Salicylohydrazide derivatives, processes and intermediates...

Details Salicylohydrazide derivatives, processes and intermediates... Salicylohydrazide derivatives, processes and intermediates...

2001-06-14

2002-09-24

Powers, Fiona T. (Department: 1626)

Drug, bio-affecting and body treating compositions

Designated organic active ingredient containing

Ortho-hydroxybenzoic acid or derivative doai

C564S148000, C564S150000, C514S159000

Reexamination Certificate

active

06455515

ABSTRACT:

Salicylohydrazide derivatives, processes and intermediates for their preparation, compositions comprising them, and their use
The present invention relates to salicylohydrazide derivatives of the formula I
in which the index and the substituents have the following meanings:
X is halogen, NO
2
, cyano, C
1
-C
4
-alkyl or C
1
-C
4
-alkoxy;
m is 0, 1, 2 or 3, it being possible for the substituents X to differ from each other if n is greater than 1;
R
1
is NO
2
, NH
2
or NH—CO—A;
A is hydrogen, C
1
-C
4
-alkyl, C
1
-C
4
-alkoxy, NH
2
, NHCH
3
or N(CH
3
)
2
;
R
2
is hydrogen, cyano, C
1
-C
6
-alkyl, C
2
-C
6
-alkenyl, C
2
-C
6
-alkynyl, C
1
-C
6
-haloalkyl, C
1
-C
6
-alkoxy or C
1
-C
6
-alkylthio;
it being possible for the hydrocarbon radicals to be unsubstituted or to be partially or fully halogenated or to have 1 to 3 groups R
a
R
a
is halogen, cyano, nitro, hydroxyl, C
1
-C
6
-alkyl, C
1
-C
6
-haloalkyl, C
1
-C
6
-alkylcarbonyl, C
3
-C
6
-cycloalkyl, C
1
-C
6
-alkoxy, C
1
-C
6
-haloalkoxy, C
1
-C
6
-alkoxycarbonyl, C
1
-C
6
-alkylthio, C
1
-C
6
-alkylamino,
di-C
1
-C
6
-alkylamino, C
2
-C
6
-alkenyl, C
3
-C
6
-alkenyloxy, C
3
-C
6
-alkynyloxy or C
1
-C
4
-alkylenedioxy which can be halogenated,
R
3
is phenyl, naphthyl, C
3
-C
10
-cycloalkyl, 5-membered or 6-membered hetaryl or 5-membered or 6-membered heterocyclyl containing one to three N atoms and/or one O or S atom or one or two O and/or S atoms, the ring systems being unsubstituted or substituted by one to three radicals R
b
:
R
b
is cyano, nitro, amino, aminocarbonyl, aminothiocarbonyl, halogen, hydroxyl, C
1
-C
6
-alkyl, C
1
-C
6
-haloalkyl, C
1
-C
6
-alkylcarbonyl, C
1
-C
6
-alkylsulfonyl, C
1
-C
6
-alkylsulfoxyl, C
3
-C
6
-cycloalkyl, C
1
-C
6
-alkoxy, C
1
-C
6
-haloalkoxy, C
1
-C
6
-alkyloxycarbonyl, C
1
-C
6
-alkylthio, C
1
-C
6
-alkylamino, di-C
1
-C
6
-alkylamino, C
1
-C
6
-alkylaminocarbonyl, di-C
1
-C
6
-alkylaminocarbonyl, C
1
-C
6
-alkylaminothiocarbonyl, di-C
1
-C
6
-alkylaminothiocarbonyl, C
2
-C
6
-alkenyl, C
2
-C
6
-alkenyloxy, phenyl, phenoxy, benzyl, benzyloxy, 5- or 6-membered heterocyclyl, 5- or 6-membered hetaryl, 5- or 6-membered hetaryloxy, C(═NOR
&agr;
)—OR
&bgr;
or OC(R
&agr;
)
2
—C (R
&bgr;
)═NOR
&bgr;
,
the cyclic radicals, in turn, being unsubstituted or substituted by one to three radicals R
c
:
R
c
is cyano, nitro, halogen, hydroxyl, amino, aminocarbonyl, aminothiocarbonyl, C
1
-C
6
-alkyl, C
1
-C
6
-haloalkyl, C
1
-C
6
-alkylsulfonyl, C
1
-C
6
-alkylsulfoxyl, C
3
-C
6
-cycloalkyl, C
1
-C
6
-alkoxy, C
1
-C
6
-haloalkoxy, C
1
-C
6
-alkoxycarbonyl. C
1
-C
6
-alkylthio, C
1
-C
6
-alkylamino, di-C
1
-C
6
-alkylamino, C
1
-C
6
-alkylaminocarbonyl, di-C
1
-C
6
-alkylaminocarbonyl, C
1
-C
6
-alkylaminothiocarbonyl, di-C
1
-C
6
-alkylaminothiocarbonyl, C
2
-C
6
-alkenyl, C
2
-C
6
-alkenyloxy, C
3
-C
6
-cycloalkyl, C
3
-C
6
-cycloalkenyl, phenyl, phenoxy, phenylthio, benzyl, benzyloxy, 5- or 6-membered heterocyclyl, 5- or 6-membered hetaryl, 5- or 6-membered hetaryloxy or C(═NOR
&agr;
)—OR
&bgr;
;
R
&agr;
, R
&bgr;
are hydrogen or C
1
-C
6
-alkyl.
Furthermore, the invention relates to processes for the preparation of these compounds, to compositions comprising them, and to their use for controlling harmful fungi.
WO-A 97/08135, DE-A 197 10 609 and WO-A 99/27783 disclose acylaminosalicylamides for controlling harmful fungi.
However, their action is unsatisfactory in many cases. Compounds with an improved action are an object of the present invention.
We have found that this object is achieved by the compounds defined at the outset. Moreover, there have been found processes for their preparation, compositions comprising them, and methods of controlling harmful fungi using the compounds I.
