Heterocyclyl-substituted phenyl compounds, processes and...

Details Heterocyclyl-substituted phenyl compounds, processes and... Heterocyclyl-substituted phenyl compounds, processes and...

1999-01-25

2001-03-13

McKane, Joseph K. (Department: 1613)

Drug, bio-affecting and body treating compositions

Designated organic active ingredient containing

Having -c-, wherein x is chalcogen, bonded directly to...

C514S364000, C514S376000, C514S384000, C548S132000, C548S227000, C548S263400, C549S450000

Reexamination Certificate

active

06200997

ABSTRACT:

The present invention relates to heterocyclyl-substituted phenyl compounds of the formula I,
where:
Y is halogen, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl or C
1
-C
4
-alkoxy;
n is 0, 1 or 2, where the radicals Y may be different if n=2;
E is a group A or B,
 where # denotes the bond to the phenyl ring;
V is oxygen or N—R
&agr;
, and
G is N—R
&bgr;
, where
R
&agr;
is C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
3
-C
6
-cycloalkyl or is arylmethylene with or without substitution;
R
&bgr;
is hydrogen or a radical R
&agr;
;
T is oxygen or oxymethylene;
Z is a group X, N═CWR
1
or N═C(R
1
)—C(R
2
)═NOR
3
;
X is heterocyclyl with or without substitution, aryl with or without substitution, hetaryl with or without substitution, arylmethylene with or without substitution or hetarylmethylene with or without substitution;
W is C
1
-C
6
-alkyl with or without substitution, C
2
-C
6
-alkenyl with or without substitution, C
2
-C
6
-alkynyl with or without substitution, C
3
-C
6
-cycloalkyl with or without substitution, C
3
-C
6
-cycloalkenyl with or without substitution, heterocyclyl with or without substitution, aryl with or without substitution or hetaryl with or without substitution;
R
1
is hydrogen, cyano, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkoxy, C
1
-C
4
-alkoxy-C
1
-C
4
-alkyl, C
3
-C
6
-cycloalkyl;
R
2
is hydrogen, cyano, halogen, C(R
d
)═NOR
3
or W, OW, SW or NR
c
W, where
R
c
is hydrogen, C
1
-C
6
-alkyl, C
2
-C
6
-alkenyl or C
2
-C
6
-alkynyl and
R
d
is hydrogen or C
1
-C
6
-alkyl;
R
3
is hydrogen, C
1
-C
6
-alkyl with or without substitution, C
2
-C
6
-alkenyl with or without substitution or C
2
-C
6
-alkynyl with or without substitution.
Additionally, the invention relates to processes and intermediates for preparing the compounds I and to the use of the compounds I for controlling harmful fungi and animal pests.
WO-A 95/14,009 and WO-A 97/02,255 disclose 4-phenyl-2,3-dihydroisoxazolones and 4-phenyl-2,4-dihydrotriazolones having substituents in the ortho position.
&agr;-Phenylacrylic acid and &agr;-phenyl-&agr;-methoximinoacetic acid derivatives having an aryl or hetaryl substituent in the ortho position are described in EP-A 253 213 and EP-A 398 692, those having an oxime ether group in the ortho position are described in DE-A 40 20 384, those having a bisoxime ether group are described in WO-A 95/21,153 and WO-A 97/05,103 and those having a trisoxime ether group are described in WO-A 97/15,552.
WO-A 95/14,009, WO-A 96/26,191, WO-A 96/36,229, WO-A 96/36,615, WO-A 96/36,616, WO-A 96/38,425, WO-A 97/00,612 and WO-A 97/05,120 disclose cyclic amides which carry an ortho-substituted phenyl ring in the position ortho to the amide carbonyl group. WO-A 96/36,633 discloses cyclic amides which carry a substituted heterocycle in the position ortho to the amide carbonyl group.
The compounds described in the abovementioned publications are suitable for use as crop protection agents against harmful fungi and, in some instances, against animal-pests.
However, in many cases their activity is unsatisfactory.
It is an object of the present invention to provide compounds having an improved activity.
We have found that this object is achieved by the substituted phenyl compounds of the formula I. Furthermore, we have found intermediates and processes for preparing the compounds I, and the use of the compounds I and of compositions comprising them for controlling harmful fungi and animal pests. Preference is given to the fungicidal activity.
