CYCLIC UREA COMPOUNDS, THEIR PRODUCTION AND USE AS HERBICIDES

[Technical Field]

The present invention relates to a novel cyclic urea compound having excellent and selective herbicidal activity, a production method for the compound, and an agrochemical composition comprising the compound. The cyclic urea compound of the invention is a novel compound having excellent herbicidal activity against paddy field and plowland weeds without inducing any material adverse responses in crop plants such as rice, wheat, barley, soybean, maize and other plants and finds application as a useful selective herbicide. [Background Art] l-aryl-3-aralkyl-cyclic urea compounds have been reported. For example, a cyclic urea compound of the formula:

wherein R represents benzyl, diphenylmethyl, or 1- phenylethyl; Rj represents phenyl, is disclosed in Chemical Abstracts Vol. 63, 1965, Col. 600, "Hydroxylamine derivatives, XIV. 3 , 5-Dioxo-l, 2 , 3-oxadi- azolidines" and a cyclic urea compound of the formula:

wherein R represents phenyl; R _[ represents benzyl, is

disclosed in Chemical Abstracts, Vol. 76, 1972, p461, 153677v. However, there is not shown a cyclic urea compound in which the methylene moiety of the benzyl group substituting one of ring-forming nitrogen atoms is mono- or di-substituted.

JP-A 176475/1991 describes a cyclic urea compound of the formula:

wherein X represents hydrogen, halogen, alkyl, or alkoxy; Y represents halogen, alkyl, alkoxy, alkyl which is substituted with halogen, or phenoxy; Z represents oxygen or sulfur; m represents 0 or 1; n represents an integer of 0 to 3. However, the literature does not disclose a cyclic urea compound having oxygen as a ring member.

Furthermore, JP-A 151364/1996 describes a cyclic urea compound of the formula:

wherein R _j represents _t , alkyl; R represents hydrogen or C _j.4 alkyl; X represents oxygen, sulfur, or NR ₃ wherein R ₃ represents hydrogen or methyl; Qj represents hydrogen, C _1-6 alkyl, C ₃ . ₇ cycloalkyl, C ₃ _ ₆ alkenyl, C ₃ _ ₆ alkynyl, phenyl which may be substituted, naphthyl which may be substituted, or heterocyclic group which may be substituted; Q ₂ represents Cι_ ₆ alkyl, C ₃ . ₇

cycloalkyl, C ₃ . ₆ alkenyl, phenyl which may be substituted, or thienyl which may be substituted; A represents carbon or nitrogen; A represents CR ₂ wherein R ₂ represents hydrogen, C^ alkyl, C ₃ . ₆ alkenyl, or C _3-6 alkynyl, NR ₂ wherein R ₂ is as defined above, oxygen, sulfur, SO or S0 ₂ ; A represents a single bond, oxygen, sulfur, or CR ₅ wherein R ₅ represents hydrogen or C _1-4 alkyl. However, there is not disclosed a cyclic urea compound in which the phenyl, heterocyclic group, or the like is bound to a nitrogen atom which is ring member through a methylene group instead of -XCO- . EP-A-520423 describes the following compounds.

However, the literature does not describe a compound in which both of two ring-forming nitrogen atoms are substituted.

The above-mentioned compounds are not fully satisfactory in herbicidal effect on weeds, potential of hazard to crop plants, toxicity to mammals, fishes and shellfishes, and risk of pollution, and the development of a more improved selective herbicide has been awaited in earnest. [Disclosure of Invention]

With the aim to developing a selective herbicide having superior herbicidal activity and not injurious to crop plants, the inventors of the present invention did intensive research and, as a consequence, have found that a cyclic urea or thiourea compound

comprising (i) a group of the formula:

wherein Q represents an aromatic ring group which may optionally be substituted; and R ¹ and R ² are the same or different and each represents a hydrocarbon group which may optionally be substituted or R ¹ and R ² may form a ring together with the adjacent carbon atom wherein the ring may optionally be substituted, as a substituent on one of the ring-forming nitrogen atoms, (ii) a group bonded through a carbon atom, a nitrogen atom, or an oxygen atom as a substituent on the other ring-forming nitrogen atom, and (iii) oxygen as a further ring member, or a salt thereof has potent herbicidal activity with remarkably improved phytotoxic toward crop plants such as rice, wheat, barley, soybean, maize, and other plants, thus showing high specificity. They have made further research with diligence and have perfected the present invention. Namely, the present invention relates to: [1] a cyclic urea or thiourea compound comprising (i) a group of the formula:

wherein Q represents an aromatic ring group which may optionally be substituted; and R and R are the same or different and each represents a hydrocarbon group which may optionally be substituted or R 1 and R2 may form a ring together with the adjacent carbon atom wherein the ring may optionally be substituted, as a substituent on one of the ring-forming nitrogen atoms, (ii) a group bonded through a carbon atom, a nitrogen atom or an oxygen atom as a substituent on the other

ring-forming nitrogen atom, and (iii) oxygen atom as a further ring member (hereinafter referred to as "compound (la)"), or a salt thereof,

[2] the compound as described in [1] above, which is a compound of the formula (I):

wherein Q represents an aromatic ring group which may optionally be substituted; Q represents an optionally substituted aromatic ring group, an optionally substituted aliphatic heterocyclic group or an optionally substituted aliphatic hydrocarbon group; A and B are the same or different and each represents a single bond or a bivalent hydrocarbon group which may optionally be substituted; R and R are the same or different and each represents a hydrocarbon group which may optionally be substituted or R 1 and R2 may form a ring together with the adjacent carbon atom wherein the ring may optionally be substituted; W represents 0 or S, provided that both of A and B do not represent a single bond; or a salt thereof, [3] the compound as described in [2] above, wherein Q and Q are the same or different and each represents a C ₆ _ ₁₄ aryl group which may optionally be substituted, [4] the compound as described in [3] above, wherein said C _6-14 aryl group is phenyl, [5] the compound as described in [2] above, wherein A and B are the same or different and each represents a single bond, a C _1-6 alkylene group which may optionally be substituted, or a C _2-6 alkenylene group which may optionally be substituted, provided that both of A and B do not represent a single bond,

[6] the compound as described in [2] above, wherein A represents a bivalent hydrocarbon group which may optionally be substituted,

[7] the compound as described in [2] above, wherein B represents a bivalent hydrocarbon group which may optionally be substituted,

[8] the compound as described in [2] above, wherein R and R are the same or different and each represents a C _1-6 alkyl group, [9] the compound as described in [2] above, wherein Q ¹ represents an aromatic ring group selected from the group consisting of a C ₆ _ ₁₄ aryl group and a 5- or 6-membered aromatic heterocyclic group or a condensed ring group thereof with benzene ring or a 5- or 6-membered aromatic heterocyclic ring, wherein said

C _6-l _, aryl group, 5- or 6-membered aromatic heterocyclic group or condensed ring may optionally be substituted with one to four substituents selected from the group consisting of hydroxy, amino, cyano, sulfamoyl, sulfamoyloxy, mercapto, nitro, halogen, sulfo and an organic residue selected from the group consisting of (1) a hydrocarbon group selected from the group consisting of a C _1-i6 alkyl group, a C _3- cycloalkyl group, a C ₂ . ₆ alkenyl group, a C _3-14 cycloalkenyl group, a C ₂ _ ₆ alkynyl group, a C ₆ . ₁₄ aryl group and a C ₇ . ₁₉ aralkyl group, and when said hydrocarbon group is an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an alkynyl group, each group may has one to three substituents selected from the group consisting of a C _1-4 alkylthio group, halogen, a C<_ ₆ alkoxy group, nitro, a C _j . ₆ alkoxy-carbonyl group, a mono- or di-C _1-6 alkylamino group, a alkoxyimino group and hydroxyimino, and when said hydrocarbon group is an aryl group or an

aralkyl group, each group may has one to five substituents selected from the group consisting of (i) a C _1-6 alkyl group, (ii) a C ₂ . ₆ alkenyl group, (iii) a C _2.6 alkynyl group, (iv) a C^ alkoxy group, (v) an acyl group selected from the group consisting of a C-_ ₇ alkanoyl group, a C ₆ . _u aryl-carbonyl group, a C,_ ₆ alkoxy-carbonyl group, a C ₆ _ ₁₄ aryloxy-carbonyl group, a C ₇ . ₁₉ aralkyl-carbonyl group, and a C ₇ _ ₁₉ aralkyloxycarbonyl group, (vi) nitro, (vii) amino, (viii) hydroxy, (ix) cyano, (x) sulfa oyl, (xi) ercapto, (xii) halogen and (xiii) a C../, alkylthio group,

(2) a 3- to 8-membered heterocyclic group or a condensed ring group thereof with benzene ring or a 3- to 8-membered heterocyclic ring, which may optionally be substituted with one to three substituents selected from the group consisting of (i) a C _1-6 alkyl group, (ii) a C ₂ _ ₆ alkenyl group, (iii) a C ₂ _ ₆ alkynyl group, (iv) a C^ alkoxy group, (v) an acyl group selected from the group consisting of a C<_ ₇ alkanoyl group, a C ₆ . ₁₄ aryl-carbonyl group, a C _1-6 alkoxy-carbonyl group, a C _6.u aryloxy-carbonyl group, C ₇ . ₁₉ aralkyl-carbonyl group, and a C ₇ _ ₁₉ aralkyloxycarbonyl group, (vi) nitro, (vii) amino, (viii) hydroxy, (ix) cyano, (x) sulfamoyl, (xi) mercapto, (xii) halogen and (xiii) a C^ alkylthio group,

(3) an acyl group selected from the group consisting of a C _L _ ₇ alkanoyl group, a C ₆ . _Kl aryl-carbonyl group, a C ₆ alkoxy-carbonyl group, a C ₆ . ₁₄ aryloxy-carbonyl group, a C ₇ . _lg aralkyl-carbonyl group, a C ₇ _< ₉ aralkyloxycarbonyl group, a 5- or 6- membered heterocyclic-carbonyl group and a 5- or 6- membered heterocyclic-acetyl group, and when the acyl group is an alkanoyl group or an alkoxy-carbonyl group, each group may has one to three substituent or substituents selected from the group

consisting of a C^ alkylthio group, halogen, a C._ ₆ alkoxy group, nitro, a C^ alkoxy-carbonyl group, a mono- or di-C-^ alkylamino group, a Cj. ₆ alkoxyimino group and hydroxyimino group, and when the acyl group is an aryl-carbonyl group, an aryloxy-carbonyl group, an aralkyl-carbonyl group, an aralkyloxycarbonyl group, 5- or 6-membered heterocyclic-carbonyl group or a 5- or 6- membered heterocyclic-acetyl group, each group may has one to five substituents selected from the group consisting of (i) a C _1-6 alkyl group, (ii) a C ₂ . ₆ alkenyl group, (iii) a C _2-6 alkynyl group, (iv) a C _1-6 alkoxy group, (v) an acyl group selected from the group consisting of a C alkanoyl group, a C ₆ . ₁₄ aryl-carbonyl group, a C _1-6 alkoxy-carbonyl group, a C ₆ . ₁₄ aryloxy-carbonyl group, a C _7-19 aralkyl-carbonyl group, and a C ₇ _ι ₉ aralkyloxycarbonyl group, (vi) nitro, (vii) amino, (viii) hydroxy, (ix) cyano, (x) sulfamoyl, (xi) mercapto, (xii) halogen and (xiii) a C^ alkylthio group,

(4) a group of the formula: -T-Q wherein Q represents a hydrocarbon group as defined in above (1), a 3- to 8- membered heterocyclic group as defined in above (2), or an acyl group as defined in above (3); T represents 0, (O)k-S wherein k is 0, 1 or 2, or S-S,

(5) a group of the formula:

P ³

—N

wherein Q represents a hydrogen atom, a hydrocarbon group as defined in above (1) or an acyl group as defined in above (3); Q represents a hydrocarbon group as defined in above (1) or an acyl group as defined in above (3), or Q and Q' may form a ring together with

the adjacent nitrogen atom,

(6) a group of the formula:

-ΞO,N

wherein Q and Q have the same meaning as defined above,

(7) a carbamoyl group which may optionally be substituted with 1 or 2 substituents selected from the group consisting of a hydrocarbon group as defined in above (1), a 3- to 8- membered heterocyclic group as defined in above (2) and an acyl group as defined in above ( 3) , (8) a carba oyloxy group which may optionally be substituted with 1 or 2 substituents selected from the group consisting of a hydrocarbon group as defined in above (1), a 3- to 8- membered heterocyclic group as defined in above (2) and an acyl group as defined in above (3),

(9) a ureido group which may optionally be substituted with 1 to 3 substituents selected from the group consisting of a hydrocarbon group as defined in above (1), a 3- to 8- membered heterocyclic group as defined in above (2) and an acyl group as defined in above (3),

(10) a thiocarbamoyl group which may optionally be substituted with 1 or 2 substituents selected from the group consisting of a hydrocarbon group as defined in above (1), a 3- to 8- membered heterocyclic group as defined in above (2) and an acyl group as defined in above ( 3) ,

(11) carboxyl group, or

(12) a group of the formula -0-S0 ₂ -Q wherein Q* has the same meaning as defined above; Q represents (a) an aromatic ring group as defined above for Q , (b) a 4- to 6- membered aliphatic

heterocyclic group which may optionally be substituted with one to four substituents selected from the group consisting of hydroxy, amino, cyano, sulfamoyl, sulfa oyloxy, mercapto, nitro, halogen, an organic residue selected from the group consisting of a hydrocarbon group as defined in above (1), a 3- to 8- membered heterocyclic group or a condensed ring group thereof with benzene ring or a 3- to 8-membered heterocyclic ring as defined in above (2) and an acyl group as defined in above (3) for Q , sulfo, oxo, thioxo and a Cι_ ₆ alkylidene;

(c) an aliphatic hydrocarbon group selected from the group consisting of a C^ alkyl group, a C ₂ . ₆ alkenyl group, a C ₂ . ₆ alkynyl group, a C ₃ . ₁₄ cycloalkyl group and a C ₃ . ₁₄ cycloalkenyl group which may optionally be substituted with one to four substituents selected from the group consisting of hydroxy, amino, cyano, sulfamoyl, sulfamoyloxy, mercapto, nitro, halogen, an organic residue selected from the group consisting of a hydrocarbon group as defined in above (1), a 3- to 8-membered heterocyclic group or a condensed ring group thereof with benzene ring or a 3- to 8-membered heterocyclic ring as defined in above (2) and an acyl group as defined in above (3) for Q , sulfo, oxo, thioxo and a C _1-6 alkylidene group;

A and B are the same or different and each represents a single bond or a bivalent hydrocarbon group selected from the group consisting of a C _1-6 alkylene group, a C _j . ₆ alkenylene group and a phenylene group, each of which may substituted with one to four substituents selected from the group consisting of hydroxy, amino, cyano, sulfamoyl, sulfamoyloxy, mercapto, nitro, halogen, an organic residue selected from the group consisting of a hydrocarbon group as defined in above (1), a 3- to 8-membered heterocyclic group or a

condensed ring group thereof with benzene ring or a 3- to 8-membered heterocyclic ring as defined in above (2) and an acyl group as defined in above (3) for Q , sulfo, oxo and thioxo, provided that both of A and B do not represent a single bond;

R and R are the same or different and each represents a hydrocarbon group selected from the group consisting of a Cj. ₆ alkyl group, a C ₃ . ₁₄ cycloalkyl group, a C _2-6 alkenyl group, a C ₃ . ₁₄ cycloalkenyl group, a C ₂ . ₆ alkynyl group, a C ₆ . aryl group and a C _7- ι ₉ aralkyl group and each of which may optionally be substituted with one to four substituents selected from the group consisting of hydroxy, amino, cyano, nitro, and halogen, or Rι and R ? may form a ring of C ₃ . ₇ cycloalkane or C _3-7 cycloalkene together with the adjacent carbon atom, and each of said cycloalkane and cycloalkene may optionally be substituted with one to four substituents selected from the group consisting of hydroxy, amino, cyano, nitro, and halogen; W represents 0 or S; or a salt thereof,

[10] the compound as described in [2] above, wherein Q ^' represents (1) a C ₆ . _u aryl group which may optionally be substituted with one to four substituents selected from the group consisting of halogen and halo-C^ alkyl or (2) a 5- or 6- membered aromatic heterocyclic group or a condensed ring group thereof with benzene ring or a 5- or 6- membered aromatic heterocyclic ring, which may optionally be substituted with one to four halogens;

Q represents (1) a C ₆ . ₁₄ aryl group which may optionally be substituted with one to four substituents selected from the group consisting of (i) a C^ alkyl group which may optionally be substituted with one to three halogens, (ii) halogen, (iii) a C[. ₆ alkoxy group, (iv)

cyano and (v) nitro, (2) a C ₃ . _1A cycloalkyl group, (3) a ₃ -i ₄ cycloalkenyl group, (4) a 5- or 6- membered aromatic heterocyclic group or a condensed ring group thereof with benzene ring or a 5- or 6- membered aromatic heterocyclic ring, (5) a 4- to 6- membered aliphatic heterocyclic group which may optionally be substituted with 1 to 4 substituents selected from the group consisting of Cι_ ₆ alkoxy-carbonyl, C ₆ . ₁₄ aryl and oxo, (6) a C ₇ . ₁₉ aralkyl group or (7) a C _1.6 alkyl group; A and B are the same or different and each represents a single bond, a _v . ₆ alkylene group which may optionally be substituted with oxo or a C _2-6 alkenylene group which may optionally be substituted with Cj. ₆ alkyl, provided that both of A and B do not represent a single bond; R and R are the same or different and each represents a C ₆ alkyl group; W represents 0 or S; or a salt thereof, [11] the compound as described in [2] above, wherein Q represents (1) phenyl which may optionally be substituted with one or two substituents selected from the group consisting of halogen and tri-halo-C^ alkyl or (2) (i) pyridyl which may optionally be substituted with a halogen, (ii) furyl, (iii) thienyl which may optionally be substituted with a halogen or (iv) imidazof 1,2-a]pyridyl which may optionally be substituted with a halogen;

Q represents (1) phenyl which may optionally be substituted with one to three substituents selected from the group consisting of (i) a C ₆ alkyl group which may optionally be substituted with 1 to 3 halogens, (ii) halogen, (iii) a C _1-i6 alkoxy group, (iv) cyano and (v) nitro, (2) a C ₃ _ ₇ cycloalkyl group, (3) a C ₃ . ₇ cycloalkenyl group, (4) thienyl, (5) thiazolyl, (6) pyridyl, (7) imidazo[ 1,2-a]pyridyl, (8) pyrrolidinyl

which may optionally be substituted with phenyl, (9) piperidyl which may optionally be substituted with C,_ _f , alkoxy-carbonyl, (10) pyrrolyl, (11) tetrahydrofuryl which may optionally be substituted with an oxo group, (12) morpholinyl, (13) benzyl or (14) a C _1-6 alkyl group;

A and B are the same or different and each represents a single bond, a C^ alkylene group which may optionally be substituted with an oxo group or a C ₂ _ ₆ alkenylene group which may optionally be substituted with 1 or 2 C,_ ₆ alkyl groups, provided that both of A and B do not represent a single bond;

R 1 and R2 are the same or different and each represents a C _1-6 alkyl group;

W represents 0 or S; or a salt thereof,

[12] the compound as described in [1] above which is

[ l-( 3 , 5-dichlorophenyl)-l-methylethyl ]-5- phenyltetrahydro-1,3, 5-oxadiazine-4-one,

[13] the compound as described in [1] above which is

[ l-(3,5-dichlorophenyl)-l-methylethyl ]-5-(2- fluorophenyl)tetrahydro-1, 3, 5-oxadiazine-4-one .

