TECHNICAL FIELD The present invention relates to novel semicarbazone derivatives and pesticides containing such derivatives as active ingredients.

BACKGROUND ART Heretofore, with respect to semicarbazone derivatives of benzamide, compounds of 4-RC ₆ H ₄ C=(NHC ₆ H ₄ R ^, -4)NNHCWNHR" (wherein R = H, MeO, Me, Cl, N0 ₂ ; R' = H, MeO, Me, Cl; R" = Ph; W = O, S) have been known in Eur. J. Med. Chem. , 26, 273 (1991). However, here, R" is limited to an unsubstituted phenyl group, and the corresponding compounds wherein R" is a substituted phenyl group are novel. Further, this literature discloses nothing about pesticidal activities although it indicates pharmaceutical activities.

In recent years, insect pests have acquired resistance due to use of insecticides over many years, and it has become difficult to control them by conventional insecticides. Further, some of insecticides have high toxicity, and some of them have residual toxicity, whereby the ecosystem tends to be disturbed. Accordingly, it is desired to develop a novel insecticide having a low toxicity and a low residual effect.

DISCLOSURE OF INVENTION

The present inventors have conducted extensive researches on semicarbazone derivatives and as a result, have found that novel semicarbazone derivatives of benzanilide exhibit excellent insecticidal activities at a low dose, and they are very useful compounds substantially free from adverse effects against mammals, fishes and beneficial insects. The present invention has been accomplished on the basis of these discoveries. The present invention provides a semicarbazone derivative of the formula (I):

wherein is an oxygen atom or a sulfur atom- each of X, Y and Z which are independent of one another, is a halogen atom, a hydroxyl group, a cyano group, a nitro group, SCN, a trimethylsilyl group, R ⁹ , OR ⁹ , S(0) _p R ⁹ , OS(0) ₂ R ⁹ , OC(0)R ⁹ , C(0)R ⁹ , C0 ₂ R ⁹ ,

C(0)N(R ⁹ )R ¹⁰ , S0 ₂ N(R ⁹ )R ¹⁰ , NHC(0)R ⁹ , N(R ⁹ )R ¹⁰ , or -CH=CH-CH=CH-, -0CH ₂ 0-, -0CH ₂ CH ₂ 0- , -OCF ₂ 0- , -0CF ₂ CF ₂ 0- or -OCF ₂ CF ₂ - bridging the adjacent carbon atoms;

R ¹ is a hydrogen atom, R ⁵ , a C _1-6 alkyl group which may be substituted by R ⁵ , or a phenyl group which may be substituted by (R ⁵ ) _q ; each of R ² , R ³ and R ⁴ which are independent of one

another, is a hydrogen atom, a C _λ _ ₆ alkyl group, a C ₂ _ ₆ alkenyl group, a C ₂ _ ₆ alkynyl group, a C _1-6 haloalkyl group, a C ₂ _ ₆ alkoxyalkyl group, a C ₂ _ ₆ alkylcarbonyl group, a C ₂ . ₆ alkoxycarbonyl group, a C ₂ _ ₆ haloalkylcarbonyl group, a _λ _ ₆ alkylthio group, a C,_ ₆ haloalkylthio group, R ⁶ OC(0)N(R ⁷ )S-, R ⁷ (R ⁸ )NS-, or a benzyl group which may be substituted by (R ⁵ )_;

R ⁵ is a halogen atom, a hydroxyl group, a cyano group, a nitro group, a C ₂ _ ₆ alkyl group, a C _1-6 haloalkyl group, a C _χ _ ₆ alkoxy group, a C _1-6 haloalkoxy group, a C _λ _ ₆ alkylthio group, a C _1-6 haloalkylthio group, a C,_ ₆ alkylsulfonyl group, a C _1-6 haloalkylsulfonyl group, a C ₂ _ ₆ alkoxycarbonyl group, an amino group, or a di C _ ₆ alkylamino group; each of R ⁶ , R ⁷ and R ⁸ which are independent of one another, is a C _χ _ ₆ alkyl group, a phenyl group which may be substituted by (R ⁵ ) _q , or a benzyl group which may be substituted by (R ⁵ ) _q ;

R ⁹ is a C _λ _ ₆ alkyl group, a C _1-6 haloalkyl group, a C ₂ _ ₆ alkenyl group, a C ₂ _ ₆ haloalkenyl group, a C ₂ _ ₆ alkynyl group, a C ₂ _ ₆ haloalkynyl group, a C ₃ _ ₆ cycloalkyl group, a C ₃ _ ₆ halocycloalkyl group, a C ₄ _ ₇ cycloalkylalkyl group, a C ₂ _ ₆ alkoxyalkyl group, a C ₂ _ ₆ alkylthioalkyl group, a C ₂ _ ₆ alkoxycarbonylalkyl group, a C ₂ _ ₆ cyanoalkyl group, a phenyl group which may be substituted by (R ⁵ )_, a benzyl group which may be substituted by (R ⁵ ) _q , or a pyridyl group which may be substituted by (R ⁵ ) _r ;

R ¹⁰ is a hydrogen atom, or a C ₁ _ ₆ alkyl group; k is an integer of from 0 to 2, provided that when k is 2, the plurality of R ¹ may be the same or different;

£ is an integer of from 0 to 5, provided that when _* ? is from 2 to 5, the plurality of X may be the same or different; m is an integer of from 0 to 5, provided that when m is from 2 to 5, the plurality of Y may be the same or different; n is an integer of from 1 to 5, provided that when n is from 2 to 5, the plurality of Z may be the same or different; p is an integer of from 0 to 2; q is an integer of from 0 to 5, provided that when q is from 2 to 5, the plurality of R ⁵ may be the same or different; and r is an integer of from 0 to 4, provided that when r is from 2 to 4, the plurality of R ⁵ may be the same or different. The present invention also provides a pesticide which contains at least one such semicarbazone derivative as an active ingredient.

Now, specific examples will be given for each substituent disclosed above. The carbon chain in each substituent may be linear, branched or cyclic. In the following description, n- means normal, i- means iso, sec- means secondary, t- means tertiary, and c- means

cyclo .

The C _χ _ ₆ alkyl group may, for example, be a methyl group, an ethyl group, a n-propyl group, an i-propyl group, a c-propyl group, a n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, a c-butyl group, a n-pentyl group, a c-pentyl group, a n-hexyl group, or a c-hexyl group.

The C ₂ _ ₆ alkenyl group may, for example, be an ethenyl group, a 2-propenyl group, a 2-methyl-2-propenyl group, or a 2-butenyl group.

The C ₂ _ ₆ alkynyl group may, for example, be an ethynyl group, a 2-propynyl group, or a 2-butynyl group.

The C ₂ _ ₆ alkoxyalkyl group may, for example, be a methoxymethyl group, an ethoxymethyl group, or a 1- ethoxyethyl group.

The C ₂ _ ₆ alkylcarbonyl group may, for example, be a methylcarbonyl group, an ethylcarbonyl group, a n- propylcarbonyl group, an i-propylcarbonyl group, a c- propylcarbonyl group, a n-butylcarbonyl group, an i- butylcarbonyl group, a sec-butylcarbonyl group, a t- butylcarbonyl group, or a c-butylcarbonyl group.

The C ₂ _ ₆ alkoxycarbonyl group may, for example, be a methoxycarbonyl group, an ethoxycarbonyl group, a n- propoxycarbonyl group, an i-propoxycarbonyl group, a c- propoxycarbonyl group, a n-butoxycarbonyl group, an i- butoxycarbonyl group, a sec-butoxycarbonyl group, a t- butoxycarbonyl group, or a c-butoxycarbonyl group.

