Ethylene derivatives and pesticides containing said derivatives

Ethylene derivatives of formula (I): where Q is an unsubstituted or substituted phenyl or heterocyclic group, especially a 4-thiazolyl, 1- or 3-pyrazolyl, 1,3-oxazol-4-yl, phenyl or pyridyl group; E is a substituent such as a cyano group; A is a substituent such as a 4-pyrazolyl or thiazolyl group; and B is a substituent such as an alkylcarbonyl group. Agricultural chemicals and agents for preventing the attachment of aquatic organisms containing one or more such ethylene derivatives.

BACKGROUND OF THE INVENTION

1. Field of the Art

The present invention relates to novel ethylene derivatives, and also to agricultural chemicals and agents for preventing the attachment of aquatic organisms containing said derivatives as an active ingredient. The agricultural chemicals as referred to herein include insecticides, acaricides, nematocides, herbicides and fungicides, etc., and are especially pesticides in the field of agriculture, horticulture, stock farming and sanitation. The agent for preventing the attachment of aquatic organisms are chemicals for preventing the attachment of harmful aquatic organisms such as shells and algae to fishing nets, the bottoms of ships, marine equipment such as buoys, marine constructions, circulating water systems in thermal and atomic power plants, inlet channels for heat exchanger cooling water in chemical industry, underwater constructions and reservoirs.

2. Description of the Related Art

For acrylonitrile derivatives, Japanese Patent Application Laid-Open No. Sho 53-92769 discloses the use of 2′-chloro-3-hydroxy-2-(4-phenyl-2-thiazolyl)-cinnamoyl nitrile as an insecticide; and International Patent Application Laid-Open No. WO-95/29591 discloses its use as an aquatic adhesion inhibitor. Japanese Patent Application Laid-open No. Sho 60-11452 discloses the use of 2-(4-chlorophenyl)-3-(3-pyridyl)-3-oxopropionitrile as a herbicide and Japanese Patent Application Laid-open No. Sho 60-11401 discloses its use as a fungicide.

With the long-term use of insecticides and fungicides, recently, some pests have become resistant to chemicals and are often difficult to exterminate with conventional insecticides and fungicides. In addition, some insecticides are highly toxic and are prone to remain long, without being decomposed, to destroy the ecosystem. Accordingly, it is always expected to develop novel, low-toxic and low-persistent insecticides and fungicides.

On the other hand, in order to prevent the adhesion and growth of marine and freshwater aquatics, it is used antifouling coatings comprising organic tin compounds such as bis(tributyltin) oxide or copper compounds such as copper sulfate and cuprous oxide. However, organic tin compounds are highly toxic, though being effective in preventing the adhesion of aquatics, and are especially prone to accumulate in the bodies of fishes and shellfishes. As so promoting the environmental pollution, the use of those compounds is now under legal controls. Copper compounds are widely used in antifouling coatings for inlet channels and for the bottoms of ships. However, like tin compounds, copper compounds contain a copper as a heavy metal. Therefore, the use of copper compounds will bring about the environmental pollution in future, and agents for preventing the attachment of aquatic organisms comprising such copper compounds are not preferred. Under the above-mentioned situation, it has been desired agents for preventing the attachment of aquatic organisms that have few influences on the ecosystem and bring about little secondary pollution.

SUMMARY OF THE INVENTION

In order to solve the above-mentioned problems, the present inventors have assiduously studied to develop agricultural chemicals and agents for preventing the attachment of aquatic organisms which can exhibit excellent pesticidal activities even when used in small amounts, and which have few negative influences on non-targeted organisms such as mammals, fishes and useful insects, and, as a result, have found that the compounds mentioned hereinunder are highly safe and have excellent pesticidal activities and activities for preventing the attachment of aquatic organisms. On the basis of these findings, the present inventors have completed the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[1] Ethylene derivatives of a formula (I):

B represents H, a C1-C4alkyl group, a C1-C4haloalkyl group, a C2-C4alkoxyalkyl group, CH3SCH2, CH3OC2H4OCH2, a C1-C4alkyl group substituted by a phenyl group optionally substituted by a halogen or a C1-C4alkyl group, a C1-C4alkyl group substituted by a benzoyl group optionally substituted by a halogen or a C1-C4alkyl group, a tetrahydropyranyl group, (CH3)3Si, a C1-C4alkylsulfonyl group, a phenylsulfonyl group optionally substituted by a halogen or a C1-C4alkyl group, —SO2CF3, a C1-C4monoalkylaminosulfonyl group, a C2-C8dialkylaminosulfonyl group, a phenylaminosulfonyl group, a C2-C5monoalkylaminothiocarbonyl group, a C3-C9dialkylaminothiocarbonyl group, a C2-C5cyanoalkyl group, a C3-C9alkoxycarbonylalkyl group, —C(═O)T1, —P(═O)T2T3, —P(═S)T2T3, an alkali metal atom, an alkaline earth metal atom, or NHT4T5T6;

provided that, when Q is a 2-thiazolyl or 2-benzothiazolyl group, then B is a C1-C4alkyl group, a C1-C4haloalkyl group, a C2-C4alkoxyalkyl group, CH3SCH2, CH3OC2H4OCH2, a C1-C4alkyl group substituted by a phenyl group optionally substituted by a halogen or a C1-C4alkyl group, a C1-C4alkyl group substituted by a benzoyl group optionally substituted by a halogen or a C1-C4alkyl group, a tetrahydropyranyl group, (CH3)3Si, a C1-C4alkylsulfonyl group, a phenylsulfonyl group optionally substituted by a halogen or a C1-C4alkyl group, —SO2CF3, a C1-C4monoalkylaminosulfonyl group, a C2-C8dialkylaminosulfonyl group, a phenylaminosulfonyl group, a C2-C5monoalkylaminothiocarbonyl group, a C3-C9dialkylaminothiocarbonyl group, a C2-C5cyanoalkyl group, a C3-C9alkoxycarbonylalkyl group, —C(═O)T1, —P(═O)T2T3, or —P(═S)T2T3;

G is a substituent freely selected from a halogen atom, a C1-C10alkyl group, a C2-C4cyanoalkyl group, a C1-C4alkyl group substituted by a phenyl group optionally substituted by a halogen or a C1-C4alkyl group, a C2-C6alkenyl group, a C2-C6alkynyl group, a C1-C6haloalkyl group, a C2-C6haloalkenyl group, a C2-C6haloalkynyl group, a C3-C6halocycloalkyl group, a C3-C6cycloalkyl group optionally substituted by a C1-C3alkyl group, a C1-C10alkoxy group, a C2-C6alkenyloxy group, a C2-C6alkynyloxy group, a C1-C4haloalkoxy group, a C2-C6haloalkenyloxy group, a C2-C6haloalkynyloxy group, a C1-C4alkylsulfenyl group, a C1-C4alkylsulfinyl group, a C1-C4alkylsulfonyl group, a C2-C6alkenylsulfenyl group, a C2-C6alkenylsulfinyl group, a C2-C6alkenylsulfonyl group, a C2-C6alkynylsulfenyl group, a C2-C6alkynylsulfinyl group, a C2-C6alkynylsulfonyl group, a C1-C4haloalkylsulfenyl group, a C1-C4haloalkylsulfinyl group, a C1-C4haloalkylsulfonyl group, a C2-C6haloalkenylsulfenyl group, a C2-C6haloalkenylsulfinyl group, a C2-C6haloalkenylsulfonyl group, a C2-C6haloalkynylsulfenyl group, a C2-C6haloalkynylsulfinyl group, a C2-C6haloalkynylsulfonyl group, CHO, NO2, CN, —NU1U2, OH, a naphthyl group, a methoxygroup substituted by a phenyl group optionally substituted by a halogen or a C1-C4alkyl group, a C2-C7alkoxycarbonyl group, a C2-C4alkoxyalkyl group, a C2-C4alkylcarbonyl group, a C2-C4haloalkylcarbonyl group, a C2-C5alkylcarbonyloxy group, a C2-C5haloalkylcarbonyloxy group, a C3-C7dialkylaminocarbonyloxy group, a phenyl group optionally substituted by Z, a phenoxy group optionally substituted by Z, a benzoyl group optionally substituted by Z, a pyridyl group optionally substituted by Z, a pyridyloxy group optionally substituted by Z, a thienyl group optionally substituted by Z, a methylenedioxy group as bonded at the adjacent substituting positions, a halomethylenedioxy group as bonded at the adjacent substituting positions, and —N═CT7T8(in which T7and T8each independently represent H, or a phenyl, benzyl or C1-C6alkyl group, or T7and T8, together with the carbon atom to which they are bonded, form a 5-, 6-, 7- or 8-membered ring), (provided that when the the substituent is two or more, then said substituents may be the same or different), and the number of the substituent, G, is 1, 2, 3 or 4; or G is an alkylene group as bonded to the adjacent substituting positions to form a 5-, 6-, 7- or 8-membered ring;

R is a substituent freely selected from a halogen atom, a C1-C10alkyl group, a C1-C4alkyl group substituted by a phenyl group optionally substituted by a halogen or a C1-C4alkyl group, a C2-C6alkenyl group, a C2-C6alkynyl group, a C1-C6haloalkyl group, a C2-C6haloalkenyl group, a C2-C6haloalkynyl group, a C3-C6halocycloalkyl group, a C3-C6cycloalkyl group optionally substituted by a C1-C3alkyl group, a C1-C6alkoxy group, a C2-C6alkenyloxy group, a C2-C6alkynyloxy group, a C1-C4haloalkoxy group, a C2-C6haloalkenyloxy group, a C2-C6haloalkynyloxy group, a C1-C4alkylsulfenyl group, a C1-C4alkylsulfinyl group, a C1-C4alkylsulfonyl group, a C2-C6alkenylsulfenyl group, a C2-C6alkenylsulfinyl group, a C2-C6alkenylsulfonyl group, a C2-C6alkynylsulfenyl group, a C2-C6alkynylsulfinyl group, a C2-C6alkynylsulfonyl group, a C1-C4haloalkylsulfenyl group, a C1-C4haloalkylsulfinyl group, a C1-C4haloalkylsulfonyl group, a C2-C6haloalkenylsulfenyl group, a C2-C6haloalkenylsulfinyl group, a C2-C6haloalkenylsulfonyl group, a C2-C6haloalkynylsulfenyl group, a C2-C6haloalkynylsulfinyl group, a C2-C6haloalkynylsulfonyl group, NO2, CN, —NU1U2, a phenoxy group, OH, a naphthyl group, a C2-C7alkoxycarbonyl group, a C2-C4alkoxyalkyl group, a C2-C4alkylcarbonyl group, a C2-C5alkylcarbonyloxy group, a C2-C6haloalkylcarbonyloxy group, a benzoyl group optionally substituted by X, a phenyl group optionally substituted by X, a pyridyl group optionally substituted by X, a thienyl group optionally substituted by X, and —N═CT7T8, (provided that when the substituent is two or more, then said substituents may be the same or different), and the number of the substituents, R, is 1, 2, 3 or 4; or R is an alkylene group as bonded to the adjacent substituting positions to form a 5-, 6-, 7- or 8-membered ring;