[14] a process for producing the compound of [1] above which comprises cyclizing a urea or thiourea compound comprising (i) a group of the formula:

wherein the respective symbols have the same meanings as defined in [1] above as a substituent on one of ring-forming nitrogen atoms and (ii) a group bonded through a carbon atom, a nitrogen atom or an oxygen atom as a substituent on the other ring-forming nitrogen atom, or a salt thereof,

[15] a process for producing the compound of [2] above

which comprises

(1) reacting a compound of the formula:

wherein the respective symbols have the same meanings as defined in [2] above or a salt thereof with a compound of the formula X -A-X wherein X and X are the same or different and each represents a leaving group; A has the same meaning as defined in [2] above or a salt thereof to provide a compound of the formula

wherein the respective symbols have the same meanings as defined in [2] above, or a salt thereof;

(2) reacting a compound of the formula:

A . ^H

OH

wherein the respective symbols have the same meanings as defined in [2] above, or a salt thereof with a compound of the formula X 1-B-X2 wherein X1 and X? are as defined above; B has the same meaning as defined in [2] above or a salt thereof to provide a compound of the formula:

wherein the respective symbols have the same meanings as defined in [2] above, or a salt thereof;

(3) reacting a compound of the formula:

wherein Y represents hydrogen or a lower alkyl group, and the other symbols have the same meanings as defined in [2] above, or a salt thereof with a compound of the formula:

O

R'

wherein R and R are the same or different and each represents hydrogen or a hydrocarbon group which may optionally be substituted or a salt thereof to provide a compound of the formula:

wherein R and R are as defined above; the other symbols have the same meanings as defined in [2] above, or a salt thereof;

(4) reacting a compound of the formula:

H H wherein the respective symbols have the same meanings as defined in [2] above, or a salt thereof with a compound of the formula:

O

R"

wherein the respective symbols are as def ined above or a salt thereof to provide a compound of the formula :

wherein R and R are as defined above; the other symbols have the same meanings as defined in [2] above, or a salt thereof; or

(5) reacting a compound of the formula:

wherein the respective symbols have the same meanings as defined in [2] above, or a salt thereof with a compound of the formula X -A-O-B-X ² wherein X ¹ and X ² are as defined above and the other symbols have the same meanings as defined in [2] above, or a salt thereof to provide a compound of the formula:

wherein the respective symbols have the same meanings as defined in [2] above, or a salt thereof, [16] an agrochemical composition comprising the compound as described in [1] above, and an agroche ically acceptable carrier,

[17] the agrochemical composition as described in [16] above, which is a herbicidal composition, [18] use of the compound as described in [1] above, as a herbicide, and [19] a method for weeding from a paddy field, plowland, orchard or non-crop land, which comprises scattering an effective amount of the compound as described in [1] above on said paddy field, plowland, orchard or non- crop land. Also, as another embodiment, the present invention relates to:

[20] the compound as described in [2] above, wherein Q represents an aromatic ring group which may

2 optionally be substituted; Q represents an optionally substituted aromatic ring group, an optionally substituted aliphatic heterocyclic group or an optionally substituted aliphatic hydrocarbon group; A represents a single bond or a bivalent hydrocarbon group which may optionally be substituted; B represents a bivalent hydrocarbon group which may optionally be substituted; R 1 and R2 are the same or different and each represents a hydrocarbon group which may optionally be substituted or R and R may form a ring together with the adjacent carbon atom wherein the ring may optionally be substituted; W represents 0 or S, or a salt thereof,

[21] the compound as described in [2] above, wherein Q represents an aromatic ring group which may

2 optionally be substituted; Q represents an optionally substituted aromatic ring group, an optionally substituted aliphatic heterocyclic group or an optionally substituted aliphatic hydrocarbon group; A represents methylmethylene, dimethylmethylene, propylene, vinylene, carbonyl or carbonyl-C _1-2 alkyl; B represents a single bond; R and R are the same or different and each represents a hydrocarbon group which may optionally be substituted or R 1 and R2 may form a ring together with the adjacent carbon atom wherein the ring may optionally be substituted; W represents 0 or S, or a salt thereof, [22] the compound as described in [2] above, wherein Q represents an aromatic ring group which may optionally be substituted; Q represents an optionally substituted aromatic heterocyclic group or an optionally substituted cyclic aliphatic hydrocarbon group; A represents a bivalent hydrocarbon group which may optionally be substituted; B represents a single bond; R and R are the same or different and each represents a hydrocarbon group which may optionally be substituted or R 1 and R2 may form a ring together with the adjacent carbon atom wherein the ring may optionally be substituted; W represents 0 or S, or a salt thereof,

[23] the compound as described in [22] above, wherein Q represents a C ₆ . _lt , aryl group which may optionally be substituted with one to four halogens; Q represents

(1) a 5- or 6- membered aromatic heterocyclic group or a condensed ring group thereof with benzene ring or a 5- or 6- membered aromatic heterocyclic ring or (2) a C _3.7 cycloalkyl group; A represents a C _1-6 alkylene group which may optionally be substituted with an oxo group

or a C ₂ . ₆ alkenylene group which may optionally be substituted with 1 to 2 C _1-6 alkyl groups; B represents a single bond; R 1 and R2 are the same or different and each represents a C _{ _ ₆ alkyl group; W represents 0 or S, or a salt thereof,

[24] the compound as described in [22] above, wherein Q represents phenyl which may optionally be substituted with one or two halogens; Q represents thienyl or cyclohexyl; A represents a C,. ₆ alkylene group; B represents a single bond; R and R are the same or different and each represents a C _1-6 alkyl group; W represents 0, or a salt thereof, [25] the compound as described in [2] above, wherein Q represents an aromatic heterocyclic group which may optionally be substituted; Q represents an optionally substituted aromatic ring group; A represents a single bond or a bivalent hydrocarbon group which may optionally be substituted; B represents a single bond; R and R are the same or different and each represents a hydrocarbon group which may optionally be substituted or R and R may form a ring together with the adjacent carbon atom wherein the ring may optionally be substituted; W represents 0 or S, or a salt thereof, [26] the compound as described in [25] above, wherein Q represents a 5- or 6-membered aromatic heterocyclic group or a condensed ring group thereof with benzene ring or a 5- or 6-membered aromatic heterocyclic ring which may optionally be substituted with one to four halogens; Q represents a C _6-1 _, aryl group; A represents a C _1-6 alkylene group which may optionally be substituted with an oxo group or a C ₂ . ₅ alkenylene group which may optionally be substituted with 1 or 2 C^ alkyl groups; B represents a single bond; R and R ² are the same or different and each represents a C _1-6 alkyl group; W represents 0 or S, or a salt thereof, and

[27] the compound as described in [25] above, wherein Q represents furyl, thienyl, pyridyl or imidazo[l,2- a]pyridyl, each of which may optionally be substituted with one or two halogens; Q represents phenyl; A represents a C _1-6 alkylene group; B represents a single bond; R and R are the same or different and each represents a C _1-6 alkyl group; W represents 0, or a salt thereof .

[Best Mode for Carrying Out the Invention] The compound (Ia) of the invention has the following three structural features. (1) The compound (Ia) has a group of formula (I')

wherein the respective symbols have the same meanings as defined hereinbefore on one of the ring-forming nitrogen atoms .

(2) The compound (la) has a group bonded through a carbon atom, a nitrogen atom or an oxygen atom on the other ring-forming nitrogen atom.

(3) The compound (Ia) has oxygen as a ring member. Referring to the above formula, Q represents an aromatic ring group which may optionally be substituted. The aromatic ring group includes aryl, a 5- or 6-membered aromatic heterocyclic group which contains 1 to 4 hetero atoms selected from nitrogen (which may be in the oxide form), oxygen, and sulfur (which may be in the mono-oxide or dioxide form) or a condensed ring group thereof with benzene ring or a 5- or 6-membered aromatic heterocyclic ring which contains 1 to 4 hetero atoms selected from nitrogen (which may be in the oxide form) , oxygen, and sulfur (which may be in the mono-oxide or dioxide form) . Specifically, said aryl includes C ₆ _ ₁₄ aryl such as phenyl, 1- or 2-naphthyl, 1-, 2-, or 5-anthranyl, etc.

The 5- or 6-membered aromatic heterocyclic group or its condensed ring group includes pyrrolyl (e.g. 1-, 2-, or 3-ρyrrolyl), pyrazolyl (e.g. 1-, 3-, 4-, or 5- pyrazolyl), imidazolyl (e.g. 1-, 2-, 4-, or 5- imidazolyl), triazolyl (e.g. 1,2, 3-triazol-4-yl , 1,2,3- triazol-1-yl, 1,2 , 3-triazol-5-yl , 1,2,4-triazol-l-yl, 1,2 ,4-triazol-3-yl, 1,2 ,4-triazol-4-yl, 1,2 ,4-triazol- 5-yl), tetrazolyl (e.g. tetrazol-1-, 2- or 5-yl), furyl (e.g. 2- or 3-furyl), thienyl (e.g. 2- or 3-thienyl), thienyl in which the sulfur atom is oxidized (e.g. 2- or 3-thienyl-l, 1-dioxide) , oxazolyl (e.g. 2-, 4-, or 5- oxazolyl), isoxazolyl (e.g. 3-, 4-, or 5-isoxazolyl) , oxadiazolyl (e.g. 1,2 , 3-oxadiazol-4- or 5-yl, 1,2,4- oxadiazol-3- or 5-yl, 1, 2 , 5-oxadiazol-3-yl, 1,3,4- oxadiazol-2-yl) , thiazolyl (e.g. 2-, 4-, or 5- thiazolyl), isothiazolyl (e.g. 3-, 4-, or 5- isothiazolyl) , thiadiazolyl (e.g. 1 , 2, 3-thiadiazol-4- or 5-yl, 1,2,4-thiadiazol-3- or 5-yl, 1, 2, 5-thiadiazol- 3-yl, 1, 3,4-thiadiazol-2-yl ) , pyridyl (e.g. 2-, 3-, or 4-pyridyl), pyridyl in which the nitrogen atom is oxidized (e.g. 2-, 3-, or 4-pyridyl-N-oxide) , pyridazinyl (e.g. 3- or 4-pyridazinyl ) , pyridazinyl in which one or both of the nitrogen atoms are oxidized (e.g. 3-, 4-, 5- or 6-pyridazinyl-N-oxide) , pyrimidinyl (e.g. 2-, 4-, or 5-pyrimidinyl ) , pyrimidinyl in which one or both of the nitrogen atoms are oxidized (e.g. 2- , 4-, 5- or 6-pyrimidinyl-N-oxide) , pyrazinyl, indolyl (e.g. 3H-indol-2-, 3-, 4-, 5-, 6- or 7-yl), quinolyl (e.g. 3-, 4-, 5-, 6-, 7-, or 8-quinolyl ) , isoquinolyl, pyrido[2 , 3-d]pyrimidinyl (e.g. pyrido[2 , 3-d]pyrimidin- 2-yl), naphthyridinyl such as 1,5-, 1,6-, 1,7-, 1,8-, 2,6-, or 2 ,7-naphthylidinyl (e.g. 1, 5-naphthylidin-2- or 3-yl), thieno[2 ,3-d]pyridyl (e.g. thieno[2,3- d]pyridin-3-yl) , pyrazinoquinolyl (e.g. pyrazino[ 2 , 3- d]quinolin-2-yl) , chromenyl (e.g. 2H-chromen-2- or 3- yl), imidazof 1, 2-a]pyridyl, imidazof2, 1-b]thiazolyl,

imidazo[1,2-a]pyrimidinyl, imidazo[ 1,2-b]pyridazinyl, imidazo[ 1, 2-a]imidazolyl, imidazo[2,1- b] ( 1.3.4)thiadiazolyl, pyrazolof 1,5-a]pyrimidinyl, pyrazolo[5, 1-b]thiazolyl, and pyrazolo[ 1 , 5-a]pyridyl . The aromatic ring group may optionally be substituted by 1 to 4 substituents selected from the group consisting of hydroxy, amino, cyano, sulfamoyl, sulfamoyloxy, mercapto, nitro, halogen, organic residues, and sulfo. Preferred among the above-mentioned substituent groups are cyano, nitro, halogen, and organic residues. Particularly preferred are halogen and organic residues .

The halogen as mentioned just above includes fluorine, chlorine, bromine, and iodine. The organic residue includes (1) a hydrocarbon group, (2) a heterocyclic group, (3) an acyl group, (4) a group of the formula -T-Q wherein Q represents a hydrocarbon group, a heterocyclic group, or an acyl group; T represents 0,

(0) _k s or S-S; and k represents 0, 1, or 2, (5) a group of the formula:

—N

wherein Q represents a hydrogen atom, a hydrocarbon group, or an acyl group; Q represents a hydrocarbon group or an acyl group or Q and Q ^* may form a ring together with the adjacent nitrogen atom, (6) a group of the formula:

wherein the respective symbols have the same meanings as defined above, (7) an optionally substituted carbamoyl, (8) an optionally substituted carbamoyloxy, (9) an optionally substituted ureido, (10) an optionally substituted thiocarbamoyl, (11) carboxy, and (12) a group of the formula wherein Q has the same meaning as defined above.

The hydrocarbon group, heterocyclic group, and acyl group for the above-mentioned organic residue, the hydrocarbon group, heterocyclic group, and acyl group for Q°, and the hydrocarbon group and acyl group for Q or Q will be described in detail hereinafter.

The above-mentioned carbamoyl, carbamoyloxy, and thiocarbamoyl may respectively be substituted by 1 or 2 substituents selected from the group consisting of the hydrocarbon group, heterocyclic group, and acyl group which will be described in detail hereinafter. Also, the above-mentioned ureido may be substituted by 1 to 3 substituents selected form the group consisting of the hydrocarbon group, heterocyclic group, and acyl group which will be described in detail hereinafter.

The heterocyclic group for said organic residue and the heterocyclic group for Q may optionally be substituted by 1 to 3 substituents selected from the group consisting of the hydrocarbon group, acyl group, and halogen which will be described in detail hereinafter.

The hydrocarbon group as used throughout this specification includes a straight-chain, branched, or cyclic aliphatic hydrocarbon group which may contain a double bond or a triple bond, an aryl group and an aralkyl group. Specifically said hydrocarbon group

includes an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group. Particularly preferred are C _1-19 hydrocarbon group.

The alkyl group mentioned above is preferably a straight-chain or branched alkyl group of 1 to 6 carbon atoms or cycloalkyl group of 3 to 14 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, etc.

The alkenyl group mentioned above is preferably a straight-chain or branched alkenyl group of 2 to 6 carbon atoms or cycloalkenyl group of 3 to 14 carbon atoms including allyl, isopropenyl, isobutenyl, 2- pentenyl, 2-hexenyl, 2-cyclohexenyl, etc.

The alkynyl group mentioned above is preferably an alkynyl group of 2 to 6 carbon atoms, such as propargyl, 2-butynyl, 3-butynyl, 3-pentynyl, 3-hexynyl, etc . The aryl group mentioned above is preferably an aryl group of 6 to 14 carbon atoms, such as phenyl, naphthyl , anthryl, etc.

The aralkyl group mentioned above is preferably an aralkyl group of 7 to 19 carbon atoms, including phenyl-C,_ ₄ alkyl such as benzyl, phenethyl , phenylpropyl; benzhydryl, and trityl.

When the hydrocarbon group is an alkyl group, an alkenyl group or an alkynyl group, said hydrocarbon group may optionally be substituted by 1 to 3 substituents selected from the group consisting of an alkylthio group (e.g. C ₄ alkylthio such as ethylthio, ethylthio, n-propylthio, isopropylthio, etc.), halogen (e.g. fluorine, chlorine, bromine, iodine), an alkoxy group (e.g. C _1-6 alkoxy such as methoxy, ethoxy, n-propoxy, tert-butoxy, n-hexyloxy, etc.), nitro, an alkoxy-carbonyl group (e.g. C<_ _fi

alkoxy-carbonyl such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl , n-butoxycarbonyl, isobutoxycarbonyl, sec- butoxycarbonyl, tert-butoxycarbonyl, etc.), an alkyla ino group [e.g. mono- or di-C _1-6 alkylamino such as methylamino, ethylamino, n-propylamino, n- butylamino, tert-butylamino, n-pentylamino, n- hexyla ino, dimethylamino, diethylamino, methylethylamino, di-(n-propyl)amino, di-(n- butyl)amino, etc.], an alkoxyi ino group (e.g. C _j . ₆ alkoxyimino such as methoxyimino, ethoxyimino, n- propoxyimino, tert-butoxyimino, n-hexyloxy-imino, etc. ) and hydroxyimino.

Also, when the hydrocarbon group is an aryl group or an aralkyl group, said hydrocarbon group may optionally be substituted by 1 to 5 (preferably 1 to 3) substituents selected from the group consisting of an alkyl group (e.g. C ₁ . ₆ alkyl such as methyl, ethyl, n- propyl , isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, n-pentyl, sec-pentyl, isopentyl, neopentyl , n- hexyl, and isohexyl, C ₃ . ₆ cycloalkyl such as cyclohexyl, etc.), an alkenyl group (e.g. C _2-6 alkenyl such as allyl, isopropenyl, isobutenyl, 1-methylallyl , 2 - pentenyl, 2-hexenyl, etc.), an alkynyl group (e.g. C ₂ . _ft alkynyl such as propargyl, 2-butynyl, 3-butynyl, 3- pentynyl, 3-hexynyl, etc.), an alkoxy group (e.g. Cι_ ₆ alkoxy such as methoxy, ethoxy, n-propoxy, tert-butoxy, n-hexyloxy, etc.), an acyl group [e.g. C,_ ₇ alkanoyl such as for yl, acetyl, propionyl , butyryl, isobutyryl, pentanoyl, hexanoyl, heptanoyl, etc.; C ₆ . ₁₄ aryl- carbonyl such as benzoyl, naphthalenecarbonyl , etc.; C- _. .. ₆ alkoxy-carbonyl such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl , tert-butoxycarbonyl, etc.; C ₆ . ₁₄ aryloxy-carbonyl such

as phenoxycarbonyl, etc.; C ₇ . ₁₉ aralkyl-carbonyl such as phenyl-Cj. ₄ alkylcarbonyl (e.g. benzylcarbonyl, phenethylcarbonyl, phenylpropylcarbonyl, etc.); C ₇ _ ₁₉ aralkyloxycarbonyl such as benzyloxycarbonyl , etc.], nitro, amino, hydroxy, cyano, sulfamoyl, mercapto, halogen (e.g. fluorine, chlorine, bromine, iodine), and an alkylthio group (e.g. Cj. ₄ alkylthio group such as methylthio, ethylthio, n-propylthio, isobutylthio, etc . ) . The heterocyclic group as used throughout this specification includes 3- to 8-membered heterocyclic group, preferably 5- or 6-membered heterocyclic group which contains 1 to 4 hetero atoms selected from nitrogen (which may be in the oxide form), oxygen, and sulfur (which may be in the mono- or dioxide form) or a condensed ring group thereof with benzene ring or a 3- to 8-membered heterocyclic ring, preferably 5- or 6- membered heterocyclic ring which may contain 1 to 4 hetero atoms selected from nitrogen (which may be in the oxide form) , oxygen, and sulfur (which may be in the mono- or dioxide form) , preferably condensed ring group of such 5- or 6-membered heterocyclic ring with a 5- or 6-membered heterocyclic ring which may contain 1 to 4 heteroatoms selected from nitrogen (which may be in the oxide form), oxygen, and sulfur (which may be in the mono- or dioxide form) .

