Synthesis 1977, 242); J. Org. Chem. 43: 2860 (1978); J. Org. Chem. 46, 3040 (1981), WO 94/05288).

So compounds of formula (II) z. B. by making N-Tri methylsilyllactams of formula (V) in the presence of a diluent such as e.g. B. diethyl ether and a strong base such as. B. lithium diisopropylamide with Pyridinecarboxylic acid esters of the formula (IV) in which R⁵ is C₁-C₄alkyl, condensed and then in the presence of aqueous mineral acid Ring opening decarboxylated and recycled.

Pyridine carboxylic acid esters of the formula (IV) are described in part or leave produce themselves in known ways. N-trimethylsilyl-2-pyrrolidone is more commercial currently available. N-trimethylsilyl-δ-valerolactam or N-trimethylsilyl-ε-capro lactam are described in the literature (Tetrahedron Lett. 25, 5513 (1984)) and can be obtained from the free lactones by deprotonation with a strong base such as B. LDA and silylation with trimethylchlorosilane.

Compounds of the formula (II) in which n = 1 (II-a) can, for. B. manufacture, by using halopyridines of the formula (VI) in which X is preferably bromine or Iodine is in the presence of a diluent such as. B. Diethyl ether first for example lithiated with n-butyllithium. This is followed by N-vinyl-2-pyrrolidone implemented and eliminated with aqueous mineral acid vinyl alcohol (Synthesis 1977, 498).

Halopyridines of the formula (VI) have been described in part or can be broken down establish known ways. N-vinyl-2-pyrrolidone is commercially available.  

Those still required to carry out process (A) according to the invention Aromatic aldehydes are generally defined by the formula (III).

Some of the aromatic aldehydes of the formula (III) are known or have not been disclosed are manufactured by generally known methods.

The pyridines required to carry out process (B) according to the invention of formula (I-b) are a subset of the compounds of the invention general formula (I-a) and z. B. by method (A).

The condensation according to process (A) is preferably carried out in the presence of a Acid performed. All inorganic and organic proto come as such nominal as well as Lewis acids, as well as all polymeric acids in question. For this ge hear for example hydrogen chloride, sulfuric acid, phosphoric acid, ants acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfone acid, toluenesulfonic acid, boron trifluoride (also as etherate), boron tribromide, alumi nium trichloride, zinc chloride, ferric chloride, antimony pentachloride, acidic ions exchanger, acidic alumina and acidic silica gel, salt or are preferred Acetic acid.

Process (A) is preferably carried out in the presence of a diluent carried out. As such come water, organic solvents and belie other mixtures thereof. Examples include: aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, Hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or Decalin; halogenated hydrocarbons, such as chlorobenzene, Di chlorobenzene, methylene chloride, chloroform, carbon tetrachloride, dichloro-, trichlor ethane or tetrachlorethylene; Ethers, such as diethyl, diisopropyl, methyl t-butyl, Methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxy ethane, diethylene glycol dimethyl ether or anisole; Ketones, such as acetone, butanone, Methyl isobutyl ketone or cyclohexanone; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides such as formamide, N, N-dimethyl form amide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or He xamethylphosphoric triamide; N-oxides such as N-methylmorpholine-N-oxide; Esters such as methyl, ethyl or butyl acetate; Sulfoxides such as dimethyl sulfoxide; Sulfones, like sulfolane; Alcohols, such as methanol, ethanol, n- or i-propanol, n-, iso-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, di  ethylene glycol monomethyl ether, diethylene glycol monoethyl ether; Water. Prefers be methanol or ethanol, also in a mixture with water.

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

When carrying out process (A) according to the invention, the Compound of formula (II) and the aldehyde of formula (III) in general molar ratio of 1: 0.5 to 1: 5, preferably 1: 1 to 1: 3 used. The Acid can be used in catalytic to molar amounts, i.e. H. per mole Aldehyde is used from 0 to 10 mol, preferably 0.1 to 2 mol, of acid equivalent.