The halogen atom may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

W is an oxygen atom or a sulfur atom, preferably an oxygen atom. Each of X, Y and Z which are independent of one another, may, for example, be a halogen atom, a hydroxyl group, a cyano group, a nitro group, SCN, a trimethylsilyl group, a C _j^g alkyl group, a C _1-6 haloalkyl group, a C ₂ _ ₆ alkenyl group, a C ₂ _ ₆ haloalkenyl group, a C ₂ _ ₆ alkynyl group, a C ₂ _ ₆ haloalkynyl group, a C ₃ _ ₆ cycloalkyl group, a C ₃ _ ₆ halocycloalkyl group, a C ₄ _ ₇ cycloalkylalkyl group, a C ₂ _ ₆ alkoxyalkyl group, a C ₂ _ ₆ alkylthioalkyl group, a C ₂ _ ₆ alkoxycarbonylalkyl group, a ^c ₂ - ₆ cyanoalkyl group, a C^ _g alkoxy group, a C^ _g haloalkoxy group, a C ₂ _ ₆ alkenyloxy group, a C ₂ _ ₆ haloalkenyloxy group, a C ₂ _ ₆ alkynyloxy group, a C ₂ _ ₆ haloalkynyloxy group, a C ₃ _ ₆ cycloalkyloxy group, a C ₃ _ ₆ halocycloalkyloxy group, a C ₄ _ ₇ cycloalkylalkyloxy group, a C ₂ _ ₆ alkoxyalkyloxy group, a C ₂ _ ₆ alkylthioalkyloxy group, a C ₃ _ ₆ alkoxycarbonylalkyloxy group, a C ₂ _ ₆ cyanoalkyloxy group, a C^ _g alkylthio group, a C _j . _g haloalkylthio group, a C ₂ _ ₆ alkenylthio group, a C ₂ _ ₆ haloalkenylthio group, a C ₂ _ ₆ alkynylthio group, a C ₂ _ ₆ haloalkynylthio group, a C ₃ _ ₆ cycloalkylthio group, a C ₃ _ ₆ halocycloalkylthio group, a C ₄ _ ₇ cycloalkylalkylthio group, a C ₂ _ ₆ alkoxyalkylthio group, a C ₂ _ ₆ alkylthioalkylthio group, a C ₂ _ ₆ alkoxycarbonylalkylthio

group, a C ₂ _ ₆ cyanoalkylthio group, a _λ _ ₆ alkylsulfinyl group, a C _j^g haloalkylsulfinyl group, a C ₂ _ ₆ alkenylsulfinyl group, a C ₂ _ ₆ haloalkenylsulfinyl group, a C ₂ _ ₆ alkynylsulfinyl group, a C ₂ _ ₆ haloalkynylsulfinyl group, a C ₃ _ ₆ cycloalkylsulfinyl group, a C ₃ _ ₆ halocycloalkylsulfinyl group, a C ₄ _ ₇ cycloalkylalkylsulfinyl group, a C ₂ _ ₆ alkoxyalkylsulfinyl group, a C ₂ _ ₆ alkylthioalkylsulfinyl group, a C^ _g alkylsulfonyl group, a C _j _ ₆ haloalkylsulfonyl group, a C ₂ _ ₆ alkenylsulfonyl group, a C ₂ _ ₆ haloalkenylsulfonyl group, a C ₂ _ ₆ alkynylsulfonyl group, a C ₂ _ ₆ haloalkylsulfonyl group, a C ₃ _ ₆ cycloalkylsulfonyl group, a C ₃ _ ₆ halocycloalkylsulfonyl group, a C ₄ _ ₇ cycloalkylalkylsulfonyl group, a C ₂ _ ₆ alkoxyalkylsulfonyl group, a C ₂ _ ₆ alkylthioalkylsulfonyl group, a C ₂ _ ₆ alkoxycarbonylalkylsulfonyl group, a C ₂ _ ₆ cyanoalkylsulfonyl group, a C _j^g alkylsulfonyloxy group, a C _j . _g haloalkylsulfonyloxy group, a C ₃ _ ₆ cycloalkylsulfonyloxy group, a C ₃ _ ₆ halocycloalkylsulfonyloxy group, a C ₂ _ ₆ cyanoalkylsulfonyloxy group, a C ₂ _ ₇ alkylcarbonyloxy group, a C ₂ _ ₇ haloalkylcarbonyloxy group, a C ₄ _ ₇ cycloalkylcarbonyloxy group, a C ₄ _ ₇ halocycloalkylcarbonyloxy group, a C ₃ _ ₇ cyanoalkylcarbonyloxy group, a C ₂ _ ₇ alkylcarbonyl group, a C ₂ _ ₇ haloalkylcarbonyl group, a C ₄ _ ₇ cycloalkylcarbonyl group, a C ₄ _ ₇ halocycloalkylcarbonyl group, a C ₃ _ ₇

cyanoalkylcarbonyl group, a C ₂ _ ₇ alkoxycarbonyl group, a

C ₂ _ ₇ haloalkoxycarbonyl group, a C ₄ _ ₇ cycloalkyloxycarbonyl group, a C ₄ _ ₇ halocycloalkyloxycarbonyl group, a C ₃ _ ₇ cyanoalkyloxycarbonyl group, a mono C _j^ . _g alkylaminocarbonyl group, a mono C _1-6 haloalkylaminocarbonyl group, a di C _1-6 alkylaminocarbonyl group, a di C _1-6 haloalkylaminocarbonyl group, a mono C _1-6 alkylaminosulfonyl group, a mono C^ _g haloalkylaminosulfonyl group, a di C _1-6 alkylaminosulfonyl group, a di C^ _g haloalkylaminosulfonyl group, an aminocarbonyl group, an aminosulfonyl group, a formylamino group, a C ₂ _ ₇ alkylcarbonylamino group, a C ₂ _ ₇ haloalkylcarbonylamino group, an amino group, a mono C _1-6 alkylamino group, a mono C^ _g haloalkylamino group, a di C _1-6 alkylamino group, a di C _1-6 haloalkylamino group,

-CH=CH-CH=CH-, -0CH ₂ 0~, -OCH ₂ CH ₂ 0-, -OCF ₂ 0-, -OCF ₂ CF ₂ 0- or -OCF ₂ CF ₂ - bridging the adjacent carbon atoms, a phenyl group which may be substituted, a phenoxy group which may be substituted, a phenylthio group which may be substituted, a phenylsulfinyl group which may be substituted, a phenylsulfonyl group which may be substituted, a phenylsulfonyloxy group which may be substituted, a phenylcarbonyloxy group which may be substituted, a phenylcarbonyl group which may be

substituted, a phenoxycarbonyl group which may be substituted, a phenylaminocarbonyl group which may be substituted, a phenylsulfonylcamino group which may be substituted, a phenylcarbonylamino group which may be substituted, a phenylamino group which may be substituted, a benzyl group which may be substituted, a benzyloxy group which may be substituted, a benzylthio group which may be substituted, a benzylsulfinyl group which may be substituted, a benzylsulfonyl group which may be substituted, a benzylsulfonyloxy group which may be substituted, a benzylcarbonyloxy group which may be substituted, a benzylcarbonyl group which may be substituted, a benzyloxycarbonyl group which may be substituted, a benzylaminocarbonyl group which may be substituted, a benzylsulfonylamino group which may be substituted, a benzylcarbonylamino group which may be substituted, a benzylamino group which may be substituted, a pyridyl group which may be substituted, a pyridyloxy group which may be substituted, a pyridylthio group which may be substituted, a pyridylsulfinyl group which may be substituted, a pyridylsulfonyl group which may be substituted, a pyridylsulfonyloxy group which may be substituted, a pyridylcarbonyloxy group which may be substituted, a pyridylcarbonyl group which may be substituted, a pyridyloxycarbonyl group which may be substituted, a pyridylaminocarbonyl group which may be substituted, a pyridnylsulfonylamino group which may be

substituted, a pyridylcarbonylamino group which may be substituted, or a pyridnylamino group which may be substituted (provided that the substituent for each group which may be substituted, may, for example, be a halogen atom, a hydroxyl group, a cyano group, a nitro group, a C^ _g alkyl group, a C _j^g haloalkyl group, a C ₁ _ ₆ alkylthio group, a C^ _g haloalkylthio group, a C _x _ ₆ alkylsulfonyl group, a C^ _g haloalkylsulfonyl group, a C^ _g alkoxycarbonyl group, an amino group, or a di C _λ _ ₆ alkylamino group) .

X may preferably be, for example, a halogen atom, a cyano group, a nitro group, a C _1-6 alkyl group, a C _j^g haloalkyl group, a ₁ _ ₆ alkoxy group, a _λ _ ₆ haloalkoxy group, a C _j^g haloalkylthio group, a C ₁ _ ₆ haloalkylsulfonyloxy group, or a C ₂ _ ₆ alkoxycarbonyl group.