Specifically, the heterocyclic group includes aziridinyl (e.g. 1- or 2-aziridinyl ) , azirinyl (e.g. 1- or 2-azirinyl), azetyl (e.g. 2-, 3- or 4-azetyl), azetidinyl (e.g. 1-, 2-, or 3-azetidinyl) , perhydroazepinyl (e.g. 1-, 2-, 3-, or 4- perhydroazepinyl) , perhydroazocinyl (e.g. 1-, 2-, 3-, 4-, or 5-perhydroazocinyl) , pyrrolyl (e.g. 1-, 2-, or 3-pyrrolyl), pyrazolyl (e.g. 1-, 3-, 4- or 5- pyrazolyl), imidazolyl (e.g. 1-, 2-, 4-, or 5- imidazolyl), triazolyl (e.g. 1 , 2 , 3-triazol-l-, 4- or 5-

yl, 1,2 ,4-triazol-l-, 3-, 4- or 5-yl), tetrazolyl (e.g. tetrazol-1-, 2- or 5-yl), furyl (e.g. 2- or 3-furyl), thienyl (e.g. 2- or 3-thienyl), thienyl in which the sulfur atom is oxidized (e.g. 2- or 3-thienyl-l, 1- dioxide), oxazolyl (e.g. 2-, 4-, or 5-oxazolyl), isoxazolyl (e.g. 3-, 4-, or 5-isoxazolyl) , oxadiazolyl (e.g. 1,2 ,3-oxadiazol-4- or 5-yl, 1,2,4-oxadiazol-3- or 5-yl, 1,2,5-oxadiazol-3-yl, 1,3, 4-oxadiazol-2-yl) , thiazolyl (e.g. 2-, 4-, or 5-thiazolyl) , isothiazolyl (e.g. 3-, 4-, or 5-isothiazolyl) , thiadiazolyl (e.g.

1,2, 3-thiadiazol-4- or 5-yl, 1,2, 4-thiadiazol-3-, or 5- yl, 1,2,5-thiadiazol-3-yl, 1, 3,4-thiadiazol-2-yl) , pyrrolidinyl (e.g. 1-, 2-, or 3-pyrrolidinyl ) , pyridyl (2-, 3-, or 4-pyridyl), pyridyl in which the nitrogen atom is oxidized (e.g. 2-, 3-, or 4-pyridyl-N-oxide) , pyridazinyl (e.g. 3- or 4-pyridazinyl) , pyridazinyl in which one or both of the nitrogen atoms are oxidized (e.g. 3-, 4-, 5- or 6-pyridazinyl-N-oxide) , pyrimidinyl (e.g. 2-, 4-, or 5-pyrimidinyl) , pyrimidinyl in which one or both of the nitrogen atoms are oxidized (e.g. 2- , 4-, 5- or 6-pyrimidinyl-N-oxide) , pyrazinyl, piperidinyl (e.g. 1-, 2-, 3-, or 4-piperidinyl ) , piperazinyl (e.g. 1- or 2-piperazinyl) , indolyl (e.g. 3H-indol-2-, 3-, 4-, 5-, 6- or 7-yl), pyranyl (e.g. 2-, 3-, or 4-pyranyl), thiopyranyl (e.g. 2-, 3-, or 4- thiopyranyl) , thiopyranyl in which the sulfur atom is oxidized (e.g. 2-, 3-, or 4-thiopyranyl-l, 1-dioxide) , morpholinyl (e.g. 2-, 3-, or 4-morpholinyl ) , thio orpholinyl, quinolyl (e.g. 2-, 3-, 4-, 5-, 6-, 7-, or 8-quinolyl), isoquinolyl, pyrido[2 , 3-d]pyrimidinyl

(e.g. pyridof2 ,3-d]pyrimidin-2-yl) , naphthyridinyl such as 1,5-, 1,6-, 1,7-, 1,8-, 2,6-, or 2 ,7-naphthyridinyl (e.g. l,5-naphthyridin-2- or 3-yl), thieno[2,3- d]pyridyl (e.g. thieno[2 , 3-d]pyridin-3-yl) , pyrazinoquinolyl (e.g. pyrazino[ 2, 3-d]quinolin-2-yl) , chromenyl (e.g. 2H-chromen-2- or 3-yl), etc.

The above-mentioned heterocyclic group may optionally be substituted by 1 to 3 substituents selected from the group consisting of an alkyl group (e.g. C _1-6 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n- pentyl, sec-pentyl, isopentyl, neopentyl, n-hexyl, and isohexyl, C ₃ . ₆ cycloalkyl such as cyclohexyl, etc.), an alkenyl group (e.g. C _2-6 alkenyl such as allyl, isopropenyl, isobutenyl, 1-methylallyl, 2-pentenyl, 2- hexenyl, etc.), an alkynyl group (e.g. C ₂ . ₆ alkynyl such as propargyl, 2-butynyl, 3-butynyl, 3-pentynyl, 3- hexynyl, etc.), an alkoxy group (e.g. C _1-i6 alkoxy such as methoxy, ethoxy, n-propoxy, tert-butoxy, n-hexyloxy, etc.), an acyl group [e.g. _{ . ₇ alkanoyl such as formyl , acetyl, propionyl, butyryl, isobutyryl, pentanoyl, hexanoyl, heptanoyl, etc.; C . ₁₄ aryl-carbonyl such as benzoyl, naphthalenecarbonyl, etc.; C._ ₆ alkoxy-carbonyl such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl , isobutoxycarbonyl, sec-butoxycarbonyl, tert- butoxycarbonyl, etc.; C ₆ . ₁₄ aryloxy-carbonyl such as phenoxycarbonyl , etc.; C ₇ . ₁₉ aralkyl-carbonyl such as phenyl-C _j . _ή alkylcarbonyl (e.g. benzylcarbonyl , phenethylcarbonyl, phenylpropylcarbonyl, etc. ); C ₇ . ₁₉ aralkyloxycarbonyl such as benzyloxycarbonyl , etc.], nitro, amino, hydroxy, cyano, sulfamoyl, mercapto, halogen (e.g. fluorine, chlorine, bromine, iodine), and an alkylthio group (e.g. C^ alkylthio group such as methylthio, ethylthio, n-propylthio, isobutylthio, etc. ) .

The acyl group as used throughout this specification includes an acyl group of 1 to 20 carbon atoms, which is derived from any organic carboxylie acid. Specifically, mention can be made of an alkanoyl group, preferably a Cι_ ₇ alkanoyl group (e.g. for yl,

acetyl, propionyl, butyryl, isobutyryl, pentanoyl , hexanoyl, heptanoyl, etc.), an arylcarbonyl group, preferably a C ₆ . ₁₄ aryl-carbonyl group (e.g. benzoyl, naphthalenecarbonyl, etc.), an alkoxycarbonyl group, preferably a C^ alkoxy-carbonyl group (e.g. methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl , iso¬ propoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, etc.), an aryloxycarbonyl group, preferably a C ₆ . ₁₄ aryloxy- carbonyl group (e.g phenoxycarbonyl etc.), an aralkylcarbonyl group, preferably a C ₇ . ₁₉ aralkyl- carbonyl group (e.g. phenyl-C-^ alkylcarbonyl such as benzylcarbonyl, phenethylcarbonyl, phenylpropylcarbonyl ; benzhydrylcarbonyl; naphthyl-Ci.,, alkylcarbonyl such as naphthylethylcarbonyl, etc.), an aralkyloxycarbonyl group, preferably a C ₇ . ₁₉ aralkyloxycarbonyl (e.g. phenyl-Cι- alkoxycarbonyl such as benzyloxycarbonyl, phenethyloxycarbonyl, phenylpropyloxycarbonyl, etc.), a 5- or 6-membered heterocyclic-carbonyl group having 1 to 4 hetero atoms selected from nitrogen (which may be in the oxide form) , oxygen, and sulfur (which may be in the mono- or dioxide form) such as 5- or 6-membered heterocyclic- carbonyl or condensed heterocycle-carbonyl (e.g. pyrrolylcarbonyl such as 2-, 3-, or 4-pyrrolylcarbonyl ; pyrazolylcarbonyl such as 3-, 4-, or 5- pyrazolylcarbonyl; imidazolylcarbonyl such as 2-, 4-, or 5-imidazolylcarbonyl; triazolylcarbonyl such as 1,2, 3-triazol-4-ylcarbonyl, and 1, 2 ,4-triazol-3-yl- carbonyl; tetrazolylcarbonyl such as 1H- or 2H- tetrazol-5-ylcarbonyl; furylcarbonyl such as 2- or 3- furylcarbonyl; thienylcarbonyl such as 2- or 3- thienylcarbonyl; oxazolylcarbonyl such as 2-, 4-, or 5- oxazolylcarbonyl; isoxazolylcarbonyl such as 3-, 4-, or 5-isoxazolylcarbonyl; oxadiazolylcarbonyl such as

1,2, 3-oxadiazol-4- or 5-ylcarbonyl, 1, 2,4-oxadiazol-3- or 5-ylcarbonyl, 1, 2,5-oxadiazol-3- or 4-ylcarbonyl, and 1,3 , 4-oxadiazol-2- or 5-ylcarbonyl; thiazolylcarbonyl such as 2-, 4-, or 5- thiazolylcarbonyl; isothiazolylcarbonyl such as 3-, 4-, or 5-isothiazolylcarbonyl; thiadiazolylcarbonyl such as 1,2 , 3-thiadiazol-4- or 5-ylcarbonyl, 1,2 ,4-thiadiazol- 3- or 5-ylcarbonyl, 1,2,5-thiadiazol-3- or 4- ylcarbonyl, and 1,3,4-thiadiazol-2- or 5-ylcarbonyl; pyrrolidinylcarbonyl such as 2- or 3- pyrrolidinylcarbonyl; pyridylcarbonyl such as 2-, 3-, or 4-pyridylcarbonyl; pyridylcarbonyl in which the nitrogen atom is oxidized such as 2-, 3-, or 4-pyridyl- N-oxidocarbonyl; pyridazinylcarbonyl such as 3- or 4- pyridazinylcarbonyl; pyridazinylcarbonyl in which one or both of nitrogen atoms are oxdiazed such as 3- or 4- pyridazinyl-N-oxidocarbonyl; pyrimidinylcarbonyl such as 2-, 4-, or 5-pyrimidinylcarbonyl; pyrimidinylcarbonyl in which one or both of the nitrogen atoms are oxidized such as 2-, 4-, or 5-pyrimidinyl- N-oxidocarbonyl; pyrazinylcarbonyl ; piperidinylcarbonyl such as 2-, 3-, or 4-piperidinylcarbonyl; piperazinylcarbonyl ; indolylcarbonyl such as 3H-indol- 2- or 3-ylcarbonyl; pyranylcarbonyl such as 2-, 3-, or 4-pyranylcarbonyl; thiopyranylcarbonyl such as 2-, 3-, or 4-thiopyranylcarbonyl; quinolylcarbonyl such as 3-, 4-, 5-, 6-, 7-, or 8-quinolylcarbonyl; isoquinolylcarbonyl; pyrido[ 2 , 3-d]pyrimidinylcarbonyl such as pyrido[ 2 , 3-d]pyrimidin-2-ylcarbonyl ; naphthyridinylcarbonyl such as 1,5-, 1,6-, 1,7-, 1,8-, 2,6-, or 2,7-naphthyridinylcarbonyl (e.g. 1,5- naphthyridin-2- or 3-ylcarbonyl ) ; thieno[2, 3-d]pyridyl¬ carbonyl such as thienof2, 3-d]pyridin-3-ylcarbonyl) ; pyrazinoquinolylcarbonyl such as pyrazino[2, 3- b]quinolin-2-ylcarbonyl; chro enylcarbonyl such as 2H- chromen-2- or 3-ylcarbonyl, etc.), and a 5- or 6-

membered heterocycle-acetyl group, such as 5- or 6- membered heterocycle-acetyl which contains 1 to 4 hetero atoms selected from nitrogen (which may be in the oxide form) , oxygen, and sulfur (which may be in the mono- or dioxide form) such as 2-pyrrolylacetyl, 3- imidazolylacetyl, 5-isoxazolylacetyl, etc.

When the acyl group is an alkanoyl group or an alkoxy-carbonyl group, said acyl group may optionally be substituted by 1 to 3 substituents selected from the group consisting of an alkylthio group (e.g. C _1-4 alkylthio such as methylthio, ethylthio, n-propylthio, isopropylthio, etc.), halogen (e.g. fluorine, chlorine, bromine, iodine), an alkoxy group (e.g. C _ ₆ alkoxy such as methoxy, ethoxy, n-propoxy, tert-butoxy, n-hexyloxy, etc.), nitro, an alkoxy-carbonyl group (e.g. C _J-5 alkoxy-carbonyl such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec- butoxycarbonyl, tert-butoxycarbonyl, etc.), an alkylamino group [e.g. mono- or di-C _1-6 alkylamino such as methylamino, ethyla ino, n-propylamino, n- butylamino, tert-butylamino, n-pentylamino, n- hexylamino, dimethylamino, diethylamino, methylethylamino, di-(n-propyl)amino, di-(n- butyl)amino, etc. ], an alkoxyimino group (e.g. C _[ _ ₆ alkoxyimino such as methoxyimino, ethoxyi ino, n- propoxyimino, tert-butoxyimino, n-hexyloxy-imino, etc.), and hydroxyimino.

Also, when the acyl group is an aryl-carbonyl group, an aryloxy-carbonyl group, an aralkyl-carbonyl group, an aralkyloxycarbonyl group, a 5- or 6-membered heterocycle-carbonyl group or a 5- or 6-membered heterocyclic-acetyl group, said acyl group may optionally be substituted by 1 to 5 (preferably 1 to 3 ) substituents selected from the group consisting of an alkyl group (e.g. C ₅ alkyl such as methyl, ethyl, n-

propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl , n-pentyl, sec-pentyl, isopentyl, neopentyl, n- hexyl, and isohexyl, C _3-6 cycloalkyl such as cyclohexyl, etc.), an alkenyl group (e.g. C _2-6 alkenyl such as allyl, isopropenyl, isobutenyl, 1-methylallyl , 2- pentenyl, 2-hexenyl, etc.), an alkynyl group (e.g. C ₂ - _fi alkynyl such as propargyl, 2-butynyl, 3-butynyl, 3- pentynyl, 3-hexynyl, etc.), an alkoxy group (e.g. C,_ ₆ alkoxy such as methoxy, ethoxy, n-propoxy, tert-butoxy, n-hexyloxy, etc.), an acyl group [e.g. C _1-7 alkanoyl such as formyl, acetyl, propionyl, butyryl, isobutyryl, pentanoyl, hexanoyl , heptanoyl, etc.; C ₆ ., ₄ aryl- carbonyl such as benzoyl, naphthalenecarbonyl , etc.; C _1-6 alkoxy-carbonyl such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl , isobutoxycarbonyl, sec-butoxycarbonyl , tert-butoxycarbonyl, etc.; C _6.14 aryloxy-carbonyl such as phenoxycarbonyl, etc.; C _7-19 aralkyl-carbonyl such as phenyl-C _1-i4 alkylcarbonyl (e.g. benzylcarbonyl , phenethylcarbonyl , phenylpropylcarbonyl, etc. ) ; C ₇ . ₁₉ aralkyloxycarbonyl such as benzyloxycarbonyl , etc. ], nitro, amino, hydroxy, cyano, sulfamoyl, mercapto, halogen (e.g. fluorine, chlorine, bromine, iodine), and an alkylthio group (e.g. C,_ ₄ alkylthio group such as methylthio, ethylthio, n-propylthio, isobutylthio, etc. ) .

The group represented by the formula -T-Q specifically includes an alkyloxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, a heterocycle-oxy group, an acyloxy group, an alkylthio group, an alkenylthio group, an arylthio group, an aralkylthio group, a heterocycle-thio group, an acylthio group, an alkyldithio group, an aryldithio group, an aralkyldithio group, an alkylsulfinyl group, an alkenylsulfinyl group, an arylsulfinyl group, an

aralkylsulfinyl group, a heterocycle-sulfinyl group, an alkylsulfonyl group, an alkenylsulfonyl group, an arylsulfonyl group, an aralkylsulfonyl gorup, and a heterocycle-sulfonyl group. The alkyloxy mentioned above is preferably a straight-chain, branched or cyclic alkyloxy group of 1 to 6 carbon atoms, e.g. C _1-5 alkoxy or C _3-6 cycloalkyloxy such as methoxy, ethoxy, n-propoxy, isopropoxy, n- butoxy, isobutoxy, sec-butoxy, tert-butoxy, n- pentyloxy, sec-pentyloxy, isopentyloxy, neopentyloxy, cyclopentyloxy, n-hexyloxy, isohexyloxy, cyclohexyloxy, etc.

The alkenyloxy group mentioned above is preferably a straight-chain, branched, or cyclic alkenyloxy group of 2 to 6 carbon atoms, such as allyloxy, isopropenyloxy, 1-butenyloxy, 2-pentenyloxy, 2- hexenyloxy, cyclohexenyloxy, etc.

The aryloxy group mentioned above is preferably an aryloxy group of 6 to 14 carbon atoms, such as phenoxy, naphthyloxy, etc.

The aralkyloxy group mentioned above is preferably an aralkyloxy group of 7 to 19 carbon atoms, such as phenyl-C^ alkyloxy, e.g. benzyloxy, phenethyloxy, phenylpropyloxy, etc. The heterocycle-oxy group mentioned above is a group of the formula T'-O- wherein T' represents above- mentioned heterocyclic group, specifically including pyrrolyloxy such as 2- or 3-pyrrolyloxy; pyrazolyloxy such as 3-, 4-, or 5-pyrazolyloxy; imidazolyloxy such as 2-, 4-, or 5-imidazolyloxy; triazolyloxy such as 1, 2, 3-triazol-4-yloxy and 1,2,4-triazol-3-yloxy; tetrazolyloxy such as 1H- or 2H-tetrazol-5-yloxy; furyloxy such as 2- or 3-furyloxy; thienyloxy such as 2- or 3-thienyloxy; thienyloxy in which the sulfur atom is oxidized such as 2- or 3-thienyloxy-l, 1-dioxide; oxazolyloxy such as 2-, 4-, or 5-oxazolyloxy, etc.

The acyloxy group mentioned above is a group of the formula T"-0- wherein T" represents above-mentioned acyl, specifically including C^ alkyl-carbonyloxy such as acetoxy, propionyloxy, butyryloxy, pentanoyloxy, and hexanoyloxy; C ₇ . ₁₉ aralkylcarbonyloxy such as phenyl-C,_,, alkylcarbonyloxy, (e.g. benzylcarbonyloxy, phenethylcarbonyloxy, etc . ); C ₆ . ₁₄ arylcarbonyloxy such as benzoyloxy and naphthoyloxy; heterocycle-carbonyloxy such as thienylcarbonyloxy and benzothienylcarbonyloxy, etc.

The alkylthio group mentioned above is preferably a straight-chain, branched, or cyclic C _1-i6 alkylthio group, e.g. C _l . ₆ alkylthio and C _3-6 cycloalkylthio such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert- butylthio, n-pentylthio, sec-pentylthio, isopentylthio, neopentylthio, cyclopentylthio, n-hexylthio, isohexylthio, cyclohexylthio, etc.

The alkenylthio group mentioned above is preferably a straight-chain, branched, or cyclic C ₂ . ₆ alkenylthio group such as allylthio, isopropenylthio, 1-butenylthio, 2-pentenylthio, 2-hexenylthio, and cyclohexenylthio, etc.

The arylthio group mentioned above is preferably a C ₆ . ₁₄ arylthio group such as phenylthio, and naphthylthio, etc.

The aralkylthio group mentioned above is preferably a C ₇ . ₁₉ aralkylthio group, e.g. phenyl-C,. ₄ alkylthio such as benzylthio, phenethylthio, and phenylpropylthio, etc.

The heterocyclethio group mentioned above is a group of the formula T'-S- wherein T' represents above- mentioned heterocyclic group, specifically including pyrrolylthio such as 2- or 3-pyrrolylthio; pyrazolylthio such as 3-, 4-, or 5-pyrazolylthio;

imidazolylthio such as 2-, 4-, or 5-imidazolylthio; triazolylthio such as 1,2,3-triazol-4-ylthio and 1,2,4- triazol-5-ylthio; tetrazolylthio such as 1H- or 2H- tetrazol-5-ylthio; furylthio such as 2- or 3-furylthio; thienylthio such as 2- or 3-thienylthio; thienylthio in which the sulfur atom of the thienyl group is oxidized such as 2- or 3-thienylthio-l, 1-dioxide; and oxazolylthio such as 2-, 4-, or 5-oxazolylthio, etc. The acylthio group mentioned above is a group of the formula T"-S- wherein T" represents above-mentioned acyl group, specifically including C _1-6 alkyl- carbonylthio such as acetylthio, propionylthio, butyrylthio, pentanoylthio, and hexanoylthio; phenyl- C,_ ₄ alkylcarbonylthio such as benzylcarbonylthio and phenethylcarbonylthio; C ₆ . ₁₄ arylcarbonylthio such as benzoylthio, and naphthoylthio; heterocycle- carbonylthio such as thienylcarbonylthio and benzothienylcarbonylthio, etc.