The hydrogenation according to process (B) can be carried out according to generally known processes either with hydrogen gas (in the presence of a heterogeneous metal catalyst such as Raney nickel, palladium on carbon or platinum dioxide or a homogeneous catalyst such as tris (triphenylphosphonium) rhodium (I) chloride) or with complex metal hydrides such as Sodium boranate, sodium cyanoboranate or lithium aluminum hydride performed will. The choice of method depends on the selectivity, which also depends on the Residues of the pyridines of formula (I-b) depends. Should only be the Imino group are hydrogenated without attacking the exocyclic double bond, sodium boranate is preferably used.

Process (B) is preferably carried out in the presence of a diluent carried out. As such come water, organic solvents and belie other mixtures thereof. Examples include: aliphatic, ali cyclic or aromatic hydrocarbons, such as petroleum ether, Hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or Decalin; Ethers, such as diethyl, diisopropyl, methyl t-butyl, methyl t-amyl ether, Dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, diethylene glycol koldimethyl ether or anisole; Esters such as methyl, ethyl or butyl acetate; Sulf oxides such as dimethyl sulfoxide; Alcohols, such as methanol, ethanol, n- or i-propanol, n-, iso-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, meth oxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; Water. Methanol, methanol-water mixtures or vinegar are preferred acid.  

When carrying out process (B) according to the invention, either per equivalent of double bond to be hydrogenated, if appropriate after prehydrogenation of the catalyst, 1.0 to 1.1 mol of hydrogen gas or 1.0 to 3.0 hydrogen equivalent complex metal hydride used.

The reaction temperature in process (B) according to the invention can be varied within a wide range. Generally you work at temperatures between -20 ° C and + 100 ° C, preferably at 0 ° C to 80 ° C.

The reactions of the processes according to the invention can be carried out at normal pressure or be carried out under increased pressure, preferably at normal pressure worked. The processing takes place according to the usual organic methods Chemistry. The end products are preferably by crystallization, chromato graphical cleaning or by removing the volatile components if necessary cleaned in vacuum.

With good plant tolerance and favorable warm-blood toxicity, the active substances are suitable for combating animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stored products and materials, and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The pests mentioned above 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 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, Trips tabaci.
From the order of Heteroptera z. B. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
From the order of Homoptera z. B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus sppe, Phrosiphumumonpp., Macrosiphumum 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 thurberiis sppia, Fpp , Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Teriaineolaellaella, Galleria mellellaella 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 chrysocephppis, Orphusus spp. , Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Giptusibbium psol. 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., Chrysomyla spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomox ., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.
From the order of the Siphonaptera z. B. Xenopsylla cheopis, Ceratophyllus spp. From the order of the Arachnida z. B. Scorpio maurus, Latrodectus mactans.
From the order of Acarina z. B. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Choroptes spp.,. Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.

Plant parasitic nematodes include Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Meloido gyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp.

The active compounds of the formula (I) according to the invention are particularly noteworthy due to its excellent action against the caterpillars' caterpillars (Plutella maculipennis), against the larvae of the green leafhopper (Neophotettix cincticeps) and against the common spider mite (Tetranychus urticae).

The active ingredients can be converted into the usual formulations, such as Lö solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient impregnated natural and synthetic materials as well as very fine encapsulation in polymeric fabrics.

These formulations are prepared in a known manner, e.g. B. by Vermi the active ingredients with extenders, i.e. liquid solvents and / or fe Most carriers, optionally using surface-active agents agents, i.e. emulsifiers and / or dispersants and / or foam-producing agents Means.

In the case of the use of water as an extender, e.g. B. also organic Solvents are used as auxiliary solvents. As a liquid solvent essentially come into question: aromatics, such as xylene, toluene, or alkylnaph thalines, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as  Chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons substances 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, 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.

In the formulations, adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers are 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 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 weight percent active ingredient, preferably between 0.5 and 90%.  

The active ingredient according to the invention can be present in its commercially available formulations and in the use forms prepared from these formulations in admixture with other active ingredients, such as insecticides, attractants, sterilants, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms and others
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-methoxylmino-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 Fuimecyc 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, tecnazene, tetraconazole, thiabendazole, Thicyofen, thiophanate-methyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
Validamycin A, vinclozolin,
Zineb, ziram.

