Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
1999-04-19
2002-02-05
Raymond, Richard L. (Department: 1624)
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Heterocyclic carbon compounds containing a hetero ring...
C514S229200, C514S245000, C544S008000, C544S067000, C544S212000
Reexamination Certificate
active
06344453
ABSTRACT:
The present invention relates to novel heterocyclic compounds, to a process for their preparation, and to their use as insecticides.
It has already been disclosed that 2-(nitromethylene) oxazolines have insecticidal activities (see ADVANCES IN PESTICIDE SCIENCE Part 2, pages 206 to 217. That article relates to symposia papers presented at the Fourth International Congress of Pesticide Chemistry, Zurich, Switzerland, Jul. 24-28, 1978, published by Pergamon Press).
There have been found novel heterocyclic compounds of the formula (I),
wherein A represents a five-membered or six-membered heteroaryl group comprising one to three hetero atoms selected from the group consisting of S, O, and N, said heteroaryl group being unsubstituted or substituted by a halogen atom or C
1-4
alkyl group, Z represents a three-membered straight chain each member being selected from the group consisting of CH
2
, O, S and N—R
2
with at least one of said three members being O, S or N—R
2
, E represents CH
2
, O, S or N—R
2
, wherein R
2
represents a hydrogen atom, a C
1-4
alkyl group, a C
1-4
alkoxy group or the group
wherein R
3
represents a hydrogen atom or halogen atom, X represents CH or N, Y represents a nitro group or cyano group, and R
1
represents a hydrogen atom or methyl group.
Novel heterocyclic compounds of the formula (I) are obtained when the compounds of the following formula (II)
wherein A and R
1
have the same meanings as mentioned above, and
Hal means a halogen atom are reacted with the compounds of the following formula (III)
wherein Z, E, X and Y have the same meanings as mentioned above,
if appropriate in the presence of an acid binder, and in the presence of inert solvents.
The novel heterocyclic compounds of the formula (I) exhibit powerful insecticidal properties.
Surprisingly, the heterocyclic compounds according to the invention exhibit a substantially greater insecticidal action than those known from the prior art, for instance, than those of the above-mentioned article “ADVANCES IN PESTICIDE SCIENCE Part 2”.
Among the heterocyclic compounds according to the invention, of the formula (I), preferred compounds are those in which
A represents 2-chloropyridin-5-yl or 2-chlorothiazol-5-yl, Z represents a three-membered straight chain, each member being selected from the group consisting of CH
2
, O, S and N—R
2
with at least one of said three members being O, S or N—R
2
, E represents CH
2
, O, S or N—R
2
, wherein R
2
represents a C
1-3
alkyl group, a C
1-3
alkoxy group or 2-chloropyridin-5-yl methyl, X represents N, and Y represents a nitro group or cyano group.
If, for example, 2-chloro-5-chloromethylpyridine and 3-cyanoiminomorpholine are used as starting materials, the course of the reaction can be represented by the following equation:
In the compound of the formula (II), A, R
1
and Hal have the same meanings as defined above, preferably A and R
1
have the same meanings as the above preferred meanings. Hal preferably stands for a chlorine atom.
The compound of the formula (II) to bemused according to the invention are already known. As examples there may be mentioned the following:
5-chloromethyl-2-chlorothiazole,
2-chloro-5-chloromethyl-pyridine,
5-chloromethyl-2-methylthiazole,
5-chloromethyl-2-fluoropyridine,
5-chloromethyl-3-methyl-isoxazole,
2-bromo-5-chloromethyl pyridine, and
5-chloromethyl-2-methylpyridine.
In the compound of the formula (III), Z, E, X and Y have the same meanings as defined above, preferably Z, E, X and Y have the same meanings as the above preferred meanings.