The alkyldithio group mentioned above is preferably a straight-chain, branched, or cyclic C,_ ₅ alkyldithio group, e.g. C _1-6 alkyldithio or C _3-6 cycloalkyldithio such as methyldithio, ethyldithio, n- propyldithio, cyclopentyldithio, etc.

The aryldithio group mentioned above is preferably a C ₅ . ₁₄ aryldithio group such as phenyldithio, naphthyldithio, etc.

The aralkyldithio group mentioned above is preferably a C ₇ . ₁₉ aralkyldithio group e.g. phenyl-C, _. _, alkyldithio such as benzyldithio, phenethyldithio, etc. The alkylsulfinyl group mentioned above is preferably a straight-chain, branched, or cyclic C,_ ₆ alkylsulfinyl group, e.g. C ₆ alkylsulfinyl or C _3.6 cycloalkylsul inyl such as methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, isopropylsulfinyl, n- hexylsulfinyl, cyclohexylsulfinyl, etc.

The alkenylsulfinyl group mentioned above is preferably a straight-chain, branched, or cyclic C ₂ . ₅ alkenylsulfinyl group such as allylsulfinyl .

The arylsulfinyl group mentioned above is preferably a C ₆ . ₁₄ arylsulfinyl group such as phenylsulfinyl .

The aralkylsulfinyl group mentioned above is preferably a C ₇ . ₁₉ aralkylsulfinyl group, e.g. phenyl-C, _{. 4} alkylsulfinyl such as benzylεulfinyl . The heterocycle-sulfinyl group mentioned above is a group of the formula T'-SO- wherein T' represents above-mentioned heterocyclic group, specifically including pyrrolylsulfinyl such as 2- or 3- pyrrolylsulfinyl; pyrazolylsulfinyl such as 3-, 4-, 5- pyrazolylsulfinyl, etc.

The alkylsulfonyl group mentioned above is preferably a straight-chain, branched, or cyclic C,^ alkylsulfonyl group, e.g. C,„ ₆ alkylsulfonyl or C ₃ _ ₆ cycloalkylsulfonyl such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl , isopropylsulfonyl , cyclohexylsulfonyl, etc.

The alkenylsulfonyl group mentioned above is preferably a straight-chain, branched, or cyclic C _2-6 alkenylsulfonyl group such as allylsulfonyl . The arylsulfonyl group mentioned above is preferably a C ₆ . ₁₄ arylsulfonyl group such as phenylsulfonyl, naphthylsulfonyl , etc.

The aralkylsulfonyl group mentioned above is preferably a C ₇ . ₁₉ aralkylsulfonyl group, e.g. phenyl-C,. ₄ alkylsulfonyl such as benzylsulfonyl , phenethylsulfonyl, phenylpropylsulfonyl, etc.

The heterocycle-sulfonyl group mentioned above is a group of the formula T'-S0 ₂ - wherein T' represents above-mentioned heterocyclic group, specifically including pyrrolylsulfonyl such as 2- or 3-

pyrrolylsulfonyl; pyrrazolylsulfonyl such as 3-, 4-, or 5-pyrazolylsulfonyl, etc.

The group of the formula:

—N

specifically includes (1) an alkylamino group, preferably a mono- or di-(C,. ₆ alkyl)amino group, e.g. methylamino, ethylamino, n-propy.lamino, n-butylamino, tert-butylamino, n-pentylamino, n-hexylamino, dimethyla ino, diethylamino, methylethyla ino, di-(n- propyl)amino, di-(n-butyl )amino, etc., (2) a cycloalkylamino group, preferably a mono- or di-(C _3-6 cycloalkyl)amino group, e.g. cyclopropylamino, cyclopentylamino, cyclohexylamino, dicyclohexylamino, etc., (3) an arylamino group, preferably a C _6- | ₄ arylamino grou e.g. anilino etc .; N-C,_ ₆ alkyl-N-C ₆ ., ₄ arylamino, e.g. N-methylanilino, e (4) an aralkyla ino group, preferably a C _7-19 aralkylamino group, e.g. phenyl-C,. ₄ alkylamino such as benzylamino, 1-phenylethylamino, benzhydrylamino, tritylamino, etc., (5) an acylamino group, i.e. a group of the formula T"T"'N- wherein T" represents above- mentioned acyl group; T" ' represents hydrogen, a hydrocarbon group as mentioned above, or an acyl group as mentioned above; T" and T" ' may form a ring together with the adjacent nitrogen atom; such as a C,_ alkylcarbonylamino, a C _6- arylcarbonylamino group, and a heterocycle-carbonylamino group wherein the alkyl, aryl, and heterocyclic group of the heterocycle- carbonyla ino are preferably those mentioned in the substituent of the aromatic ring group for Q I thus specifically including acetamido, propionamido, butyryla ino, pentanoyla ino, hexanoylamino, succini ido, benzylcarbonylamino, phenethylcarbonylamino, benzoyla ino, naphthoylamino,

phthalimido , thienylcarbonylamino , benzothienylcarbonylamino , etc . , and ( 6 ) a cyc l ic amino

3 group. Here, Q and Q may form a ring together with the adjacent nitrogen atom, preferably a 3- to 7- membered ring, e.g. pyrrolidino, piperidino, morpholino, thiomorpholino, 1-piperazinyl , aziridino, azetidino, etc.

The group of the formula:

specifically includes (1) a mono- or di-alkylsulfamoyl group, preferably a mono- or alkyl) sulfamoyl group, e.g. methylsulfamoyl, ethylsulfamoyl, n- propylsulfamoyl, n-hexylsulfamoyl , dimethylsulfamoyl , diethylsulfamoyl, methylethylsulfamoyl , di(n- butyl)sulfamoyl, etc., (2) a cycloalkylsulfamoyl group, preferably a C ₃ . ₆ cycloalkylsulfamoyl group, e.g. cyclopropylsulfamoyl, cyclohexylsulfamoyl, etc. , (3) an arylsulfamoyl group, preferably a C ₆ .,,, arylsulfamoyl group, e.g. phenylsulfamoyl etc., (4) an aralkylsulfamoyl group, preferably a C ₇ . ₁₉ aralkylsulfamoyl group, e.g. phenyl-C,. ₄ alkylsulfamoyl such as benzylsulfamoyl; benzhydrylsulfamoyl, tritylsulfamoyl, etc., and (5) an acylsulfamoyl group, i.e. a group of the formula T"T"'NS0 ₂ - wherein the respective symbols have the same meanings as defined hereinbefore, e.g. C,_ ₆ alkylcarbonylsulfamoyl such as acetylsulfamoyl, phenyl-C,_ ₄ alkylcarbonylsulfamoyl such as benzylcarbonylsulfamoyl, heterocycle -carbonylsulfamoyl such as thienylcarbonylsulfamoyl, etc. Here, Q and Q' may form a ring together with the adjacent nitrogen atom, e.g. pyrrolidino, morpholino, thiomorpholino, 1- piperidinyl, aziridino, azetidino, etc.

The group of the formula Q ^A -S0 ₂ -0- specifically includes (1) an alkylsulfonyloxy group, preferably a C,_ ₆ alkylsulfonyloxy group, e.g. methanesulfonyloxy, ethanesulfonyloxy, etc., (2) an arylsulfonyloxy group, preferably a C ₆ . ₁₄ arylsulfonyloxy group, e.g. benzenesulfonyloxy, etc., (3) an aralkylsulfonyloxy group, preferably a C ₇ . ₁₉ aralkylsulfonyloxy group, e.g. phenyl-C^ alkylsulfonyloxy such as benzylsulfonyloxy, phenethylsulfonyloxy, etc., and (4) an acylsulfonyloxy group, e.g. C,_ ₆ alkylcarbonylsulfonyloxy such as acetylsulfonyloxy, butyrylsulfonyloxy, etc.

R 1 and R2 are the same or different and each represents hydrocarbon group, which may optionally be substituted or R 1 and R2 may form a ring together with the adjacent carbon atom, wherein the ring may optionally be substituted. The hydrocarbon group and its substituent or substituents mentioned just above includes those mentioned hereinbefore.

The ring formed by R 1 and R2 together with the adjacent carbon atom and which may optionally be substituted includes C ₃ . ₇ cycloalkanes, e.g. cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, etc. and C _3.7 cycloalkenes, e.g. cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, etc., each of which may optionally be substituted by the substituent or substituents as mentioned for the hydrocarbon group for R 1 and R2.

The group bonded through a carbon atom which is present as a substituent on one of nitrogen atoms of compound (la) is not particularly limited but can be any group which is bonded through a carbon atom. For example, a hydrocarbon group which may optionally be substituted, an acyl group which may optionally be substituted, cyano, a carbamoyl group which may optionally be substituted, an amidino group which may

optionally be substituted, or a heterocyclic group bonded through a carbon atom which may optionally be substituted, can be mentioned. The hydrocarbon group, its substituent or substituents, and the acyl group, its substituent or substituents may be the same groups as mentioned hereinbefore for substituents on Q ¹ . The carbamoyl group may have 1 or 2 substituents, and the amidino group may have 1 to 3 substituents. The substituents for said carbamoyl and amidino may for example be the above-mentioned hydrocarbon group, heterocyclic group or acyl group.

The above-mentioned heterocyclic group bonded through a carbon atom includes a 3- to 8-membered heterocyclic group which contains 1 to 4 hetero atoms selected from nitrogen (which may be in the oxide form) , oxygen, and sulfur (which may be in the mono- or dioxide form) besides carbon and a condensed ring group thereof with benzene ring or a 3- to 8-membered heterocyclic ring which contains 1 to 4 hetero atoms selected from nitrogen (which may be in the oxide form) oxygen, and sulfur (which may be in the raono- or dioxide form) .

Specifically, mention can be made of aziridinyl (e.g. 2-aziridinyl) , azirinyl (e.g. 2-azirinyl), azetyl (e.g. 2- or 3-azetyl), azetidinyl (e.g. 2- or 3- azetidinyl), perhydroazepinyl (e.g. 2-, 3-, 4- perhydroazepinyl) , perhydroazocinyl (e.g. 2-, 3-, 4-, 5-perhydroazocinyl) , thienyl (e.g. 2- or 3-thienyl), furyl (e.g. 2- or 3-furyl), pyrrolidinyl (e.g. 2- or 3- pyrrolidinyl), pyrrolyl (e.g. 2- or 3-pyrrolyl), oxazolyl (e.g. 2-, 4-, or 5-oxazolyl), thiazolyl (e.g. 2-, 4-, or 5-thiazolyl) , pyrazolyl (e.g. 3-, 4-, or 5- pyrazolyl), imidazolyl (e.g. 2-, 4-, or 5-imidazolyl) , isoxazolyl (e.g. 3-, 4-, or 5-isoxazolyl) , isothiazolyl (e.g. 3-, 4-, or 5-isothiazolyl) , oxadiazolyl (e.g.

1, 2,4-oxadiazol-3- or 5-yl), oxadiazolyl (e.g. 1,3,4-

oxadiazolyl), thiadiazolyl (e.g. 1,2,4-thiadiazol-3- or 5-yl, 1, 3,4-thiadiazolyl, 1,2, 3-thiadiazol-4- or 5-yl, 1,2,5-thiadiazolyl) , triazolyl (e.g. 1,2 , 3-triazolyl, l,2,4-triazol-3- or 5-yl), tetrazolyl (e.g. 1H- or 2H- tetrazol-5-yl) , pyridyl (e.g. 2-, 3-, or 4-pyridyl), pyridyl in which the nitrogen atom is oxidized (e.g. 2-, 3- or 4-pyridyl-N-oxido) , pyrimidinyl (e.g. 2-, 4-, or 5-pyrimidinyl) , pyrimidinyl in which one or both of the nitrogen atoms are oxidized (e.g. 2-, 4-, 5- or 6- pyrimidinyl-N-oxido) , thiomorpholinyl (e.g. 2- or 3- thiomorpholinyl) , morpholinyl (e.g. 2- or 3- morpholinyl) , triazinyl (e.g. 1,2 , 4-triazin-3-, 5- or 6-yl), piperidinyl (e.g. 2- or 3-piperidinyl ) , pyranyl (e.g. 2- or 3-pyranyl), thiopyranyl (e.g. 2- or 3- thiopyranyl), oxazinyl (e.g. 1 , 4-oxazin-2- or 3-yl), thiazinyl (e.g. 1, 4-thiazin-2- or 3-yl), thiazinyl (e.g. 1, 3-thiazinyl) , piperazinyl (e.g. 2- or 3- piperazinyl) , pyridazinyl (e.g. 3- or 4-pyridazinyl) , pyrazinyl, pyridazinyl in which one or both of the nitrogen atoms are oxidized (e.g. 3-, 4-, 5- or 6- pyridazinyl-N-oxido) , benzofuryl, benzothiazolyl , benzoxazolyl, tetrazolo[ 1,5-b]pyridazinyl , triazolo[4,5-b]pyridazinyl, imidazo[ 1, 2-aJpyridinyl , benzimidazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, indolidinyl, quinolidinyl, naphthyridinyl (e.g. 1, 8-naphthyridinyl ) , purinyl, pteridinyl, dibenzofuranyl, carbazolyl, acridinyl, phenanthridinyl, chromanyl , benzoxazinyl, phenazinyl, phenothiazinyl, phenoxazinyl, etc. The substituent for said heterocyclic group bonded through a carbon atom includes (1) nitro, (2) hydroxy, (3) oxo, (4) thioxo, (5) cyano, (6) carbamoyl, (7) carboxy, (8) a C ₆ alkoxy-carbonyl group (e.g. methoxycarbonyl, ethoxycarbonyl, etc.), (9) sulfo, (10) halogen (e.g. fluorine, chlorine, bromine, iodine),

(11) a C ₁ _ ₆ alkoxy group (e.g. methoxy, ethoxy, propoxy,

isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy, etc.), (12) a C ₆ . ₁₄ aryloxy group (e.g. phenoxy, naphthyloxy, etc.), (13) a C ₆ . ₁₄ aryloxy group which is halogenated by 1 to 3 halogens (e.g. halophenyloxy such as o-, -, or p-chlorophenoxy, o-, m-, or p- bromophenoxy, etc.), (14) a C^ alkylthio group (e.g. methylthio, ethylthio, n-propylthio, isopropylthio, n- butylthio, t-butylthio, etc.), (15) a C ₆ . ₁₄ arylthio group (e.g. phenylthio etc.), (16) a C,_ ₆ alkylsulfinyl group (e.g. methylsulfinyl, ethylsulfinyl, etc.), (17) a C _1-i6 alkylsulfonyl group (e.g. methylsulfonyl, ethylsulfonyl , etc.), (18) amino, (19) a C,. ₆ alkylcarbonylamino group (e.g. acetylamino, propionylamino, etc.), (20) a mono- or di-C,. ₆ alkylamino group (e.g. methylamino, ethylamino, n- propylamino, isopropylamino, n-butylamino, dimethylamino, diethylamino, etc.), (21) imino, (22) a Ci.s alkylimino group (e.g. methylimino, ethylimino, propylimino, butylimino, etc.), (23) hydroxyimino, (24) a Ci. ₆ alkoxyimino group (e.g. methoxyimino, ethoxyimino, n-propoxyimino, etc.), (25) hydrazono, (26) a mono- or di-C,_ ₄ alkylhydrazono group (e.g. methylhydrazono, ethylhydrazono, dimethylhydrazono, etc.), (27) a C^ alkylcarbonyl group (e.g. formyl, acetyl, propionyl, etc.), (28) a C ₆ . ₁₄ arylcarbonyl group (e.g. benzoyl), (29) a 5- or 6-membered heterocyclic group which contains 1 to 4 hetero atoms selected from oxygen, sulfur, and nitrogen, besides carbon, and which may optionally be substituted by 1 to 4 substituents selected from the group consisting of

(a) halogen (e.g. fluorine, chlorine, bromine, iodine),

(b) a C,_ ₄ alkyl group (e.g. methyl, ethyl, propyl , isopropyl, etc.), and (c) halophenoxy (e.g. phenoxy which is substituted by 1 to 3 halogens such as o-, -, or p-chlorophenoxy, o-, m-, or p-bromophenoxy, etc.);

for example, thienyl such as 2- or 3-thienyl, furyl such as 2- or 3-furyl, pyrazolyl such as 3-, 4-, or 5- pyrazolyl, thiazolyl such as 2-, 4-, or 5-thiazolyl, isothiazolyl such as 3-, 4-, or 5-isothiazolyl, oxazolyl such as 2-, 4-, or 5-oxazolyl, isoxazolyl such as 3-, 4-, or 5-isoxazolyl, imidazolyl such as 2-, 4-, or 5-imidazolyl, triazolyl such as 1,2,3- or 1,2,4- triazolyl, tetrazolyl such as 1H- or 2H-tetrazolyl, pyridyl such as 2-, 3-, or 4-pyridyl, pyrimidyl such as 2-, 4-, or 5-pyrimidyl, pyridazinyl such as 3- or 4- pyridazinyl, quinolyl, isoquinolyl, indolyl, etc., and (30) a Cι_ ₆ alkyl which is halogenated by 1 to 5 halogens (e.g. difluoromethyl, trifluoromethyl, trifluoroethyl, trichloroethyl, etc.) . The number of substituents may range from 1 to 5 within the limit of substitutable positions available and preferably 1 to 3.

The group bonded through a nitrogen atom which is present as a substituent on one of the nitrogen atoms of compound (la) is not particulary limited but can be any group which is bonded through a nitrogen atom. For example, there can be used any of (1) nitro, (2) a group of the formula -NR R wherein each of R and R represents hydrogen, a hydrocarbon group which may optionally be substituted, an acyl group which may optionally be substituted, a heterocyclic group which may optionally be substituted, hydroxy, or a group of the formula -SO _p R wherein R represents hydrogen or hydrocarbon group which may optionally be substituted; p represents 1 or 2, (3) a heterocyclic group bonded through a nitrogen atom, which may optionally be substituted, and (4) a group of the formula -N=C(R ^a )R ⁹

8 9 wherein R and R are the same or different and each represents hydrogen, a hydrocarbon group which may optionally be substituted, a heterocyclic group which may optionally be substituted, a hydrocarbon-oxy group

which may optionally be substituted, or a group of the formula -NR R wherein R and R each represents hydrogen or a hydrocarbon group which may optionally be substituted. The hydrocarbon group which may optionally be substituted as mentioned for R , R ⁶ , R , R ⁸ , R ⁹ , R ¹⁰ , or R includes the same hydrocarbon group which may optionally be substituted as mentioned above for the substituent of the aromatic ring group for Q ¹ . The optionally substituted hydrocarbon group of the hydrocarbon-oxy group which may optionally be substituted as mentioned for R or R includes the same hydrocarbon group which may optionally be substituted as mentioned above for the substituent of the aromatic ring group for Q .

The acyl group which may optionally be substituted mentioned for R or R includes the same acyl group which may optionally be substituted as mentioned above for the substituent of the aromatic ring group for Q . The heterocyclic group mentioned for R , R , R , or R includes the same 3- to 8-membered heterocyclic group which contains 1 to 4 heteroatoms selected from nitrogen (which may be in the oxide form) , oxygen, sulfur (which may be in the mono- or dioxide form) , besides carbon and its condensed ring group with benzene ring or a 3- to 8-membered heterocyclic ring which may contain 1 to 4 hetero atoms selected from nitrogen (which may be in the oxide form), oxygen, and sulfur (which may be in the mono- or dioxide form) as mentioned above for the substituent of the aromatic ring group for Q .

