Tricyclic triazolobenzazepine derivatives, process for producing the same, and antiallergic agents

1. A compound represented by formula (II) or a salt or solvate thereof:

wherein

R 2 , R 3 , R 4 , and R 5 , which may be the same or different, represent any of the following (a) to (n):

(a) a hydrogen atom;

(b) a halogen atom;

(c) a hydroxyl group optionally protected by acetyl, chloroacetyl, dichloroacetyl, trichloroacetyl, benzoyl, 4-nitrobenzoyl, 3-oxobutyryl, benzyl, diphenylmethyl, triphenylmethyl, 4-methoxybenzyl, 3,4-dimethoxybenzyl, methoxymethyl, methoxyethoxymethyl, benzyloxymethyl, trimethylsilyl, tert-butyldimethylsilyl, triphenysilyl, 2-tetrahydropyranyl, or trimethylsilylethoxymethoxy;

(d) formyl;

(e) C 1-12 alkyl which may be substituted by a halogen atom;

(f) C 2-12 alkenyl which has one or more carbon-carbon double bonds and may be substituted by

(1) a halogen atom,

(2) cyano,

(3) —COR 9 wherein R 9 represents a hydrogen atom or C 1-6 alkyl,

(4) —COOR 10 wherein R 10 represents a hydrogen atom or C 1-6 alkyl,

(5) —CONR 11 R 12 wherein R 11 and R 12 , which may be the same or different, represent

(i) a hydrogen atom,

(ii) C 1-6 alkyl which may be substituted by amino optionally substituted by C 1-4 alkyl, phenyl optionally substituted by C 1-4 alkyl which may be substituted by a saturated five- to seven-membered heterocyclic ring containing one or two nitrogen atoms (the nitrogen atoms may be substituted by C 1-4 alkyl), or a saturated or unsaturated five- to seven-membered heterocyclic ring,

(iii) phenyl which may be substituted by carboxyl, or

(iv) a saturated or unsaturated five to seven-membered heterocyclic ring,

(6) a saturated or unsaturated five- to seven-membered heterocyclic ring which may be substituted by C 1-4 alkyl or may form a bicyclic ring fused with another ring;

(g) C 1-12 , alkoxy which may be substituted by

(1) a halogen atom,

(2) a hydroxyl group,

(3) cyano,

(4) C 3-7 cycloalkyl,

(5) phenyl,

(6) C 1-4 alkoxy,

(7) phenoxy,

(8) amino which may be substituted by C 1-4 alkyl,

(9) —COR 13 wherein R 13 represents a hydrogen atom, C 1-6 alkyl, phenyl optionally substituted by halogen or C 1-4 alkoxy, or phenyl C 1-4 alkyl,

(10) —COOR 14 wherein R 14 represents a hydrogen atom or C 1-6 alkyl,

(11) —CONR 15 R 15 wherein R 15 and R 16 , which may be the same or different, represent a hydrogen atom or C 1-6 alkyl which may be substituted by a saturated or unsaturated five to seven-membered heterocyclic ring, or

(12) a saturated or unsaturated five- to seven-membered heterocyclic ring which may be substituted by C 1-4 alkyl or phenyl C 1-4 alkyl;

(h) —CH═N—OR 16a wherein R 16a represents a hydrogen atom, C 1-6 alkyl, phenyl C 1-4 alkyl, or phenyl;

(i) —(CH 2 ) m OR 17 wherein m is an integer of 0 to 4, and R 17 represents a hydrogen atom, C 1-6 alkyl, or phenyl C 1-4 alkyl of which one or more hydrogen atoms on the benzene ring may be substituted by C 1-4 alkyl;

(j) —(CH 2 ) k COR 18 wherein k is an integer of 1 to 4, and R 18 represents a hydrogen atom or C 1-4 alkyl;

(k) —(CH 2 ) j COOR 19 wherein j is an integer of 0 to 4, and R 19 represents a hydrogen atom or C 1-6 alkyl;

(l) —(CH 2 ) p —NR 20 R 21 wherein p is an integer of 1 to 4, and R 20 and R 21 which may be the same or different, represent

(1) a hydrogen atom,

(2) C 1-6 alkyl which may be substituted by amino optionally substituted by C 1-4 alkyl,

