Pyridine derivatives, process for preparing the same and...

Details Pyridine derivatives, process for preparing the same and... Pyridine derivatives, process for preparing the same and...

1999-03-17

2001-05-08

Shah, Mukund J. (Department: 1624)

Plant protecting and regulating compositions

Plant growth regulating compositions

Organic active compound containing

C504S255000, C546S286000, C546S290000, C546S296000, C546S297000, C546S300000, C546S306000

Reexamination Certificate

active

06228810

ABSTRACT:

The present invention relates to pyridine derivatives of the formula I
where the index and the substituents have the following meanings:
X is cyano, nitro, halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy, C
1
-C
4
-haloalkoxy and C
3
-C
6
-cycloalkyl;
n is 0, 1, 2 or 3, it being possible for the substituents X to be different when n is greater than 1;
Y is oxygen or nitrogen, the nitrogen atom having attached to it a hydrogen atom or a C
1
-C
4
-alkyl group;
R is C(CO
2
CH
3
)═CHCH
3
, C(CO
2
CH
3
)═CHOCH
3
, C(CO
2
CH
3
)═NOCH
3
, C (CONH
2
)═NOCH
3
or C (CONHCH
3
)═NOCH
3
;
R
1
is hydrogen, hydroxyl, cyano, halogen,
C
1
-C
6
-alkyl, C
1
-C
6
-haloalkyl, C
1
-C
6
-alkoxy, C
1
-C
6
-haloalkoxy, C
1
-C
6
-alkylthio, C
3
-C
6
-cycloalkyl, C
3
-C
6
-cycloalkyl-C
1
-C
4
-alkyl,
aryl, aryl-C
1
-C
4
-alkyl, aryloxy-C
1
-C
4
-alkyl and aryl-C
1
-C
4
-alkoxy, it being possible for the aromatic rings to be partially or fully halogenated and/or to have attached to them one to three of the following radicals: cyano, nitro, C
1
-C
6
-alkyl, C
1
-C
6
-haloalkyl, C
1
-C
6
-alkoxy, C
1
-C
6
-haloalkoxy, and C (CH
3
)═N—A
1
—Ra;
R
a
is C
1
-C
6
-alkyl,
A
1
is oxygen or nitrogen, the nitrogen atom having attached to it a hydrogen atom or a C
1
-C
4
-alkyl group;
R
2
is hydrogen, cyano,
unsubstituted or substituted alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and hetaryl;
unsubstituted or substituted alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, heterocyclyloxy, aryloxy and hetaryloxy;
unsubstituted or substituted arylthio and hetarylthio;
—Q—C(R
3
)═N—Y
1
—R
4
or —Q—O—N═CR
5
R
6
where
Q is a direct bond, CH
2
, CH(CH
3
), CH(CH
2
CH
3
) or 1,1-cyclopropyl;
Y
1
is oxygen or nitrogen, the nitrogen atom having attached to it a hydrogen atom or a C
1
-C
4
-alkyl group;
R
3
is one of the groups mentioned for R
1
, or unsubstituted or substituted cycloalkoxy, heterocyclyloxy, aryloxy, hetaryloxy, arylthio and hetarylthio;
R
4
is unsubstituted or substituted C
1
-C
10
-alkyl, C
3
-C
6
-cycloalkyl, C
2
-C
10
-alkenyl, C
2
-C
10
-alkynyl, C
1
-C
10
-alkylcarbonyl, C
2
-C
10
-alkenylcarbonyl, C
2
-C
10
-alkynylcarbonyl or C
1
-C
10
-alkylsulfonyl; unsubstituted or substituted aryl, hetaryl, arylcarbonyl, hetarylcarbonyl, arylsulfonyl or hetarylsulfonyl;
R
5
, R
6
are methyl, ethyl, phenyl and benzyl, it being possible for the aromatic rings to have attached to them one to three of the following substituents: cyano, nitro, halogen, C
1
-C
6
-alkyl, C
1
-C
6
-haloalkyl, C
1
-C
6
-alkoxy and C
1
-C
6
-haloalkoxy;
R
1
and R
2
together with the carbon atom to which they are bonded are a four- to eight-membered ring which, in addition to carbon atoms, can contain one or two oxygen and/or sulfur atoms and/or NH and/or N(C
1
-C
4
-alkyl) groups and whose carbon atoms can have attached to them one of the following substituents: halogen, C
1
-C
6
-alkyl or C
1
-C
4
-alkoxyimino;
R
1
and R
2
not being bonded simultaneously to the carbon atom via hetero atoms;
and the salts thereof.
Moreover, the invention relates to processes for the preparation of these compounds, to compositions comprising them, and to their use for controlling animal pests and harmful fungi.
Compounds of the type I where Y is oxygen and R
2
is unsubstituted or substituted aryl or hetaryl are described in the literature in general form as fungicides (WO-A 95/06,033). However, only compounds which have attached to them an unsubstituted or substituted aryl group which is bonded to the pyridyl radical via oxygen, sulfur, oxymethylene or CH
2
—ON═C(CH
3
)— are disclosed in this publication.