The substituent for this heterocyclic group includes the same substituent as those mentioned for the heterocyclic group bonded through a carbon atom. The heterocyclic group bonded through a nitrogen

atom includes a 3- to 8-membered heterocyclic group which contains 1 to 4 hetero atoms selected from nitrogen, oxygen, and sulfur besides carbon and a condensed ring thereof with benzene ring or a 3- to 8- membered heterocyclic ring which may contains 1 to 4 hetero atoms selected from nitrogen, oxygen, and sulfur.

Specifically, there can be mentioned 1-aziridinyl , 1-azirinyl, 1-azetyl, 1-azetidinyl, 1-perhydroazepinyl, 1-perhydroazocinyl, 1-pyrrolidinyl, 1-pyrrolinyl , 1- pyrrolyl, 1-pyrazolyl, 1-imidazolyl, 1,2, 3-triazol-l- or 2-yl, 1,2,4-triazol-l- or 4-yl, lH-tetrazol-1-yl, 2H-tetrazol-2-yl, 1-piperidinyl, 4-thiomorpholinyl , 4- morpholinyl, 1-dihydropyridyl, 1-tetrahydropyridyl, 2- or 4-oxodihydropyridin-l-yl, 1-tetrahydropyrimidyl, 1- perhydropyri idyl, 1-dihydrotriazinyl, 1- tetrahydrotriazinyl, 2-oxodihydrotriazin-l-yl, 1,4- oxazin-4-yl, 1,4-thiazin-4-yl, 1, 3-thiazin-3-yl, 1- piperazinyl, 1-perhydropyridazinyl , indol-1-yl, indolin-1-yl, isoindol-2-yl, isoindolin-2-yl , 1H- indazol-1-yl, 2 ,3-dihydrobenzoxazol-3-yl, 2,3- dihydrobenzothiazol-3-yl, 7-purinyl, 9-carbazolyl , etc. The substituent for this heterocyclic group bonded through a nitrogen atom includes the same substituent as those mentioned for the heterocyclic group bonded through a carbon atom.

The group bonded through an oxygen atom which is present as a substituent on one of the nitrogen atoms of compound (Ia) is not particularly limited but can be any group which is bonded through an oxygen atom. For example, it may for example be a group of the formula - OR wherein R represents (1) hydrogen, (2) a hydrocarbon group which may optionally be substituted, (3) a heterocyclic group which may optionally be substituted, (4) an acyl group, or (5) -SiR ₃ wherein

R 13 represents a hydrocarbon group which may optionally

be substituted.

The hydrocarbon group which may optionally be substituted as mentioned for R or R includes the same hydrocarbon group which may optionally be substituted as those mentioned hereinbefore for the substituent of the aromatic ring group for Q .

The heterocyclic group which may optionally be substituted as mentioned for R includes the same heterocyclic group which may optionally be substituted as mentioned above for R or R .

The acyl group for R includes the same acyl group as mentioned for the substituent of the aromatic ring group for Q .

Among the above-mentioned groups bonded through a carbon atom, a nitrogen atom, or an oxygen atom which is present as a substituent on one of nitrogen atom of compound (la), a group as represented by Q mentioned below is particularly preferred.

The number of oxygen as a ring member in compound (la) is preferably one.

The compound (Ia) includes both cyclic urea compounds and cyclic thiourea compounds.

Compound (la) is preferably a compound of the following formula (I), or a salt thereof (hereinafter referred to as "compound (I ) _" );

wherein Q represents an optionally substituted aromatic ring group, an optionally substituted aliphatic heterocyclic group or an optionally substituted aliphatic hydrocarbon group; A and B are the same or different and each represents a single bond or a bivalent hydrocarbon group which may optionally be

substituted, provided that both of A and B do not represent a single bond; W represents O or S; the other symbols have the same meanings as defined hereinbefore. The optionally substituted aromatic ring group as mentioned for Q includes the same aromatic ring group which may optionally be substituted as mentioned for Q ¹ .

The aliphatic heterocyclic group of said optionally substituted aliphatic heterocyclic group as mentioned for Q includes 4- to 6-membered aliphatic heterocyclic group which contains 1 to 3 hetero atoms selected from nitrogen, oxygen, and sulfur, such as oxiranyl, azetidinyl, oxetanyl, thietanyl, pyrrolidinyl, tetrahydrofuryl, thiolanyl, piperidyl, tetrahydropyranyl, morpholinyl, thiomorpholinyl, piperazinyl, etc.

The aliphatic hydrocarbon group of the optionally substituted aliphatic hydrocarbon group as mentioned for Q includes a straight-chain or branched C,_ hydrocarbon group and an alicyclic C ₃ . ₁₄ hydrocarbon group.

The above-mentioned straight-chain or branched aliphatic hydrocarbon group includes a C,. ₆ alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl , sec-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, etc., a C ₂ . ₆ alkenyl group such as allyl, isopropenyl, isobutenyl, 2-pentenyl, 2-hexenyl, etc., and a C ₂ . ₆ alkynyl group such as propargyl, 2-butynyl, 3-butynyl, 3-pentynyl, 3- hexynyl , etc.

The above-mentioned alicyclic hydrocarbon group includes a C ₃ . ₁₄ cycloalkyl group, preferably C _3-7 cycloalkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, perhydronaphthyl , perhydro- anthranyl, bicyclof2.2.1 ]heptyl, etc. and C ₃ ., ₄ cyclo-

alkenyl group, preferably C ₃ . ₇ cycloalkenyl group such as cyclopropenyl, cyclobuten-1- or 3-yl, cyclopenten-1- , 3-, or 4-yl, cyclohexen-1- or 3-yl, etc.

The aliphatic heterocyclic group and aliphatic hydrocarbon group may respectively have 1 to 4 substituents, for example, hydroxy, amino, cyano, sulfamoyl, sulfamoyloxy, mercapto, nitro, halogen, organic residue, sulfo, oxo, thioxo, and a C,_ ₆ alkylidene group. The above-mentioned halogen and organic residue have the same meaning as defined in substituent of the aromatic ring group for Q ¹ as mentioned above.

Preferred, among the above-mentioned substituent, are cyano, nitro, halogen, organic residue, and oxo. Particularly preferred are halogen and organic residue. The bivalent hydrocarbon group mentioned for A and B includes an alkylene group, an alkenylene group, and phenylene. Preferred are an alkylene group and an alkenylene group. The above-mentioned alkylene group is preferably a straight-chain or cyclic C,_ ₆ alkylene group such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, cyclopropylene, 1,2- cyclobutylene, 1, 3-cyclobutylene, cyclopentylene, 1,3- cyclopentylene, cyclohexylene, 1, 3-cyclohexylene, 1,4- cyclohexylene, etc.

The above-mentioned alkenylene group is preferably a straight-chain, branched, or cyclic alkenylene group of 1 to 6 carbon atoms, such as vinylene, propenylene, 1-propen-l,2-ylene, 2-propen-l, 2-ylene, butenylene (e,g, 1-buten-l,4-ylene, 2-buten-1 , 4-ylene, etc.), pentenylene (e.g. 1-penten-l, 5-ylene, 2-penten-l ,5- ylene, etc.), hexenylene (e.g. 1-hexen-l, 6-ylene, 2- hexen-l,6-ylene, 3-hexen-l ,6-ylene, etc.), cyclopropenylene (e.g. 1-cyclopropen-l,2-ylene, 2-

cyclopropen-1, 2-ylene) , cyclobutenylene (e.g. 1- cyclobuten-1,2-ylene, 1-cyclobuten-l, 3-ylene, 2- cyclobuten-l,2-ylene, 3-cyclobuten-l, 2-ylene) , cyclopentenylene (e.g. 1-cyclopenten-l, 2-ylene, 1- cyclopenten-1, 3-ylene, 2-cyclopenten-l,2-ylene, 3- cyclopenten-1,2-ylene, 3-cyclopenten-l, 3-ylene, 4- cyclopenten-1, 3-ylene, ), cyclohexenylene (e.g. 1- cyclohexen-1, 2-ylene, 1-cyclohexen-l ,3-ylene, 1- cyclohexen-1,4-ylene, 2-cyclohexen-l,2-ylene, 2- cyclohexen-1, 4-ylene, 3-cyclohexen-l, 2-ylene, 3- cyclohexen-1, 3-ylene, 4-cyclohexen-l,2-ylene, 4- cyclohexen-1, 3-ylene) , etc.

The phenylene mentioned above includes o- phenylene, m-phenylene, and p-phenylene. The bivalent hydrocarbon group for A and B may have 1 to 4 substituents which is the same or different, as selected from for example, hydroxy, amino, cyano, sulfamoyl, sulfamoyloxy, mercapto, nitro, halogen, organic residue, sulfo, oxo, and thioxo. The above-mentioned halogen includes fluorine, chlorine, bromine, and iodine. The organic residue includes the same groups mentioned for the substituent of the aromatic ring group for Q .

Preferably, A and B each represents a single bond, a C,_ ₆ alkylene group which may optionally be substituted, or a C ₂ . ₆ alkenylene group, and both of A and B do not represent a single bond. B is preferably a bivalent hydrocarbon residue which may optionally be substituted. The preferable substituent for above-mentioned C. _.6 alkylene group is oxo. Also, the preferable substituent for above-mentioned C _2-6 alkenylene group is C,_ ₆ alkyl, especially methyl. The number of substituent is 1 to 3, preferably 1 to 2. represents 0 or S .

Regarding compounds (I) and (Ia), all the

compounds corresponding to various combinations of groups or residues satisfying the above definitions are included but the following compounds are particularly preferred. (1) The compound (I) wherein Q represents (1) a C ₆ ., ₄ aryl group which may optionally be substituted with one to four substituents selected from the group consisting of halogen and halo-C,^ alkyl or (2) a 5- or 6- membered aromatic heterocyclic group or a condensed ring group thereof with benzene ring or a 5- or 6- membered aromatic heterocyclic ring, which may optionally be substituted with one to four halogens; Q ^z represents (1) a C ₆ . ₁₄ aryl group which may optionally be substituted with one to four substituents selected from the group consisting of (i) a C,_ ₆ alkyl group which may optionally be substituted with one to three halogens, (ii) halogen, (iii) a C,_ ₆ alkoxy group, ( iv) cyano and (v) nitro, (2) a C ₃ . ₁₄ cycloalkyl group, (3) a C ₃ . ₁₄ cycloalkenyl group, (4) a 5- or 6- membered aromatic heterocyclic group or a condensed ring group thereof with benzene ring or a 5- or 6- membered aromatic heterocyclic ring, (5) a 4- to 6- membered aliphatic heterocyclic group which may optionally be substituted with 1 to 4 substituents selected from the group consisting of C,_ ₆ alkoxy-carbonyl, C ₆ ., ₄ aryl and oxo, (6) a C ₇ . ₁₉ aralkyl group or (7) a C _1-5 alkyl group; A and B are the same or different and each represents a single bond, a C,_ ₆ alkylene group which may optionally be substituted with oxo or a C ₂ . ₆ alkenylene group which may optionally be substituted with C,_ ₆ alkyl, provided that both of A and B do not represent a single bond; R ¹ and R ² are the same or different and each represents a C _1-5 alkyl group; W represents 0 or S; or a salt thereof,

(2) the compound (I) as described in (1) above, wherein Q represents (1) phenyl which may optionally be substituted with one or two substituents selected from the group consisting of halogen and tri-halo-C,^ alkyl or (2) pyridyl (e.g. 2-, 3- or 4- pyridyl) which may optionally be substituted with a halogen, furyl (e.g. 2- or 3-furyl), thienyl (e.g. 2- or 3- thienyl) which may optionally be substituted with a halogen or imidazof 1,2-a]pyridyl (e.g. 2-, 3-, 5-, 6-, 7- or 8- imidazo[ 1,2-a]pyridyl) which may optionally be substituted with a halogen;

Q ² represents (1) phenyl which may optionally be substituted with one to three substituents selected from the group consisting of (i) a C,_ ₆ alkyl group which may optionally be substituted with 1 to 3 halogens, (ii) halogen, (iii) a C,_ alkoxy group, (iv) cyano and (v) nitro, (2) a C ₃ . ₇ cycloalkyl group, (3) a C ₃ . ₇ cycloalkenyl group, (4) thienyl (e.g. 2- or 3- thienyl), (5) thiazolyl (e.g. 2 - , 4- or 5-thiazolyl) , (6) pyridyl (e.g. 2-, 3- or 4-pyridyl), (7) imidazof 1, 2-a]pyridyl (e.g. 2-, 3-, 5-, 6-, 7- or 8- imidazo[ 1,2-a]pyridyl ) , (8) pyrrolidinyl (e.g. 1-, 2- or 3-pyrrolidinyl) which may optionally be substituted with a phenyl group, (9) piperidyl (e.g. 1-, 2-, 3- or 4-piperidyl) which may optionally be substituted with a C,. ₆ alkoxy-carbonyl group, (10) pyrrolyl (e.g. 1-, 2- or 3-pyrrolyl), (11) tetrahydrofuryl (e.g. tetrahydro- 2- or 3-furyl) which may optionally be substituted with an oxo group, (12) morpholinyl (e.g. 2-, 3- or 4- morpholinyl) ,( 13) benzyl or (14) a C,_ ₆ alkyl group;

A and B are the same or different and each represents a single bond, a C _1-6 alkylene group which may optionally be substituted with an oxo group or a C ₂ . ₆ alkenylene group which may optionally be substituted with 1 or 2 C,. ₆ alkyl groups, provided that both of A and B do not

represent a single bond;

R and R are the same or different and each represents a C,. ₆ alkyl group; W represents O or S; or a salt thereof,

(3) the compound (I) wherein Q ¹ represents an aromatic ring group which may optionally be substituted; Q represents an optionally substituted aromatic ring group, an optionally substituted aliphatic heterocyclic group or an optionally substituted aliphatic hydrocarbon group; A represents a single bond or a bivalent hydrocarbon group which may optionally be substituted; B represents a bivalent hydrocarbon group which may optionally be substituted; R and R are the same or different and each represents a hydrocarbon group which may optionally be substituted or R and R may form a ring together with the adjacent carbon atom wherein the ring may optionally be substituted; W represents O or S, or a salt thereof, (4) the compound (I) wherein Q represents an aromatic

2 ring group which may optionally be substituted; Q represents an optionally substituted aromatic ring group, an optionally substituted aliphatic heterocyclic group or an optionally substituted aliphatic hydrocarbon group; A represents methylmethylene, dimethylmethylene, propylene, vinylene, carbonyl or carbonyl-Ci. ₂ alkyl; B represents a single bond; R and R are the same or different and each represents a hydrocarbon group which may optionally be substituted or R ¹ and R may form a ring together with the adjacent carbon atom wherein the ring may optionally be substituted; represents 0 or S, or a salt thereof, (5) the compound (I) wherein Q represents an aromatic

2 ring group which may optionally be substituted; Q represents an optionally substituted aromatic

heterocyclic group or an optionally substituted cyclic aliphatic hydrocarbon group; A represents a bivalent hydrocarbon group which may optionally be substituted;

B represents a single bond; R 1 and R2 are the same or different and each represents a hydrocarbon group which may optionally be substituted or R 1 and R2 may form a ring together with the adjacent carbon atom wherein the ring may optionally be substituted; represents 0 or S, or a salt thereof, (6) the compound (I) as described in (5) above, wherein Q represents a C ₆ . ₁₄ aryl group which may optionally be substituted with one to four halogens; Q represents (1) a 5- or 6- membered aromatic heterocyclic group or a condensed ring group thereof with benzene ring or a 5- or 6- membered aromatic heterocyclic ring or (2) a C ₃ . ₇ cycloalkyl group; A represents a Cj.g alkylene group which may optionally be substituted with an oxo group or a C ₂ . ₆ alkenylene group which may optionally be substituted with 1 or 2 C,_ ₆ alkyl groups; B represents a single bond; R 1 and R? are the same or different and each represents a C<_ ₆ alkyl group; W represents 0 or S, or a salt thereof,

(7) the compound (I) as described in (5) above, wherein Q represents phenyl which may optionally be substituted with one or two halogens; Q represents thienyl (e.g. 2- or 3- thienyl) or cyclohexyl; A represents a _1→6 alkylene group; B represents a single bond; R and R are the same or different and each represents a C,_ ₆ alkyl group; represents 0, or a salt thereof,

(8) the compound (I) wherein Q represents an aromatic heterocyclic group which may optionally be substituted; Q represents an optionally substituted aromatic ring group; A represents a single bond or a bivalent hydrocarbon group which may optionally be substituted;

B represents a single bond; R 1 and R 2 are the same or different and each represents a hydrocarbon group which may optionally be substituted or R and R may form a ring together with the adjacent carbon atom wherein the ring may optionally be substituted; represents 0 or S, or a salt thereof,

(9) the compound (I) as described in (8) above, wherein Q represents a 5- or 6-membered aromatic heterocyclic group or a condensed ring group thereof with benzene ring or a 5- or 6-membered aromatic heterocyclic ring which may optionally be substituted with one to four halogens; Q represents a C ₆ . ₁₄ aryl group; A represents a C,_ ₆ alkylene group which may optionally be substituted with an oxo group or a C ₂ . ₆ alkenylene group which may optionally be substituted with 1 or 2 C,_ ₆ alkyl groups; B represents a single bond; R and R are the same or different and each represents a C,. ₆ alkyl group; W represents 0 or S, or a salt thereof, and (10) the compound (I) as described in (8) above, wherein Q represents furyl (e.g. 2- or 3-furyl), thienyl (e.g. 2- or 3-thienyl), pyridyl (e.g. 2-, 3- or 4- pyridyl) or imidazo[ 1, 2-aJpyridyl (e.g. 2-, 3-, 5-, 6-, 7- or 8-imidazo( 1 , 2-a]pyridyl ) , each o£ which may optionally be substituted with one or two halogens; Q represents phenyl; A represents a C,_ ₆ alkylene group; B represents a single bond; R and R are the same or different and each represents a C,_ ₆ alkyl group; W represents 0, or a salt thereof. When the compounds of the present invention contain acidic groups such as sulfo and carboxy in substituents, they may form agrochemically acceptable salts with bases such as inorganic or organic bases, and when the compounds contain the basic nitrogen atom and basic groups such as amino in substituents, they may form agrochemically acceptable acid addition

salts with inorganic or organic acids.

The salt of compound (la) with an inorganic base includes salts with alkali metals (e.g. sodium, potassium, etc.), alkaline earth metals (e.g. calcium etc.), and ammonia, and the salt of compound (Ia) with an organic base includes salts with dimethylamine, triethyla ine, N,N-dimethylaniline, piperazine, pyrrolidine, piperidine, pyridine, 2-phenylethylamine, benzyla ine, ethanolamine, diethanolamine, 1,8- diazabicyclo[5,4, 0]-7-undecene (hereinafter sometimes referred to briefly as DBU) .