Bactericides

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

Insecticides / acaricides / nematicides

Abamectin, Abamectin, AC 303 630, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin,
Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyluthrin, Bifen thrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157 419, CGA 184699, Chloethocarb, Chlorethoxyfos, Chlorfenvinphos, Chlor fluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Cis-Resmethrin, Clocy thrin, Chrinophhrin, Clophin Cyhalothrin, cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflubenzuron, Dimethoat, Dimethylvinphos, Dioxathion, Disulfoton,
Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Etho prophos, Etrimphos,

Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenothxatophion, Fufionophon, Fufionophon, Fufionophon, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufon, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufox
HCH, heptenophos, hexaflumuron, hexythiazox,
Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivemectin,
Lamda-cyhalothrin, Lufenuron,
Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,
Naled, NC 184, NI 25, Nitenpyram,
Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,
Parathion A, parathion M, permethrin, 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.

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

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 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, hygiene and stored-product pests, but also in the veterinary sector against animal parasites (ectoparasites) such as tick ticks, leather ticks, mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, hair lice, Featherlings and fleas. These parasites include:
From the order of the Anoplurida z. B. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.
From the order of the Mallophagida and the subordinates Amblycerina and Ischnocerina z. B. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.
From the order Diptera and the subordinates Nematocerina and Brachycerina z. B. Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp ., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp.
From the order of the Siphonapterida z. B. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.
From the order of the Heteropterida z. B. Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.
From the order of the Blattarida z. B. Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp.
From the subclass of Acaria (Acarida) and the orders of the Meta and Mesostigmata z. B. Argas spp., Ornithodorus spp., Otabius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemaphysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp. Pneu monyssus spp., Sternostoma spp., Varroa spp.
From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata) z. B. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp. Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp.
For example, they show excellent effectiveness against Boophilus microplus and Lucilia cuprina.

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

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

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

It has also been found that the compounds of the formula (I) show a high insecticidal activity against insects, the technical mate destroy rialien.

The following insects may be mentioned by way of example and preferably, but without limitation:
Beetle like
Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearesces, Lyctus pubis linearis, Lyctus pubis linearis, speculum Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus
Skin wings like
Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur
Termites like
Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.
Bristle tails, such as Lepisma saccharma.

In the present context, technical materials include non-living ones Understand materials, such as preferably plastics, adhesives, glues, Paper and cardboard, leather, wood and wood processing products and paint medium.

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

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

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

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

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

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

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

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

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

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

The organic non-volatile oily or oily solvents with a Evaporation rate above 35 and a flash point above 30 ° C, preferably above 45 ° C, can be partially organic or slightly volatile chemical solvents are replaced, provided that the solvent mix also an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide fungicide Mixture is soluble or emulsifiable in this solvent mixture.

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

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

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

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

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

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

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

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

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

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

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

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

Manufacturing examples Example I-1 (Method A)

To a solution of 1.5 g of 3- (4,5-dihydro-3H-pyrrol-2-yl) pyridine in 20 ml Ethanol was 3.5 g of 2,4-dimethoxybenzaldehyde at 20 ° C and then 10 Drops conc. Given hydrochloric acid. The reaction mixture was after heating held at 60 ° C for about 24 h at this temperature. After sales control by DC (Thin layer chromatography) the product was added by adding tert-butyl precipitated methyl ether. After sucking off the mother liquor and drying 1.65 g (56% of theory) 3- (2,4-dimethoxybenzylidene) -2- (3-pyridyl) -4,5-dihydro- 3H-pyrrole obtained from the melting point 196-198 ° C.