The compounds of the formula I differ from those known from the prior art by the hydrazide group.
Compared with the known compounds, the compounds of the formula I exhibit an increased efficacy against harmful fungi.
For example, compounds of the formula I can be synthesized starting from hydrazides of the formula II by subjecting hydrazides and carbonyl compounds of the formula III to a condensation reaction. The compounds of the formula IA are also used as intermediates for the preparation of further compounds I.
This reaction is usually carried out at temperatures from 20° C. to 100° C., preferably 20° C. to 50° C., in an inert organic solvent in the presence of an acid [cf. Indian J. Chem. B, (1983), Vol. 24, p. 979].
Suitable solvents are 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 methylether, dioxane and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, alcohols such as methanol, ethanol, n-propanol, isopropanol and n-butanol, and also dimethyl sulfoxide, dimethylformamide and dimethylacetamide, especially preferably alcohols such as methanol, ethanol, n-propanol, isopropanol and n-butanol. Mixtures of these solvents may also be used.
Acid and acidic catalysts which are used are inorganic acids such as hydrofluoric acid, (aqueous) hydrochloric acid, tetrabromic acid, sulfuric acid and perchloric acid, Lewis acids such as boron trifluoride, aluminum trichloride, iron(III) chloride, tin(IV) chloride, titanium(IV) chloride and zinc(II) chloride, and organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, citric acid, trifluoroacetic acid, p-toluenesulfonic acid, benzenesulfonic acid and camphorsulfonic acid.
In general, the acids are employed in catalytic amounts, but they may also be used in equimolar amounts, in an excess or, if appropriate, as solvent.
In general, the starting materials are reacted with each other in equimolar amounts. It may be advantageous for the yield to employ III in an excess based on II.
The starting materials II and III required for the preparation of compounds I are commercially available, known from the literature [ZA 70/00662; Labdev, (1973), part A, Vol. 11A(1-2), p. 35] or can be prepared in accordance with the literature cited.
To prepare compounds I where R
1
is NH
2
or NH—CO—A, hydrazides of the formula IA are reduced to aminophenol compounds of the formula IB.
The nitro group of IA can be reduced under generally customary conditions by reduction with iron, tin or zinc in the presence of an acid or by enzyme-catalyzed reduction [cf. Houben-Weyl, Vol. IV/1c, 4th Ed., p. 506, Thieme Verlag Stuttgart and New York (1980); ibid. Vol. IV/1d, 4th Ed., p. 473 (1981); Heterocycles (1990), Vol. 31. p. 2201].
The reaction with hydrogen is preferably carried out by catalytic hydrogenation at −20° C. and +180° C., preferably between −5 and +40° C. The minimum temperature is only determined by the freezing point of the solvent used. Normally, the hydrogenation is carried out at a hydrogen pressure between atmospheric pressure and at an superatmospheric pressure of 30 bar. Normally, the hydrogen is passed in under atmospheric or slight superatmospheric pressure [cf. WO-A 97/08135].
Catalysts which are employed for the catalytic hydrogenation are commercially available catalysts which comprise, for example, platinum, platinum oxide or palladium on a support, or else Raney nickel or Raney cobalt.
The use of platinum catalysts or palladium catalysts is preferred. The platinum or palladium content of the catalyst is not critical and can be varied within wide limits. A content of from 0.1 to 15% by weight, preferably from 0.5 to 10% by weight, based on the support material, is expedient. The amount of the platinum or palladium employed is between 0.001 and 10% by weight, preferably between 0.01 and 0.1% by weight, based on the nitro compound. In the preferred embodiment, carbon is used as support material. Other non-amphoteric supports such as graphite, BaSO
4
or SiC, are also suitable.
Suitable diluents are esters such as ethyl acetate, alcohols such as methanol, ethanol, n-propanol, n-, i-, sec- or tert-butanol, et

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