The inorganic acid addition salt of compound (Ia) includes salts with hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, and perchloric acid and the organic acid addition salt of compound (la) includes salts with formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, benzoic acid, p-toluenesulfonic acid, methanesulfonic acid, and trifluoroacetic acid. The compound or a salt thereof of the present invention can be used as a highly safe agrochemical typically herbicide. It is especially of value as a herbicide, since the compound or salt exhibits a broad spectrum against weeds, such as those listed below, at low concentrations substantially without doing any harm to crop plants such as rice, wheat, barley, maize, soybean, and other useful plants, that is to say with high safety. The list of weeds which can be controlled include paddy field weeds such as Echinochloa crus- σalli var. oryzicola, Cγperus difformis Linnaeus, Scirpus iuncoides Roxburgh var. hotarui Ohwi, Monochoria vaσinalis Presl, Saαittaria pyσmaea Miquel, Eleocharis acicularis Romer et Schultes [Scirpus acicularis Linnaeus], Cyperus serotinus Rottboell [Junceus serotinus Clarke], Eleocharis kuroguwai Ohwi [Eleocharis tuberosa Schultes var. kuroguwai Makino],

Alisma canaliculaturn A. Braun et Bouche, Saqittaria trifolia Linnaeus, Fimbristylis subbispicata, Lindernia pyxidaria Linnaeus, Rotala indica, Potamogeton distinctus A. Bennett, Jussiaea prostrata Lέveillέ [Ludwiqia prostrata Roxburgh], Elatine triandra Schkuhr [Elatine orientalis Makino], etc. and plowland weeds such as Digitaria sanquiπalis Scopoli [Dj itaria adscendens Henrard], Setaria viridis Beauvois, A aranthus retroflexus Linnaeus, Indian mallow, Chenopodium album var. centrorubrum- Polyqonu blumei Meisner [Persicaria blumei Gross], Portulaca oleracea Linnaeus, America kingojiga, Datura alba, Ipomoea purpurea, Xanthium strumarium. Echinochloa crus- alli var. praticola, ohkusakibi, Sorghum halepense, Cyperus rotundus Linnaeus, Avena fatua, black grass, umanochahiki, Stellaria media Villars, mustard plant, Cassia obtusifolia, Matricaria chamomilla, Commelina communis , etc. The compound or a salt thereof of the invention shows a high selectivity against crop-weeds in its action, and is least toxic to mammals, fishes and shellfishes and can be used very safely as a herbicide for the paddy field, plow-land, orchard, and non-crop land without polluting the environment.

For application of the compound or a salt thereof of the present invention as an agrochemical, particularly a herbicide, it can be used in any application form that is known or available for agro- chemicals in general. Thus, according to the intended mode of use, one or more species of the compound or a salt thereof are dissolved or. dispersed in a suitable liquid vehicle or admixed with, or adsorbed on, a suitable solid carrier for use as an e ulsifiable liquids, an oil-soluble, a spray, wettable powders, dusts, driftless (DL) powders, granules, fine granules, fine granules F, flowables, dry flowables, jumbo granules, and tablets. Those application forms may be

optionally supplemented with an emulsifier, dispersant, spreader, penetrating agent, wetting agent, mucilage, stabilizer, etc. and can be manufactured by the per se known production technique. The liquid vehicle (solvent) that can be used includes water, alcohols (e.g. methanol, ethanol, 1- propanol, 2-propanol, ethylene glycol, etc.), ketones (e.g. acetone, methyl ethyl ketone, etc.), ethers (e.g. dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.), aliphatic hydrocarbons (e.g. kerosene, fuel oil, machine oil, etc.), aromatic hydrocarbons (e.g. benzene, toluene, xylene, solvent naphtha, methylnaphthalene, etc.), halogenated hydrocarbons (e.g. dichloromethane, chloroform, carbon tetrachloride, etc.), acid amides (e.g. N,N- dimethylformamide, N,N-dimethylacetamide, etc.), esters (e.g. ethyl acetate, butyl acetate, fatty acid glycerol esters, etc), and nitriles (e.g. acetonitrile, propionitrile, etc.). Those solvents can be used either singly or in combination.

The solid carrier (diluent/volume builder) includes vegetable powders (e.g. soybean meal, tobacco flour, wheat flour, sawdust, etc.), mineral powders (e.g. clays such as kaolin, bentonite, acid clay, and clay, and talcs such as talc powder, pyrophyllite (agalmatolite) powder, silicas such as diatomaceous earth, mica powder, etc.), alumina, sulfur powder, activated carbon, etc. Those materials can be used either singly or in combination.

The liquid vehicle or solid carrier is used in a proportion of generally about 1 to 99 weight % and preferably about 1 to 80 weight % based on the whole composition. The surfactant which can be used as said emulsifier, spreader, penetrating agent, or dispersant

as necessary are not limited but includes nonionic and anionic surfactans such as soaps, polyoxyethylene alkyl

TM TM aryl ethers [e.g. Noigen and E-A142 (TM stands for trademark and the same applies below; Dai-ichi Kogyo Seiyaku Co. Ltd.)], polyoxyethylene aryl esters (e.g. Nonal™; Toho Chemical), alkyl sulfates (e.g. Emal 10™,

E al 40 TM; Kao Corporation), alkylbenzenesulfonic acid

TM TM salts (e.g. Neogen , Neogen T , Dai-ichi Kogyo Seiyaku

TM

Co. Ltd.; Neopelex , Kao Corporation), polyethylene glycol ethers (e.g. Nonipol 85 , Nonipol 100 , Nonipol 160™; Sanyo Chemical Industries, Ltd.), and polyhydric alcohol esters (e.g. Tween 20 TM, Tween 80TM; Kao Corporation) .

The surfactant can be used in a proportion of generally about 0.1% to about 50% and preferably about 0.1% to about 25% with respect to the whole composition.

The preferred concentration of the compound or a salt thereof of the invention in herbicidal compositions is about 1 to 90 weight % for emulsifiable liquids and wettable powders, about 0.01 to 10 weight % for oil-solubles, dusts, and DL powders, and about 0.05 to 10 weight % for fine granules F and granules, although the concentration may be adjusted according to the intended application. Emulsifiable liquids and wettable powders may be diluted (for example, 100- 100 ,000-fold) with water or the like in advance in the field and applied.

The amount of the compound or salt of the invention for use as a herbicide varies with the type of field, season, application method, weeds to be controlled, and crop plants under cultivation. Generally, however, the proper amount in terms of the active ingredient, i.e. compound (la) or its salt is about 0.05 to 50 g, preferably about 0.1 to 10 g, per

are of paddy field, or about 0.05 to 50 g, preferably about 0.1 to 10 g, per are of plowland.

For the control of paddy field weeds, the compound or s salt thereof of the invention can be used with advantage as a preemergence soil treatment or a leaf- stem-soil treatment. For example, the herbicidal composition of the invention can be safely applied without harm to crop plants immediately after transplanting of rice seedlings or even 2-3 weeks after the transplanting, with a lasting herbicidal effect . The agrochemical composition containing the compound or a salt thereof of the present invention can be supplemented, where necessary, with other herbicides, plant growth regulators, germicides (e.g. organochlorine fungicides, organosulfur fungicides, azole fungicides, antibiotics, etc.), insecticides (e.g. pyrethroid insecticides, organophosphorus insecticides, carbamate insecticides, etc.), acaricides, nematocides, synergists, attractants, repellents, pigments, and fertilizers. As said other herbicides, there can be mentioned (1) sulfonylurea herbicides [bensulfuron-methyl , pyrazosulfuron-ethyl , i azosulfuron, sulfosulfuron, cinosulfuron, azimsulfuron, halosulfuron, ethoxysulfuron, l-(2- cyclopropylcarbonylphenylsulfamoyl ) -3-( 4 , 6- dimethoxypyrimidin-2-yl )urea, etc.], (2) pyrazole herbicides [pyrazolate, pyrazoxyfen, benzofenap, etc. ], (3) carbamate herbicides [benthiocarb, molinate, esprocarb, pyributycarb, dimepiperate, swep, etc. ], (4) chloroacetanilide herbicides [butachlor, pretilachlor, thenylchlor, etc.], (5) diphenyl ether herbicides [chloromethoxynil, bifenox, etc.], (6) triazine herbicides [simetryn, dimethametryn, etc.), (7) phenoxy acid herbicides [2,4-PA, MCP, MCPB, phenothiol, etc. ], (8) acid amide or urea herbicides [mefenacet, chlo eprop, naproanilide, bromobutide, dymron,

cumylron, ethobenzanide, 3-( l-( 3,5-dichlorophenyl)-1- methylethyl)-2, 3-dihydro-6-methyl-5-phenyl-4H-l, 3- oxazin-4-one, etc.], (9) organophosphorus herbicides [piperophos, butamifos, anilofos, etc.]. (10) As herbicides in other series, there can be mentioned bentazon, benfuresate, oxadiazon, oxadiargyl, pentoxazon, cyhalohop butyl, cafenstrol, piriminovac methyl, bispyrivac sodium, 1-( 2-chlorophenyl ) -4-(N- cyclohexyl-N-ethylcarbamoyl)-5(4H) -tetrazolinone, 2-( 2- ( 3-chlorophenyl) -2 , 3-epoxypropyl ) -2-ethylindan-1 , 3- dione, ACN, etc.

The compound or a salt thereof of the present invention can also be used as a pesticide or germicide in the same manner as above. The compound (I) or (Ia) or a salt thereof of the present invention can be synthesized by a process in which a urea or thiourea compound, or a salt thereof, which has a group of the formula (I') on one of the ring-forming nitrogen atoms and a group bonded through a carbon atom, a nitrogen atom, or an oxygen atom on the other ring-forming nitrogen atom is subjected to cyclization reaction.

More specifically, said compound (I) or a salt thereof can be produced in accordance with the following reaction schemes 1 to 6. As regards salts of the following compounds (I), (II), (III), (IV), (V), (VI), and (VII), those of the same kinds as the salt of compound (la) described hereinbefore can be employed. Reaction Scheme 1

( K b) wherein the respective symbols have the same meanings as defined hereinbefore.

The leaving group represented by X and X includes halogen (e.g. fluorine, chlorine, bromine, etc.) and a group of the formula:

-0-Q°, -S(0) _k -Q°, or -0-S0 ₂ -Q° wherein Q and k have the same meanings as defined hereinbefore, e.g. methylsulfonylox , trifluoromethyl- sulfonyloxy, p-toluenesulfonyloxy, benzenesulfonyloxy, etc. Particularly preferred is halogen, with chlorine or bromine being most advantageous .

For this reaction, compound (II) or a salt thereof and compound (III) or a salt thereof are used generally in substantially equimolar proportions. Also, the compound (III) or a salt thereof may be used in excess proportion if it does not interfere with the reaction. This reaction can be carried out in a solvent that does not interfere with the reaction. The solvent suitable for this reaction includes aromatic hydrocarbons such as benzene, toluene, xylene, etc., halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, etc., ethers such as ethyl ether, isopropyl ether, dioxane, tetrahydrofuran (hereinafter briefly, THF) , 1,2- dimethoxyethane, etc., nitriles such as acetonitrile,

propionitrile, etc., ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., esters such as ethyl acetate, butyl acetate, etc., amides such as N,N-dimethylformamide (hereinafter briefly, DMF), N,N- dimethylacetamide, etc., dimethyl sulfoxide (briefly, DMSO) , water, and mixtures of such solvents.

When the mixtures of such solvents does not solve each other, a phase transfer catalyst can be used. The phase transfer catalyst includes trioctylmethylammonium chloride, cetyltrimethylammonium bromide, triethylbenzylammonium chloride and 18-crosn-6.

This reaction can be generally promoted by adding a base. The base that can be used for this purpose includes organic bases such as triethylamine, tri-n- propylamine, N,N-dimethylaniline, pyridine, DBU, 1,4- diazabicyclo[2.2.2 ]octane, 1, 5-diazabicyclo[4.3.0 ]non- 5-ene, etc.; inorganic bases such as sodium hydride, potassium hydroxide, potassium carbonate, sodium carbonate, sodium hydroxide, etc.; n-butyllithium, lithium diisopropylamide, etc. The base can be used generally in a proportion of about 0.01 to 3 moles per mole of compound (II) or a salt thereof. The reaction temperature is generally about -10°C to 150°C and preferably about 10° to 100°C. The reaction goes to completion in about 30 minutes to about 20 hours and the completion of reaction can be ascertained by thin- layer chromatography or high-performance liquid chromatography.

This reaction is a two-stage reaction. The compound (IXa) or (IXb) or a salt thereof produced by the first-stage reaction between compound (II) or a salt thereof and compound (III) or a salt thereof may be isolated and submitted to the second-stage reaction or may be subjected to the second-stage reaction without prior isolation. Reaction Scheme 2

wherein the respective symbols have the same meanings as defined hereinbefore.

, 2

The leaving group represented by X and X includes halogen (e.g. fluorine, chlorine, bromine, etc.) and a group of the formula:

-0-Q°, -S(0) _k -Q°, or -0-S0 ₂ -Q° wherein Q and k have the same meanings as defined hereinbefore, e.g. methylsulfonyloxy, trifluoromethyl- sulfonyloxy, p-toluenesulfonyloxy, benzenesulfonyloxy, etc. Particularly preferred is halogen, with chlorine or bromine being most advantageous.

For this reaction, compound (IV) or a salt thereof and compound (V) or a salt thereof are used generally in a substantially equimolar ratio. Also, the compound (V) or a salt thereof may be used in excess proportion if it does not interfere with the reaction. This reaction can be carried out in a solvent that does not interfere with the reaction. The solvent thus may be any of the solvents mentioned for the reaction according to Reaction Scheme 1.

This reaction can be generally promoted by adding a base. The base that can be used for this purpose includes the same bases as those mentioned for the reaction according to Reaction Scheme 1. The base can be used generally in a proportion of about 0.01 to 3

moles per mole of compound (IV) or a salt thereof. The reaction temperature is generally about -10°C to 150°C and preferably about 10° to 100°C. The reaction goes to completion in about 30 minutes to about 20 hours, and the completion of reaction can be ascertained by thin-layer chromatography or high-performance liquid chromatography.

This reaction is a two-stage reaction. The compound (Xa) or (Xb) or a salt thereof produced by the first-stage reaction between compound (IV) or a salt thereof and compound (V) or a salt thereof may be isolated and submitted to the second-stage reaction or may be subjected to the second-stage reaction without prior isolation. Reaction Scheme 3

wherein the respective symbols have the same meanings as defined hereinbefore. This reaction is an addition-condensation reaction between 1 mole of compound (VII) and 2 moles of compound ( I ) .

For this reaction, relative to compound (VII) or a salt thereof, generally about 2 molar equivalents to a large excess of compound (VI) or a salt thereof is used. This reaction can be carried out in a solvent that does not interfere with the reaction, and the solvent that can be used includes the same solvents as those mentioned for the reaction according to Reaction Scheme 1.

This reaction can be generally promoted by adding

an acid. The acid mentioned just above includes inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, etc. and organic acids such as formic acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid, etc. The acid can be used generally in a proportion of about 0.01 to 3 molar equivalents relative to compound (VII). The reaction temperature is generally about -10°C to 150°C and preferably about 10° to 100°C. The reaction goes to completion in about 30 minutes to about 20 hours and the completion of reaction can be ascertained by thin-layer chromatography or high- performance liquid chromatography. Reaction Schema 4

wherein Y represents hydrogen or a lower alkyl group (preferably a C _1-6 alkyl group), and the other symbols have the same meanings as defined hereinbefore. For this reaction, compound (II) or a salt thereof and compound (VI) or a salt thereof are used generally in substantially equimolar ratio. Also, the compound (VI) or a salt thereof may be used in excess proportion if it does not interfere with the reaction. This reaction can be carried out in a solvent that does not interfere with the reaction. The solvent which can be used includes the same solvents as those mentioned for the reaction according to Reaction Scheme 1.

This reaction can be generally promoted by adding an acid. The acid which can be used for this purpose includes the same acids as those mentioned for the

reaction according to Reaction Scheme 3. The acid can be used generally in a proportion of about 0.01 to 3 moles per mole of compound (II) or a salt thereof. The reaction temperature is generally about -10°C to 150°C and preferably about 10° to 100°C. The reaction goes to completion in about 30 minutes to about 20 hours and the completion of reaction can be ascertained by thin- layer chromatography or high-performance liquid chromatography. Reaction Scheme 5

wherein the respective symbols have the same meanings as defined hereinbefore.

For this reaction, compound (IV) or a salt thereof and compound (VI) or a salt thereof are used generally in a substantially equimolar ratio. Also, the compound (VI) or a salt thereof may be used in excess proportion if it does not interfere with the reaction. This reaction can be carried out in a solvent which does not interfere with the reaction. The solvent that can be used includes the same solvents as those mentioned for the reaction according to Reaction Scheme 1. This reaction can be generally promoted by adding an acid. The acid that can be used for this purpose includes the same acids as those mentioned for the reaction according to Reaction Scheme 3. The acid can be used generally in a proportion of about 0.01 to 3 moles per mole of compound (IV) or a salt thereof. The reaction temperature is generally about -10°C to 150°C

and preferably about 10° to 100°C. The reaction goes to completion in about 30 minutes to about 20 hours and the completion of reaction can be ascertained by thin- layer chromatography or high-performance liquid chromatography.

Reaction Scheme 6

( Kb) wherein the respective symbols have the same meanings as defined hereinbefore.

For this reaction, compound (VII) or a salt thereof and compound (VIII) or a salt thereof are used generally in a substantially equimolar ratio. Also, the compound (VIII) or a salt thereof may be used in excess proportion if it does not interfere with the reaction. This reaction can be carried out in a solvent that does not interfere with the reaction. The solvent may be any of the solvents mentioned for the reaction according to Reaction Scheme 1.

This reaction can be generally promoted by adding a base. The base that can be used for this purpose includes the same bases as those mentioned for the reaction according to Reaction Scheme 1. The base can be used generally in a proportion of about 0.01 to 3 moles per mole of compound (VII) or a salt thereof. The reaction temperature is generally about -10°C to 150°C and preferably about 10° to 100°C. The reaction goes to completion in about 30 minutes to about 20 hours, and the completion of reaction can be

ascertained by thin-layer chromatography or high- performance liquid chromatography.

This reaction is a two-stage reaction. The compound (IXa) or (IXb) or a salt thereof produced by the first-stage reaction between compound (VII) or a salt thereof and compound (VIII) or a salt thereof may be isolated and submitted to the second-stage reaction or may be subjected to the second-stage reaction without prior isolation. When the compound (I) obtained by the above reaction contains an acidic group such as sulfo or carboxyl within its molecule, the reaction product may be in the form of a salt with the base used in the reaction. If such is the case, the salt can be converted to a free form of the compound by adding an acid such as the above-mentioned acid. When the compound (I) produced is a free form of the compound, it can be converted to a base salt by adding the corresponding base such as the above-mentioned base. When compound (I) contains a basic group such as amino within its molecule, the above reaction conducted in the presence of an acid may yield a salt with the acid used. If such is the case, the salt can be converted to a free form of the compound by adding a base such as the above-mentioned base. When the compound (I) is obtained as a free form of the compound, it can be converted to form an acid addition salt with the corresponding acid such as the above-mentioned acid. The compound (I) or a salt thereof thus obtained can be isolated and purified by the per se known procedures such as concentration, concentration under reduced pressure, extraction, redistribution, crystallization, recrystallization, and chromatography. The starting compounds (II), (III), (IV), (V), (VI), and (VII), inclusive of their salts, are either known compounds or compounds which can be easily

prepared from known compounds .

For example, compound (II) or a salt thereof can be produced by the process described in Archiv der Pharmazie, 296. 420-426, 1963) or any process analogous thereto, e.g. in accordance with the following reaction scheme.

Reaction Scheme 7

wherein the respective symbols have the same meanings as defined hereinbefore. Compound (IV) or a salt thereof can be produced by the process described in JP-A 8243/1985 or any process analogous thereto, e.g. in accordance with the following reaction scheme. Reaction Scheme 8

wherein the respective symbols have the same meanings as defined hereinbefore.

Compound (II) or a salt thereof or Compound (IV) or a salt thereof can be produced by the process described in Heterocycles, 22, pp.527, 1984 or any process analogous thereto, e.g. in accordance with the following reaction scheme. Reaction Scheme 9

wherein the respective symbols have the same meanings as defined hereinbefore.

Compounds (III) and (V), such as bro ochloromethane, 1,2-dichloroethane, chloroacetyl chloride, etc., are either known compounds or compounds which can be easily produced from known compounds .

Compound (VI), which is a carbonyl compound such as formaldehyde, acetone or the like, is either a known compound or a compound which can be easily produced from a known compound. Equivalent carbonyl compounds, such as paraformaldehyde and dialkoxymethane for formaldehyde, for instance, are also either known compounds or compounds which can be easily produced from known compounds .