X is preferably substituted at the 3-position, the 4- position and/or the 5-position, preferably at the 3- position. Y- may preferably be, for example, a halogen atom, a cyano group, a nitro group, a C _χ _ ₆ alkyl group, a _λ _ ₆ haloalkyl group, a C _j^g alkoxy group, a C ₂ _ ₆ alkoxycarbonyl group, a C _1-6 haloalkoxy group, a C _1-6 alkylthio group, a C _1-6 haloalkylthio group, a C _χ _ ₆ alkylsulfonyl group, a C _1-6 haloalkylsulfonyl group, a C ₁ _ ₆ alkylsulfonyloxy group, a C _χ _ ₆ haloalkylsulfonyloxy group, or -OCF ₂ 0- or -OCF ₂ CF ₂ 0- bridging the adjacent

carbon atoms.

Y is preferably substituted at the 3-position, the 4- position and/or the 5-position, more preferably at the 4- position. Z may preferably be, for example, a halogen atom, a cyano group, a nitro group, a C ₁ _ ₆ alkyl group, a C^ _g haloalkyl group, a C ₂ _ ₆ haloalkoxy group, a C _x _ ₆ alkylthio group, a C ₁ _ ₆ haloalkylthio group, a C^ _g alkylsulfinyl group, a C _j _ ₆ haloalkylsulfinyl group, a C _1-6 alkylsulfonyl group, a C _x _ _g haloalkylsulfonyl group, a C _λ _ ₆ alkylsulfonyloxy group, a C ₁ _ ₆ haloalkylsulfonyloxy group, or -OCF ₂ 0-, -OCF ₂ CF ₂ 0- or -OCF ₂ CF ₂ - bridging the adjacent carbon atoms.

Z is preferably substituted at the 3-position and/or the 4-position, more preferably at the 4-position.

R ¹ may, for example, be a halogen atom, a hydroxyl group, a cyano group, a nitro group, a C _1-6 alkyl group, a C _1-6 haloalkyl group, a C ₁ _ ₆ alkoxy group, a _λ _ ₆ haloalkoxy group, a C _1-6 alkylthio group, a C ₁ _ ₆ haloalkylthio group, a C ₁ _ ₆ alkylsulfonyl group, a C _χ _ ₆ haloalkylsulfonyl group, a C ₂ _ ₆ alkoxycarbonyl group, an amino group, a di C ₁ _ ₆ alkylamino group, or a phenyl group which may be substituted (provided that the substituent for the group which may be substituted, may, for example, be a halogen atom, a hydroxyl group, a cyano group, a nitro group, a C _x _ ₆ alkyl group, a C ₁ _ ₆ haloalkyl group, a C ₁ _ ₆ alkoxy group, a C ₁ _ ₆ haloalkoxy group, a

C ₁ _ ₆ alkylthio group, a C _1-6 haloalkylthio group, a _λ _ ₆ alkylsulfonyl group, a C ₂ _ ₆ alkoxycarbonyl group, an amino group, or a di C^ _g alkylamino group) .

R ¹ is preferably a hydrogen atom, or a C^ _g alkyl group.

Each of R ² , R ³ and R ⁴ may, for example, be a hydrogen atom, a C _1-6 alkyl group, a C ₂ _ ₆ alkenyl group, a C ₂ _ ₆ alkynyl group, a C _j^g haloalkyl group, a C ₂ _ ₆ alkoxyalkyl group, a C ₂ _ ₆ alkylcarbonyl group, a C ₂ _ ₆ alkoxycarbonyl group, a C ₂ _ ₆ haloalkylcarbonyl group, a C _x _ ₆ alkylthio group, a C _j^g haloalkylthio group, a C ₂ _ ₁₂ dialkylaminothio group, a C ₃ _ ₁₂

(alkyl)alkoxycarbonylaminothio group, or a benzyl group which may be substituted (provided that the substituent for the group which may be substituted, may, for example, be a halogen atom, a hydroxyl group, a cyano group, a nitro group, a C _1-6 alkyl group, a C ₁ _ ₆ haloalkyl group, a C ₁ _ ₆ alkoxy group, a C _1-6 haloalkoxy group, a C ₁ _ ₆ alkylthio group, a C _j^g haloalkylthio group, a C^ _g alkylsulfonyl group, a C ₂ _ ₆ alkoxycarbonyl group, an amino group, or a di C _j^g alkylamino group) .

R ² may preferably be, for example, a hydrogen atom, a C ₁ _ ₆ alkyl group, a C ₂ _ ₆ alkenyl group, a C ₂ _ ₆ alkynyl group, a _λ _ ₆ haloalkyl group, a C ₂ _ ₆ alkoxyalkyl group, a C ₂ _ ₆ alkylcarbonyl group, a C ₂ _ ₆ alkoxycarbonyl group, a C ₂ _ ₆ haloalkylcarbonyl group, a C _j^g alkylthio group, a C _λ _ ₆ haloalkylthio group, R ⁶ OC(0)N(R ⁷ )S-, R ⁷ (R ⁸ )NS-, or a

benzyl group which may be substituted by (R ⁵ )_.

Each of R ³ and R ⁴ is preferably a hydrogen atom or a C _χ _ ₆ alkyl group. k is preferably an integer of from 0 to 2, more preferably 0. is preferably an integer of from 0 to 2, more preferably 1. m is preferably an integer of from 0 to 2, more preferably 1. n is preferably an integer of from 1 to 3, more preferably 1.

The following compounds may be mentioned as preferred compounds of the present invention.

(1) The semicarbazone derivative of the formula (I) wherein

X is a halogen atom, a cyano group, a nitro group, a C ₁ _ ₆ alkyl group, a C _x _ ₆ haloalkyl group, a C ₁ _ ₆ alkoxy group, a C _λ _ ₆ haloalkoxy group, a C ₂ _ ₆ haloalkylthio group, a C _j^ . _g haloalkylsulfonyloxy group, or a C ₂ _ ₆ alkoxycarbonyl group;

Y is a halogen atom, a cyano group, a nitro group, a C^ _g alkyl group, a C _1-6 haloalkyl group, a C _1-6 alkoxy group, a C ₂ _ ₆ alkoxycarbonyl group, a C _x _ ₆ haloalkoxy group, a C^ _g alkylthio group, a C _1-6 haloalkylthio group, a C^ _g alkylsulfonyl group, a C ₂ _ ₆ haloalkylsulfonyl group, a _λ _ ₆ alkylsulfonyloxy group, a C-^ _g haloalkylsulfonyloxy group, or -OCF ₂ 0- or -OCF ₂ CF ₂ 0-

bridging the adjacent carbon atoms;

Z is a halogen atom, a cyano group, a nitro group, a C _1-6 alkyl group, a C _1-6 haloalkyl group, a C^ _g haloalkoxy group, a C _1-6 alkylthio group, a C _j^g haloalkylthio group, a C _x _ _g alkylsulfinyl group, a C^ _g haloaklylsulfinyl group, a C _1-6 alkylsulfonyl group, a C _λ _ ₆ haloalkylsulfonyl group, a C _χ _ ₆ alkylsulfonyloxy group, a C _j^g haloalkylsulfonyloxy group, or -0CF ₂ 0-, -0CF ₂ CF ₂ 0- or -OCF ₂ CF ₂ - bridging the adjacent carbon atoms; each of R ¹ , R ³ and R ⁴ which are independent of one another, is a hydrogen atom or a C _1-6 alkyl group;

R ² is a hydrogen atom, a C _j^g alkyl group, a C ₂ _ ₆ alkenyl group, a C ₂ _ ₆ alkynyl group, a C _x _ ₆ haloalkyl group, a C ₂ _ ₆ alkoxyalkyl group, a C ₂ _ ₆ alkylcarbonyl group, a C ₂ _ ₆ alkoxycarbonyl group, a C ₂ _ ₆ haloalkylcarbonyl group, a C^ _g alkylthio group, a C _1-6 haloalkylthio group, R ⁶ OC(0)N(R ⁷ )S-, R ⁷ (R ⁸ )NS-, or a benzyl group which may be substituted by (R ⁵ ) _q ; each of £ and m which are independent of each other, is an integer of from 0 to 2; and n is an integer of from 1 to 3.