Example I-2 (Method A)

To a solution of 1.5 g of 3- (4,5-dihydro-3H-pyrrol-2-yl) pyridine in 30 ml Methanol was 3 g of 4-nitrobenzaldehyde, 1 g of acetic acid and 1.5 g at 20 ° C. Given sodium acetate. It was heated to 60 ° C and 2 h at this temperature reacted calmly. After sales control by DC, the solution was in a vacuum constricted. The solution was saturated with semisaturated NH₄Cl solution and Washed NaCl solution and dried with sodium sulfate. The raw product was purified by column chromatography (stationary phase: silica gel; mobile phase Dichloromethane: methanol = 2: 1). 1.80 g (65% of theory) of 3- (4- Nitrobenzylidene) -2- (3-pyridyl) -4,5-dihydro-3H-pyrrole, melting point 146- 148 ° C  

Example I-3 (Method A)

0.875 g of anabasein dihydrochloride were dissolved in 15.5 ml of a methanolic Buffer containing 0.6 mol / l glacial acetic acid and 0.2 mol / l sodium acetate, dissolved and with 1.133 g of m-nitrobenzaldehyde were added. The mixture was stirred at 60 ° C for 48 h. The solvent was then evaporated, the residue with 25 ml Water added and to remove the excess aldehyde with Extracted ethyl acetate. The free base was then removed from the aqueous phase Addition of sodium carbonate released and shaken out with ethyl acetate. The combined organic phases were dried and evaporated. Of the Residue was taken up in hydrochloric acid ethanol and again evaporated. 1.09 g (79.3% of theory) of crystalline 3- (4-nitro) were obtained benzylidene) -2- (6-methyl-3-pyridyl) -3,4,5,6-tetrahydropyridine dihydrochloride, the can be recrystallized from methanol.

Example I-4 (Method A)

To a suspension of 0.875 g anabasein dihydrochloride in 10 ml abs. Ethanol 1.15 g of isovanillin and 7 drops of conc. Given hydrochloric acid. The mixture was stirred at 60 ° C for 24 h. After the reaction was allowed to cool and precipitated the product by adding 50 ml of ethyl acetate. By suction and 1.25 g (87.4% of theory) of 3- (3-hydroxy-4-methoxy) were dried benzylidene) -2- (6-methyl-3-pyridyl) -3,4,5,6-tetrahydropyridine dihydrochloride receive.  

Examples I-5 to I-88

Analogous to Examples I-1 to I-4 and according to the general information on Method (A) in the description were set out in Table 1 below led compounds of formula (I-a-1-1) or (I-a-1-5) or their dihydro get chloride.

Table 1

Example II-1 (Method A)

Analogous to Example I-2 and according to the information in the general description of the Process (A) was made from 4- (4,5-dihydro-3H-pyrrol-2-yl) pyridine and 3-nitro benzaldehyde 3- (3-nitrobenzylidene) -2- (4-pyridyl) -4,5-dihydro-3H-pyrrole as an oil receive.

Manufacture of intermediate products Example III-1

A solution of 12 g of 2-chloro-5-iodopyridine in 150 ml of diethyl ether was added -78 ° C. 17 ml of 23% solution of n-butyllithium in n-hexane was added dropwise. Thereon was at this temperature a solution of 6 g of N-vinyl-2-pyrrolidone in 20 ml Ether added dropwise. The mixture was left to react at -78 ° C. for 1 h. After warming to 0 ° C was carefully concentrated with 30 ml. Hydrochloric acid hydrolyzed. After dilution with 100 ml of water, the phases were separated and the hydrochloric acid with ether washed. This was made alkaline with potassium hydroxide solution and the base released extracted with dichloromethane. The combined dichloromethane phases were over Dried sodium sulfate, concentrated in vacuo and chromato over a column graphed (stationary phase: silica gel; mobile phase n-hexane: acetic acid = 7: 3). 2.50 g (28% of theory) of 2-chloro-5- (4,5-dihydro-3H-pyrrol-2-yl) - pyridine obtained from melting point 95-97 ° C.  

Examples of use Example A 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 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%. Here means 100% that all caterpillars have been killed; 0% means that no caterpillars were killed.

In this test z. B. the specified kill:  

Table A

Example B 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 specified amount of emulsifier and dilute the concentrate with water to the desired concentration.

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

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

This test shows at an active ingredient concentration of 0.1% after 6 days e.g. B. the compound from preparation example I-1 a degree of kill of 90%.  

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

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

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

Bean plants (Phaseolus vulgaris), strongly of all stages of the 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, e.g. B. the following compounds the specified Effect:  

Table C.