Compound (VII) or a salt thereof can be produced by the process described in Chemical Review, 4_3, 203, 1948 or any process analogous thereto, e.g. in accordance with the following reaction scheme. Reaction Scheme 10

wherein the respective symbols have the same meanings

as defined hereinbefore.

Compound (VII) can also be produced by the process described in JP-A 6943/1976 or any process analogous thereto, e.g. in accordance with the following reaction scheme.

Reaction Scheme 11

wherein Y' represents halogen; the other symbols have the same meanings as defined hereinbefore. Compound (VIII) is for example bischloromethylether, and such a compound is a known compound or can be produced from known compound easily. [Industrial Application]

The compound or a salt thereof of the present invention has potent herbicidal activity against a broad spectrum of weeds including paddy field weeds and plow-land weeds at low concentrations. Furthermore, it is least phytotoxic to crop plants such as rice, wheat, barley, soybean, and corn plants, thus having very satisfactory selective herbicidal activity. Moreover, this selective herbicidal action lasts long. In addition, the compound or a salt thereof does no substantial harm to mammalian animals and fish, is free from the pollution problem, and can be used very safely as a herbicide in paddy fields, plowlands, orchards, and non-crop lands .

[Examples ]

The following reference examples, working examples, formulation examples, and test examples are all intended to describe the present invention in

further detail and should by no means be construed as limiting the scope of the invention.

In the reference examples and working examples, the term "room temperature" is generally used to mean a temperature within the range of about 10 to 30°C.

H-NMR stands for proton nuclear magnetic resonance spectrum. The NMR spectra were recorded with Bruker AC200P Spectrometer (200 MHz) using tetra ethylsilane as internal standard and the chemical shifts (δ) were expressed in ppm. IR stands for infrared absorption spectrum. The IR spectra were recorded with Shimadzu IR420 or IR435 Infrared Spectrophotometer and the absorption bands were expressed in wave-numbers (cm ^" ) . The other symbols used in the reference examples and working examples have the following meanings. DMS0-d ₆ : deuterated dimethyl sulfoxide; s: singlet; d: doublet; t: triplet; q: quartet; dd: doublet doublet; ddd: doublet doublet doublet; dt: doublet triplet; td: triplet doublet; qd: quartet doublet; m: multiplet, br. : broad; J: coupling constant; %: weight percent; v/v: volume-to-volume ratio; Me: methyl; Et: ethyl; n- Pr: n-propyl ; i-Pr: isopropyl; n-Bu: n-butyl ; dec.: decomposition. [Reference Example 1] Synthesis of l-hydroxy-l-phenyl-3-[ l-( 3,5- dichlorophenyl)-1-methylethyl ]urea

To a solution of 0.60 g (5.5 mmol) of N-phenyl- hydroxylamine in 20 ml of THF was added a solution of 1.32 g (5.74 mmol) of 1-( 3, 5-dichlorophenyl ) -1- methylethyl isocyanate in 20 ml of THF dropwise with ice-cooling and the mixture was stirred at room temperature for 15 hours . This reaction mixture was concentrated and the residue was purified by silica gel column chromatography (chloroform-ethyl acetate = 20:1) to provide 1.00 g (2.95 mmol, 53%) of 1-hydroxy-l- phenyl-3-[ 1-( 3,5-dichlorophenyl)-1-methylethyl ]urea as

light-yellow crystals. .p. 127-128°C

^-NMR (200 MHz, DMSO-d ₆ ) δ pp : 1.62 (6H, s),

6.95-7.05 (1H, ) , 7.20 (3H, m) , 7.35-7.55 (5H, m) , 10.42 (1H, s).

IR (Nujol) v cm ^"1 : 3400, 3140, 1640, 1560, 1510, 1450,

1415, 1375, 1280, 1255, 760. [Reference Example 2]

Synthesis of l-[ l-(3,5-bistrifluoromethylphenyl )-1- methylethyl]-l-hydroxy-3-phenylurea

In 20 ml of diethyl ether was dissolved 2.14 g (7.45 mmol) of N-[ 1-( 3, 5-bistrifluoromethylphenyl )-1- methylethyl]hydroxyamine, and a solution of 0.85 ml (7.8 mmol) of phenyl isocyanate in 5 ml of diethyl ether was added dropwise over 20 minutes at room temperature. The mixture was stirred at the prevailing temperature for 30 minutes and, then, concentrated under reduced pressure. The residue was treated with small volumes of diethyl ether and hexane and the resulting crystals were recovered by filtration, washed with hexane, and dried to provide 2.50 g (6.15 mmol) of l-[ 1-( 3, 5-bistrifluoromethylphenyl ) -1-methylethyl ]-l- hydroxy-3-phenylurea as white crystals. Yield 83%. m.p. 137-138°C *H-NMR (200 MHz, DMS0-d ₆ ) S ppm: 1.65 (6H, s), 6.94

(1H, t, J=7.3 Hz), 7.19 (2H, t, J=8.1 Hz), 7.47

(2H, d, J=7.6 Hz), 7.90 (1H, s) , 7.97 (2H, s),

9.11 (1H, s) , 9.97 (1H, s) . IR (Nujol) v cm ¹ : 3400, 3120, 1644, 1520, 1281, 1173, 1126, 897.

[Reference Example 3]

Synthesis of 1-[ 1-(3,5-dichlorophenyl )-1-methylethyl ]-

1-hydroxy-3-phenylurea

In 80 ml of diethyl ether was dissolved 2.26 g (10.3 mmol) of N-[ 1-( 3,5-dichlorophenyl ) -1- methylethyl]hydroxyamine, followed by addition of 1.2

ml (11 mmol) of phenyl isocyanate at room temperature. The mixture was stirred at the prevailing temperature for 8 hours and then concentrated under reduced pressure. The residue was treated with small volumes of diethyl ether and hexane and the resulting crystals were recovered by filtration, washed with hexane, and dried to provide 3.04 g (8.96 mmol) of l-[l-(3,5- dichlorophenyl)-1-methylethyl]-l-hydroxy-3-phenylurea as white crystals. Yield 87%. m.p. 127-128°C (decomp.)

Η-NMR (200 MHz, DMS0-d ₆ ) δ ppm: 1.58 (6H, s),

6.94 (1H, t, J=7.3 Hz), 7.20 (2H, t, J=7.8 Hz), 7.38-7.37 (3H, m) , 7.56-7.48 (2H, ) , 9.04 (1H, s), 9.88 (1H, s). IR (Nujol) v cm ^"1 : 3387, 1646, 1594, 1565, 1519, 1314, 1222, 1173, 798, 749, 690. [Reference Example 4]

Synthesis of 3-[ 1-( 3,5-dichlorophenyl)-1-methylethyl )- 1-phenylurea To a solution of 5.01 g (24.6 mmol) of l-(3,5- dichlorophenyl) -1-methylethylamine in 90 ml of toluene was added a solution of 2.93 g (24.6 mmol) of phenyl isocyanate in 10 ml of toluene dropwise over 20 minutes with ice-cooling and the mixture was stirred at room temperature for 2 hours. The resulting crystals were recovered by filtration and washed with diethyl ether to provide 7.76 g (24.0 mmol, 98 %) of 3-[l-(3,5- dichlorophenyl) -1-methylethyl ]-1-phenylurea as white crystals . m.p. 266.0-267.0°C

^L H NMR (200MHz, DMS0-d ₆ )S ppm: 1.57 (6H, s), 6.70 (1H, s), 6.87(1H, t, J=7.2 Hx) , 7.10-7.48 (7H, ) , 8.43 (1H, br s) IR (Nujol) v cm ^"1 : 3320, 1645, 1600, 1545, 1445, 1310, 1250, 1165, 860, 800, 745, 690

EI-MS m/z: 322 (M ⁺ )

[Reference Example 5]

Synthesis of 3-[ l-( 3 ,5-dichlorophenyl)-1-methylethyl]- l-(2, 6-difluorophenyl)urea

Under nitrogen gas atomosphere, to a solution of 0.29 g (2.2 mmol) of 2,6-difluoroaniline (97 %) in 20 ml of THF was added a solution of 1.09 ml (2.2 mmol) of lithiumdiisopropylamide (2.0 M heptane-THF-ethylbenzene solution) dropwise over 9 minutes. The mixture was stirred at the prevailing temperature for 10 minutes and then a solution of 0.50 g (2.2 mmol) of l-(3,5- dichlorophenyl)-1-methylethyl isocyanate in 8 ml of THF was added dropwise over 20 minutes . The mixture was stirred for 2.5 hours. After the mixture was allowed to room temperature, 40 ml of saturated aqueous ammonium chloride solution was added, and then the mixture was extracted 3 times with 30 ml of ethyl acetate. The combined organic layer was washed twice with 30 ml of 0. IN hydrochloric acid and saturated aqueous sodium chloride solution, dried and concentrated. The resulting crystals was washed with a mixed solution of hexane-ethyl acetate to provide 0.43 g (1.2 mmol, 54 %) of 3-[ 1-( 3,5-dichlorophenyl) -1- methylethyl ]-1-(2 ,6-difluorophenyl )urea as white crystals . m.p.: 237.5-238.0 °C

^X H NMR (200MHz, DMSO-d ₆ )δ ppm: 1.56 (6H, s), 6.93 (1H, s), 6.98-7.29 (3H, m) , 7.29-7.43 (3H, m) , 7.83 (1H, s) IR (Nujol) v cm ^"1 : 3331, 1652, 1564, 1466, 1241, 1021, 849, 797, 769

EI-MS m/z: 358 (M ⁺ ) [Reference Example 6]

Synthesis of l-methoxymethyl-l-phenyl-3-( 1-phenyl-l- methylethyl)urea Under nitrogen gas atomosphere, a solution of 1- phenyl-3-( 1-phenyl-l-methylethyl)urea [0.50 g (2.0

mmol)] in 5 ml of DMSO was added a suspension of [0.24 g (6.0 mmol)] of sodium hydride (60 % in oil) in 5 ml of DMSO dropwise over 7 minutes at room temperature and the mixture was stirred at room temperature for 30 minutes, and then a solution of chloromethyl methyl ether [0.20 g (2.0 mmol)] in 2 ml of DMSO was added dropwise over 3 minutes. After the mixture was stirred at room temperature for 3 hours, 30 ml of water was added under ice-cooling, and the mixture was extracted with 50 ml of chloroform. The organic layer was dried over anhydrous magnesium sulfate, and concentrated to provide 3.49 g of yellow oil. This oil was dissolved in 30 ml of diethyl ether, and then washed 3 times with 30 ml of saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated to provide 0.41 g of slight yellow crystals. The crystals was purified by silica gel column chromatography (CHC1 ₃ : hexane: acetone=10 : 30: 1 ) to provide 0.17 g (0.57 mmol, 29 %) of 1- methoxymethyl-l-phenyl-3-( 1-phenyl-l-methylethyl )urea as light-yellow oil.

^X H NMR (200MHz, CDC1 ₃ ) δ ppm: 1.60 (6H, s), 3.37 (3H, s), 4.85 (1H, br), 4.97 (2H, s), 7.17-7.49 (10H, m) IR(Neat) v cm ^"1 : 3438, 2977, 2937, 1682, 1495, 1273, 1090, 1066, 762, 699, 561

The compounds which were or can be synthesized by the same procedures as Reference Examples 1 to 6 as well as the compounds obtained in Reference Examples 1 to 6 are shown in Tables 1 to 5.

77

Table 1

No. Q ¹ W mp( C)

A-1 X ⁾ CHa CHa H OH 127-128

A-2 A) CH3 CH3 H OH 140-141

A-3 ^c, χx X) CH3 CH3 H OH amorphous

A-4 CH3 CH3 OH 103-105

A-6 O ^{CH3 CH3} O OH H 127-128(decomp)

Cl

Table 2

No. R ¹ R ² W G ¹ G ² mppC)

B-1 CH ₃ CH ₃ O H H 171.0-174.0

B-3 CH ₃ CH ₃ O H H 214.5-215.0

B-4 CH ₃ CH ₃ O H H 230.0-231.0

B-5 CH ₃ CH ₃ O H H 178.0-181.0 ,

Table 3

No. Q' W πippC)

C-1 CH ₃ CH ₃ 0 H H 266-267

C-2 ^{CH3 CH} 3 0 H H 254.5-255.5

C-3 J J -. ^CH 3 CH ₃ 0 H H 246.0-247.5

C-4 CH ₃ CH ₃ 0 H H 246.5-247.5

C-5 ^{CH;J CH} 3 O H H 254.5-255.5

C-6 CH ₃ CH ₃ O H H 222.0-223.0

79

Table 4

No. Q ¹ R ¹ R ² W G ¹ G ^{2 m} P(' ^C )

C-13 CH, CH, 224.0-225.0

C-15 CH, CH, 237.5-238.0

Cl

C-16 CH, CH,

> 203.5-204.5

Cl

C-17 CH ₃ CH ₃ O H H 224.5-225.5

C-18 CH ₃ CH ₃ O H H 213.5-214.5

C-19 CH ₃ CH ₃ O H H 201.0-203.0

C-20 CH ₃ CH ₃ O H H 211.0-211.5

C-21 CH ₃ CH ₃ O H H 178.0-180.0

C-22 CH ₃ CH ₃ O H H 204.5-205.5

C-23 CH ₃ CH ₃ O H H 189.0-191.0

C-24 jT ) CH ₃ CH ₃ O H H 172.0-173.0

CH ₃

C-25 ^a x CH, C ^H ^π ₃ 3 CH ^π ₃ 3 O H H 203.0-204.0

Cl o CH ₃ CH ₃ O H H 185.0-186.0

80

Table 5

No. Q ¹ Q ² R ¹ R ² W G ¹ G ² rnp(lC)

C-29 ^CH 3 CH ₃ O H H 174.0-176.0

C-30 J jζ ^{CH3 CH} 3 O H H 226.0-227.5

Cl

C-31 ) N- ^CH CH ₃ O H H 190.0-191.0

Cl

C-33 j N-V ^{CH CH} 3 O H H 120.5-123.5

Cl

C-34 WJ J ^CH 3 CH ₃ O H H 226.0-227.5

Cl

C-35 ^CH 3 CH ₃ O H H 193.0-194.0

C-36 v ^{N Ph CH} 3 CH ₃ O H H 164.5-166.5

Cl.

C-37 ζj CH ₃ CH ₃ O H H

Cl

C-39 J ^} CH ₃ CH ₃ O H H

[Example 1]

Synthesis of 2-phenyl-4-[ 1-(3,5-dichlorophenyl) -1- methylethyl]-l,2,4-oxadiazolidin-3-one (compound 1-1)

Under nitrogen gas atomosphere, a solution of 1- hydroxy-l-phenγl-3-[ 1-( 3,5-dichlorophenyl)-1- methylethyl)urea (0.45 g, 1.33 mmol) in DMSO (4 ml) was added to a suspension of sodium hydride (66% in oil; 65.0 mg, 1.79 mmol) in DMSO (10 ml) dropwise at 19-21°C and the mixture was stirred at room temperature for 25 minutes. Then, a solution of bromochloromethane (0.25 g, 1.93 mmol) in DMSO (3 ml) was added dropwise over 3 minutes at 24-26°C. After completion of dropwise addition, the reaction mixture was stirred at room temperature for 5.5 hours. At room temperature, the reaction mixture was diluted with water (5 ml) and extracted with ethyl acetate. After phase separation, the organic layer was washed 3 times with 15 ml each of saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate (MgS0 ₄ ) , subjected to filtration and concentrated. The residue was purified by silica gel column chromatography (hexane-ethyl acetate = 4:1) to provide 171 mg (0.48 mmol, 36%) of 2- phenyl-4-[ l-( 3,5-dichlorophenyl)-1-methylethyl ]-1, 2 , 4- oxadiazolidin-3-one as light-yellow powders . m.p. 101-103°C ^-NMR (200 MHz, DMSO-d ₆ ) δ ppm: 1.68 (6H, s), 5.55

(2H,s), 7.10-7.25 (1H, m) , 7.30-7.45 (4H, ) , 7.48

(3H, m) . IR (Nujol) v cm ^"1 : 1735, 1585, 1560, 1485, 1455, 1410,

1370, 1250, 1115, 1040, 790, 765. [Example 2]

Synthesis of 2-phenyl-4-[1-( 3,5-dichlorophenyl)-1- ethylethyl]-4H-l,2,4-oxadiazin-3-one (compound 1-2)

(1) l-(2-Chloroethoxy)-l-phenyl-3-[l-(3,5- dichlorophenyl)-1-methylethyl]urea

Under nitrogen gas atomosphere, a solution of 1- hydroxy-l-phenyl-3-[ 1-(3,5-dichlorophenyl)-1- methylethyl)urea (0.50 g, 1.47 mmol) in DMSO ( 8 ml ) was added a suspension of sodium hydride (66% in oil; 87.6 mg, 2.41 mmol) in DMSO (20 ml) dropwise over 6 minutes at 21-23°C and the mixture was stirred at room temperature for 55 minutes. At 22-24°C, a solution of l-bromo-2-chloroethane (0.43 g, 3.00 mmol) in DMSO (8 ml) was added dropwise over 3 minutes and the mixture was further stirred at room temperature for 6 hours . This reaction mixture was diluted with 10 ml of water and extracted with ethyl acetate. After phase separation, the organic layer was washed 3 times with 20 ml each of saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate (MgS0 ₄ ) , subjected to filtration and concentrated. The residue was purified by silica gel column chromatography (hexane-ethyl acetate = 4:1) to provide 213 mg (0.53 mmol, 36%) of 1-( 2-chloroethoxy)-1-phenyl- 3-[ l-( 3,5-dichlorophenyl)-1-methylethyl]urea as yellow oil. ^- MR (200 MHz, DMSO-d ₆ ) δ ppm: 1.64 (6H, s),

3.90-4.00 (2H, m), 4.10-4.20 (2H, ) , 7.10-7.20

(1H, m), 7.25 (1H, s), 7.30-7.45 (7H, m) . IR (neat) v cm ^"1 : 3410, 1690, 1590, 1565, 1480, 1415,

1385, 1245, 1190, 1160, 1015, 855, 795, 755. (2) 2-Phenyl-4-[ 1-(3,5-dichlorophenyl)-1-methylethyl]- 4H-1,2,4-oxadiazin-3-one

Under nitrogen gas atomosphere, a solution of 1- (2-chloroethoxy)-l-phenyl-3-[ l-( 3, 5-dichlorophenyl) -1- methylethyl]urea (196 mg, 0.488 mmol) in DMSO (5 ml) was added to a suspension of sodium hydride (66% in oil; 29.0 mg, 0.798 mmol) in DMSO (10 ml) dropwise over 5 minutes at 25°C and the mixture was stirred at room temperature for 3.5 hours. To this reaction mixture was added 10 ml of water in small portions under cooling, followed by extraction with ethyl acetate. After phase separation, the organic layer was washed 3 times with 20 ml each of saturated aqueous sodium chloride solution, dried over MgS0 ₄ , subjected to filtration and concentrated. The residue was purified by silica gel column chromatography (hexane-ethyl acetate = 3:1) to provide 171 mg (0.468 mmol, 96%) of 2-phenyl-4-[ 1-( 3, 5-dichlorophenyl ) -1-methylethyl ]-4H- 1,2, 4-oxadiazin-3-one as white powders, m.p. 129-130°C ^X H-NMR (200 MHz, DMSO-d ₆ ) δ ppm: 1.64 (6H, s), 3.78 (2H, t, J=5.6 Hz), 4.31 (2H, t, J=5.6 Hz), 7.00-

7.15 (1H, m), 7.20-7.40 (7H, m) . IR (Nujol) v cm ¹ : 1660, 1590, 1565, 1495, 1450, 1425,

1360, 1305, 1245, 1175, 855, 795, 745. [Example 3] Synthesis of 3-[ 1-( 3, 5-dichlorophenyl)-1-methylethyl]- 5-phenyltetrahydro-l, 3,5-oxadiazin-4-one (compound 5-1)