Y is a substituent freely selected from a halogen atom, a C1-C10alkyl group, a C1-C6haloalkyl group, a C1-C6alkoxy group, a C2-C6alkenyloxy group, a C2-C6alkynyloxy group, a C1-C4haloalkoxy group, a C2-C6haloalkenyloxy group, a C2-C6haloalkynyloxy group, a C1-C4alkylsulfenyl group, a C1-C4alkylsulfinyl group, a C1-C4alkylsulfonyl group, a C2-C6alkenylsulfenyl group, a C2-C6alkenylsulfinyl group, a C2-C6alkenylsulfonyl group, a C2-C6alkynylsulfenyl group, a C2-C6alkynylsulfinyl group, a C2-C6alkynylsulfonyl group, a C1-C4haloalkylsulfenyl group, a C1-C4haloalkylsulfinyl group, a C1-C4haloalkylsulfonyl group, a C2-C6haloalkenylsulfenyl group, a C2-C6haloalkenylsulfinyl group, a C2-C6haloalkenylsulfonyl group, a C2-C6haloalkynylsulfenyl group, a C2-C6haloalkynylsulfinyl group, a C2-C6haloalkynylsulfonyl group, NO2, CN, —NU1U2, OH, a C2-C7alkoxycarbonyl group, a C2-C4alkoxyalkyl group, a C2-C5alkylcarbonyloxy group, a C2-C5haloalkylcarbonyloxy group, a C3-C7dialkylaminocarbonyloxy group, a phenyl group optionally substituted by X, and —N═CT7T8(in which T7and T8each independently represent H, or a phenyl, benzyl or C1-C6alkyl group, or T7and T8may, together with the carbon atom to which they are bonded, form a 5-, 6-, 7- or 8-membered ring), (provided that when the substituent is two or more, then said substituents may be the same or different), and the number of the substituent, Y, is 1, 2, 3 or 4; or Y is an alkylene groupas bonded to the adjacent substituting positions to form a 5-, 6-, 7- or 8-membered ring;

T1represents a C1-C20alkyl group, a C2-C6alkenyl group, a C1-C6haloalkyl group, a C1-C4alkoxy-C1-C4alkyl group, a C3-C6halocycloalkyl group, a C1-C4alkyl group substituted by a phenyl group optionally substituted by a halogen or a C1-C4alkyl group, a C3-C6cycloalkyl group optionally substituted by a C1-C3alkyl group, a cycloalkyl group substituted by a phenyl group optionally substituted by a halogen or a C1-C4alkyl group, a cyclopropyl group substituted by both a phenyl group optionally substituted by a halogen or a C1-C4alkyl group and a C1-C4alkyl group, a C3-C4cycloalkyl group substituted by both a phenyl group optionally substituted by a halogen or a C1-C4alkoxy group, and a halogen, a cyclopropyl group substituted by both a C2-C4alkenyl group optionally substituted by a halogen, and a C1-C4alkyl group, a C2-C4alkenyl group substituted by a phenyl group optionally substituted by a halogen or a C1-C4alkyl group, a C1-C12alkoxy group, a C1-C4haloalkoxy group, a C2-C5alkenyloxy group, a C3-C6cycloalkoxy group optionally substituted by a C1-C3alkyl group, a benzyloxy group, a C2-C6alkoxycarbonyl group, —NU1U2, a phenylamino group, a phenyl group optionally substituted by Z, a phenoxy group optionally substituted by Z, a phenylthio group optionally substituted by Z, a naphthyl group optionally substituted by Z, or a 5-membered or 6-membered heterocyclic group optionally substituted by Z, (said heterocyclic group being selected from thienyl, furyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, imidazolyl, 1,3,4-oxadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,4-triazolyl, 1,2,3-thiadiazolyl, 1,2,3-triazolyl, 1,2,3,4-tetrazolyl, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, 1,3,5-triazinyl, 1,2,4-triazinyl, pyrazolinyl, imidazolinyl, oxazolinyl, isoxazolinyl, thiazolinyl and 3(2H)-pyridazinone-groups);

T4, T5and T6each independently represent H, a C1-C6alkyl group, a C1-C6alkenyl group, a C3-C6cycloalkyl group optionally substituted by a C1-C3alkyl group, or a benzyl group; or any two of T4, T5and T6may, together with the nitrogen atom to which they are bonded, form a 5-, 6-, 7- or 8-membered cyclic group optionally containing oxygen, nitrogen and/or sulfur atoms;

X and Z are independently substituents as freely selected from a halogen atom, a C1-C4alkyl group, a C1-C4haloalkyl group, a C1-C4alkoxy group, a C1-C4haloalkoxy group, a C1-C4alkylsulfenyl group, a C1-C4alkylsulfinyl group, a C1-C4alkylsulfonyl group, a C2-C5alkenylsulfenyl group, a C2-C5alkenylsulfinyl group, a C2-C5alkenylsulfonyl group, a C1-C4haloalkylsulfenyl group, a C1-C4haloalkylsulfinyl group, a C1-C4haloalkylsulfonyl group, NO2, CN, CHO, OH, —NU1U2, a phenyl group, a phenoxy group, and a C2-C5alkoxycarbonyl group, (provided that when the substituent is two or more, then said substituents may be the same or different), and the number of the substituent, X and Z, is 1, 2, 3, 4 or 5 each;

T7and T8each independently represent H, or a phenyl, benzyl or C1-C6alkyl group, or T7and T8may, together with the carbon atom to which they are bonded, form a 5-, 6-, 7- or 8-membered ring; and

U1and U2each independently represent H, a C1-C6alkyl, C2-C5alkylcarbonyl, phenyl or benzyl group, or U1and U2may, together with the nitrogen atom to which they are bonded, form a 5-, 6-, 7- or 8-membered ring.

[2] Ethylene derivatives of the above-mentioned [1], in which;

B is H, a C1-C4alkyl group, a C1-C4haloalkyl group, a C2-C4alkoxyalkyl group, CH3OC2H4OCH2, a C1-C4alkylsulfonyl group, a phenylsulfonyl group optionally substituted by a halogen or a C1-C4alkyl group, —SO2CF3, a C2-C8dialkylaminosulfonyl group, a C2-C9dialkylaminothiocarbonyl group, a C3-C9alkoxycarbonylalkyl group, —C(═O)T1, —P(═O)T2T3, —P(═S)T2T3, an alkali metal atom, an alkaline earth metal atom, or NHT4T5T6; and

T1is a C1-C20alkyl group, a C2-C6alkenyl group, a C1-C4haloalkyl group, a C1-C4alkoxy-C1-C4alkyl group, a C1-C4alkyl group substituted by a phenyl group optionally substituted by a halogen or a C1-C4alkyl group, a C3-C6halocycloalkyl group, a C3-C6cycloalkyl group optionally substituted by a C1-C3alkyl group, a cycloalkyl group substituted by a phenyl group optionally substituted by a halogen or a C1-C4alkyl group, a cyclopropyl group substituted by both a phenyl optionally substituted by a halogen or a C1-C4alkyl group, and a C1-C4alkyl group, a C3-C4cycloalkyl group substituted by both a phenyl group optionally substituted by a halogen or a C1-C4alkoxy group and a halogen, a cyclopropyl group substituted by both a C2-C4alkenyl group optionally substituted by a halogen and a C1-C4alkyl group, a C2-C4alkenyl group substituted by a phenyl group optionally substituted by a halogen or a C1-C4alkyl group, a C1-C12alkoxy group, a C1-C4haloalkoxy group, a C2-C5alkenyloxy group, a C3-C6cycloalkoxy group optionally substituted by a C1-C3alkyl group, a benzyloxy group, a C2-C6alkoxycarbonyl group, a phenyl group optionally substituted by Z, a phenoxy group optionally substituted by Z, a phenylthio group, a naphthyl group, or a heterocyclic group optionally substituted by Z, said heterocyclic group being selected from thienyl, furyl, oxazolyl, thiazolyl, pyrazolyl and pyridinyl groups.

3] Ethylene derivatives of the above-mentioned [2], in which;

Q is a phenyl group optionally substituted by G, a naphthyl group optionally substituted by G, or a heterocyclic group optionally substituted by R, said heterocyclic group being

A is a phenyl group optionally substituted by W, a naphthyl group optionally substituted by W, or a heterocyclic group optionally substituted by Y, said heterocyclic group being

R1is selected from a halogen atom, a C1-C10alkyl group, a C2-C6alkenyl group, a C2-C8alkynyl group, a C1-C6haloalkyl group, a C1-C8alkoxy group, a C2-C6alkenyloxy group, NO2, CN, —NU1U2, OH, a C2-C7alkoxycarbonyl group, a C2-C4alkoxyalkyl group, a C2-C4alkylcarbonyl group, a phenyl group optionally substituted by X, a pyridyl group optionally substituted by X, a thienyl group optionally substituted by X, and —N═CT7T8(in which T7and T8each independently represent H, a phenyl, benzyl or C1-C6alkyl group, or T7and T8may, together with the carbon atom to which they are bonded, form a 5-, 6-, 7- or 8-membered ring); or may, together with the adjacent R, form a 5-, 6-, 7- or 8-membered ring as an alkylene group;

Y1is selected from a halogen atom, a C1-C10alkyl group, a C1-C6haloalkyl group, a C1-C6alkoxy group, a C2-C6alkenyloxy group, NO2, CN, —NU1U2, OH, a C2-C7alkoxycarbonyl group, a C2-C4alkoxyalkyl group, a phenyl group optionally substituted by X, and —N═CT7T8(in which T7and T8each independently represent H, or a phenyl, benzyl or C1-C6alkyl group, or T7and T8may, together with the carbon atom to which they are bonded), form a 5-, 6-, 7- or 8-membered ring); or may, togeher with the adjacent Y1, form a 5-, 6-, 7- or 8-membered ring an alkylene group;

X is a substituent of which the number is from 1 to 4 and which is freely selected from a halogen atom, a C1-C4alkyl group, a C1-C4haloalkyl group, a C1-C4alkoxy group, a C1-C4haloalkoxy group, a C1-C4alkylsulfenyl group, a C1-C4alkylsulfinyl group, a C1-C4alkylsulfonyl group, a C2-C5alkenylsulfenyl group, a C2-C5alkenylsulfinyl group, a C2-C5alkenylsulfonyl group, a C1-C4haloalkylsulfenyl group, a C1-C4haloalkylsulfinyl group, a C1-C4haloalkylsulfonyl group, NO2, CN, CHO, OH, —NU1U2, a phenyl group, a phenoxy group, and a C2-C5alkoxycarbonyl group, (provided that when the number of the substituent, X, is two or more then said substituents may be the same or different);

Z is a substituent of which the number is from 1 to 4 and which is freely selected from a halogen atom, a C1-C4alkyl group, a C1-C4haloalkyl group, a C1-C4alkoxy group, a C1-C4haloalkoxy group, a C1-C4alkylsulfenyl group, a C1-C4alkylsulfinyl group, a C1-C4alkylsulfonyl group, a C1-C4alkenylsulfenyl group, a C1-C4alkenylsulfinyl group, a C1-C4alkenylsulfonyl group, NO2, CN, —NU1U2, a phenyl group, a phenoxy group, and a C2-C6alkoxycarbonyl group, (provided that when the number of the substituent, Z, is two or more, then said substituents may be the same or different);

m indicates the number of the substituents, and is 0, 1, 2 or 3;

n indicates the number of the substituents, and is 0, 1, 2, 3, or 4;

p indicates the number of the substituents, and is 0, 1 or 2;

q indicates the number of the substituents, and is 0 or 1;

(provided that when m, n and p each are an integer of 2 or more, the substituents may be the same or different).

[4] Ethylene derivatives of the above-mentioned [2], in which E is CN.