(2) The semicarbazone derivative of the above (1) wherein X is a halogen atom, a cyano group, a nitro group, a C _j . _g alkyl group, a C _j^g haloalkyl group, a C _1-6 alkoxy group, a C _1-6 haloalkoxy group, or a C ₂ _ ₆ alkoxycarbonyl

group, and it is substituted at the 3-position, the 4- position, the 3- and 4-positions, or the 3- and 5- positions;

Y is a halogen atom, a cyano group, a nitro group, a C ₁ _ ₆ alkyl group, a C ₁ _ ₆ haloalkyl group, a C _1-6 alkoxy group, a C ₁ _ ₆ haloalkoxy group, a C ₁ _ ₆ alkylthio group, a C _λ _ ₆ haloalkylthio group, a C ₂ _ ₆ alkoxycarbonyl group, or a C _j . _g alkylsulfonyloxy group, and it is substituted at the 3-position, the 4-position or the 3- and 4-positions; and

Z is a halogen atom, a cyano group, a C^ _g alkyl group, a C _1-6 haloalkyl group, a C-^ _g alkoxy group, a C _1-6 haloalkoxy group, a C _χ _ ₆ alkylthio group, a ₁ _ ₆ haloalkylthio group, or a C _l _ ₆ alkylsulfonyloxy group, and it is substituted at the 3-position, the 4-position or the 3- and 4-positions;

R ² is a hydrogen atom; each of R ³ and R ⁴ which are independent of each other, is a hydrogen atom, or a C _1-6 alkyl group; k is 0; each of £ and m which are independent of each other, is an integer of from 0 to 2; and n is i.

(3) The semicarbazone derivative of the above (1) wherein

X is a halogen atom, a cyano group, a nitro group, a C _j^ . _g alkyl group, a C ₁ _ ₆ haloalkyl group, a C _1-6 alkoxy

group, a C ₁ _ ₆ haloalkoxy group, or a C ₂ _ ₆ alkoxycarbonyl group, and it is substituted at the 3-position, the 4- position, the 3- and 4-positions, or the 3- and 5- positions; Y is a halogen atom, a cyano group, a nitro group, a C _χ _ ₆ alkyl group, a _λ _ ₆ haloalkyl group, a C _j^g alkoxy group, a C _j^g haloalkoxy group, a C ₁ _ ₆ alkylthio group, a ^c ι- ₆ haloalkylthio group, a C ₂ _ ₆ alkoxycarbonyl group, or a C _j^g alkylsulfonyloxy group, and it is substituted at the 3-position, the 4-position, or the 3- and 4- positions;

Z is a halogen atom, a cyano group, a C^ _g alkyl group, a C _j^g haloalkyl group, a C _1-6 alkoxy group, a C _1-6 haloalkoxy group, a C _λ _ ₆ alkylthio group, a C _χ _ _g haloalkylthio group, or a C _j^g alkylsulfonyloxy group, and it is substituted at the 3-position, the 4-position, or the 3- and 4-positions;

R ² is a C _1-6 alkyl group, a C ₂ _ ₆ alkenyl group, a C ₂ _ ₆ alkynyl group, a C ₁ _ ₆ haloalkyl group, a C ₂ _ ₆ alkoxyalkyl group, a C ₂ _ ₆ alkylcarbonyl group, a C ₂ _ ₆ alkoxycarbonyl group, a C ₂ _ ₆ haloalkylcarbonyl group, a C-^ _g alkylthio group, a C _χ _ ₆ haloalkylthio group, R ⁶ OC(0)N(R ⁷ )S-, R ⁷ (R ⁸ )NS-, or a benzyl group which may be substituted by

⁽ R ⁵⁾ _q ^; each of R ³ and R ⁴ which are independent of each other, is a hydrogen atom, or a C _1-6 alkyl group; k is 0;

each of £ and m which are independent of each other, is an integer of from 0 to 2; and n is 1.

(4) The semicarbazone derivative of the above (2) wherein

W is an oxygen atom;

X is a halogen atom, a C _λ _ ₆ alkyl group, a C _x _ ₆ haloalkyl group, a C^ _g alkoxy group, or a _ ₆ haloalkoxy group, and it is substituted at the 3-position; Y is a halogen atom, a cyano group, a nitro group, a C _1-6 haloalkyl group, a C^ _g haloalkoxy group, or a C _1-6 haloalkylthio group, and it is substituted at the 4- position;

Z is a halogen atom, a C _1-6 haloalkyl group, a C^ _g haloalkoxy group, or a C ₁ _ ₆ haloalkylthio group, and it is substituted at the 4-position; each of R ³ and R ⁴ is a hydrogen atom; k is 0; and each of £ , m and n is 1. (5) The semicarbazone derivative of the above (3) wherein is an oxygen atom;

X is a halogen atom, a C _1-6 alkyl group, a C ₁ _ ₆ haloalkyl group, a C^ _g alkoxy group, or a C ₁ _ ₆ haloalkoxy group, and it is substituted at the 3-position;

Y is a halogen atom, a cyano group, a nitro group, a C _1-6 haloalkyl group, a _λ _ ₆ haloalkoxy group, or a C _χ _ ₆

haloalkylthio group, and it is substituted at the 4- position;

Z is a halogen atom, a C _1-6 haloalkyl group, a C _j^g haloalkoxy group, or a C _j . _g haloalkylthio group, and it is substituted at the 4-position; each of R ³ and R ⁴ is a hydrogen atom; k is 0; and each of £ , m and n is 1.

When the compound of the present invention has an asymmetric carbon atom, it includes optically active compounds of (+)-form and (-)-form. Further, when stereoisomerism is present, it includes cis-form and trans-form. Furthermore, when R ² is a hydrogen atom, the compound of the present invention may be in the form of the following tautomers, and such structures are also covered by the present invention.

Specific examples of the compound of the present invention include the compounds shown in Table 1. However, the compounds in Table 1 are merely illustrative, and the present invention is by no means limited to such specific examples.

Ql to Q7 in Table 1 represent the following formulas

- 19 -

Q2 Q3 Q4

Q5 Q6 Q7

Table 1

R ² R ³

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

o o o o o o o o o o o o o o o o X

X X X X X X X X X X X X X X X X

x x x x x x x x x x x x x x x x 30 x x x x x x x x x x x x x x x x 33 cn co cn en en cn cn en cn en tn tn p p p

O

W Xi

In the present invention, the pesticide means, in particular, an agent for controlling insect pests. The compound of the present invention exhibits pesticidal effects against various insect pests at an extremely low dose. The insect pests include, for example, agricultural insect pests such as green rice leafhopper (Nephotettix cincticeps) , brown rice planthopper (Nilaparvata luqens) , green peach aphid (Myzus persicae) , 28-spotted ladybird (Epilachna viqintioctopunctata) , tobacco budworm (Heliothis virescens) , european corn borer (Ostrinia nubilalis) , fall armyworm (Spodoptera fruqiperda) , corn earwor (Helicoverpa zea) , cabbage armyworm (Mamestra brassicae) , common cutworm (Spodoptera litura) , common white (Pieris rapae crucivora) , cabbage sawfly (Athalia rosae ruficornis) , smaller tea tortrix (Adoxofhyes sp.), oriental tea tortrix (Homona maqnanima) , rice leafroller (Cnaphalocrocis medinalis) , diamondback moth (Plutella xylostella) , southern corn rootworm (Diabrotica undecimpunctata howardi) , northern corn rootworm (D. lonqicornis barberi) , western corn rootworm (D_;_ virqifera virqifera) , Colorado potato beetle (Leptinotarsa decemlineata) ; sanitary insect pests such as common gnat (Culex pipiens pallens) , housefly, German cockroach (Blattela qermanica) , ants, fleas and louses; stored grain insect pests such as maize weevil (Sitophilus zeamais) , red flour beetle (Tribolium castaneum) and

almond moth (Cadra cautella); house pests such as Formosan subterranean termite (Coptotermes formosanus) ; animal pests such as mites, fleas and louses; indoor dust mites such as acarid mites (Acaridae) , Dermatopha oides farinae, and Chenyletus malaccensis; and mollusks such as slugs (Philomycidae) and snails. Namely, the compound of the present invention is capable of effectively controlling pests such as orthoptera, hemiptera, lepidoptera, coleoptera, hymenoptera, diptera, isoptera and acarina at a low dose. On the other hand, the compound of the present invention has been found to be an extremely useful compound which is substantially free from adverse effects against mammals, fishes, Crustacea and beneficial insects. On the basis of this discovery, the present invention has been accomplished.