A mixed suspension of 1-[ 1-( 3,5-dichlorophenyl)-l- methylethyl]-3-phenylurea (3.74 g, 11.6 mmol), paraformaldehyde (90%, 0.79 g, 24 mmol), p- toluenesulfonic acid onohydrate (0.66 g, 3.5 mmol), DMF (0.26 g, 3.6 mmol), dioxane (40 ml), and toluene (120 ml) was stirred at 80°C for 20 minutes. The reaction mixture was allowed to cool, washed with water (100 ml x 3), dried over MgS0 ₄ , and concentrated. The oily residue was purified by silica gel column chromatography (hexane-chloroform-acetone = 10:10:1) to provide 0.83 g (2.3 mmol, 20%) of l-[l-(3,5- dichlorophenyl)-1-methylethyl]-3-phenylurea as white crystals. m.p. 153.5-155.5°C

^L H-NMR (200 MHz, CDC1 ₃ ) δ ppm: 1.71 (6H, s), 5.07 (2H, s), 5.15 (2H, s), 7.10-7.40 (8H, m) . IR (Nujol) v cm ^"1 : 1660, 1590, 1565, 1490, 1450, 1420, 1310, 1255, 1200, 1165, 850, 810, 795, 765, 750, 695. [Example 4]

Synthesis of 5-[1-(3,5-dichlorophenyl)-1-methylethyl]- 3-( l-pyrrolyl)-4-oxotetrahydro-l, , 5-oxadiazin (compound 5-31)

Under nitrogen gas atmosphere, a solution of 3-[l- (3,5-dichlorophenyl)-1-methylethyl]-1-( 1-pyrrolyl)urea [0.40 g (1.3 mmol)] in 5 ml of DMF was added a suspension of [0.12 g (3.3 mmol)] of sodium hydride (66 % in oil) in 15 ml of DMF dropwise over 5 minutes under ice-cooling. The mixture was stirred on an ice-bath for 10 minutes, and then a solution of bischloromethylether [0.17 g (1.5 mmol)] in 2 ml of DMF was added dropwise over 5 minutes . The mixture was stirred for 2 hours with an spontaneous increase in temperature to a room temperature. The resulting solution was added to 50 ml of ice-water, and then the mixture was extracted with 50 ml of diethylether. The organic layer was washed 3 times with 30 ml of saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated. The resulting crystals was washed with a mixed solution of hexane-ethyl acetate (20-1) to provide 0.18 g (0.51 mmol, 40%) of 5-[l-(3,5- dichlorophenyl)-1-methylethyl]-3-( 1-pyrrolyl)-4- oxotetrahydro-1,3, 5-oxadiazin (compound 5-31) as white crystals . m.p. 116.5-118.0°C ^X H-NMR (CDC1-,) δ ppm: 1.72 (6H, s), 5.00 (2H, s), 5.11 (2H, s), 6.08-6.19 (2H, ) , 6.59-6.72 (2H, m) , 7.21 (1H, t, J=1.8 Hz), 7.24 (2H, d, J=1.8 Hz) IR (Nujol) v cm ^"1 : 1689 (C=0), 1587, 1567, 1301, 1258, 1062, 796, 719 EI-MS m/z: 353 (M ⁺ ) [Example 5]

Synthesis of 3-phenyl-5-{ 1-phenyl-l- methylethyl)tetrahydro-1,3 ,5-oxadiazin-4-one (compound

5-40)

A mixture of l-methoxymethyl-l-phenyl-3- ( 1-phenyl-l- methylethyl)urea [0.18 g (0.60 mmol)], DMF [0.01 g (0.1 mmol)], dioxane [0.5 ml], paraformaldehyde (content of formaldehyde: 90 %) [0.02 g (0.6 mmol)], p- toluenesulfonic acid onohydrate [0.22 g (0.1 mmol)] and toluene (5 ml) was stirred on an oil-bath at 40°C for 3 hours, on an oil-bath at 50°C for 1.5 hours and on an oil-bath at 60°C for 30 minutes. The reaction mixture was allowed to cool, washed with 10 ml of saturated aqueous sodium chloride, dried over anhydrous magnesium sulfate, and concentrated. The yellow oily residue was purified by silica gel column chromatography (CHC1 ₃ : hexane: acetone=10 : 30 : 1) to provide 0.02 g (0.07 mmol, 11 %) of 3-phenyl-5-( 1- phenyl-1-methylethyl)tetrahydro-1 , 3 , 5-oxadiazin-4-one . m.p. : 63-87°C

Η-NMR (CDClj) δ ppm: 1.81 (6H, s), 4.85 (2H, s),

5.11 (2H, s) , 7.12-7.51 (10H, m) . IR (Nujol) v cm ^"1 : 2954, 2924, 2854, 1662, 1494, 1337,

1292, 1260, 1228, 1166, 954, 797, 764, 722, 700 The compounds which were or can be synthesized by the same procedures as Examples 1 to 5 as well as the compounds obtained in Examples 1 to 5 are shown in Tables 6 to 14.

Table 6

No. B W mpfC)

CU

V CH, CH, -CH ₂ - — O 101-103

C Cll X) CU 1-2 U JI £ J CH, CH, -CH,CH_- — O 129-130

Cl CU

1.3 -ς r" ^CH 3 ^CH J -CH,CH ₂ - — o

C Crl- J? ^CCHHj

Cl 1-5 V C _ CH, CH, -CH ₂ CO- — o

C Cll JO 1-6 CH, CH, -CH.CHj- — O

Cl 1-7 V U J C I CH, CH, -CH-CH- — O

C Cll X)

Cl

1-10 ky> " CH, CH, -CH.CH,- — O C Cll

1-11 f ^ r I CH, CH, -CH.CH,- — O

1-12

Cl -"^-^

¹ - ¹³ Y ^{CHΪ CH:} - ^CH I ^CH 2- — ^{O 9} 7- ⁹⁸

1.14 lT ^{CHj CH3} " ^CH . ^CH .- — ^O oil " ι-i5 ^C ' < ' ^{CHΪ CH3} -CHJCHJ- — ^O oil"

1-16 J ^{CH3 CH>} -CHjCH.- — o oil " Cl

1): 'HNMR(Z00 Hz. COCIJ i ppm: 1.78<6H, t|, 3.β3(2H. I, J-5.7H_|.4.31(2H. I. J-5.7Hι|.7.00-7.1S(2H. m).

7.20-7.3S(3H. m|, 7.4O-7.50(ZH. m).7.57(1H. !. J-7.8HI) . 2): ΗNMR(200MHr, COCIJ J ppm: l.88(βH. ι|.3.«.3.β0(2H.m|.4.l6-4.30(2H..n).6.72(IH, d . J-3.flHι|. β.7S(1H, . J-3.9Hz|, 7.05-7.t5(1H. m).7.30-7.40(2H, m|.7.45-7.55(2H. m) 3): 'HNMR(200 H-. COCI-),. ppm; 1.00-t.90(tOH.m). I.64(6H. »|.3.50-3.60(2H.m).3.85.4.05(1H.m),

1.IO-4.20(2H.m|.7.16(1H. IJ-1.9HZ).719{2H. d J-1.9HZ)

Table 7

2-5 _. ^a CH ₃ CH ₃ — -CH-CO- o Cl 2-G Joγ CH ₃ CH ₃ — -CHjCHj- O

C Cll FF 2-7 CH- CH, — -CH-CH- O

2-8 'XT ^j |; II C CHH,, C CHH,, - — - ^C - _ό -* _u - ^« . ^< - o

C Cll Cl.

2-9 \Υ ) CH, CH, - - ^<•« .-§ O

Cl

2-10 CH ₃ CH, — -CHjCHj- O 2-12 CH ₃ CH, — -CH,CH ₂ - O F,C-

2-13 ^ |; || CH ₃ CH, — -CH,- O G4-65

C CFF,,

2-14 I] CH, CH- — -CH-CHj- O oil"

^2-15 jO ^{CH3 CHJ ~ ~} 6H ^C , ^H~ ° °" ^Z)

1): ΗNMRfΣOO Hz.CDCI,)^ ppm: 1.78 {GH. s).3.81 (2H, I J=6.0Hz), 4.41 (2H. t J-6.0 Hz).

7.39-7.21 (SH, m) 7.71 (1H. s).7.88 (2H, s) 2): 'HNMR(200 Hz.CDCI,)J ppm: 1.4S (3H. d J-G.8 Hz), 2.04 (3H, s).2.05 (3H. s).

4.51 (1H. q J-G.8 Hz).7.43-7.17 (SH. m).7.78(3H. s)

89

Table 8

No. Q ¹ R' W mp(tT)

1): 'HN R(200 Hz. CDCI ₃ ) S ppm: 1.46 (3H. d J=6.8 Hz), 1.97 (3H. s), 1.97 (3H, s).4.50 (1 H. q J=6.8Hz), 7.13-7.26 (3H, m).7.34-7.39 (4H, m) 2): ¹ HNMR(200 Hz,CDCI ₃ )<y ppm: 1.50 (3H, d J=5.2 Hz), 1.82 (6H, s), 5.72 (1H, q J=5.2 Hz),

7.20-7.26 (3H. m), 7.34-7.42 (2H, m).7.78 (1 H, def.s).7.99 (2H, def.s)

Table 9

No. Q ¹ Q ² R' R ² A B W mp( ^" C)

Table 10

No. O' Q ² R' R ² A B W mp( ^" C)

Cl CH ₃ 4-2 * jQ U) CCHH ₃₃ CCHH ₃₃ — — C— O

CH ₃

Cl

90

Table 11

No. θ' Q ^z W mp('C)

Cl.

5-1 V 1 J CH, CH, -CH, -CH ₇ - O 153.5-155.5

CCll ^{CH3 CH "CH2}

^cι γγ ^ ^CH3 ? ^H3

5-3 Kf> JQ^) CCHH ₃₃ CCHH- _α --CC-- -C- O

^C C ^l l CCH ₃ CH ₃

5-4 IJ ^ CH ₃ CH ₃ -CH ₂ - -CH ₂ - O 129.0-1300

Cl Cl

5-5 r O , ^{CH3 CH} ' - ^CH 2- - ^CH 2- O 172.5- ¹ 7 ⁴ .5 Cl

5-6 > f CH ₃ CH ₃ -CH ₂ - -CH _Z - O oi _l ¹ '

C Cll ^ Cl X. 5-7 T J s*ps > CH ₃ CH ₃ -CH ₂ - -CH ₂ - o 121.5-123.5

C Cll CCHH- ₃

Cl.

5-8 " AJ _CH ^CH 3 ^CH 3 -CH ₂ - -CH ₂ - O 128.5-129.5

C Cll ³ Cl.

5-9 _T OT ^{3 CH3 CH]} - ^CH 2- - ^CH 2- ° 7 ³ .5-7 ⁴ .5

C Cll ^ Cl. 5-10 H J , y CH ₃ CH ₃ -CH ₂ - -CH ₂ - O 131.5-1330

Cl OCH ₃

5-11 ° CH ₃ CH ₃ -CH ₂ - -CH ₂ - O oil ² '

5-12 CH ₃ CH ₃ -CH ₂ - -CH ₂ - O _oi |3>

1): 'HNMR (200MHz. CDCI ₃ )<y ppm: 1.70 (6H, s), 5.06 (2H, s), 5.11 (2H, s), 7.03-7.35 (7H, m) 2): 'HNMR (200MHz. CDCt ₃ )<y ppm: 1.70 (6H, s), 3.77 (3H, s), 5.06 (2H, s), 5.08 (2H. s),

6.77-6.92 (2H, m).7.05-7.22 (3H, m), 7.22-7.33 (2H, m) 3): 'HNMR (200MHz, CDCI. ppm: 1.71 (6H, s), 5.06 (2H, s), 5.10 (2H, s), 7.01-7.32 (7H, m)

91

Table 12

1 ): ' HNMR (200MHz, CDCI ₃ )<y ppm: 1.32-1.92 (12H, m), 1.63 (6H, s), 3.99-4.22 (1 H, br m), 4.78 (2H. s),

4.87 (2H, s), 7.17 (1 H, t J-1.8 Hz), 7.20 (2H, d J-1.8 Hz) 2): 'H ΠNΓ MIVIRΠ ( i20υ0uMiviHπz,, s a)j,, 4 <+..42 (1 H, sep J-6.9 Hz), 4 _.77C6 o (2uH, s cl), 4 A. A88n ( ra2wH. s <_)\, 77. -1I A8 M (1 MH, t t . J1--11. A8 H Hz7),, 77.0211 f (92MH, rt d . J1--11. S8 μ H?z\)

92

Table 13

No. Q R ¹ W mp(-C)

5-25 ^CI CH ₃ CH, -CH,- -CH, 163.5-165.0

Cl.

5-26 X σT CJ C CHH ₃ , CH _a -CH ₂ - -CH, 133.5-135.0

Cl ^CF 3

5-27 X. CH ₃ CH ₃ -CH ₂ - -CH ₂ - o 138-140

Cl F

5-2 ^{8 C 2} ° ^{2HS CHa CH3 "CH "CHz"} ° 1 ³⁶ .5- ¹ 3 ⁸ . ⁰ Cl

Cl.

5-29 X J j£) CH ₃ CH ₃ -CHj- -CH ₂

Cl

5-30 ^a X 0 CH3 CH ₃ -CH ₂ - -Cr * O

Cl Cl.

5-31 XX ( ^{CH3 CH3} " ^CHr " ^CHz " ° ¹¹ 6.5- ¹¹⁸ . ⁰

Cl

5-32 XX ^{CH3 CH3} " ^{CH2" "CHz"} ° 1 ⁶ 8-1 ⁶⁹

Cl °

5-3 ₃ CH ₃ CH ₃ -CH ₂ - -CH ₂ - O

5-3 ₄ X CH ₃ CH ₃ -CH ₂ - -CH ₂ - O 117-118

Cl Cl.

5-.. xf " Ph CH ₃ CH ₃ -CH ₂ - -CH ₂ - O

CH ₃ CH ₃ -CH ₂ - -CH ₂ - O 128-130

5-37 X I ^CH 3 ^CH a " ^CH 2- " ^CH 2- ° 98.5-100.5

Cl Cl.

.... ? CH ₃ CH ₃ -Cr- - -CHo

Cl Cl.

S-39 X O ^CH 3 ^CH 3 " ^CH 2" " ^CH *" ° ¹ 96.0- ¹ 9 ⁸ .0

93

Table 14

- 3 3 ^" Z- ^" 2 Ol

5-49 ^c, V 11 CHa CH ₃ -CH, -CH,-

C CτlI ^CH

5-50 1 f j JQ] CCHH ₃₃ CCHH ₃₃ -CH ₂ - -CH ₂ - O

C Cll

5-53 U JT \J CCHH ₃₃ CCHH ₃₃ --CCHH ₂₂ - -CH _Z - O 136.5-137.5 Cl

1): ⁽ HNMR (200MHz. COCI ₃ )cT ppm: 1.76 (6H. s).5.01 (2H, s).5.05 (2H. s).7.09-7.36 (8H. m)

[Formulation Example 1]

An emulsifiable liquids

Compound 1-2 20 weight %

Xylene 57 weight % N,N-dimethylformamide 18 weight %

Polyethylene glycol ether (Nonipol 85™) 5 weight %

(To be diluted with water for use when necessary)

[Formulation Example 2]

Wettable powders Compound 1-2 50 weight %

Sodium ligninsulfonate 5 weight %

Polyethylene glycol ether (Nonipol 85™) 5 weight % Clay 35 weight %

White carbon 5 weight % (To be diluted with water for use when necessary)

[Formulation Example 3]

Granules

Compound 1-2 1.5 weight %

Sodium ligninsulfonate 2 weight % Bentonite 56.5 weight %

Talc 40 weight %

The above components are kneaded with water and granulated to provide granules .

[Formulation Example 4] Granules

Compound 1-2 1.5 weight %

Sodium ligninsulfonate 5 weight %

Bentonite 93.5 weight %

The above components are kneaded with water and granulated to provide granules .

[Formulation Example 5]

Granules

Compound 1-2 3.0 weight %

Sodium ligninsulfonate 6.0 weight % Bentonite 91.0 weight %

The above components are kneaded with water and

granulated to provide granules.

[Formulation Example 6]

Granules

Compound 1-2 1.5 weight % Sodium ligninsulfonate 5 weight %

Bentonite 30.0 weight %

Clay 63.5 weight %

The above components are kneaded with water and granulated to provide granules . [Formulation Example 7]

An emulsifiable liquids

Compound 5-1 20 weight %

Xylene 57 weight %

N, -dimethylformamide 18 weight % Polyethylene glycol ether (Nonipol 85 TM) 5 weight % (To be diluted with water for use when necessary) [Formulation Example 8] Wettable powders

Compound 5-1 50 weight % Sodium ligninsulfonate 5 weight %

Polyethylene glycol ether (Nonipol 85 TM) 5 weight % Clay 35 weight %

White carbon 5 weight %

(To be diluted with water for use when necessary) [Formulation Example 9] Granules

Compound 5-1 1.5 weight %

Sodium ligninsulfonate 2 weight %

Bentonite 56.5 weight % Talc 40 weight %

The above components are kneaded with water and granulated to provide granules . [Formulation Example 10] Granules Compound 5-1 1.5 weight %

Sodium ligninsulfonate 5 weight %

Bentonite 93.5 weight %

The above components are kneaded with water and granulated to provide granules .

[Formulation Example 11] Granules

Compound 5-1 3.0 weight %

Sodium ligninsulfonate 6.0 weight %

Bentonite 91.0 weight %

The above components are kneaded with water and granulated to provide granules .

[Formulation Example 12]

Granules

Compound 5-1 1.5 weight %

Sodium ligninsulfonate 5 weight % Bentonite 30.0 weight %

Clay 63.5 weight %

The above components are kneaded with water and granulated to provide granules .

[Test Example 1]

Paddy field postemergence treatment

Rectangular pTastic pots with a capacity of 150 cm were filled in with paddy field soil, flooded with water, and tilled, and seeds of Echinochloa crus-σalli var. orvzicola , Cvperus difformis , Scirpus iuncoides , and Rotala indica were sown and cultivated at a submersion depth of 2 cm for a predetermined time. When the monocotyledons had grown to the one-leaf stage and Rotala indica to the two-leaf stage, the depth of flooding water was increased to 3 cm and dilutions of compound (Ia) were dripped over the body of water in the pots at a predetermined dose (g/a) . The dilutions mentioned above were prepared by dissolving 3.0 mg of compound (la) in 1 ml of acetone containing 2% of Tween 20, adding pure water to make 10 ml, and diluting it further with pure water to predetermined

concentrations. After the treatment, the plants were grown in a greenhouse and after 3 weeks the herbicidal effect on each weed was evaluated according to the criteria shown in Table 15. The results are presented in Table 16. [Table 15]

Herbicidal effect

Index Effect Control rate (%) (killing rate)

Hazard to crop plants

Index Hazard Hazard rate (%) 0

0.1-12.5

12.6-25.0

25.1-50.0

50.1-99.9 re (complete 100 extermination)

[Table 16]

Postemergence treatment

It is clear from Table 16 that the compounds of the present invention have very satisfactory herbicidal activity. [Test Example 2] Paddy field pree ergence treatment

Rectangular plastic pots with a capacity of 150 cm were filled in with paddy field soil, flooded with water, and tilled. Seeds of Echinochloa crus-αalli var. orvzicola and Scirpus iuncoides were sown and one stock of rice seedlings was transplanted. Under 3 cm- deep flooding, dilutions of compound (la) were dripped over the body of water in the pots at a predetermined dose (g/a). The dilutions were prepared by the same procedure as described in Test Example 1. After the treatment, the plants were further grown in a greenhouse and at 3 weeks after treatment, the herbicidal effect on each weed and the possible harmful effect on the rice plant were scored in accordance with the criteria shown in Table 15. The results are shown in Table 17.

[ Table 17 ]

Preemergence treatment

It is apparent from Table 17 that the compounds of the present invention exhibit a very satisfactory herbicidal actions without adverse effects on crop plants .