[5] Ethylene derivatives of the above-mentioned [3], in which E is CN.

[6] Ethylene derivatives of the above-mentioned [2], in which E is a heterocyclic group optionally substituted by a C1-C4alkyl or C1-C4haloalkyl group—(said heterocyclic group being a 2-oxazolyl, 2-thiazolyl, 2-imidazolyl, 1,2,4-triazol-3-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-thiadiazol-3-yl or 1,3,4-oxadiazol-2-yl group)—or is a halogen atom, a C2-C4alkynyl group, a phenylethynyl group optionally substituted by Z, a C1-C4haloalkyl group, CN, NO2, N3, CHO, a C2-C5alkylcarbonyl group, a C2-C5alkoxycarbonyl group, a C2-C4alkylaminocarbonyl group, a C3-C9dialkylaminocarbonyl group, a benzoyl group optionally substituted by Z, an aminothiocarbonyl group, a C1-C4alkylsulfenyl group, a C1-C4alkylsulfinyl group, a C1-C4alkylsulfonyl group, a phenylsulfenyl group optionally substituted by Z, a phenylsulfinyl group optionally substituted by Z, a phenylsulfonyl group optionally substituted by Z, —P(═O)T2T3, or —P(═S)T2T3.

[7] Ethylene derivatives of the above-mentioned [3], in which E is a heterocyclic group optionally substituted by a C1-C4alkyl or C1-C4haloalkyl group—(said heterocyclic group being a 2-oxazolyl, 2-thiazolyl, 2-imidazolyl, 1,2,4-triazol-3-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-thiadiazol-3-yl or 1,3,4-oxadiazol-2-yl group)—or is a halogen atom, a C2-C4alkynyl group, a phenylethynyl group optionally substituted by Z, a C1-C4haloalkyl group, CN, NO2, N3, CHO, a C2-C5alkylcarbonyl group, a C2-C5alkoxycarbonyl group, a C2-C4alkylaminocarbonyl group, a C3-C9dialkylaminocarbonyl group, a benzoyl group optionally substituted by Z, an aminothiocarbonyl group, a C1-C4alkylsulfenyl group, a C1-C4alkylsulfinyl group, a C1-C4alkylsulfonyl group, a phenylsulfenyl group optionally substituted by Z, a phenylsulfinyl group optionally substituted by Z, a phenylsulfonyl group optionally substituted by Z, —P(═O)T2T3, or —P(═S)T2T3.

[8] Ethylene derivatives of the above-mentioned [4], in which Q is a phenyl group optionally substituted by G, an oxazolyl group optionally substituted by R, a thiazolyl group optionally substituted by R, a pyrazolyl group optionally substituted by R, a 1,2,3-triazolyl group optionally substituted by R, a pyridinyl group optionally substituted by R, or a pyrimidinyl group optionally substituted by R.

[9] Ethylene derivatives of the above-mentioned [8], in which Q is a phenyl group optionally substituted by G.

[10] Ethylene derivatives of the above-mentioned [8], in which Q is an oxazolyl group optionally substituted by R or a 1,2,3-triazolyl group optionally substituted by R.

[11] Ethylene derivatives of the above-mentioned [8], in which Q is a thiazolyl group optionally substituted by R.

[12] Ethylene derivatives of the above-mentioned [8], in which Q is a pyrazolyl group optionally substituted by R.

[15] Ethylene derivatives of the above-mentioned [13], in which Q is Q-10, Q-44, Q-45, Q-46 or Q-47.

[16] Ethylene derivatives of the above-mentioned [13], in which Q is Q-12, Q-13 or Q-14.

[17] Ethylene derivatives of the above-mentioned [13], in which Q is Q-25, Q-26, Q-27, Q-28, Q-29 or Q-30.

[18] Ethylene derivatives of the above-mentioned [13], in which Q is a phenyl group optionally substituted by G.

[19] Ethylene derivatives of the above-mentioned [2], in which A is a phenyl group optionally substituted by W, a thiazolyl group optionally substituted by Y, a pyrazolyl group optionally substituted by Y, a pyridinyl group optionally substituted by Y, or a pyrimidinyl group optionally substituted by Y.

[20] Ethylene derivatives of the above-mentioned [3], in which;

Y3is a halogen atom, a C1-C4alkyl group, a C1-C6haloalkyl group, a C2-C4alkoxyalkyl group, or a phenyl group optionally substituted by X.

[21] Ethylene derivatives of the above-mentioned [20], in which E is CN.

[22] Ethylene derivatives of the above-mentioned [20], in which E is a heterocyclic group optionally substituted by a C1-C4alkyl or C1-C4haloalkyl group—(said heterocyclic group being a 2-oxazolyl, 2-thiazolyl, 2-imidazolyl, 1,2,4-triazol-3-yl, 1,2,4-oxadiazol-3-yl, 1,2,4-thiadiazol-3-yl or 1,3,4-oxadiazol-2-yl group)—or is a halogen atom, a C2-C4alkynyl group, a phenylethynyl group optionally substituted by Z, a C1-C4haloalkyl group, CN, NO2, N3, CHO, a C2-C5alkylcarbonyl group, a C2-C5alkoxycarbonyl group, a C2-C4alkylaminocarbonyl group, a C3-C9dialkylaminocarbonyl group, a benzoyl group optionally substituted by Z, an aminothiocarbonyl group, a C1-C4alkylsulfenyl group, a C1-C4alkylsulfinyl group, a C1-C4alkylsulfonyl group, a phenylsulfenyl group optionally substituted by Z, a phenylsulfinyl group optionally substituted by Z, a phenylsulfonyl group optionally substituted by Z, —P(═O)T2T3, or —P(═S)T2T3.

[23] Ethylene derivatives of the above-mentioned [1], which are selected from the following:

[24] An agricultural chemical comprising, as the active ingredient, one or more ethylene derivatives of the above-mentioned [1] to [23].

[25] An agent for preventing the attachment of aquatic organisms containing, as an active ingredient, one or more ethylene derivatives of the above-mentioned [1] to [23].

MODES OF CARRYING OUT THE INVENTION

The moiety —C(E)═C(OB)— of the compounds (I) of the present invention includes two isomers of E-form and Z-form, both of which are within the scope of the invention.

It will be understood that the compounds of formula (I) of the present invention where the substituent B is a hydrogen atom exist as tautomers to be represented by the following:
Although the compounds (I) will exist essentially as the enol-form (1′), they could be as the tautomer form (2) under some conditions. It should be understood that the present invention includes all these three tautomers and their mixtures.

The heterocyclic group for Q, A and B indicates the following meanings.

Preferred scope of Q is the following groups.

Preferred scope of A is the following groups.

Preferred scope of B is the following groups.

Preferred scope of E is the following groups.

Preferred scope of G is the following groups.

Preferred scope of R is the following group.

RI: substituents freely selected from halogen, C1-C6alkyl, C1-C3alkyl substituted by phenyl optionally substituted by halogen or C1-C4alkyl, C1-C6haloalkyl, C3-C6cycloalkyl optionally substituted by C1-C3alkyl, C1-C4alkoxy, C2-C4alkenyloxy, C2-C4alkynyloxy, C1-C4haloalkoxy, C2-C4haloalkenyloxy, C2-C4haloalkynyloxy, C1-C4alkylsulfenyl, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, C2-C4alkenylsulfenyl, C2-C4alkenylsulfinyl, C2-C4alkenylsulfonyl, C2-C4alkynylsulfenyl, C2-C4alkynylsulfinyl, C2-C4alkynylsulfonyl, C1-C4haloalkylsulfenyl, C1-C4haloalkylsulfinyl, C1-C4haloalkylsulfonyl, C2-C4haloalkenylsulfenyl, C2-C4haloalkenylsulfinyl, C2-C4haloalkenylsulfonyl, NO2, CN, —NU1U2, naphthyl, C2-C4alkoxycarbonyl, C2-C4alkoxyalkyl, phenyl optionally substituted by X, pyridyl optionally substituted by X, and thienyl optionally substituted by X (provided that when the substituent is two or more, said substituents may be the same or different), and the number of the substituent, R, is 1, 2 or 3, or R is an alkylene group as bonded to the adjacent substituting positions to form a 5-, 6-, 7- or 8-membered ring.

RII: substituents freely selected from halogen, C1-C6alkyl, C1-C3alkyl substituted by phenyl optionally substituted by halogen or C1-C4alkyl, C1-C4haloalkyl, C3-C6cycloalkyl optionally substituted by C1-C3alkyl, NO2, CN, —NU1U2, naphthyl, C2-C4alkoxycarbonyl, C2-C4alkoxyalkyl, phenyl optionally substituted by X, and pyridyl optionally substituted by X (provided that when the substituents is two or more, said substituents may be the same or different), and the number of the substituent, R, is 1, 2 or 3.

RIII: substituents freely selected from halogen, C1-C6alkyl, C1-C3alkyl substituted by phenyl optionally substituted by halogen or C1-C4alkyl, C1-C4haloalkyl, C3-C6cycloalkyl optionally substituted by C1-C3alkyl, NO2, CN, —NU1U2, naphthyl, C2-C4alkoxycarbonyl, phenyl optionally substituted by X, and pyridyl optionally substituted by X (provided that when the substituent is two or more, said substituents may be the same or different), and the number of the substituent, R, is 1 or 2.

Depending on the type of the heterocyclic group to be substituted by R, the number of R differs. For the group of 1,3,4-oxadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,3-oxadiazolyl, 1,2,3-thiadiazolyl or 1,2,3,4-tetrazolyl, the number of R is 0 or 1, preferably 1. For the group of thiazolyl, oxazolyl, isoxazolyl, isothiazolyl, 1,3,4-triazolyl, 1,2,4-triazolyl, 1,2,3-triazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl or 1,2,4-triazinyl, the number of R is an integer of from 0 to 2, preferably 1 or 2. For the group of thienyl, furyl, pyrazolyl, imidazolyl, pyrimidinyl, pyrazinyl or pyridazinyl, the number of R is an integer of from 0 to 3, preferably an integer of from 0 to 2, more preferably 1 or 2. For the group of pyrrolyl, pyridinyl, pyrazolinyl, imidazolinyl, oxazolinyl, isoxazolinyl or thiazolinyl, the number of R is an integer of from 0 to 4, preferably an integer of from 0 to 3, more preferably 1 or 2.

Preferred scope of Y is the following groups.

YII: substituents freely selected from halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4alkylsulfenyl, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, C1-C4haloalkylsulfenyl, C1-C4haloalkylsulfinyl, C1-C4haloalkylsulfonyl, NO2, CN, C2-C4alkoxycarbonyl, and phenyl optionally substituted by X (provided that when the substituent is two or more, said substituents may be the same or different) and the number of the substituent, Y, is 1, 2 or 3.

Depending on the type of the heterocyclic group to be substituted by Y, the number of Y differs. For the group of 1,3,4-oxadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,3-thiadiazolyl or 1,2,3,4-tetrazolyl, the number of Y is 0 or 1, preferably 1. For the group of thiazolyl, oxazolyl, isoxazolyl, isothiazolyl, 1,3,4-triazolyl, 1,2,4-triazolyl, 1,2,3-triazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl or 1,2,4-triazinyl, the number of Y is an integer of from 0 to 2, preferably 1 or 2. For the group of thienyl, furyl, pyrazolyl, imidazolyl, pyrimidinyl, pyrazinyl or pyridazinyl, the number of Y is an integer of from 0 to 3, preferably an integer of from 0 to 2, more preferably 1 or 2. For the group of pyrrolyl, pyridinyl, pyrazolinyl, imidazolinyl, oxazolinyl, isoxazolinyl or thiazolinyl, the number of Y is an integer of from 0 to 4, preferably an integer of from 0 to 3, more preferably 1 or 2.