Claims (6)

1. Agent for controlling pests, characterized in that it contains at least one compound of the formula (I) in which
A for one of the groups stands,
wherein
n stands for one of the numbers 1, 2 or 3 and
B represents substituted aryl or optionally substituted het aryl and
R¹ represents hydrogen, halogen, hydroxy, amino, nitro, cyano, each optionally substituted by halogen-substituted alkyl or alkoxy, represents alkylamino, dialkylamino, alkylcarbonyl or alkoxycarbonyl,
and their biologically active salts. 2. 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. 3. Use of compounds of formula (I) according to claim 1 for Pest control. 4. Process for the preparation of pesticides, thereby characterized in that compounds of the formula (I) according to Claim 1 mixed with extenders and / or surface-active substances. 5. Compounds of formula (Ia) in which
A¹ for one of the residues and
in which
[A] n represents one of the numbers 1, 2 or 3,
B¹ represents optionally substituted aryl or hetaryl and
R ^{1-1 stands} for halogen, hydroxy, amino, nitro, cyano, in each case optionally substituted by halogen substituted alkyl or alkoxy, stands for alkylamino, dialkylamino, alkylcarbonyl or alkoxy carbonyl,
except for the compound 3- (2,4-dimethoxybenzylidene) -2- (6-methyl-3-pyridyl) -3,4,5,6-tetrahydropyridine,
or in which
[B] n represents the numbers 1 or 3,
B¹ represents substituted aryl or optionally substituted hetaryl and
R ^{1-1 represents} hydrogen,
or in which
[C] n represents 2,
B¹ for by fluorine, 2-chlorine, 3-chlorine, 5-chlorine, 6-chlorine, bromine, iodine, 3-hydroxy, 5-hydroxy, 2-nitro, 3-nitro, 5-nitro, 6-nitro, 2 -Methyl, 3-methyl, 5-methyl, 6-methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, C₅-C₁₆ alkyl, haloalkyl, ethoxy, haloalkoxy , Tetra hydropyranyloxy, phenylalkyloxy, alkylcarbonyloxy, a radical -NR²R³, 2-amino, 3,4-dihydroxy, 3-hydroxy-4-methoxy, 4-diethylamino-2-hydroxy, 4-methoxy-2,5-methyl, 3 , 4-dimethoxy, 3,4,5-trimethoxy, 4-N, N-di- (2-acetoxy ethyl) amino-2-methoxy, 4-ethoxycarbonylamino-2,5-dimethoxy, 2,5-bis - (ethoxycarbonylamino) -4-methoxy, 2-ethoxy-5-dimethylamino, 4-dimethylamino-2-ethoxycarbonylamino, each optionally substituted phenyl, triazolyl or pyrazolyl substituted phenyl; for each optionally substituted naphthyl or anthryl, except 4-dimethylamino-2-naphthyl; or for optionally substituted and optionally benzanellated 5- or 6-membered hetaryl, with the exception of unsubstituted 2- and 3-furyl; or stands for 1,2,3,5,6,7-hexahydro-pyrido [3,2,1-ÿ] quinolinyl,
R² and R³ independently of one another represent hydrogen, optionally substituted by fluorine, chlorine, hydroxy, cyano, alkylcarbonyloxy or triazolyl alkyl or a radical -COR⁴, but not both at the same time each represent hydrogen, methyl or ethyl,
R⁴ represents alkyl, alkylamino, alkoxy or optionally substituted phenyl or benzyl and
R ^{1-1 represents} hydrogen,
and their salts. 6. A process for the preparation of compounds of formula (Ia), characterized in that

• A) compounds of the formula (Ib) in which
  B¹ and R ^{1-1 have} the meanings given in claim 5,
  obtained when iminoheterocyclyl-substituted pyridines of the formula (II) in which
  R ^{1-1 has} the meaning given above,
  with aromatic aldehydes of the formula (III) B¹-CHO (III) in which
  B¹ has the meaning given above condensed,
• B) Compounds of the formula (Ic) in which
  B¹ and R ^{1-1 have} the meanings given above,
  obtained when hydrogenating pyridines of the formula (Ib).