It was an object of the present invention to provide compounds with an improved activity and a broadened spectrum of action.
We have found that this object is achieved by the compounds I defined at the outset. Furthermore, we have found processes for the preparation of these compounds, compositions comprising them, and their use for controlling animal pests and harmful fungi.
The compounds I can be prepared by various routes, it generally being irrelevant whether the group —Y—N═CR
1
R
2
or the radical R is first synthesized.
1. In the preparation of the compounds I where R is C(CO
2
CH
3
)═CHCH
3
, C(CO
2
CH
3
)═CHOCH
3
or C(CO
2
CH
3
)═NOCH
3
, a procedure is followed, for example, in which a pyridinecarboxylic acid of the formula IIa is first converted in a manner known per se into the acid chloride IIb and subsequently into the acid cyanide IIc; IIc is reacted via a Pinner reaction to give the corresponding &agr;-keto ester IIIa; IIIa is subsequently reacted with an oxime of the formula IV in the presence of a base to give the corresponding &agr;-keto ester IIIb; and IIIb is subsequently converted in a manner known per se either
a) with a Wittig or Wittig-Horner reagent of the formula Va into the corresponding compound Ia [R=C(CO
2
CH
3
)═CHOCH
3
], or
b) with a Wittig or Wittig-Horner reagent of the formula Vb into the corresponding compound Ib [R=C(CO
2
CH
3
)═CHCH
3
], or
c) with O-methylhydroxylamine or a salt thereof (Vc) into the corresponding compound Ic [R=C(CO
2
CH
3
)═NOCH
3
].
L
1
in formula IIa is a nucleophilically exchangeable leaving group such as [lacuna]
R# in formula IIa is hydrogen or a C
1
-C
4
-alkyl group, in particular hydrogen.
P* in formulae Va and Vb is a phosphonate or a phosphonium halide radical which is suitable for a Wittig or Wittig-Horner reaction, in particular PO(OCH
3
)
2
, PO(OCH
2
CH
3
)
2
and [(C
6
H
5
)
3
P
+
Cl
−
].
Z
−
in formula Vc is the anion of an inorganic acid, especially a halide anion, in particular chloride.
1A. The reaction of the pyridinecarboxylic acid IIa to give the acid chloride IIb is carried out in a manner known per se [Houben-Weyl, Supplementary Volume 5, p.59 et seq., 225 et seq. and 664 et seq.; J.Heterocycl.Chem, 30, (1993), 771] by means of customary chlorinating agents at from 0° C. to 150° C., preferably 10° C. to 100° C., in the presence or absence of an inert organic solvent.
Suitable chlorinating agents are all reagents customary for this purpose, in particular SOCl
2
, (COCl)
2
, PCl
3
, AlCl
3
and PCl
5
. In general, the chlorinating agents are used in an excess or, if appropriate, as the solvent.
Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, nitrites such as acetonitrile and propionitrile, especially preferably halogenated hydrocarbons or mixtures of these.
In general, the starting materials are reacted with each other in equimolar amounts. It may be advantageous for the yield to employ the chlorinating agent in an excess based on IIa.
The starting materials required for the preparation of the compounds I which are not already known from the literature [WO-A 95/06,033; J.Heterocycl.Chem. 30, (1993), 717; DE Appl. No. 19 540 989.2; DE Appl. No. 19 548 370.7] can be prepared in accordance with the literature cited.
1B. The reaction of the acid chloride IIb to give the cyanide IIc is carried out in a manner known per se [DE Appl. No. 19 603 990.8] at from 0° C. to 150° C., preferably 10° C. to 100° C., using an inorganic cyanide in an inert organic solvent, if appropriate as a mixture with water, in the presence of a customary phase-transfer catalyst (eg. tetraalkylammonium halides such as tetrabutylammonium chloride or tetrabutylammonium bromide).
Suitable inorganic cyanides are cyanides of metals of the first main group or of the sub-groups of the Periodic Table, for example lithium, sodium, potassium, copper and silver, in particular copper and sodium, and inorganic cyanides such as trimethylsilyl cyanide.
Suitable solvents are aromatic hydrocarbons such as toluene, o-, m- and p-xylene, nitrites such as acetonitrile and propionitrile, especia

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