Preferred scope of W is the following group.

WIII: substituents freely selected from halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylsulfenyl, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, C1-C4haloalkylsulfenyl, C1-C4haloalkylsulfinyl, C1-C4haloalkylsulfonyl, NO2, and CN (provided that when the substituent is two or more, the substituents may be the same or different) and the number of the substituent, W, is 1 or 2.

Preferred scope of T1is the following groups.

Preferred scope of T2is the following groups.

Preferred scope of T3is the following groups.

Preferred scope of T4is the following groups.

T4I: H, C1-C4alkyl, C3-C6cycloalkyl or benzyl. Also preferred is such that any two of T4, T5and T6, together with the nitrogen atom to which they are bonded, forms a 5-, 6- or 7-membered ring optionally having oxygen, nitrogen and/or sulfur atoms.

Preferred scope of T5is the following groups.

T5I: H, C1-C4alkyl, C3-C6cycloalkyl or benzyl. Also, preferred is such that any two of T4, T5and T6, together with the nitrogen atom to which they are bonded, forms a 5-, 6- or 7-membered ring optionally having oxygen, nitrogen and/or sulfur atoms.

Preferred scope of T6is the following groups.

T6I: H, C1-C4alkyl, C3-C6cycloalkyl or benzyl. Also, preferred is such that any two of T4, T5and T6, together with the nitrogen atom to which they are bonded, forms a 5-, 6- or 7-membered ring optionally having oxygen, nitrogen and/or sulfur atoms.

Preferred scope of X is the following groups.

XII: substituents freely selected from halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylsulfenyl, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, C2-C5alkenylsulfenyl, C1-C4haloalkylsulfenyl, C1-C4haloalkylsulfinyl, C1-C4haloalkylsulfonyl, and NO2(provided that when the substituent is two or more, said substituents may be the same or different) and the number of the substituent, X, is 1, 2 or 3.

XIII: substituents freely selected from halogen, C1-C4alkyl, C1-C4haloalkyl, and C1-C4alkoxy (provided that when the substituent is two or more, said substituents may be the same or different) and the number of the substituent, X, is 1 or 2.

Depending on the type of the ring to be substituted by X, the number of X differs. For phenyl, the number of X is an integer of from 0 to 5, preferably an integer of from 0 to 3, more preferably an integer of from 0 to 2. For pyridyl, the number of X is an integer of from 0 to 4, preferably 0, 1 or 2, more preferably 0 or 1. For thienyl, the number of X is an integer of from 0 to 3, preferably 0 or 1.

Preferred scope of Z is the following groups.

Depending on the type of the ring to be substituted by Z, the number of Z differs. For phenyl, the number of Z is an integer of from 0 to 5, preferably an integer of from 0 to 4, more preferably 0, 1, 2 or 3, even more preferably 0, 1 or 2. For naphthyl, the number of Z is an integer of from 0 to 7, preferably 0. Where the ring to be substituted by Z is a heterocyclic group, the number of the substituents of Z also differs depending on the type of the heterocyclic group. For the group of 1,3,4-oxadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,3-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,3,4-tetrazolyl or 1,2,3,5-tetrazolyl, the number of Z is 0 or 1. For the group of thiazolyl, oxazolyl, isoxazolyl, isothiazolyl, 1,3,4-triazolyl, 1,2,4-triazolyl, 1,2,3-triazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl or 1,2,4-triazinyl, the number of Z is an integer of from 0 to 2, preferably 1 or 2. For the group of thienyl, furyl, pyrazolyl, imidazolyl, pyrimidinyl, pyrazinyl or pyridazinyl, the number of Z is an integer of from 0 to 3, preferably an integer of from 0 to 2, more preferably 1 or 2. For the group of pyrrolyl, pyridinyl, pyrazolinyl, imidazolinyl, oxazolinyl, isoxazolinyl or thiazolinyl, the number of Z is an integer of from 0 to 4, preferably an integer of from 0 to 2, more preferably 1 or 2.

Preferred scope of T7is the following groups.

T7I: H, phenyl, benzyl or C1-C4alkyl. Also preferred is such that T7and T8, together with the carbon atom to which they are bonded, form a 5-membered or 6-membered ring.

Preferred scope of T8is the following groups.

T8I: phenyl, benzyl or C1-C4alkyl. Also preferred is such that T7and T8, together with the carbon atom to which they are bonded, form a 5-membered or 6-membered ring.

Preferred scope of U1is the following groups.

U1I: H, C1-C4alkyl or C2-C5alkylcarbonyl. Also preferred is such that U1and U2, together with nitrogen atom to which they are bonded, form a 5-, 6- or 7-membered ring.

Preferred scope of U2is the following groups.

U2I: H, C1-C4alkyl or C2-C5alkylcarbonyl. Also preferred is such that U1and U2, together with the carbon atom to which they are bonded, form a 5-, 6- or 7-membered ring.

Preferably, m is 1, 2, or 3, more preferably 1 or 2.

Preferably n is 0, 1, 2 or 3, more preferably 1 or 2.

Preferably, p is 1 or 2.

The above-mentioned preferred groups in the scopes of the preferred substituents can be optionally combined and show the scopes of the preferred compounds of the present invention. Hereinunder mentioned are especially preferred scopes.

The halogen atom for E, G, R, R1, W, X, Y, Y1, Y2, Y3and Z includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Preferred are a fluorine atom, a chlorine atom and a bromine atom.

For T1, the cyclopropyl group substituted by both a phenyl group optionally substituted by a halogen atom or a C1-C4alkyl group and a C1-C4alkyl group includes, for example, 2,2-dimethyl-1-phenylcyclopropyl, 1-(4-chlorophenyl)-2,2-dimethylcyclopropyl, 2,2-dimethyl-3-phenylcyclopropyl, 3-(3-chlorophenyl)-2,2-dimethylcyclopropyl, (4-chlorophenyl)-2,2-dimethyl-3-phenylcyclopropyl, (4-bromophenyl)-2,2-dimethyl-3-phenylcyclopropyl, 2,2-dimethyl-3-(4-methylphenyl)cyclopropyl and (4-tert-butylphenyl)-2,2-dimethyl-3-phenylcyclopropyl groups.

For T1, the C3-C4cycloalkyl group substituted by both a phenyl group optionally substituted by a halogen atom or a C1-C4alkoxy group and a halogen atom includes, for example, 2,2-dichloro-1-phenylcyclopropyl, 2,2-dichloro-1-(3-chlorophenyl)cyclopropyl, 2,2-dichloro-1-(4-methoxyphenyl)cyclopropyl, 2,2-dichloro-1-(4-ethoxyphenyl)cyclopropyl, 2,2-dichloro-(4-i-propyloxyphenyl)cyclopropyl, 2,2-dichloro-1-(4-t-butylphenyl)cyclopropyl, 2,2-dichloro-1-(4-methoxyphenyl)-3-phenylcyclopropyl and 1-(4-ethoxyphenyl)-2,2,3,3-tetrafluorobutyl groups.

For T1, the cyclopropyl group substituted by both a C2-C4alkenyl group optionally substituted by a halogen atom, and a C1-C4alkyl group includes, for example, 2,2-dimethyl-3-(2,2-dimethylethenyl)cyclopropyl, 3-(2,2-dibromoethenyl)-2,2-dimethylcyclopropyl, 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropyl and 3-(2,2-chlorotrifluoroethenyl)-2,2-dimethylcyclopropyl groups.

The C2-C6haloalkylcarbonyl group for G and W includes, for example, chloroacetyl, trifluoroacetyl, 3,3,3-trifluoropropionyl and pentafluoropropionyl groups.

The C2-C5haloalkylcarbonyloxy group for G, R and Y includes, for example, chloroacetyloxy, trifluoroacetyloxy, 3,3,3-trifluoropropionyloxy and pentafluoropropionyloxy groups.

The C3-C7dialkylaminocarbonyloxy group for G and Y includes, for example, dimethylaminocarbonyloxy, diethylaminocarbonyloxy and di-i-propylaminocarbonyloxy groups.

The naphthyl group for R, Y, Z and T1includes, for example, 1-naphthyl and 2-naphthyl groups.

The pyridyl group optionally substituted by Z for G and T1includes, for example, 2-pyridyl, 3-pyridyl and 4-pyridyl groups all optionally substituted by Z. Preferred are 2-pyridyl and 3-pyridyl groups both optionally substituted by Z; and more preferred is a 2-pyridyl group optionally substituted by Z.

The pyridyloxy group optionally substituted by Z for G and T1includes, for example, 2-pyridyloxy, 3-pyridyloxy and 4-pyridyloxy groups all optionally substituted by Z.

The pyridyl group optionally substituted by X for R and R1includes, for example, 2-pyridyl, 3-pyridyl and 4-pyridyl groups all optionally substituted by X. Preferred are 2-pyridyl and 3-pyridyl groups both optionally substituted by X; and more preferred is a 2-pyridyl group optionally substituted by X.

The pyridyloxy group optionally substituted by X for R and R1includes, for example, 2-pyridyloxy, 3-pyridyloxy and 4-pyridyloxy groups all optionally substituted by X.

The thienyl group optionally substituted by X for R and R1includes, for example, 2-thienyl and 3-thienyl groups both optionally substituted by X.

The thienyl group optionally substituted by Z for G and Y1includes, for example, 2-thienyl and 3-thienyl groups both optionally substituted by Z.

The C2-C4alkylaminocarbonyl group for E includes, for example, methylaminocarbonyl, ethylaminocarbonyl and n-propylaminocarbonyl groups.

The C1-C4alkyl group substituted by a benzoyl group optionally substituted by a halogen atom or a C1-C4alkyl group for B includes, for example, phenacyl, 2-fluorophenacyl, 3-chlorophenacyl, 4-bromophenacyl, 2-methylphenacyl, 3-ethylphenacyl, 4-i-propylphenacyl and 4-t-butylphenacyl groups.

The C2-C5cyanoalkyl group for G and B includes, for example, cyanomethyl, 2-cyanoethyl, 3-cyanopropyl and 1-cyano-1-methylethyl groups.

The alkali metal for B includes, for example, lithium sodium and potassium.

The alkaline earth metal for B includes, for example, magnesium, calcium, strontium and barium. Preferred are magnesium, calcium and barium.

The methoxy group substituted by a phenyl group optionally substituted by a halogen atom or a C1-C4alkyl group for G includes, for example, benzyloxy, 2-chlorobenzyloxy, 3-chlorobenzyloxy, 4-chlorobenzyloxy, 3-methylbenzyloxy, 4-t-butylbenzyloxy, 2,6-difluorobenzyloxy and 2-fluoro-4-chlorobenzyloxy groups.

The haloalkenyl group for G, R, T1and W may be a straight chain or branched C2-C4haloalkenyl group, including, for example, 2-chloroethenyl, 2-bromoethenyl and 2,2-dichloroethenyl groups.

The haloalkenyloxy group for G, R, W and Y may be a straight chain or branched C2-C4haloalkenyloxy group, including, for example, 3-chloro-2-propenyloxy, 3,3-dichloro-2-propenyloxy, 4-chloro-2-butenyloxy, 4,4-dichloro-3-butenyloxy and 4,4-difluoro-3-butenyloxy groups.