The compounds of the formula I differ from the compounds which are known from the abovementioned publications in the design of the group E: in the compounds of the formula IA, the group E is a dioxolanedione if V is oxygen and an oxazolidinedione if V is N—R
&agr;
. In the compounds of the formula IB, the group E is an oxadiazolidinedione if V is oxygen and a triazolidinedione if V is N—R
&agr;
.
Compared with the prior art compounds, the compounds of the formula I have increased activity against harmful fungi and animal pests.
The compounds I can be obtained by various routes, it being immaterial for the synthesis whether the heterocycles E or the group T—Z is built up first. For clarity, the term
E
#
is therefore used for group A or B, or an appropriate precursor thereof, and
Z
#
is used for the group T—Z, or a suitable precursor thereof in the descriptions of the reactions hereinbelow.
For compounds of the formula IA
preference is given to introducing the group T—Z at the stage where E
#
is C(OH)COOR′, where R′ is C
1
-C
4
-alkyl.
For compounds of the formula IB
preference is given to introducing the group T—Z at the stage where E
#
is NH—NH
2
.
The group T—Z in the compounds of the formula I can be obtained by methods similar to those described in WO-A 96/07,633, or WO-A 97/24,317.
The synthesis route described hereinbelow is equally suitable for compounds of the formulae I in which T is oxygen or oxymethylene.
The oxazolidinediones of the formula IAa
#
are obtained in a particularly advantageous manner by acylating an alkyl &agr;-hydroxy-&agr;-phenylacetate of the formula IIA
#
with phosgene or a phosgene equivalent to give dicarbonyl compounds of the formula IIIA
#
, which are cyclized by reaction with primary amines of the formula IVa to give the oxadiazolidinediones of the formula IAa
#
.
In the formula IIA
#
, R′ is C
1
-C
4
-alkyl. Compounds of the formula IIA
#
are known from the literature, or they can be prepared by methods known from the literature [cf. WO-A 96/07,633].
1) The reaction of IIA
#
with phosgene or a phosgene equivalent, such as, for example, di- or triphosgene, is usually carried out at from −10° C. to 250° C., preferably at from 10° C. to 110° C., in an inert organic solvent in the presence of a base or a catalyst [cf. Chem. Ber., 72 (1972), p. 457; Chem. Soc. Rev., 3 (1974), p. 209; Angew. Chem., 107 (1995), p. 2746].
Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles, and also dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably tetrahydrofuran, dimethylformamide, chlorobenzene and toluene. It is also possible to employ mixtures of the abovementioned solvents.
Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal oxides, alkali metal and alkaline earth metal hydrides, alkali metal amides, alkali metal and alkaline earth metal carbonates, and also alkali metal bicarbonates, organometallic compounds, in particular alkali metal alkyls, alkylmagnesium halides, and furthermore organic bases, for example tertiary amines such as trimethylamine, triethylamine, triisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and also bicyclic amines. Particular preference is given to triethylamine and pyridine. The bases are generally employed in equimolar amounts, in excess or, if appropriate, as solvent.
The starting materials are generally reacted with one another in equimolar amounts. It may be advantageous in terms of yield to employ phosgene or the phosgene equivalent in excess, based on IIA
#
.
2) This reaction is usually carried out at from −10° C. to 250° C., preferably at from 0° C. to 100° C., in an inert organic solvent [cf. Chem. Ber., 33. (1900), p. 455 ff.]. Suitable solvents are aliphatic hydrocarbons, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles, alcohols such as methanol, ethanol, n-propano

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