(3) phenyl C 1-4 alkyl,

(4) —COR 22 wherein R 22 represents a hydrogen atom or C 1-4 alkyl which may be substituted by carboxyl, or

(5) —SO 2 R 23 wherein R 23 represents C 1-4 alkyl or phenyl which may be substituted by a halogen atom;

(m) —(CH 2 ) q —CONR 24 R 25 wherein q is an integer of 0 to 4, and R 24 and R 25 , which may be the same or different, represent a hydrogen atom, a saturated or unsaturated five to seven-membered heterocyclic ring, or C 1-6 alkyl which may be substituted by a saturated or unsaturated five to seven-membered heterocyclic ring, or alternatively R 24 and R 25 may form a saturated or unsaturated five to seven-membered heterocyclic ring together with a nitrogen atom to which they are attached (the heterocyclic ring may further contain at least one oxygen, nitrogen, or sulfur atom, may form a bicyclic ring fused with another ring, or may be substituted by C 1-4 alkyl); and

(n) —NR 26 R 27 wherein R 26 and R 27 , which may be the same or different, represent a hydrogen atom or —COR 28 wherein R 28 represents a hydrogen atom, C 1-6 alkyl, or phenyl which may be substituted by C 1-4 alkyl or C 1-6 alkoxy optionally substituted by phenyl;

R 31 and R 32 , which may be the same or different, represent a hydrogen atom or C 1-6 alkyl which may be substituted by a halogen atom; and

Q represents a group selected from the following groups (i) to (iv) or a halogen atom or C 1-6 alkoxy:

 wherein

R 33 represents

C 1-6 alkyl which may be substituted by C 1-6 alkoxy optionally substituted by C 1-6 alkoxy, phenyl optionally substituted by C 1-6 alkoxy, amino, or nitro, or a saturated or unsaturated five to seven-membered heterocyclic ring optionally substituted by C 1-6 alkoxy, amino, or nitro,

phenyl which may be substituted by C 1-6 alkoxy, amino, or nitro, or

a saturated or unsaturated five- to seven-membered heterocyclic ring which may be substituted by C 1-6 alkoxy, amino, or nitro, or

R 33 may form C 1-4 alkylene together with R 31 or R 32 ,

R 34 represents

C 1-16 alkyl which may be substituted by a halogen atom, carboxyl, phenyl optionally substituted by C 1-6 alkoxy, amino, or nitro, or a saturated or unsaturated five- to seven-membered heterocyclic ring optionally substituted by C 1-6 alkoxy, amino, or nitro,

phenyl which may be substituted by C 1-6 alkoxy, amino, or nitro, or

a saturated or unsaturated five- to seven-membered heterocyclic ring which may be. substituted by C 1-6 alkoxy, amino, or nitro,

R 35 and R 36 , which may be the same or different, represent a hydrogen atom or C 1-6 alkyl which may be substituted by amino optionally substituted by C 1-4 alkyl or

R 35 and R 36 may form a saturated or unsaturated five- to seven-membered heterocyclic ring together with a nitrogen atom to which they are attached, and

R 37 and R 38 , which may be the same or different, represent C 1-6 alkyl,

R 51 represents nitro or amino, and

R 52 represents a hydrogen atom or a protective group for carboxyl selected from the group consisting of methyl, ethyl, tert-butyl, benzyl, 4-methoxybenzyl, diphenylmethyl, 4-nitrobenzyl, tert-butyldimethylsilyl, triphenylsilyl, 2-phenylsulfonylethyl, 2-methoxycarbonylethyl, 2-cyanoethyl, and 2-trimethylsilylethyl,

provided that the group —CR 31 R 32 Q does not represent C 1-6 alkyl substituted by a halogen atom or C 1-6 alkoxy.