The alkenylsulfenyl group for G, R, W, X, Y and Z may be a straight chain or branched C2-C4alkenylsulfenyl group, including, for example, allylsulfenyl, 2-propenylsulfenyl, 2-butenylsulfenyl and 2-methyl-2-propenylsulfenyl groups.

The alkenylsulfinyl group for G, R, W, X, Y and Z may be a straight chain or branched C2-C4alkenylsulfinyl group, including, for example, allylsulfinyl, 2-propenylsulfinyl, 2-butenylsulfinyl and 2-methyl-2-propenylsulfinyl groups.

The alkenylsulfonyl group for G, R, W, X, Y and Z may be a straight chain or branched C2-C4alkenylsulfonyl group, including, for example, allylsulfonyl, 2-propenylsulfonyl, 2-butenylsulfonyl and 2-methyl-2-propenylsulfonyl groups.

The haloalkenylsulfenyl group for G, R, W and Y may be a straight chain or branched C2-C4haloalkenylsulfenyl group, including, for example, 3-chloro-2-propenylsulfenyl, 4-chloro-2-butenylsulfenyl, 3,3-dichloro-2-propenylsulfenyl, 4,4-dichloro-3-butenylsulfenyl and 4,4-difluoro-3-butenylsulfenyl groups.

The haloalkenylsulfinyl group for G, R, W and Y may be a straight chain or branched C2-C4haloalkenylsulfinyl group, including, for example, 3-chloro-2-propenylsulfinyl, 3,3-dichloro-2-propenylsulfinyl, 4-chloro-2-butenylsulfinyl, 4,4-dichloro-3-butenylsulfinyl and 4,4-difluoro-3-butenylsulfinyl groups.

The haloalkenylsulfonyl group for G, R, W and Y may be a straight chain or branched C2-C4haloalkenylsulfonyl group, including, for example, 3-chloro-2-propenylsulfonyl, 3,3-dichloro-2-propenylsulfonyl, 4-chloro-2-butenylsulfonyl, 4,4-dichloro-3-butenylsulfonyl and 4,4-difluoro-3-butenylsulfonyl groups.

The C2-C4alkynyloxy group for G, R, W and Y includes, for example, 2-propynyloxy, 2-butynyloxy and 1-methyl-2-propynyloxy groups.

The C2-C4haloalkynyloxy group for G, R, W and Y includes, for example, 3-chloro-2-propynyloxy, 3-bromo-2-propynyloxy and 3-iodo-2-propynyloxy groups.

The C2-C6alkynylsulfenyl group for G, R, W and Y includes, for example, 2-propynylsulfenyl, 2-butynylsulfenyl and 1-methyl-2-propynylsulfenyl groups.

The C2-C6alkynylsulfinyl group for G, R, W and Y includes, for example, 2-propynylsulfinyl, 2-butynylsulfinyl and 1-methyl-2-propynylsulfinyl groups.

The C2-C6alkynylsulfonyl group for G, R, W and Y includes, for example, 2-propynylsulfonyl, 2-butynylsulfonyl and 1-methyl-2-propynylsulfonyl groups.

The C2-C6haloalkynylsulfenyl group for G, R, W and Y includes, for example, 3-chloro-2-propynylsulfenyl, 3-bromo-2-propynylsulfenyl and 3-iodo-2-propynylsulfenyl groups.

The C2-C6haloalkynylsulfinyl group for G, R, W and Y includes, for example, 3-chloro-2-propynylsulfinyl, 3-bromo-2-propynylsulfinyl and 3-iodo-2-propynylsulfinyl groups.

The C2-C6haloalkynylsulfonyl group for G, R, W and Y includes, for example, 3-chloro-2-propynylsulfonyl, 3-bromo-2-propynylsulfonyl and 3-iodo-2-propynylsulfonyl groups.

Even at low concentration, the compounds of the present invention effectively prevent various pests, which include, for example, so-called agricultural insect pests that injure agricultural and horticultural crops and trees, so-called livestock insect pests that live on livestock and poultry, so-called sanitary insect pests that have various negative influences on the human living environment including houses, so-called stored products insect pests that injure grains stored in storehouses, and also acarids, nematodes, molluscs and crustaceans that live in the same sites as above and injure those mentioned above.

Examples of insect pests, acarids, nematodes, molluscs and crustaceans capable of being exterminated by the compounds of the present invention are mentioned below, which, however, are not limitative.

Pests of VARROIDAE, such as bee brood mite (Varroa jacobsoniOudemans), etc.;

The plant diseases to be controlled by the compounds of the present invention are as follows:

Alternaria leaft spot (Alternaria japonica) and white spot (Cerocosporella brassicae) of vegetable of the family crucifers.

Leaf spot (Mycosphaerella personatum) and Brown leaf spot (Cercospora arachidicola) of peanut,

Gray mold (Botrytis cinerea) of various kinds of crops, and,

Sclerotinia rot (Sclerotinia sclerotiorum) of various kinds of crops.

In addition, the compounds of the present invention are effective in preyenting the attachment of aquatic organisms, even at extremely low concentrations. Aquatic organisms to which the invention is directed are, for example, shellfishes and algae, such as mussel, barnacle, oyster, hydrozoan, hydra,Serpula, ascidian, seamoss,Bagula, mud pond snail, sea lettuce, green laver,Ectocarpus, etc.

Specifically, the compounds of the present invention can effectively exterminate various pests and phytopathogenic microbes of, for example, Orthoptera, Hemiptera, Lepidoptera, Coleoptera, Hymenoptera, Diptera, Temitidae, and also mites and louses, even when used at low concentrations. In addition, the compounds of the invention are effective in preventing the attachment of various aquatic organisms living in sea water and fresh water to aquatic constructions, etc. On the other hand, the compounds of the present invention contains useful compounds that have few negative influences on mammals, fishes, shellfishes and useful insects.

Of the compounds of the invention, those having CN as E can be produced according to the following methods (Scheme 1).

In (Scheme 1), Q, A and B have the same meanings as defined above; L represents a suitable leaving group, such as a chlorine atom, a bromine atom, an iodine atom, an alkoxy group having from 1 to 4 carbon atoms, a phenoxy group, an alkylsulfonyloxy group having from 1 to 4 carbon atoms, a benzenesulfonyloxy group, a toluenesulfonyloxy group, a phenoxy group, a 1-pyrazolyl group or a 1-imidazolyl group; L′ represents a halogen atom; and alkyl represents an alkyl group preferably having from 1 to 4 carbon atoms.

Method A in (Scheme 1) is to react an acetonitrile derivative of formula (3) with an acid chloride, ester or amide of formula (4) or with an acid anhydride of formula (5) to give compounds (1′) of the present invention. The compound (1′) of the invention is optionally reacted with an alkyl halide, an alkyl sulfonate, a trimethylsilyl halide, a sulfonyl chloride, a sulfamoyl chloride, a thiocarbamoyl chloride, an acid chloride or an ester of formula (8) to be converted into compounds (1) of the invention. Depending on the type of B in the compounds (1) of the invention, the compound (1′) is reacted with a dihydropyran, an isocyanate or a thioisocyanate to give the compounds (1). In Method A, if the compound of formula (4) or (5) is used in an excessive amount, the compounds (1) can be directly obtained without isolating the compounds (1′).

Where Q is bonded to the acrylonitrile moiety via a nitrogen atom, compounds (1′) may be produced according to Method B. Method B is to react a heterocyclic compound of formula (6) with a halogenocyanoketone derivative of formula (7) to give compounds (1′) of the invention.

Where A is bonded to the acrylonitrile moiety via a nitrogen atom, compounds (1′) may be produced according to Method C. Method C is to react a cyanoacetic acid derivative of formula (9) with a heterocyclic compound of formula (10) to give compounds (1′) of the invention. As the case may be, the compound of formula (9) will be prepared -by reacting an acetonitrile derivative of formula (3), such as that used in Method A, with a carbonic acid ester in the presence of a base.

Of the compounds of the invention, those where E is

Method D in (Scheme 2) is to react a compound of formula (11) with an acid chloride, ester or amide of formula (4) or with an acid anhydride of formula (5) to give the compounds (1′) of the present invention. The compound (1′) of the invention is optionally reacted with an alkyl halide, an alkyl sulfonate, a trimethylsilyl halide, a sulfonyl chloride, a sulfamoyl chloride, a thiocarbamoyl chloride, an acid chloride or an ester of formula (8) to be converted into the compounds (1) of the invention. Depending on the type of B in the compounds (1) of the invention, the compound (1′) is reacted with a dihydropyran, an isocyanate or a thioisocyanate to give the compounds (1). In Method A, if the compound of formula (4) or (5) is used in an excessive amount, the compounds (1) can be directly obtained without isolating the compounds (1′).

Where Q is bonded to the ethylene moiety via a nitrogen atom, the compounds (1′) may be produced according to Method E. Method E is to react a heterocyclic compound of formula (6) with a compound of formula (12) in the presence of a base to give compounds (1′) of the invention.

Where A is bonded to the ethylene moiety via a nitrogen atom, the compounds (1′) may be produced according to Method F. Method F is to react a compound of formula (13) with a heterocyclic compound of formula (10) through dealcoholation to give the compounds (1′) of the invention. As the case may be, the compound of formula (13) will be prepared by reacting a compound of formula (11), such as that used in Method D, with a carbonic acid ester in the presence of a base.

If desired, the compounds (1′) where E is an alkoxycarbonyl group may be hydrolyzed, decarboxylated and halogenated to give the compounds of the invention where E is a halogen atom. As the case may be, the compounds of the invention where E is a halogen atom may be reacted with a nucleophilic reagent corresponding to E (e.g., triester phosphites, alkyl mercaptans, thiophenols, metal acetylides, metal cyanides, metal azides, nitrites) to give different compounds of the invention. Also as the case may be, the compounds to be obtained through decarboxylation of the compounds (1′) where E is an alkoxycarbonyl group may be reacted with an electrophilic reagent under basic conditions to give the compounds of the invention.

As the case may be, the processes of (Scheme 1) and (Scheme 2) are preferably effected in the presence of a base. The base to be used includes, for example, alkali metal alkoxides such as sodium ethoxide, sodium methoxide and t-butoxy potassium; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; organic bases such as triethylamine, pyridine and DBU; organic lithium compounds such as butyl lithium; lithium amides such as lithium diisopropylamide and lithium bistrimethylsilylamide; and sodium hydride.

The reactions of (Scheme 1) and (Scheme 2) may be effected in a solvent that is inert to the reaction. The solvent includes, for example, lower alcohols such as methanol and ethanol; aromatic hydrocarbons such as benzene and toluene; etherd such as diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane and 1,2-diethoxyethane; halogenated hydrocarbons such as methylene chloride, chloroform and 1,2-dichloroethane; amides such as dimethylformamide and dimethylacetamide; acetonitrile; dimethylsulfoxide; and mixed solvents of these. As the case may be, also employable are mixed solvent comprising said solvents and water. Also as the case may be, a quaternary ammonium salt such as tetra-n-butylammonium bromide may be added to the reaction system as a catalyst to obtain good results. The reaction temperature may be freely settled within a range between −30° C. and 200° C. Preferably, the reaction temperature falls between 0° C. and 150° C., or between 0° C. and the boiling point of the solvent if used. The base may be used in an amount of from 0.05 to 10 equivalents, preferably from 0.05 to 3 equivalents, of the reaction substrate.

