Iminooxy-substituted benzyl phenyl ethers, processes and...

Details Iminooxy-substituted benzyl phenyl ethers, processes and... Iminooxy-substituted benzyl phenyl ethers, processes and...

2001-01-17

2002-11-19

Kumar, Shailendra (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Amino nitrogen containing

C564S165000, C560S035000, C514S539000, C514S620000

Reexamination Certificate

active

06482984

ABSTRACT:

The present invention relates to iminooxy-substituted benzyl phenyl ethers of the formula I
in which the substituents and the index have the following meanings:
Y is H, CH
3
, F or Cl;
Q is C(═CHOCH
3
)—COOCH
3
, C(═CHCH
3
)—COOCH
3
, C(═NOCH
3
)—COOCH
3
, C(═NOCH
3
)—CONHCH
3
or N(—OCH
3
)—COOCH
3
;
X is hydrogen, halogen, C
1
-C
4
-alkyl, C
1
-C
4
-alkoxy or CF
3
;
m is 1 or 2, where the radicals x may be different if m=2;
R
1
is C
1
-C
4
-alkyl and
R
2
is hydrogen or C
1
-C
4
-alkyl; or
R
1
and R
2
together are cyclopropyl, cyclopentyl or cyclohexyl;
R
3
is C
1
-C
6
-alkyl or CF
3
; and
R
4
is C
1
-C
4
-alkyl, C
3
-C
4
-alkenyl, C
3
-C
4
-alkynyl, C
1
-C
4
-haloalkyl, C
3
-C
4
-haloalkenyl or C
3
-C
4
-haloalkynyl;
and their salts.
In addition, the invention relates to processes and intermediates for preparing the compounds I, and also to compositions, and to the use of the compounds I for controlling harmful fungi.
Phenylcarbamates having a phenoxymethylene group in the ortho position are disclosed in WO-A 93/15046. &agr;-phenylacrylic acid and &agr;-phenyl-&agr;-methoximinoacetic acid derivatives having a phenoxymethylene grouping in the ortho position are known from EP-A 253 213, EP-A 280 185, EP-A 386 561, EP-A 477 631, EP-A 513 580 and EP-A 579 124. Some of the compounds described in these publications carry an oximino radical on the phenoxy grouping.
The compounds described in the abovementioned publications are suitable for use as crop protection agents against harmful fungi.
However, their action is frequently unsatisfactory. It is an object of the present invention to provide compounds having improved activity.
We have found that this object is achieved by the substituted benzyl phenyl ethers of the formula I. Furthermore, we have found intermediates and processes for preparing the compounds I, and the use of the compounds I and compositions comprising them for controlling harmful fungi.
The compounds of the formula I differ from the compounds known from the abovementioned publications in that the phenoxy group is substituted by the oximino radical, which is attached via oxygen. Compared to known compounds, the compounds of the formula I have increased activity against harmful fungi.
Compounds of the formula I are obtained, for example, starting from hydroxy compounds of the formula II
which are obtainable by oxidation of acetyl compounds of the formula II.1.
The oxidation is usually carried out at temperatures of from −20° C. to 60° C., preferably from 0° C. to 30° C., in an inert organic solvent or water in the presence of a base or a buffer, such as, for example, Na
2
HPO
4
[cf. Synthesis, (1991), 63; Heterocycles (1993), 819; Tetrahedron (1995), 3197]. Suitable oxidizing agents are, for example, hydrogen peroxide, m-chloroperbenzoic acid, peracetic acid, H
2
O
2
×BF
3
, peroxytrifluoroacetic acid or K
2
S
2
O
7
/H
2
SO
4
.
Suitable solvents are, in general, 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, and suitable bases are inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide. Particular preference is given to sodium hydroxide.
In general, the base is employed in catalytic amounts; however, it can also be employed in equimolar amounts or in excess.
The oxidation of the acetyl compounds II.1 can also be carried out in two steps. Primarily, it leads to acetyloxy compounds of the formula II.2 from which, directly or, if desired, in a separate step, the hydroxy compound II can be released under basic conditions.
Compounds of the formula I in which Q is C(═NOCH
3
)—CONHCH
3
are preferably prepared using compounds II.1 in which Q is C(═NOCH
3
)—COOCH
3
as starting materials in the reaction sequence outlined above, and using methylamine as base in the second step.
The starting materials II.1 required for the preparation of the compounds I are known from the literature [Cf. EP-A 513 580; EP-A 621 264], or they can be prepared in accordance with the quoted literature.
Hydroxy compounds of the formula II are reacted with keto compounds of the formula III to give compounds of the formula IV.
In formula III, L is a nucleophilically exchangeable group, such as halogen,preferably chlorine. The reaction is usually carried out at temperatures of from −10° C. to 120° C., preferably from 20° C. to 90° C., in an inert organic solvent in the presence of a base [cf. DE-A 38 27 222].
Suitable solvents are ethers, nitriles, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and also dimethyl sulfoxide, dimethyl formamide and dimethyl acetamide, particularly preferably dimethyl formamide, acetone and dimethyl acetamide. It is also possible to use mixtures of the solvents mentioned.
Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal hydrides, alkali metal amides, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicarbonates, such as sodium bicarbonate, alkali metal and alkaline earth metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxymagnesium. Particular preference is given to sodium bicarbonate, potassium carbonate, sodium methoxide and sodium hydroxide.
In general, the bases are employed in catalytic amounts; however, they can also be employed in equimolar amounts or in excess.
The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to use an excess of III, based on II.
Keto compounds of the formula III are known. Some of them are commercially available, or they can be prepared by known methods [(Synthesis (1990), 595; DE-A 27 16 895; Can.J.Chem. (1972), 2387; Tetrahedron (1970), 5191; Synthesis (1977), 189-191; EP-A 297 383; EP-A 298 332; Bull.Soc.Chim.Fr. (1973), 2732; J.Org.Chem. (1995), 8320; J.Organomet.Chem. (1975), 325].
The conversion of IV into the compounds of the formula I is carried out using amino compounds V which are preferably employed as aqueous solution or in the form of their acid addition salts, for example as hydrochlorides.
This reaction is usually carried out at temperatures of from 0° C. to 120° C., preferably from 20° C. to 80° C., in an inert organic solvent in the presence of a base [cf. EP-A 386 561].
Suitable solvents are aromatic hydrocarbons, such as toluene, or alcohols, such as methanol or ethanol, particularly preferably methanol. It is also possible to use mixtures of the solvents mentioned.
Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicarbonates, such as sodium bicarbonate; furthermore organic bases, for example tertiary amines, such as trimethylamine, triethylamine, triisopropylamine. Particular preference is given to sodium hydroxide, potassium carbonate and triethylamine.
The bases are generally employed in catalytic amounts; however, they can also be employed in equimolar amounts, in excess or, if appropriate, as solvent.
The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an excess of V, based on IV.
The reaction mixtures are worked up in a customary manner, for example by mixing with water, phase separation and, if appropriate, chromatographic purification of the crude products. In some cases, t

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