2. A compound represented by formula (II′) or a salt or solvate thereof:

wherein

R 2 , R 3 , R 4 , and R 5 , which may be the same or different, represent any of the following (a) to (n):

(a) a hydrogen atom;

(b) a halogen atom;

(c) a hydroxyl group optionally protected by acetyl, chloroacetyl, dichloroacetyl, trichloroacetyl, benzoyl, 4-nitrobenzoyl, 3-oxobutyryl, benzyl, diphenylmethyl, triphenylmethyl, 4-methoxybenzyl, 3,4-dimethoxybenzyl, methoxymethyl, methoxyethoxymethyl, benzyloxymethyl, trimethylsilyl, tert-butyldimethylsilyl, triphenysilyl, 2-tetrahydropyranyl, or trimethylsilylethoxymethoxy;

(d) formyl;

(e) C 1-12 alkyl which may be substituted by a halogen atom;

(f) C 2-12 alkenyl which has one or more carbon-carbon double bonds and may be substituted by

(1) a halogen atom,

(2) cyano,

(3) —COR 9 wherein R 9 represents a hydrogen atom or C 1-6 alkyl,

(4) —COOR 10 wherein R 10 represents a hydrogen atom or C 1-6 alkyl,

(5) —CONR 11 R 12 wherein R 11 and R 12 , which may be the same or different, represent

(i) a hydrogen atom,

(ii) C 1-6 alkyl which may be substituted by amino optionally substituted by C 1-4 alkyl, phenyl optionally substituted by C 1-4 alkyl which may be substituted by a saturated five- to seven-membered heterocyclic ring containing one or two nitrogen atoms (the nitrogen atoms may be substituted by C 1-4 alkyl), or a saturated or unsaturated five- to seven-membered heterocyclic ring,

(iii) phenyl which may be substituted by carboxyl, or

(iv) a saturated or unsaturated five to seven-membered heterocyclic ring,

(6) a saturated or unsaturated five- to seven-membered heterocyclic ring which may be substituted by C 1-4 alkyl or may form a bicyclic ring fused with another ring;

(g) C 1-12 alkoxy which may be substituted by

(1) a halogen atom,

(2) a hydroxyl group,

(3) cyano,

(4) C 1-7 cycloalkyl,

(5) phenyl,

(6) C 1-4 alkoxy,

(7) phenoxy,

(8) amino which may be substituted by C 1-4 alkyl,

(9) —COR 13 wherein R 13 represents a hydrogen atom, C 1-6 alkyl, phenyl optionally substituted by halogen or C 1-4 alkoxy, or phenyl C 1-4 alkyl,

(10) —COOR 14 wherein R 14 represents a hydrogen atom or C 1-6 alkyl,

(11) —CONR 15 R 16 wherein R 15 and R 16 , which may be the same or different, represent a hydrogen atom or C 1-6 alkyl which may be substituted by a saturated or unsaturated five- to seven-membered heterocyclic ring, or

(12) a saturated or unsaturated five- to seven-membered heterocyclic ring which may be substituted by C 1-4 alkyl or phenyl C 1-4 alkyl;

(h) —CH═N—OR 16a wherein R 16a represents a hydrogen atom, C 1-6 alkyl, phenyl C 1-4 alkyl, or phenyl;

(i) —(CH 2 ) m OR 17 wherein m is an integer of 0 to 4, and R 17 represents a hydrogen atom, C 1-6 alkyl, or phenyl C 1-4 alkyl of which one or more hydrogen atoms on the benzene ring may be substituted by C 1-4 alkyl;

(j) —(CH 2 ) k COR 18 wherein k is an integer of 1 to 4, and R 18 represents a hydrogen atom or C 1-4 alkyl;

(k) —(CH 2 ) j COOR 19 wherein j is an integer of 0 to 4, and R 19 represents a hydrogen atom or C 1-6 alkyl;

(l) —(CH 2 ) p —NR 20 R 21 wherein p is an integer of 1 to 4, and R 20 and R 21 , which may be the same or different, represent

(1) a hydrogen atom,

(2) C 1-6 alkyl which may be substituted by amino optionally substituted by C 1-4 alkyl,

(3) phenyl C 1-4 alkyl,

(4) —COR 22 wherein R 22 represents a hydrogen atom or C 1-4 alkyl which may be substituted by carboxyl, or

(5) —SO 2 R 23 wherein R 23 represents C 1-4 alkyl or phenyl which may be substituted by a halogen atom;

(m) —(CH 2 ) q —CONR 24 R 25 wherein q is an integer of 0 to 4, and R 24 and R 25 , which may be the same or different, represent a hydrogen atom, a saturated or unsaturated five- to seven-membered heterocyclic ring, or C 1-6 alkyl which may be substituted by a saturated or unsaturated five- to seven-membered heterocyclic ring, or alternatively R 24 and R 25 may form a saturated or unsaturated five- to seven-membered heterocyclic ring together with a nitrogen atom to which they are attached (the heterocyclic ring may further contain at least one oxygen, nitrogen, or sulfur atom, may form a bicyclic ring fused with another ring, or may be substituted by C 1-4 alkyl); and