The compounds of the present invention may be separated from reaction mixtures according to any ordinary methods. If the purification of the compounds of the invention is needed, the can be separated and purified by any ordinary methods of, for example, recrystallization or column chromatography.

Of the compounds of the invention, those having an asymmetric carbon atom include optically-active compounds of (+) form and (−) form.

Methods of producing the compounds (3) to be used in (Scheme 1) are referred to hereinunder. The compounds (3) can be produced according to the following (Scheme 3).

1) A benzyl halide, a benzyl alkylsulfonate, a benzyl arylsulfonate, a halomethyl-heterocyclic compound, an alkylsulfonyloxymethyl-heterocyclic compound or an arylsulfonyloxymethyl-heterocyclic compound of formula (14) is reacted with a suitable cyanating reagent to give compounds (3). Alternatively, a phenylacetic acid derivative or a heterocyclic acetic acid derivative is converted into the corresponding amide derivative, which is then dehydrated to give compounds (3).

2) A heterocyclic halide (15) is condensed with a cyanoacetate (16) in the presence of a base to give a compound (17), which is then hydrolyzed and decarboxylated to give compounds (3).

3) To obtain compounds (3) where Q is bonded to the ethylene moiety via a nitrogen atom, a heterocyclic derivative (6) where the nitrogen atom of Q is unsubstituted is reacted with a haloacetonitrile derivative in the presence of a base. Alternatively, the compound (6) is reacted with a compound (18) in the presence of a base to give a compound (17), said compound (18) being obtained through halogenation of a cyanoacetate, and thereafter the compound (17) is hydrolyzed and decarboxylated to obtain the compounds (3).

The compounds (11) to be used in (Scheme 2) can be produced in the same manner as in the production of the compounds (3) mentioned above.

The compounds (7) to be used in (Scheme 1) can be produced by condensing a benzoic acid halide or heterocyclic carboxylic acid halide with a cyanoacetate in the presence of a base followed by halogenating the resulting condensate.

The above-mentioned halomethyl-heterocyclic compounds, alkylsulfonyloxymethyl-heterocyclic compounds and arylsulfonyloxymethyl-heterocyclic compounds can be derived from heterocyclic methane derivatives or heterocyclic carboxylate derivatives that are produced according to ordinary methods (see Alan R. Katritzky, and Charles W. Rees; Comprehensive Heterocyclic Chemistry, Vol. 2, Vol. 3, Vol. 4, Vol. 5 or Vol. 6). To produce the compounds (14) where Q is an oxazol-4-yl or thiazol-4-yl group, a carboxylic acid amide or thioamide can be reacted with 1,3-dichloro-2-propanone.

Examples of the compounds of the present invention are shown in Table 1 to Table 14 below. The abbreviations in these Tables are for the meanings mentioned below:

Where the compounds of the present invention are used as pesticides, in general, they can be mixed with a suitable carrier, for example a solid carrier, such as clay, talc, bentonite, diatomaceous earth or white carbon, or a liquid carrier such as water, alcohols (e.g., isopropanol, butanol, benzyl alcohol, furfuryl alcohol), aromatic hydrocarbons (e.g., toluene, xylene), ethers (e.g., anisole), ketones (e.g., cyclohexanone, isophorone), esters (e.g., butyl acetate), acid amides (e.g., N-methylpyrrolidone) or halogenated hydrocarbons (e.g., chlorobenzene), optionally along with other additives such as surfactant, emulsifier, dispersing agent , penetrating agent, spreading agent, thickener, anti-freezing agent, anti-caking agent and stabilizer, and can be formulated into any desired forms for practical use, such as liquid preparations, emulsions, wettable powders, dry flowables, flowables, dusts and granules.

Where the compounds of the present invention are used as agricultural chemicals, they can be combined with any other herbicides, various insecticides, acaricides, nematecides, fungicides, plant growth regulators, synergists, fertilizer and soil improvers, when they are formulated into preparations for practical use or while they are actually used through spraying or the like.

In particular, the combination of the compounds of the invention and other agricultural chemicals or plant hormones will be advantageous in that the amount of the chemicals to be used can be reduced thereby resulting in the reduction of the costs for the treatment, and that the mixed chemicals exhibit synergistic effects to broaden the insecticidal spectrum while displaying higher pesticidal activities. If desired, the compounds of the invention can be combined with a plurality of known agricultural chemicals. For the agricultural chemicals capable of being combined with the compounds of the invention, for example, the compounds described in Farm Chemicals Handbook, 1994 are referred.

Their concrete general names are raised below. However, the present invention is not necessarily limited by them.

The dose of the compounds of the present invention varies depending on an application place, an application time, an application method, cultivation crops, etc. In general, it may be between approximately 0.005 kg and 50 kg per hectare (ha) in terms of the amount of the active ingredient.

Now, formulation examples comprising the compounds of the invention are mentioned below, which, however, are not intended to restrict the scope of the invention. In the following formulation examples, “part” or “parts” are by weight.

Where the compounds of the present invention are used as an agent for preventing the attachment of aquatic organisms, they may be formulated into various preparations of, for example, coating paints, solutions, emulsions, pellets or flakes to be applicable to various objects. Depending on the application place, the object and the form, the preparations can be used in any ordinary manners of, for example, coating, spraying, dipping, adding to water or installing in water. To prepare such coating paints, solutions, emulsions and others, employable are any ordinary methods. Apart from the above-mentioned preparations and modes of using the compounds of the present invention, the compounds may also be used, for example, by incorporating them into ropes or fiber materials for fishingnets in the stage of preparing the ropes or fiber materials to thereby making them have the ability to prevent the attachment of aquatic organisms thereto. The agents for preveting the attachment of aquatic organisms according to the present invention can be used either singly or as combined with any other agents for preventing the attachment of aquatic organisms.

Where the aquatic adhesion inhibitors of the invention are used in the form of antifouling coatings, for example, the compounds of the invention may be mixed with film-forming agents to prepare coatings. The film-forming agents include oil varnishes, synthetic resins, artificial rubbers, etc. If desired, solvents, pigments and others can be added to the coatings. To prepare the paints, the uppermost limit of the concentration of the compounds of the invention to be therein is not specifically limited, provided that the resulting coatings can form film, but may be from 1 to 50% by weight, preferably from 5 to 20% by weight, relative to the weight of the antifouling coatings.

Where the agents for preventing the attachment of aquatic organisms of the present invention are used in the form of solutions, for example, the compounds of the invention may be dissolved in solvents along with film-forming agents to prepare solutions. The film-forming agents include synthetic resins, artificial rubbers, natural resins, etc. The solvents include xylene, toluene, cumene, methyl ethyl ketone, methyl isobutyl ketone, acetone, etc. If desired, additives such as plasticizer may be added to the solutions. To prepare the solutions, the uppermost limit of the concentration of the compounds of the invention to be therein is not specifically limited, provided that the compounds are dissolved to give solutions, but may be from 1 to 50% by weight, preferably from 5 to 30% by weight, relative to the weight of the solutions.

Where the agents for preventing the attachment of aquatic organisms of the present invention are used in the form of emulsions, surfactants are added to the compounds of the invention to prepare the intended emulsions according to ordinary methods of preparing general emulsions. In this, the type of the surfactants to be used is not specifically limited. To prepare the emulsions, the uppermost limit of the concentration of the compounds of the invention to be therein is not specifically limited, provided that the compounds are emulsified to give emulsions, but may be from 1 to 50% by weight, preferably from 5 to 30% by weight, relative to the weight of the emulsions.

Where the agents for preventing the attachment of aquatic organisms of the present invention are used in the form of pellets or flakes, for example, the constitutive components of the compounds of the invention and optionally plasticizers, surfactants and others are added to the base of hydrophilic resins which are solid at room temperature, such as polyethylene glycol in a solid form, and the resulting mixtures are shaped into pellets or flakes through meltting molding, compression molding or the like. To prepare the pellets or flakes, the uppermost limit of the concentration of the compounds to be therein is not specifically limited, provided that the compounds can be shaped into pellets or flakes, but may be from 20 to 95% by weight, preferably from 30 to 90% by weight, relative to the weight of the pellets or flakes.

EXAMPLES

The present invention is illustrated specifically by referring to the following Synthesis Examples, Formulation Examples and Test Examples, which, however, are not intended to restrict the scope of the invention.

Synthesis Example 1

1) 3.0 g of 3-(2,6-difluorophenyl)pyrazole was dissolved in 20 ml of acetonitrile, and 2.52 g of chloroacetonitrile and 4.61 g of potassium carbonate were added thereto at room temperature, and heated under reflux for 5 hours. After acetonitrile was distilled off under reduced pressure, ethyl acetate was added to the residue, which was then washed with a small amount of water. The organic layer was dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The residual product was recrystallized from a mixed solvent of isopropylether and diethyl ether to obtain 1.74 g of 1-cyanomethyl-3-(2,6-difluorophenyl)pyrazole.

2) A solution of 0.5 g of 1-cyanomethyl-3-(2,6-difluorophenyl)pyrazole dissolved in 10 ml of THF was dropwise added to a suspension of 0.15 g of 55% sodium hydride in 10 ml of THF, at 50° C. After the resulting product was stirred for 30 minutes, a solution of 0.67 g of 1-(1-methyl-3,5-dichloropyrazole-4-carbonyl)pyrazole dissolved in 10 ml of THF was dropwise added thereto at 50° C. and then stirred overnight at room temperature. The reaction mixture was poured into water, then extracted with ethyl acetate and washed with a small amount of water. The resulting product was dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The residual product was recrystallized from a mixed solvent of isopropyl ether/ethyl acetate=3/1 to obtain 0.52 g of 2-{3-(2,6-difluorophenyl)pyrazol-1-yl}-3-(1-methyl-3,5-dichloropyrazol-4-yl)-3-hydroxyacrylonitrile.

Synthesis Example 2

1) 2.33 g of thiobenzamide was dissolved in 20 ml of dry methanol, and 2.16 g of 1,3-dichloroacetone was added thereto at room temperature and then heated under reflux for 1 hour. The solvent was distilled off under reduced pressure, and ice water was added to the remaining product, which was then neutralized with an aqueous solution of sodium hydrogen carbonate. The resulting product was extracted with ethyl acetate, washed with saturated saline, and dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The residual product was purified through silica gel column chromatography to obtain 2.03 g of 4-chloromethyl-2-phenylthiazole, was obtained from the fraction eluted with chloroform/n-hexane=1/2.

2) 1.39 g of 4-chloromethyl-2-phenylthiazole was dissolved in 10 ml of acetonitrile, and 0.65 g of potassium cyanide and 0.05 g of dibenzo-18-crown-6-ether were added thereto at room temperature, and then heated under reflux for 10 hours. After the temperature was returned to room temperature, ethyl acetate was added the resulting mixture, and the insoluble solid was removed through filtration. The resulting ethyl acetate solution was washed with saturated saline and water, and dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The residual product was purified through silica gel column chromatography to obtain 0.98 g of 4-cyanomethyl-2-phenylthiazole from the fraction eluted with chloroform.