Now, methods for preparing the compounds of the present invention will be described. The compounds of the present invention are novel semicarbazone derivatives, and representative methods for their production will be described specifically.

In the respective methods (methods A to F) , W, X, Y, Z, R ¹ , R ² , R ³ , R ⁴ , k, £ , m and n are as defined above, and each of L ¹ , L ² and L ³ is an excellent leaving group such as a chlorine atom, a bromine atom, an iodine atom, an alkylsulfonate group or an arylsulfonate group.

Method A

Process 1

(II) (III)

Process 2

(V)

Process 3

(I)

A compound of the formula (III) can be obtained by reacting a compound of the formula (II) with phosphorus pentachloride in an inert solvent or without any solvent, or by reacting a compound of the formula (II) with

thionyl chloride in an inert solvent or without any solvent. In the case of the reaction with thionyl chloride, the reaction proceeds more efficiently if dimethylformamide is added. Then, the compound of the formula (III) and a compound of the formula (IV) are reacted in the presence or absence of a base in an inert solvent to obtain a compound of the formula (V) of the present invention (a compound of the formula (I) wherein R ² is a hydrogen atom). Further, a compound of the formula (I) of the present invention can be obtained by reacting the compound of the formula (V) of the present invention and a compound of the formula (VI) in the presence of a base in an inert solvent.

The solvent to be used in Process 1 may, for example, be an aromatic hydrocarbon such as benzene or toluene, or a halogenated hydrocarbon such as carbon tetrachloride or 1,1,2-trichloroethane. It is preferred to employ an excess amount of phosphorus pentachloride in toluene. The reaction temperature can be set at an optional level within a range of from 0°C to the reflux temperature of the reaction mixture. However, it is preferred to conduct the reaction at a temperature of from 60°C to the reflux temperature.

The base to be used in Process 2 may, for example, be an alkali metal alkoxide such as sodium ethoxide or potassium tert-butoxide, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkali

metal carbonate such as sodium carbonate, potassium carbonate or sodium hydrogen carbonate, an alkali metal hydride such as sodium hydride or potassium hydride, or an organic base such as triethylamine or pyridine. The solvent to be used may be any solvent so long as it does not hinder the reaction. For example, a lower alcohol such as methanol or ethanol, an aromatic hydrocarbon such as benzene or toluene, an ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran or 1,4-dioxane, a halogenated hydrocarbon such as dichloromethane or 1,2- dichloroethane, an amide such as dimethylformamide or dimethylacetamide, acetonitrile, dimethylsulfoxide, or water, may be mentioned. These inert solvents may be used alone or in combination as a mixture. Usually, it is preferred to use as the base, an organic base such as triethylamine or pyridine and as a solvent an aromatic hydrocarbon such as benzene or toluene, or an ether such as tetrahydrofuran or diethyl ether. The reaction temperature may be set at an optional level within a range of from -60°C to the reflux temperature of the reaction mixture. However, it is preferred to conduct the reaction within a range of from 0°C to reflux temperature of the reaction mixture.

The base to be used in Process 3 may, for example, be an alkali metal alkoxide such as sodium ethoxide or potassium tert-butoxide, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkali

metal carbonate such as sodium carbonate, potassium carbonate or sodium hydrogen carbonate, an alkali metal hydride such as sodium hydride or potassium hydride, or an organic base such as triethylamine or pyridine. The solvent to be used may be any solvent so long as it does not hinder the reaction. For example, it may be a lower alcohol such as methanol or ethanol, an aromatic hydrocarbon such as benzene or toluene, an ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran or 1,4-dioxane, a halogenated hydrocarbon such as dichloromethane or 1,2-dichloroethane, an amide such as dimethylformamide or dimethylacetamide, acetonitrile, dimethylsulfoxide, or water. Such inert solvents may be used alone or in combination as a mixture. Usually, it is preferred to employ as the base sodium hydride, potassium hydride, potassium tert-butoxide, or potassium hydroxide in a polar solvent such as tetrahydrofuran or dimethylformamide. The reaction temperature can be set at an optional level within a range of from -60°C to the reflux temperature of the reaction mixture. However, it is preferred to conduct the reaction at a temperature of from 0°C to 90°C.

Method B

(ID (vπ)

Process 2

H ₂ N-NH ₂ ^■ m Ci CHτ-N H ₂

(VIII)

Process 3

(I)

A compound of the formula (VII) can be obtained by reacting a compound of the formula (II) and diphosphorus pentasulfide in an inert solvent or without solvent, or

by reacting a compound of the formula (II) with a Lawesson's reagent in an inert solvent or without solvent. Then, the compound of the formula (VII) and hydrazine are reacted in the presence or absence of a base in an inert solvent or without solvent, to obtain a compound of the formula (VIII). Further, the compound of the formula (VIII) and a compound of the formula (IX) are reacted in an inert solvent in the presence or absence of a base to obtain a compound of the formula (I) of the present invention. The compound of the formula (VIII) can also be obtained by reacting hydrazine to the compound of the formula (III) obtained in Process 1 of Method A.

The solvent to be used in Process 1 may be any solvent so long as it does not hinder the reaction. For example, it may be an aromatic hydrocarbon such as benzene or toluene, an ether such as diethyl ether, 1,2- dimethoxyethane, tetrahydrofuran or 1,4-dioxane, a halogenated hydrocarbon such as dichloromethane or 1,2- dichloroethane, an amide such as dimethylformamide or dimethylacetamide, acetonitrile, pyridine, dimethylsulfoxide, or water. These inert solvents may be used alone or in combination as a mixture. Usually, it is preferred to employ a slightly excess amount of diphosphorus sulfide in pyridine. The reaction temperature can be set at an optional level within a range of from 0°C to the reflux temperature of the

reaction mixture. However, it is preferred to conduct the reaction at a temperature of from 60°C to the reflux temperature.

The base to be used in Process 3 may, for example, be an alkali metal alkoxide such as sodium ethoxide or potassium tert-butoxide, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkali metal carbonate such as sodium carbonate, potassium carbonate or sodium hydrogen carbonate, an alkali metal hydride such as sodium hydride or potassium hydride, or an organic base such as triethylamine or pyridine. The solvent to be used may be any solvent so long as it does not hinder the reaction. For example, it may be a lower alcohol such as methanol or ethanol, an aromatic hydrocarbon such as benzene or toluene, an ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran or 1,4-dioxane, a halogenated hydrocarbon such as dichloromethane or 1,2-dichloroethane, an amide such as dimethylformamide or dimethylacetamide, acetonitrile, dimethylsulfoxide, or water. These inert solvents may be used alone or in combination as a mixture. Usually, it is preferred to employ as the base an organic base such as triethylamine or pyridine and as the solvent a halogenated hydrocarbon such as dichloromethane. The reaction temperature can be set at an optional level within a range of from 0°C to the reflux temperature of the reaction mixture. However, it is preferred to

conduct the reaction at a temperature of from 0 ^β C to

50°C .

Method C

(X)

(xπ)

( I )

This method is a method of introducing R ³ and R ⁴ into a compound of the formula (I) of the present invention

wherein R ³ = R ⁴ = hydrogen atom. A compound of the formula (XII) of the present invention can be obtained by reacting a compound of the formula (X) of the present invention and a compound of the formula (XI) in the presence of a base in an inert solvent. Then, the compound of the formula (XII) of the present invention and a compound of the formula (XIII) is reacted in the presence of a base in an inert solvent to obtain a compound of the formula (I) of the present invention. The base to be used in this reaction may, for example, be an alkali metal alkoxide such as sodium ethoxide, potassium tert-butoxide, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkali metal carbonate such as sodium carbonate, potassium carbonate or sodium hydrogen carbonate, an alkali metal hydride such as sodium hydride or potassium hydride, or an organic base such as triethylamine or pyridine. The solvent to be used may be any solvent so long as it does not hinder the reaction. For example, it may be a lower alcohol such as methanol or ethanol, an aromatic hydrocarbon such as benzene or toluene, an ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran or 1,4-dioxane, a halogenated hydrocarbon such as dichloromethane or 1,2-dichloroethane, an amide such as dimethylformamide or dimethylacetamide, acetonitrile, dimethylsulfoxide, or water. These inert solvents may be used alone or in combination as a mixture. Usually, it

is preferred to employ as the base sodium hydride, potassium hydride, potassium tert-butoxide or potassium hydroxide in a polar solvent such as tetrahydrofuran or dimethylformamide. The reaction temperature can be set at an optional level within a range of from -60 ^β C to the reflux temperature of the reaction mixture. However, it is preferred to conduct the reaction at a temperature of from 0°C to 90°C. In this reaction, in the case where R ³ = R ⁴ , a compound of the formula (I) of the present invention can be obtained without isolating the compound of the formula (VII) by using two equivalents of the compound of the formula (XI) and two equivalents of a base.