(n) —NR 26 R 27 wherein R 26 and R 27 , which may be the same or different, represent a hydrogen atom or —COR 28 wherein R 28 represents a hydrogen atom, C 1-6 alkyl, or phenyl which may be substituted by C 1-4 alkyl or C 1-6 alkoxy optionally substituted by phenyl;

R 31 and R 32 , which may be the same or different, represent a hydrogen atom or C 1-6 alkyl which may be substituted by a halogen atom; and

Q represents a group selected from the following groups (i) to (iv) or a halogen atom or C 1-6 alkoxy:

 wherein

R 33 represents

C 1-6 alkyl which may be substituted by C 1-6 alkoxy optionally substituted by C 1-6 alkoxy, phenyl optionally substituted by C 1-6 alkoxy, amino, or nitro, or a saturated or unsaturated five- to seven-membered heterocyclic ring optionally substituted by C 1-6 alkoxy, amino, or nitro,

phenyl which may be substituted by C 1-6 alkoxy, amino, or nitro, or

a saturated or unsaturated five to seven-membered heterocyclic ring which may be substituted by C 1-6 alkoxy, amino, or nitro, or

R 33 may form C 1-4 alkylene together with R 31 or R 32 ,

R 34 represents

C 1-16 alkyl which may be substituted by a halogen atom, carboxyl, phenyl optionally substituted by C 1-6 alkoxy, amino, or nitro, or a saturated or unsaturated five- to seven-membered heterocyclic ring optionally substituted by C 1-6 alkoxy, amino, or nitro,

phenyl which may be substituted by C 1-6 alkoxy, amino, or nitro, or

a saturated or unsaturated five to seven-membered heterocyclic ring which may be substituted by C 1-6 alkoxy, amino, or nitro,

R 35 and R 36 , which may be the same or different, represent a hydrogen atom or C 1-6 alkyl which may be five- to seven-membered heterocyclic ring, or C 1-6 alkyl which may be substituted by a saturated or unsaturated five- to seven-membered heterocyclic ring, or alternatively R 24 and R 25 may form a saturated or unsaturated five- to seven-membered heterocyclic ring together with a nitrogen atom to which they are attached (the heterocyclic ring may further contain at least one oxygen, nitrogen, or sulfur atom, may form a bicyclic ring fused with another ring, or may be substituted by C 1-4 alkyl); and

(n) —NR 26 R 27 wherein R 26 and R 27 , which may be the same or different, represent a hydrogen atom or —COR 28 wherein R 28 represents a hydrogen atom, C 1-6 alkyl, or phenyl which may be substituted by C 1-4 alkyl or C 1-6 alkoxy optionally substituted by phenyl;

R 52 represents a hydrogen atom or a protective group for carboxyl; and

R 61 represents a protective group for triazole.

3. A process for preparing a compound represented by formula (IIa′)

wherein

R 2 , R 3 , R 4 , and R 5 , which may be the same or different, represent any one of the following (a) to (n):

(a) hydrogen atom;

(b) halogen atom;

(c) a hydroxyl group optionally protected by acetyl, chloroacetyl, dichloroacetyl, trichloroacetyl, benzoyl, 4-nitrobenzoyl, 3-oxobutyryl, benzyl, diphenylmethyl, triphenylmethyl, 4-methoxybenzyl, 3,4-dimethoxybenzyl, methoxymethyl, methoxyethoxymethyl, benzyloxymethyl, trimethylsilyl, tert-butyldimethylsilyl, triphenysilyl, 2-tetrahydropyranyl, or trimethylsilylethoxymethoxy;

(d) formyl;

(e) C 1-12 alkyl which may be substituted by a halogen atom;

(f) C 2-12 alkenyl which has one or more carbon-carbon double bonds and may be substituted by

(1) a halogen atom,

(2) cyano,

(3) —COR 9 wherein R 9 represents a hydrogen atom or C 1-6 alkyl,

(4) —COOR 10 wherein R 10 represents a hydrogen atom or C 1-6 alkyl,

(5) —CONR 11 R 12 wherein R 11 and R 12 , which may be the same or different, represent