3) 0.72 g of 4-cyanomethyl-2-phenylthiazole was dissolved in 10 ml of dry THF, and 4.6 ml of n-butyl lithium (1.56 M hexane solution) was dropwise added thereto at −60° C. or lower in an argon atmosphere. After the resulting product was stirred at −60° C. or lower for 20 minutes, 0.84 g of 1-methyl-3,5-dichloropyrazole-4-carbonyl chloride as dissolved in 3 ml of dry THF was dropwise added thereto at −60° C. or lower. Then, the resulting product was gradually heated, and stirred for 4 hours at room temperature. The reaction mixture was poured into ice water, acidified with diluted hydrochloric acid, extracted with ethyl acetate, and washed with saturated saline. The resulting product was dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The residual product was purified through silica gel column chromatography to obtain the intended product from the fraction eluted with chloroform. The resulting product was crystallized and washed with diethyl ether to obtain 0.86 g of 3-(1-methyl-3,5-dichloropyrazol-4-yl)-2-(2-phenylthiazol-4-yl)-3-hydroxyacrylonitrile.

Synthesis Example 3

0.5 g of 3-(1-methyl-3-trifluoromethyl-5-chloropyrazol-4-yl)-2-(4-tert-butylthiazol-2-yl)-3-hydroxyacrylonitrile and 0.14 g of triethylamine were added to 15 ml of THF at room temperature and stirred to give a uniform solution. 0.16 g of pivaloyl chloride was dropwise added to the solution with cooling with ice, then gradually heated, and stirred at room temperature for 8 hours. The reaction mixture was poured into ice water, extracted with ethyl acetate, and washed thrice with saturated saline. After having been dried over sodium sulfate, the resulting product was passed through a short column filled with silica gel. The solvent was distilled off under reduced pressure, and the residual product was applied to silica gel thin-layer chromatography (developer solvent: chloroform) to obtain 0.16 g of 3-(1-methyl-3-trifluoromethyl-5-chloropyrazol-4-yl)-2-(4-tert-butylthiazol-2-yl)-3-pivaloyloxyacrylonitrile (III-6) and 0.35 g of its geometric isomer (III-15).

Reference Example

Synthesis of 1-methyl-3-trifluoromethyl-5-chloropyrazole-4-carboxylic acid

1) 21.35 g of phosphorus oxychloride was dropwise added to 4.72 g of DMF at 10° C. or lower. After the temperature of the reaction solutio was returned to room temperature, the reaction mixture was stirred for 1 hour, and 10.71 g of 1-methyl-3-trifluoromethyl-5-pyrazolone was added thereto. The resulting mixture was heated up to 110° C., and stirred for 7 hours. After having been left to be at 70° C., the reaction mixture was poured into ice water. After pH of the mixture was made to be about 4 with an aqueous solution of sodium hydroxide added thereto, and precipitated crystals were taken out through filtration and dried to obtain 10.55 g of 1-methyl-3-trifluoromethyl-5-chloropyrazole-4-carbaldehyde.

2) 8.88 g of 1-methyl-3-2-(tert-trifluoromethyl-5-chloropyrazole-4-carbaldehyde and 7.24 g of potassium permanganate were added to an aqueous solution of 0.23 g of potassium hydroxide in 85 ml of water, at room temperature. After having been heated upto 60° C., the resulting mixture was stirred for 2 hours. Next, the temperature of the mixture was return to room temperature, and the solid was removed through filtration. The resulting filtrate was acidified with an aqueous solution of hydrochloric acid, and precipitated crystals were taken out through filtration, washed with water, and dried. The thus-obtained crystals were added to 150 ml of chloroform, and heated under reflux, and the insoluble solid was removed through filtration at a heating time. Chloroform was distilled off under reduced pressure, and 6.24 g of 1-methyl-3-trifluoromethyl-5-chloropyrazole-4-carboxylic acid was obtained.

Synthesis Example 4

In the same manner as above, the above-mentioned compound was synthesized (viscous liquid, E-Z mixture).

Synthesis Example 5

1.0 g of 4-(trifluoromethyl)phenylacetonitrile and 2.31 g of 1-methyl-3,5-dichloropyrazole-4-carbonyl chloride were dissolved in 30 ml of dry THF, and 0.61 g of potassium t-butoxide was added thereto, at room temperature. After having been heated, the resulting product was kept heated under reflux for 3 hours. 0.61 g of potassium t-butoxide was again added thereto and further heated under reflux for 2 hours. THF was distilled off under reduced pressure, and water was added to the residual product, which was then extracted with ethyl acetate. The resulting organic layer was washed with a dilute aqueous solution of sodium hydroxide and then with water. This was dried with sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified through silica gel column chromatography to obtain 1.92 g of 3-(1-methyl-3,5-dichloropyrazol-4-yl)-2-(4-trifluoromethylphenyl)-3-(1-methyl-3,5-dichloropyrazole-4-carbonyloxy)acrylonitrile from the fraction eluted with n-hexane:ethyl acetate=2:1.

Synthesis Example 6

0.22 g of dibenzo-18-crown-6-ether and 1.57 g of sodium cyanide were suspended in 20 ml of DMSO, and 5.00 g of 4-tert-butylbenzyl bromide was dropwise added thereto with cooling with water. After having been stirred overnight at room temperature, the resulting mixture was further stirred at 50° C. for 5 hours. After this was left to be at room temperature, water was added thereto and extracted with ether. The organic layer was washed with water, and dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The residual product was purified through silica gel column chromatography to obtain 1.19 g of 4-tert-butylphenylacetonitrile was obtained from the fraction eluted with n-hexane:ethyl acetate=5:1.

1.00 g of 4-tert-butylphenylacetonitrile and 1.23 g of 1-methyl-3,5-dichloropyrazole-4-carbonyl chloride were dissolved in 20 ml of THF, and 1.01 g of potassium t-butoxide was added thereto with cooling with ice. After the resulting mixture was stirred overnight at room temperature, water was added thereto, acidified with diluted hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with water, and dried with sodium sulfate, and the solvent was distilled off under reduced pressure. The residual product was dissolved in a mixed solvent of 10 ml of water and 10 ml of dioxane, and 0.38 g of potassium hydroxide was added thereto and heated under reflux for 4 hours. After having been left to be at room temperature, this was acidified with diluted hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with water, and dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The residual product was purified through silica gel column chromatography to obtain 0.64 g of 2-(4-tert-butylphenyl)-3-(1-methyl-3,5-dichloropyrazol-4-yl)-3-hydroxyacrylonitrile from the fraction eluted with n-hexane:ethyl acetate=2:1.

Synthesis Example 7

In the same manner as above, the above-mentioned compound was synthesized (viscous liquid).

Synthesis Example 8

In the same manner as above, the above-mentioned compound was synthesized (vitreous, E-Z mixture).

Synthesis Example 9

1) 25 g of pivalic acid amide and 25 g of 1,3-dichloro-2-propanone were mixed and heated on an oil bath at 135° C. for 2.5 hours. After having been cooled with ice, the mixture was made alkaline with an aqueous solution of sodium hydroxide added thereto. Then, the resulting product was extracted with ethyl acetate, washed with water, and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residual product was purified through column chromatography (silica gel; ethyl acetate:n-hexane=1:8) to obtain 17.5 g of 2-tert-butyl-4-chloromethyloxazole.

2) 6.2 g of sodium cyanide was weighed, 50 ml of dimethylsulfoxide was added thereto, and a dimethylsulfoxide solution of 16.9 g of 2-tert-butyl-4-chloromethyloxazole was dropwise added thereto, and heated on an oil bath at 65° C. for 1 hour with stirring. After the resulting product was cooled to room temperature, 150 ml of a dilute aqueous solution of sodium hydroxide was added thereto, and extracted with toluene. The organic layer was fully washed with water, and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 14.8 g of 2-tert-butyl-4-cyanomethyloxazole.

3) 2.87 g of potassium tert-butoxide was suspended in 20 ml of THF, and a solution of 2.00 g of 2-tert-butyl-4-cyanomethyloxazole and 2.37 g of 3,5-dichloro-1-methylpyrazole-4-carbonyl chloride as dissolved in 10 ml of THF was dropwise added thereto with cooling with ice, and then stirred overnight at room temperature. The reaction mixture was poured into ice water, extracted with ethyl acetate, and washed with a small amount of water. After the resulting product was dried with anhydrous sodium sulfate, the solvent was evaporated out under reduced pressure. The residual product was purified through column chromatography (silica gel; n-hexane:ethyl acetate=4:1) to obtain 3.26 g of the intended compound.

Synthesis Example 10

0.6 g of 2-{2-tert-butyloxazol-4-yl}-3-(5-chloro-3-trifluoromethyl-1-methyl-pyrazol-4-yl)-3-hydroxyacrylonitrile was dissolved in 5 ml of THF, and 0.07 g of 60% sodium hydride was added thereto with cooling with ice, and then stirred for 15 minutes at room temperature. 0.17 g of ethoxymethyl chloride was added thereto and stirred for 6 days at room temperature. The reaction mixture was poured into ice water, extracted with ethyl acetate, and washed with saturated saline. The resulting product was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The resulting residual product was purified through silica gel thin-layer chromatography (ethyl acetate:n-hexane=1:4) to obtain 0.1 g of the intended compound in vitreous state.

Synthesis Example 11

8.2 g (50 mmols) of ethyl phenylacetate and 10.7 g (50 mmols) of 3,5-dichloro-1-methylpyrazole-4-carboxylic acid chloride were dissolved in 100 ml of dry tetrahydrofuran, and 14 g (125 mmols) of potassium tert-butoxide at room temperature. The reaction mixture was stirred at room temperature for 1 hour, and 300 ml of water was added thereto, and extracted with ethyl acetate. The organic layer was washed with water and saturated saline, and dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 17 g of the intended ethyl 2-phenyl-3-(3,5-dichloro-1-methylpyrazol-4-yl)-3-hydroxyacrylate.

Synthesis Example 12

1) 17 g (50 mmols) of ethyl 2-phenyl-3-(3,5-dichloro-1-methylpyrazol-4-yl)-3-hydroxyacrylate was dissolved in 50 ml of 6 N HCl and 250 ml of 1,4-dioxane, and heated under reflux for 15 hours. The reaction mixture was poured into 500 ml of ice water, and precipitated crystals were taken out through filtration to obtain 8 g of the intended 1-(3,5-dichloro-1-methylpyrazol-4-yl)-2-phenylethanone as white crystals. m.p.: 94-96° C.

2) 5.38 g (20 mmols) of 1-(3,5-dichloro-1-methylpyrazol-4-yl)-2-phenylethane was dissolved in 50 ml of chloroform, and stirred at room temperature for 1 hour, and the solvent was distilled off under reduced pressure to obtain the intended 1-(3,5-dichloro-1-methylpyrazol-4-yl)-2-phenyl-2-bromoethanone as white crystals. m.p.: 74.5-75.5° C.

Synthesis Example 13

0.55 g (1.58 mmols) of 1-(3,5-dichloro-1-methylpyrazol-4-yl)-2-phenyl-bromoethane and 0.18 g (1.74 mmols) of triethylamine were dissolved in 4 ml of dry tetrahydrofuran, and 0.19 g (1.58 mmols) of pivalic acid chloride was added thereto at room temperature. After the reaction mixture was stirred for 16 hours at room temperature, 10 ml of water was added thereto, and extracted with ethyl acetate. The organic layer was washed with water and saturated saline, and dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified through silica gel column chromatography to obtain 0.23 g of the intended 1-(3,5-dichloro-1-methylpyrazol-4-yl)-1-pivaloyloxy-2-phenyl-2-bromoethylene as a colorless liquid (E-Z mixture).