Method D

A compound of the formula (II) as starting material can be obtained by reacting a compound of the formula

(XIV) and a compound of the formula (XV) in the presence of a base in an inert solvent. The base to be used in this method may, for example, be an alkali metal carbonate such as sodium carbonate, potassium carbonate or sodium hydrogen carbonate, an alkali metal hydride such as sodium hydride or potassium hydride, or an organic base such as triethylamine or pyridine. The

solvent to be used may be any solvent so long as it does not hinder the reaction. For example, it may be an aromatic hydrocarbon such as benzene or toluene, an ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran or 1,4-dioxane, a halogenated hydrocarbon such as dichloromethane or 1,2-dichloroethane, an amide such as dimethylformamide or dimethylacetamide, acetonitrile, dimethylsulfoxide, or water. These inert solvents may be used alone or in combination as a mixture. Usually, it is preferred to employ an organic base such as triethylamine or pyridine and as a solvent, an aromatic hydrocarbon such as benzene or toluene, or an ether such as tetrahydrofuran or diethyl ether. The reaction temperature may be set at an optional level within a range of from -60°C to the reflux temperature of the reaction mixture. However, it is preferred to conduct the reaction at a temperature of from 0°C to 120°C.

In the case of the compound of the formula (II) wherein R ² = H, a compound of the formula (II) wherein R ² ≠ H can be obtained by reacting a compound of the formula (VI) in the presence of a base in an inert solvent.

Method E

(rx) (XVI)

This method is directed to a synthesis of a starting material where R ³ = R ⁴ = hydrogen atom (a compound of the formula (IV) wherein R ³ = R ⁴ = hydrogen). A compound of the formula (XVI) can be obtained by reacting a compound of the formula (IX) and hydrazine in the presence or absence of a catalyst in an inert solvent. The catalyst to be used in this reaction may, for example, be an organic base such as triethylenediamine or diazabicycloundecene. The amount of the catalyst to be used can be set at an optional level within a range of from 0.001 wt% to 10 wt%, relative to the compound of the formula (IX). However, an amount of from 0.1wt% to 1 wt% is preferred. The solvent may be any solvent so long as it does not hinder the reaction. For example, it may be an aromatic hydrocarbon such as benzene or toluene, an ether such as diethyl ether or tetrahydrofuran, a halogenated hydrocarbon such as dichloromethane or chloroform, an amide such as dimethylformamide or dimethylacetamide, acetonitrile, dimethylsulfoxide, or

water. These inert solvents may be used alone or in combination as a mixture. The reaction temperature can be set at an optional level within a range of from -60°C to the reflux temperature of the reaction mixture. However, it is preferred to conduct the reaction at a temperature of from 0 ^β C to 50°C. In this reaction, the molar ratio of the reactants is not particularly limited. However, in order to obtain the compound of the formula (XVI) in good yield, it is preferred to employ hydrazine in a slightly excess amount relative to the compound of the formula (IX). Method F

(XVII) (IX)

Process 1

(XVIII)

Process 2

This method is an alternative method of Method E and

directed to a synthesis of a starting material where R ³ = R ⁴ = hydrogen atom (a compound of the formula (IV) wherein R ³ = R ⁴ = hydrogen atom) . A compound of the formula (XVIII) can be obtained by reacting a compound of the formula (XVII) and a compound of the formula (IX) in the presence or absence of a catalyst in an inert solvent. The catalyst, the solvent and the reaction conditions such as the temperature to be used in this reaction may be similar to those in Method E. It is a feature of this method that the compound of the formula (XVIII) can be obtained in good yield by using equimolar amounts of the compound of the formula (XVII) and the compound of the formula (IX). In Process 2, the compound of the formula (XVIII) is reacted in the presence of an acid in an inert solvent to obtain a compound of the formula (XIX). The acid to be used may, for example, be an inorganic acid such as hydrochloric acid or sulfuric acid, or an organic acid such as paratoluenesulfonic acid or trifluoroacetic acid. The solvent may be any solvent so long as it does not hinder the reaction. For example, it may be a lower alcohol such as methanol or ethanol, an aromatic hydrocarbon such as benzene or toluene, an ether such as diethyl ether or tetrahydrofuran, a halogenated hydrocarbon such as dichloromethane or carbon tetrachloride, an amide such as dimethylformamide or dimethylacetamide, acetonitrile, dimethylsulfoxide, acetic acid, or water. These inert solvents may be used

alone or in combination as a mixture. Usually, it is preferred to employ an excess amount of hydrochloric acid in a lower alcohol such as methanol or ethanol. The reaction temperature can be set at an optional level within a range of from -60°C to the reflux temperature of the reaction mixture. However, it is preferred to conduct the reaction at a temperature of from 0°C to the reflux temperature of the reaction mixture.

In the respective methods, the molar ratios of the respective reactants are not particularly limited.

However, it is advantageous to conduct the reactions in equimolar or close to equimolar amounts.

When it is necessary to purify the compound of the present invention, the compound can be separated and purified by an optional purification method such as recrystallization, column chromatography or thin layer chromatography.

When the compound of the present invention is to be used as a pesticide, it is usually applied as admixed with a suitable carrier, for example, a solid carrier such as clay, pulp, bentonite, diato aceous earth or fine silica powder, or a liquid carrier such as water, an alcohol (such as isopropanol, butanol, benzyl alcohol or furfuryl alcohol), an aromatic hydrocarbon (such as toluene or xylene), an ether (such as anisol), a ketone (such as cyclohexanone or isophorone), an ester (such as butyl acetate), an acid amide (such as N-

methylpyrrolidone) or a halogenated hydrocarbon (such as chlorobenzene) . If desired, a surfactant, an emulsifier, a dispersant, a penetrating agent, an extender, a thickener, an anti-freezing agent, an anti-solidification agent and/or a stabilizer may be added. It may be practically used in the form of an optional formulation such as a liquid formulation, an emulsifiable concentrate, a wettable powder, a dry flowable, a flowable, a dust or a granule. Further, at the time of formulation or application, the compound of the present invention may be mixed with various other herbicides, insecticides, miticides, nematocides, fungicides, plant growth regulating agents, synergists, fertilizers or soil improving agents, as the case requires.

Particularly by mixing it with other agricultural chemicals or plant hormones, it can be expected to reduce the cost by a reduction of the dose in its application, to broaden the insecticidal spectrum due to synergistic effects of the mixed agents or to obtain higher pesticidal effects. In such a case, it is possible to combine it with a plurality of known agricultural chemicals. Compounds disclosed in 1994 Issue of Farm Chemicals Handbook may, for example, be mentioned as types of agricultural chemicals which can be used in admixture with the compound of the present invention. The dose in application of the compound of the

present invention varies depending upon the application site, the application season the manner of application and the type of the crop plant. However, it is usually in an amount of from 0.005 to 50 kg/ha as the amount of active ingredient.

Now, Formulation Examples will be given in which compounds of the present invention are used. However, it should be understood that the present invention is by no means restricted to such specific Formulation Examples. In the following Formulation Examples, "parts" means "parts by weight". Wettable powder

Compound of the present invention 5 to 80 parts Solid carrier 10 to 85 parts Surfactant 1 to 10 parts

Others 1 to 5 parts

As "others" an antisolidification agent may, for example, be mentioned. Emulsifiable concentrate Compound of the present invention 1 to 30 parts Liquid carrier 30 to 95 parts

Surfactant 5 to 15 parts

Flowable

Compound of the present invention 5 to 70 parts Liquid carrier 15 to 65 parts

Surfactant 5 to 12 parts

Others 5 to 30 parts

As "others" an antifreezing agent and a thickener may, for example, be mentioned.