(i) a hydrogen atom,

(ii) C 1-6 alkyl which may be substituted by amino optionally substituted by C 1-4 alkyl, phenyl optionally substituted by C 1-4 alkyl which may be substituted by a saturated five- to seven-membered heterocyclic ring containing one or two nitrogen atoms (the nitrogen atoms may be substituted by C 1-4 alkyl), or a saturated or unsaturated five- to seven-membered heterocyclic ring,

(iii) phenyl which may be substituted by carboxyl, or

(iv) a saturated or unsaturated five to seven-membered heterocyclic ring,

(6) a saturated or unsaturated five- to seven-membered heterocyclic ring which may be substituted by C 1-4 alkyl or may form a bicyclic ring fused with another ring;

(g) C 1-12 alkoxy which may be substituted by

(1) a halogen atom,

(2) a hydroxyl group,

(3) cyano,

(4) C 3-7 cycloalkyl,

(5) phenyl,

(6) C 1-4 alkoxy,

(7) phenoxy,

(8) amino which may be substituted by C 1-4 alkyl,

(9) —COR 13 wherein R 13 represents a hydrogen atom, C 1-6 alkyl, phenyl optionally substituted by halogen or C 1-4 alkoxy, or phenyl C 1-4 alkyl,

(10) —COOR 14 wherein R 14 represents a hydrogen atom or C 1-6 alkyl,

(11) —CONR 15 R 16 wherein R 15 and R 16 , which may be the same or different, represent a hydrogen atom or C 1-6 alkyl which may be substituted by a saturated or unsaturated five- to seven-membered heterocyclic ring, or

(12) a saturated or unsaturated five- to seven-membered heterocyclic ring which may be substituted by C 1-4 alkyl or phenyl C 1-4 alkyl;

(h) —CH═N—OR 16a wherein R 16a represents a hydrogen atom, C 1-6 alkyl, phenyl C 1-4 alkyl, or phenyl;

(i) —(CH 2 ) m OR 17 wherein m is an integer of 0 to 4, and R 17 represents a hydrogen atom, C 1-6 alkyl, or phenyl C 1-4 alkyl of which one or more hydrogen atoms on the benzene ring may be substituted by C 1-4 alkyl;

(j) —(CH 2 ) k —COR 18 wherein k is an integer of 1 to 4, and R 18 represents a hydrogen atom or C 1-4 alkyl;

(k) —(CH 2 ) j —COOR 19 wherein j is an integer of 0 to 4, and R 19 represents a hydrogen atom or C 1-6 alkyl;

(l) —(CH 2 ) p —NR 20 R 21 wherein p is an integer of 1 to 4, and R 20 and R 21 , which may be the same or different, represent

(1) a hydrogen atom,

(2) C 1-6 alkyl which may be substituted by amino optionally substituted by C 1-4 alkyl,

(3) phenyl C 1-4 alkyl,

(4) —COR 22 wherein R 22 represents a hydrogen atom or C 1-4 alkyl which may be substituted by carboxyl, or

(5) —SO 2 R 23 wherein R 23 represents C 1-4 alkyl or phenyl which may be substituted by a halogen atom;

(m) —(CH 2 ) q —CONR 24 R 25 wherein q is an integer of 0 to 4, and R 24 and R 25 , which may be the same or different, represent a hydrogen atom, a saturated or unsaturated five- to seven-membered heterocyclic ring, or C 1-6 alkyl which may be substituted by a saturated or unsaturated five- to seven-membered heterocyclic ring, or alternatively R 24 and R 25 may form a saturated or unsaturated five- to seven-membered heterocyclic ring together with a nitrogen atom to which they are attached (the heterocyclic ring may further contain at least one oxygen, nitrogen, or sulfur atom, may form a bicyclic ring fused with another ring, or may be substituted by C 1-4 alkyl); and

(n) —NR 26 R 27 wherein R 26 and R 27 , which may be the same or different, represent a hydrogen atom or —COR 28 wherein R 28 represents a hydrogen atom, C 1-6 alkyl, or phenyl which may be substituted by C 1-4 alkyl or C 1-6 alkoxy optionally substituted by phenyl;

R 31 and R 32 , which may be the same or different, represent a hydrogen atom or C 1-6 alkyl which may be substituted by a halogen atom;