Some of the starring materials of the formula (III) are novel, and can be obtained as outlined below. For example, 3-cyano-iminomorpholine can be obtained when compounds of the formula (IV)
wherein R
4
represents a lower alkyl group are reacted with cyanamide in the presence of an inert solvent,
The compounds of the formula (IV) are novel and can be obtained when 3-morpholinone of the following formula
is reacted with compounds of the following formula (V)
(R
4
O)
2
SO
2
(V)
wherein R
4
has the same meaning as mentioned above, in the presence of an inert solvent. 3-Morpholinone is already known from Chemical Abstracts, Vol.47, 2761e. and the compounds of the formula (V) are also known compounds in the field of organic chemistry.
3-Nitroiminomorpholine of the formula (III) can be obtained when 3-amino-2H-1,4-dihydrooxazine of the following formula (VI)
is reacted with fuming nitric acid, in the presence of an inert solvent.
The compound of formula (VI) is novel and can be obtained, for example, when the compounds of the formula (IV) are reacted with ammonia.
3-nitromethylene morpholine of the above-mentioned formula (III) can be obtained when compounds of the formula (IV) are reacted with nitromethane, in the presence of inert solvents.
In the case where the compounds of formula (III) are represented by the following general formula (III′):
wherein R
2
and Y have the same meanings as mentioned above,
those compounds of formula (III′) can be obtained when compounds of the formula (VII)
R
2
—NH
2
(VII)
wherein R
2
has the same meaning as mentioned above, are reacted with nitroguanidine or cyanoguanidine in the presence of formaldehyde.
In carrying out process (a) mentioned above, any inert solvent can be used as diluent.
Examples of such diluents are water; aliphatic, cycloaliphatic and aromatic, optionally chlorinated, hydrocarbons, such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene and the like; ethers such as diethyl ether, methyl ethyl ether, di-isopropyl ether, dibutyl ether, propylene oxide, dioxane, tetrahydrofuran and the like; ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone and the like; nitrites such as acetonitrile, propionitrile, acrylonitrile and the like; alcohols such as methanol, ethanol, iso-propanol, butanol, ethylene glycol and the like; esters such as ethyl acetate, amyl acetate and the like; acid amides such as dimethyl formamide, dimethyl acetamide and the like; and sulfones and sulfoxides such as dimethyl sulfoxide, sulfolane and the like; and bases, for example, pyridine, etc.
The above-mentioned process (a) may be carried out in the presence of an acid binder such as, for example, a hydroxide, carbonate, bicarbonate, alcoholate of an alkali metal, and tertiary amines such as, for example, triethylamine, diethyl aniline, pyridine, etc.
In the process (a), the reaction temperature can be varied within a wide range. In general, the reaction is carried out at a temperature of about 0 to 100° C., preferably at about 30-80° C. In general, the reaction is allowed to proceed under normal pressure, although it is also possible to employ a higher or lower pressure.
When the process (a) according to the invention is carried out, use is made, for instance, of about 1 to 1.1 moles of the compounds of the general formula (II) per mole of the compounds of the general formula (III) in the presence of an inert solvent such as acetonitril and 1.0 to 1.2 moles of potassium carbonate to obtain the desired compounds.
The active compounds are well tolerated by plants, have a favorable level of toxicity to warm-blooded animals, and can be used for combating arthropod pests, espesically insects which are encountered in agriculture, in forestry, in the protection of stored products and of materials, and in the hygiene field. They are active against normally sensitive and resistant species and against all or some stages of development. The above-mentioned pests include:
from the class of the Isopoda, for example Oniscus Asellus,
Armadillidium vulgare
and
Porcellio scaber;
from the class of the Diplopoda, for example
Blaniulus guttulatus;
from the class of the Chilopoda, for example
Geophilus carpophagus
and Scutigera spec.;
from the class of the Symphyla, for example
Scutigerella immaculata;
from the order of the Thysanura, for
Moriya Koichi
Shibuya Katsuhiko
Shiokawa Kozo
Tsuboi Shin-ichi
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