Dry flowable

Compound of the present invention 20 to 90 parts Solid carrier 10 to 60 parts

Surfactant 1 to 20 parts

Granule

Compound of the present invention 0.1 to 10 parts Solid carrier 90 to 99.99 parts Others 1 to 5 parts

Dust

Compound of the present invention 0.01 to 30 parts Solid carrier 67 to 99.5 parts

Others 0 to 3 parts Now, the present invention will be described in further detail with reference to Examples (Preparation

Examples, Formulation Examples and Test Examples).

PREPARATION EXAMPLES

The compounds of the present invention were prepared or can be prepared in accordance with the following

Preparation Examples. However, it should be understood that the present invention is by no means restricted by such specific Preparation Examples.

PREPARATION EXAMPLE 1 N-(4-chlorophenyl)-4-chlorobenzamide-4- trifluoromethoxyphenylsemicarbazone (Compound No. 1 of the present invention)

1.0 g of N-(4-chlorophenyl)-4-chlorobenzamide and 1.2 g of phosphorus pentachloride were gradually heated and dissolved and then stirred under reflux for 3 hours. Then, phosphorus oxychloride formed as a by-product was distilled off under reduced pressure. The residue and 1.00 g of N-(4-trifluoromethoxyphenyl)hydrazine carboxamide were dissolved in a solvent mixture composed of 20 ml of benzene and 20 ml of tetrahydrofuran, and 0.50 g of triethylamine was dropwise added thereto with stirring at room temperature. The mixture was further stirred at room temperature for 3 hours. The reaction mixture was poured into 200 ml of ice water and then extracted by an addition of 100 ml of ethyl acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate. Then, the solvent was distilled off under reduced pressure to obtain 2.05 g of a crude product. The crude product was purified by thin layer chromatography and further recrystallized from isopropyl ether to obtain 0.38 g of the desired product. Melting point: 206.5-208.0°C ppm:6.50-7.65(12H, m). 8.08(lH.s). 8.41(1H. s). 9.510H. s).

REFERENCE EXAMPLE 1

N-(4-chlorophenyl)-4-chlorobenzamide 3.3 g of 4-chloroaniline and 3.3 g of triethylamine were dissolved in 50 ml of benzene, and 20 ml of a benzene solution of 5.3 g of 4-chlorobenzoyl chloride was

dropwise added thereto with stirring under cooling with ice. Then, the mixture was further stirred at room temperature for one hour. The reaction mixture was poured into 200 ml of ice water and then extracted with 200 ml of ethyl acetate. The organic layer was washed with IN hydrochloric acid and then with a saturated sodium chloride aqueous solution and then dried over anhydrous sodium sulfate. Then, the solvent was distilled off under reduced pressure to obtain 6.33 g of N-(4-chlorophenyl)-4-chlorobenzamide. PREPARATION EXAMPLE 2

N-(4-cyanophenyl)-N-methyl-3-fluorobenzamide 4- trifluoromethoxyphenylsemicarbazone (Compound No. 93 of the present invention) 0.54 g of N-(4-cyanophenyl)-N-methyl-3- fluorobenzamidrazone, 0.41 g of 4-trifluoromethoxyphenyl isocyanate and two drops of triethylamine were added to 10 ml of dichloromethane and stirred at room temperature for 3 days. Then, 100 ml of ethyl acetate was added thereto, and the mixture was washed twice with water. Then, the solvent was distilled off under reduced pressure. The residue was washed with isopropyl ether to obtain 0.57 g of the desired compound. Melting point: 210.0-213.0°C REFERENCE EXAMPLE 2

N-(4-cyanophenyl)-3-fluorobenzamide

31.01 g of 4-aminobenzonitrile and 30.36 g of

triethylamine were dissolved in 950 ml of benzene, and 50 ml of a benzene solution of 39.64 g of 3-fluorobenzoyl chloride was dropwise added thereto with stirring under cooling with ice. After completion of the dropwise addition, the mixture was stirred at room temperature overnight, and then the solvent was distilled off under reduced pressure. The residue was dissolved in 500 ml of ethyl acetate, washed twice with water and then dried over anhydrous sodium sulfate. Then, the solvent was distilled off under reduced pressure. The residue was washed with diisopropyl ether to obtain 55.92 g of the desired compound. Melting point: 148.6-150.3°C N-(4-cyanophenyl)-N-methyl-3-fluorobenzamide 0.52 g of sodium hydride (purity: 55%) was added to 10 ml of dimethylformamide, and 2.40 g of N-(4- cyanophenyl)-3-fluorobenzamide was added thereto with stirring under cooling ice. The mixture was stirred at room temperature for one hour, and then 2.13 g of methyl iodide was added thereto. The mixture was further stirred at room temperature overnight. Then, 150 ml of diethyl ether was added thereto, and the mixture was washed twice with a saturated sodium chloride aqueous solution and then dried over anhydrous sodium sulfate. Then, the solvent was distilled off under reduced pressure. The residue was recrystallized from diisopropyl ether to obtain 1.87 g of the desired

compound .

Melting point: 103.2-106.1°C

N-(4-cyanophenyl)-N-methyl-3-fluorobenzenecarbothioamide 1.87 g of N-(4-cyanophenyl)-N-methyl-3- fluorobenzamide and 1.80 g of diphosphorus pentasulfide were added to 10 ml of pyridine, and the mixture was stirred for 2 hours under reflux under heating. Then, the mixture was poured into 100 ml of ice water. The mixture was turned into alkaline with an aqueous potassium hydroxide solution and then extracted by an addition of 150 ml of ethyl acetate. The organic layer was washed twice with dilute hydrochloric acid and then dried over anhydrous sodium sulfate. Then, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography

(developer: chloroform) to obtain 1.99 g of the desired compound as an oily substance.

'H-NMRCCDCl.^όppm 3.9(s. 3H). 6.8-7.6(m. 8H).

N-(4-cyanophenyl)-N-methyl-3-fluorobenzamidrazone 1.99 g of N-(4-cyanophenyl)-N-methyl 3- fluorobenzenecarbothioamide and 1.85 g of hydrazine monohydrate were added to 40 ml of ethanol, and the mixture was stirred for 3 hours under reflux under heating. Then, 100 ml of water was added thereto, and ethanol was distilled off under reduced pressure. The residue was extracted by an addition of 150 ml of ethyl acetate, and the organic layer was washed twice with

water and then dried over anhydrous sodium sulfate. Then, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developer: hexane/ethyl acetate = 1/1) to obtain 1.27 g of the desired compound. Melting point: 129.5-131.0°C PREPARATION EXAMPLE 3

N-(4-cyanophenyl)-N-methyl-3-fluorobenzamide 4-(4- trifluoromethoxyphenyl)-2-methylsemicarbazone (Compound No. 102 of the present invention)

0.2 g of sodium hydride (purity: 55%) was added to 5 ml of dimethylformamide, and a solution of 1.0 g of N-(4- cyanophenyl)-N-methyl-3-fluorobenzamide 4- trifluoromethoxyphenylsemicarbazone and 10 ml of dimethylformamide, was dropwise added thereto with stirring under cooling with ice. The mixture was stirred at room temperature for 30 minutes, and a solution of 0.36 g of methyl iodide and 3 ml of dimethylformamide, was added thereto. The mixture was further stirred at room temperature for 3 hours. The reaction mixture was poured into ice water, and formed crystals were collected by filtration and washed with water and hexane and then dried. The crystals were recrystallized from ethyl acetate/hexane to obtain 0.14 g of the desired compound. Melting point: 209.0-210.0°C REFERENCE EXAMPLE 3 N-(4-cyanophenyl)-3-fluorobenzenecarbothioamide

9.61 g of N-(4-cyanophenyl)-3-fluorobenzamide and 9.34 g of diphosphorus pentasulfide were added to 40 ml of pyridine, and the mixture was stirred for 2 hours under reflux under heating and then poured into 400 ml of ice water. The mixture was turned into alkaline with an aqueous potassium hydroxide solution, and precipitated solid was collected by filtration, dried and then washed with diisopropyl ether to obtain 8.17 g of the desired compound. N-(4-cyanophenyl)-3-fluorobenzamidrazone 7.69 g of N-(4-cyanophenyl)-3- fluorobenzenecarbothioamide and 7.51 g of hydrazine monohydrate were added to 150 ml of ethanol, and the mixture was stirred for 2 hours under reflux under heating. Then, 150 ml of water was added thereto, and ethanol was distilled off under reduced pressure. The residue was extracted by an addition of 300 ml of ethyl acetate, and the organic layer was washed twice with water and then dried over anhydrous sodium sulfate. Then, the solvent was distilled off under reduced pressure. The residue was washed with diisopropyl ether to obtain 5.33 g of the desired compound.