R 52 represents a hydrogen atom or a protective group for carboxyl selected from the group consisting of methyl, ethyl, tert-butyl, benzyl, 4-methoxybenzyl, diphenylmethyl, 4-nitrobenzyl, tert-butyldimethylsilyl, triphenylsilyl, 2-phenylsulfonylethyl, 2-methoxycarbonylethyl, 2-cyanoethyl, and 2-trimethylsilylethyl, and

Q represents

 wherein

R 33 represents

C 1-6 alkyl which may be substituted by C 1-6 alkoxy optionally substituted by C 1-6 alkoxy, phenyl optionally substituted by C 1-6 alkoxy, amino, or nitro, or a saturated or unsaturated five- to seven-membered heterocyclic ring optionally substituted by C 1-6 alkoxy, amino, or nitro,

phenyl which may be substituted by C 1-6 alkoxy, amino, or nitro, or a saturated or unsaturated five- to seven-membered heterocyclic ring which may be substituted by C 1-6 alkoxy, amino, or nitro, or

R 33 may form C 1-4 alkylene together with R 31 or R 32 ,

which comprises:

(1) reacting a compound represented by formula (V)

 wherein R 2 to R 5 and R 52 are as defined above,

 with a compound represented by R 31 R 32 C═O wherein R 31 and R 32 are as defined above;

(2) reacting the compound prepared in (1) with a compound represented by R 71 —C(═O)—R 72 wherein R 71 and R 72 each independently represent a chlorine atom, 4-nitrophenyl, or 1-imidazolyl; and

(3) reacting the compound prepared in (2) with a compound represented by R 33 OH wherein R 33 is as defined above.

4. A process for preparing a compound represented by formula (IIa′)

wherein

R 2 , R 3 , R 4 , and R 5 , which may be the same or different, represent any one of the following (a) to (n):

(a) hydrogen atom;

(b) halogen atom;

(c) a hydroxyl group optionally protected by acetyl, chloroacetyl, dichloroacetyl, trichloroacetyl, benzoyl, 4-nitrobenzoyl, 3-oxobutyryl, benzyl, diphenylmethyl, triphenylmethyl, 4-methoxybenzyl, 3,4-dimethoxybenzyl, methoxymethyl, methoxyethoxymethyl benzyloxymethyl, trimethylsilyl, tert-butyldimethylsilyl, triphenysilyl, 2-tetrahydropyranyl, or trimethylsilylethoxymethoxy;

(d) formyl;

(e) C 1-12 alkyl which may be substituted by a halogen atom;

(f) C 2-12 alkenyl which has one or more carbon-carbon double bonds and may be substituted by

(1) a halogen atom,

(2) cyano,

(3) —COR 9 wherein R 9 represents a hydrogen atom or C 1-6 alkyl,

(4) —COOR 10 wherein R 10 represents a hydrogen atom or C 1-6 alkyl,

(5) —CONR 11 R 12 wherein R 11 and R 12 , which may be the same or different, represent

(i) a hydrogen atom,

(ii) C 1-6 alkyl which may be substituted by amino optionally substituted by C 1-4 alkyl, phenyl optionally substituted by C 1-4 alkyl which may be substituted by a saturated five- to seven-membered heterocyclic ring containing one or two nitrogen atoms (the nitrogen atoms may be substituted by C 1-4 alkyl), or a saturated or unsaturated five- to seven-membered heterocyclic ring,

(iii) phenyl which may be substituted by carboxyl, or

(iv) a saturated or unsaturated five to seven-membered heterocyclic ring,

(6) a saturated or unsaturated five- to seven-membered heterocyclic ring which may be substituted by C 1-4 alkyl or may form a bicyclic ring fused with another ring;

(g) C 1-12 alkoxy which may be substituted by

(1) a halogen atom,

(2) a hydroxyl group,

(3) cyano,

(4) C 3-7 cycloalkyl,

(5) phenyl,

(6) C 1-4 alkoxy,

(7) phenoxy,

(8) amino which may be substituted by C 1-4 alkyl,

(9) —COR 13 wherein R 13 represents a hydrogen atom, C 1-6 alkyl, phenyl optionally substituted by halogen or C 1-4 alkoxy, or phenyl C 1-4 alkyl,