Synthesis Example 14

1) 4.15 g (18.1 mmols) of 2-(1-methyl-cyclohexan-1-yl)-4-chloromethylthiazole and 3.32 g (20 mmols) of trimethyl phosphite were mixed and heated under reflux for 16 hours. The reaction mixture was cooled to room temperature, and purified through silica gel column chromatography to obtain 4.63 g of the intended diethyl{2-(1-methylcyclohexan-1-yl)-thiazol-4-yl}methylphosphonate as a colorless liquid.

2) 0.85 g (4 mmols) of 3,5-dichloro-1-methylpyrazole-4-carboxylic acid chloride and 1.32 g (4 mmols) of diethyl {2-(1-methylcyclohexan-1-yl)-thiazol-4-yl}methylphosphonate were dissolved in 15 ml of dry tetrahydrofuran, and 1.12 g (10 mmols) of potassium t-butoxide was added thereto at room temperature. The reaction mixture was stirred for 1 hour at room temperature, and 20 ml of water was added thereto, and extracted with ethyl acetate. The organic layer was washed with water and saturated saline, and dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified through silica gel column chromatography to obtain 0.4 g of the intended 1-(3,5-dichloro-1-methylpyrazol-4-yl)-2-{2-(1-methylcyclohexan-1-yl)-thiazol-4-yl}-2-diethylphosphonoethanone.

Synthesis Example 15

1) Potassium carbonate (1.53 g) was added to an acetonitrile (10 mL) solution of 3-(2,6-difluorophenyl)-pyrazole (1 g) and allyl 2-bromoacetate (1.49 g), and refluxed for 3 hours. The resulting product was extracted with acetate and diluted hydrochloric acid added thereto at room temperature. The organic layer was dried over anhydrous magnesium sulfate and concentrated, and the resulting concentrate was purified through silica gel column chromatography (chloroform) to obtain allyl 2-{3-(2,6-difluorophenyl)pyrazol-1-yl}acetate (1.5 g).

2) Potassium butoxide (0.5 g) was added to a THF (10 mL) solution of allyl 2-{3-(2,6-difluorophenyl)pyrazol-1-yl}acetate (0.5 g) and 5-chloro-1-methyl-3-trifluoromethylpyrazole-4-carbonyl chloride (0.44 g) at 0° C., and stirred for 5 minutes. Water (5 ml) was added thereto, and then extracted with diluted hydrochloric acid and ethyl acetate. After the organic layer was dried over anhydrous magnesium sulfate, and then concentrated, and the resulting concentrate was purified through silica gel column chromatography (chloroform) to obtain the intended product, Compound No. I-133 (0.89 g).

Synthesis Example 16

1) Formic acid (60 mg) was added to a THF (1 mL) solution of palladium acetate (7 mg) and triphenylphosphine (17 mg) and stirred for 5 minutes at room temperature in a nitrogen atmosphere. A THF (5 mL) solution of Compound I-133 (0.32 g) was added thereto and refluxed for 1 hour. The reaction mixture was left to be at room temperature, and concentrated, and the resulting concentrate was purified through silica gel column chromatography (chloroform) and recrystallization (chloroform-diisopropyl ether) to obtain 2-{3-(2,6-difluorophenyl)pyrazol-1-yl}-3-(5-chloro-1-methyl-3-trifluoromethylpyrazol-4-yl)ethan-1-one (0.1 g). m.p.: 152-154° C.

2) A THF solution (0.27 mL) of 1M lithium hexamethyldisilazide was added to a THF solution of 2-{3-(2,6-difluorophenyl)pyrazol-1-yl}-3-(5-chloro-1-methyl-3-trifluoromethylpyrazol-4-yl)ethan-1-one (0.1 g) at −78° C. and stirred at the same temperature in a nitrogen atmosphere. To the resulting solution was added a THF (2 mL) solution of carbon tetrabromide (0.098 g), and then gradually heated up to room temperature. Water (1 mL) was added thereto, and then extracted with diluted hydrochloric acid and ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and recrystallized from chloroform-diethyl ether) to obtain the intended product, Compound No. I-134 (0.062 g). m.p.: 123-125° C.

Synthesis Example 17

Triethylamine (0.3 g) and pivalic acid chloride (0.23 g) were added in that order to a chloroform (25 mL) solution of Compound No. I-134 (0.47 g) at 0° C., and stirred at room temperature for 1 hour. The resulting product was extracted with water and chloroform. The organic layer was dried with anhydrous magnesium sulfate, concentrated, and purified through silica gel column chromatography (chloroform) to obtain the intended product, Compound No. I-135 (0.4 g).

In accordance with the above-mentioned reaction schemes or Examples, various compounds of the present invention were produced, of which the structure and the melting point are shown in Table 15 to Table 19 below. Unless otherwise specifically indicated, the compounds shown in these are in the form of a mixture of E-form and Z-form. The abbreviations in these have the same meanings as those mentioned above.

Formulation Examples

Now, Formulation Examples of pesticides comprising the compounds of the present invention as the active ingredient are shown below, which, however, are not intended to restrict the scope of the invention. In the following Formulation Examples, “part” or “parts” are by weight.

Formulation Example 1

Wettable Powder

The above-mentioned components were homogeneously mixed and ground to form a wettable powder.

Formulation Example 2

Emulsion

The above-mentioned components were homogeneously mixed to form an emulsion.

Formulation Example 3

The above-mentioned components were homogeneously mixed to prepare a flowable.

Formulation Example 4

The above-mentioned components were homogeneously mixed and finely ground to form a dry flowable.

Formulation Example 5

Granules

The above-mentioned components were homogeneously mixed and ground, to which was added a small amount of water, stirred, mixed and kneaded. The resulting mixture was granulated and dried into granules, using an extrusion granulator.

Formulation Example 6

The above-mentioned components were homogeneously mixed and ground to form a dust.

Upon use, the wettable powder, emulsion, flowable and dry flowable are diluted from 50 to 20000 times with water, and applied in an amount of from 0.005 to 50 kg/ha in terms of the active ingredient.

Now, Formulation Examples of agents for preventing the attachment of aquatic organisms of the present invention are shown below, which, however, are not intended to restrict the scope of the invention.

Formulation Example 7

The above-mentioned components were homogeneously mixed to form an agent for preventing the attachment of aquatic organisms of the invention. This agent can be used as a coating paint.

Formulation Example 8

The above-mentioned components were homogeneously mixed to form an agent for preventing the attachment of aquatic organisms of the invention. This agent can be used as a coating paint.

Formulation Example 9

The above-mentioned components were homogeneously mixed to form an agent for preventing the attachment of aquatic organisms the invention. This agent can be used as a coating paint.

Formulation Example 10

The above-mentioned components were homogeneously mixed to form an agent for preventing the attachment of aquatic organisms of the invention. This agent can be used as a coating paint.

Test Examples

Now, the following Test Examples are to demonstrate the usefulness of the compounds of the present invention as pesticides.

Test Example 1

Insecticidal Test for Brown Rice Planthopper (Nilaparvata lugensStal)

A 5% emulsion (or 25% wettable powder) of a compound of the present invention was diluted with water containing a spreading agent to give a 500 ppm solution of the compound.

The stems and leaves of rice-plants in 1/20,000 are pot were sufficiently applied with the resulting solution. After the thus-applied chemical solution was dried in air, each pot was covered with a cylindrical cover. Ten (10) second instar nymphae of brown rice planthoppers (Nilaparvata lugens) were released in each pot. After having been thus covered, the pots were stored in a thermostatic chamber. After 6 days passed, the insects in each pot were observed, and the mortality thereof was determined according to the following equation. Each compound was tested in that manner for two groups of pots.
Mortality(%)=[number of insect killed/(number of insect killed+number of living insect)]×100

Test Example 2

Insecticidal Test for Green Rice Leafhoppers (Nephotettix cincticepsUhler)

Test Example 3

Insecticidal Test for Green Peach Aphids (Myzus persicaeSulzer)

Moistured filter paper was placed in each laboratory glass dish having an inner diameter of 3 cm, and a leaf cabbage having the same diameter as that of the dish was put on the filter paper. Four female, apterous adults of green peach aphids (Myzus persicae) were put on the cabbage leaf. Fllowing day, a chemical sample (2.5 mg/cm2) was sprayed over the dishes, using a rotary sprinkler. The chemical solution herein was prepared by diluting a 5% emulsion (or 25% wetttable powder) of a compound of the invention to 500 ppm with water containing a spreading agent. After 6 days passed, the insects in each cylinder were observed, and mortality of the insects (larvae and adults) was determined according to the following equation. Each compound was tested in that manner for two groups of dishes.
Mortality (%)=[number of insect killed/(number of insect killed+number of living insect)]×100

Test Example 4

Insecticidal Test for Diamond Back Moth (Plutella xylostellaLinne)

Test Example 5

Insecticidal Test for Cucurbit Leaf Beetles (Aulacophora femoralisMotschulsky)

A 5% emulsion (or 25% wettable powder) of a compound of the present invention was diluted with water containing a spreading agent to give a 500 ppm solution of the compound. The leaves of cucumbers were dipped in this chemical solution for about 10 seconds, dried in air, and put into a laboratory dish. Ten (10) second instar nymphae of cucurbit leaf beetles (Aulacophora femoralis) were released in each dish. Each dish was covered with a cover, and stored in a thermostatic chamber at 25° C. After 6 days passed, the insects in each dish were observed, and mortality of the insects was determined according to the same equation as in Test Example 1. Each compound was tested in that manner for two groups of dishes.

Test Example 6

The leaves of kidney bean plants were punched into 3 cm-diameter discs, using a leaf punch, and put onto moistured filter paper in a 7 cm-diameter styrol cup. Ten (10) larvae of two-spotted spider mites (Tetranychus urticae) were put to each leaf. A 5% emulsion (or 25% wettable powder) of a compound of the invention was diluted with water containing a spreading agent to give a 500 ppm solution of the compound. The solution was sprayed over each cup in an amount of 2 ml/cup, using a rotary sprinkler, and the cups were stored in a thermostatic chamber at 25° C. After 96 hours passed, the mites in each cup were observed, and mortality of the mites was determined according to the same equation as in Test Example 1. Each compound was tested in that manner for two groups of cups.

Test Example 7

A chemical solution obtained by diluting an emulsion of a compound of the invention to 500 ppm with water was sprayed on wheat plants (Norin No. 61) grown to 1.5- to 2.0-leaf in a pot having a diameter of 5.5 cm-diameter at a dose of 20 ml/pot using a spraygun.

The following day, a spore suspension (2×105spore/ml) of leaft rust (brown rust) (Puccinia recondita) was sprayed over the plant-pots were placed overnight in an inoculation box having a temparature of 25° C. and a humidity of 95% or more. Then, -the pots were put in a green house. After 7 days of the inoculation, a ratio of an infected and spored area formed to the leaf inoculated was measured, and a preventive vlaue was calculated according to the following equation.
Preventive value=[1−(infected and spotted area ratio in treated region/infected and spotted area ratio in untreated region)]×100

In this test, the following compounds had an protective value of from 70 to 100.Compounds of the invention: Nos. I-9, I-108, I-127, I-128, II-14, II-15, IV-2, IV-7, V-15, V-10.

With the long-term use of insecticides and microbicides, recently, some pests have become resistant to chemicals and are often difficult to exterminate with conventional insecticides and microbicides. In addition, some insecticides are highly toxic and are prone to remain long, without being decomposed, to destroy the ecosystem. Accordingly, the present invention provides novel, non-toxic and non-persistent insecticides and fungicides, and provides agents for preventing the attachment of aquatic organisms having few influences on the ecosystem and causing little secondary pollution.