Melting point: 104.0-105.0°C

N-( -cyanophenyl)-3-fluorobenzamidrazone 9.61 g of N-(4-cyanophenyl)-3-fluorobenzamide and

9.16 g of phosphorus pentachloride were added to 40 ml of toluene, and the mixture was stirred for 2 hours under

reflux under heating. Then, the solvent was distilled off under reduced pressure. The residue was dissolved in 50 ml of benzene, and the solution was dropwise added to 50 ml of a benzene solution of 6.01 g of hydrazine monohydrate with stirring at room temperature. The mixture was stirred at room temperature overnight, and then 100 ml of water was added thereto. Benzene was distilled off under reduced pressure. The residue was extracted by an addition of 400 ml of ethyl acetate, and the organic layer was washed twice with water and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure. The residue was washed with diisopropyl ether to obtain 4.88 g of the desired compound. In accordance with the above Preparation Examples, compounds identified in Table 2 were prepared.

Table 2

'1: 3 , 5-dichloro-4- (3-chloro-5-trifluoromethyl-2-pyridiloxy)

FORMULATION E: AMPLES

Now, Formulation Examples will be given for pesticides containing compounds of the present invention as active ingredients. However, it should be understood that the present invention is by no means restricted to such specific Examples. In the following Formulation Examples, "parts" means "parts by weight". FORMULATION EXAMPLE 1: Wettable powder

Compound of the present invention 50 parts Zeeklite PFP (tradename for Kaoline-type clay, manufactured by Zeeklite Mining Industries Co., Ltd.)

43 parts Sorpol 5050 (tradename for anionic surfactant, manufactured by Toho Chemicals Ind. Co., Ltd.)

2 parts Lunox 1000C (tradename for anionic surfactant, manufactured by Toho Chemicals Ind. Co., Ltd.)

3 parts Carplex #80 (antisolidification agent) (tradename for fine silica, manufactured by Shionogi & Co., Ltd.)

2 parts

The above components are uniformly mixed and triturated to obtain a wettable powder. FORMULATION EXAMPLE 2: E ulsifiable concentrate Compound of the present invention 3 parts

Xylene 76 parts

Isophorone 15 parts

Sorpol 3005X (tradename for a mixture of a nonionic surfactant and an anionic surfactant, manufactured by Toho Chemicals Ind. Co., Ltd.)

6 parts

The above components are uniformly mixed to obtain an emulsifiable concentrate.

FORMULATION EXAMPLE 3: Flowable

Compound of the present invention 35 parts

Agrisol S-711 (tradename for a nonionic surfactant, manufactured by Kao Corporation)

8 parts Lunox 1000C (tradename for anionic surfactant, manufactured by Toho Chemicals Ind. Co., Ltd.)

0.5 part

1% Rodopol water (tradename for a thickener, manufactured by Loan Puran)

20 parts

Ethylene glycol (antifreezing agent) 8 parts Water 28.5 parts

The above components are uniformly mixed to obtain a flowable. FORMULATION EXAMPLE 4: Dry flowable

Compound of the present invention 75 parts Isoban No. 1 (tradename for an anion surfactant, manufactured by Klaray Isoprene Chemical K.K.)

10 parts

Anilex N (tradename for anionic surfactant, manufactured by Sanyo Kokusaku Pulp K.K.)

5 parts

Carplex #80 (tradename for fine silica, manufactured by Shionogi & Co., Ltd.) 10 parts

The above components are uniformly mixed and finely pulverized to obtain a dry flowable.

FORMULATION EXAMPLE 5: Granule

Compound of the present invention 0.1 part

Bentnite 55.0 parts

Talc 44.9 parts The above components are uniformly mixed and triturated. Then, a small amount of water is added thereto. The mixture is stirred, kneaded and then granulated by an extrusion-type granulator, followed by drying to obtain a granule. FORMULATION EXAMPLE 6: Dust

Compound of the present invention 3.0 parts

Carplex #80 (tradename for fine silica, manufactured by Shionogi & Co., Ltd.)

0.5 part

Clay 95 parts Diisopropyl phosphate 1.5 parts

The above components are uniformly mixed and triturated to obtain a dust.

In use, the above wettable powder, emulsifiable concentrate, flowable or dry flowable is diluted from 50 to 20,000 times with water and applied so that the active ingredient will be from 0.05 to 50 kg/ha. TEST EXAMPLES

Now, usefulness of the compounds of the present invention as pesticides will be described in detail with reference to the following Test Examples.

TEST EXAMPLE 1: Insecticidal test on common cutworm (Spodoptera litura)

5% emulsifiable concentrates of the compounds of the present invention (25% wettable powders in the case of certain compounds) were diluted with water containing a spreader to prepare the samples of liquid insecticides with a concentration of 1,000 ppm. Leaves of cabbage were immersed in the respective samples of liquid insecticides for about 10 seconds. After air drying, the leaves were placed in the Petri dishes and the second instar nymphae of common cutworm (Spodoptera litura) were released in the said dishes (10 insects per dish). The dishes were closed with a perforated cover and kept in a 25°C thermostatic chamber. The percentage of mortality of the insects after the lapse of 6 days was calculated by the following formula. The tests were conducted twice for each compound. number of insects killed

Mortality (%) = x 100 number of insects released

In the test results, the following compounds of the present invention exhibited a mortality of 100%.

Compound Nos.: 3, 4. 5. 6, 9, 1 0. 1 1, 1 2. 1 3, 1 4, 1 5. 1 6, 1 7. 1 9, 20, 21. 22, 23, 24. 26. 27, 28. 2 9. 32, 33, 34, 35, 36, 38. 39, 40, 4 1 , 4 2 , 43, 4 4. 45, 46, 47, 4 8 , 4 9, 50, 5 1, 52, 53, 54, 55, 5 6, 57, 58, 59. 60, 61, 62, 63, 64, 67. 68. 70, 7 2. 73, 76, 77, 78, 79. 80, 8 1. 82, 83. 85. 8 6, 8 8 ^, 89. 90, 9 1, 92, 93, 94, 95, 96, 97, 98, 99. 1 0 1. 1 02. 1 03. TEST EXAMPLE 2: Insecticidal test on twenty eight-spotted ladybird (Epilachna viqintioctopunctata)

5% emulsifiable concentrates of the compounds of the present invention (25% wettable powders in the case of certain compounds) were diluted with water containing a spreader to prepare the samples of liquid insecticides with a concentration of 1,000 ppm. Leaves of tomato were immersed in the respective samples of liquid insecticides for about 10 seconds. Then, after air drying the leaves, they were placed in the Petri dishes and the second instar nymphae of twenty eight-spotted ladybird (Epilachna viqintioctopunctata) were released in the respective dishes (10 insects per dish). After covered, the dishes were kept in a 25°C thermostatic chamber. The percentage of mortality after the lapse of 6 days was calculated by the following formula. The tests were conducted twice for each compound.

number of insects killed

Mortality (%) = x 100 number of insects released

In the results, the following compounds of the present invention exhibited a mortality of 100%.

Compound Nos.: 1, 2, 3, 4. 5, 6, 8. 9, 1 0. 1 1, 1 2, 1

3, 14, 15, 16. 1 7, 18, 1 9, 20, 21. 22, 23. 24. 2

6, 27, 28, 29, 32. 33, 34, 35, 36, 38, 39, 40, 4 1, 42. 43, 44, 45, 46. 47, 48, 49. 50, 51. 52. 5 3, 54, 55, 56, 57, 58, 59, 60, 61. 62, 63. 64, 6

7, 68, 69, 70, 71, 72, 73. 74, 76, 77, 78, 79. 8 0, 81. 82. 83, 85, 86, 88, 89, 90, 91, 92, 93, 9

4, 95. 9 6, 97, 98, 99, 1 0 1, 1 02, 1 03. The compounds of the present invention exhibit excellent insecticidal and miticidal activities against many agricultural insect pests and spider mites and no substantial adverse effects against mammals, fishes and beneficial insects. Thus, the compounds of the present invention present useful pesticides.