(10) —COOR 14 wherein R 14 represents a hydrogen atom or C 1-6 alkyl,

(11) —CONR 15 R 16 wherein R 15 and R 16 , which may be the same or different, represent a hydrogen atom or C 1-6 alkyl which may be substituted by a saturated or unsaturated five- to seven-membered heterocyclic ring, or

(12) a saturated or unsaturated five- to seven-membered heterocyclic ring which may be substituted by C 1-4 alkyl or phenyl C 1-4 alkyl;

(h) —CH═N—OR 16a wherein R 16a represents a hydrogen atom, C 1-6 alkyl, phenyl C 1-4 alkyl, or phenyl;

(i) —(CH 2 ) m R 17 wherein m is an integer of 0 to 4, and R 17 represents a hydrogen atom, C 1-6 alkyl, or phenyl C 1-4 alkyl of which one or more hydrogen atoms on the benzene ring may be substituted by C 1-4 alkyl;

(j) —(CH 2 ) k —COR 18 wherein k is an integer of 1 to 4, and R 18 represents a hydrogen atom or C 1-4 alkyl;

(k) —(CH 2 ) j —COOR 19 wherein j is an integer of 0 to 4, and R 19 represents a hydrogen atom or C 1-6 alkyl;

(l) —(CH 2 ) p —NR 20 R 21 wherein p is an integer of 1 to 4, and R 20 and R 21 , which may be the same or different, represent

(1) a hydrogen atom,

(2) C 1-6 alkyl which may be substituted by amino optionally substituted by C 1-4 alkyl,

(3) phenyl C 1-4 alkyl,

(4) —COR 22 wherein R 22 represents a hydrogen atom or C 1-4 alkyl which may be substituted by carboxyl, or

(5) —SO 2 R 23 wherein R 23 represents C 1-4 alkyl or phenyl which may be substituted by a halogen atom;

(m) —(CH 2 ) q —CONR 24 R 25 wherein q is an integer of 0 to 4, and R 24 and R 25 , which may be the same or different, represent a hydrogen atom, a saturated or unsaturated five- to seven-membered heterocyclic ring, or C 1-6 alkyl which may be substituted by a saturated or unsaturated five- to seven-membered heterocyclic ring, or alternatively R 24 and R 25 may form a saturated or unsaturated five- to seven-membered heterocyclic ring together with a nitrogen atom to which they are attached (the heterocyclic ring may further contain at least one oxygen, nitrogen, or sulfur atom, may form a bicyclic ring fused with another ring, or may be substituted by C 1-4 alkyl); and

(n) —NR 26 R 27 wherein R 26 and R 27 , which may be the same or different, represent a hydrogen atom or —COR 28 wherein R 28 represents a hydrogen atom, C 1-6 alkyl, or phenyl which may be substituted by C 1-4 alkyl or C 1-6 alkoxy optionally substituted by phenyl;

R 31 and R 32 , which may be the same or different, represent a hydrogen atom or C 1-6 alkyl which may be substituted by a halogen atom;

R 52 represents a hydrogen atom or a protective group for carboxyl selected from the group consisting of methyl, ethyl, tert-butyl, benzyl, 4-methoxybenzyl, diphenylmethyl, 4-nitrobenzyl, tert-butyldimethylsilyl, triphenylsilyl, 2-phenylsulfonylethyl, 2-methoxycarbonylethyl, 2-cyanoethyl, and 2-trimethylsilylethyl, and

Q represents

 wherein

R 33 represents

C 1-6 alkyl which may be substituted by C 1-6 alkoxy optionally substituted by C 1-6 alkoxy, phenyl optionally substituted by C 1-6 alkoxy, amino, or nitro, or a saturated or unsaturated five- to seven-membered heterocyclic ring optionally substituted by C 1-6 alkoxy, amino, or nitro,

phenyl which may be substituted by C 1-6 alkoxy, amino, or nitro, or

a saturated or unsaturated five- to seven-membered heterocyclic ring which may be substituted by C 1-6 alkoxy, amino, or nitro, or

R 33 may form C 1-4 alkylene together with R 31 or R 32

which comprises:

(1) reacting a compound represented by formula (V)

 wherein R 2 to R 5 and R 52 are as defined above,

 with a compound represented by R 31 R 32 C═O wherein R 31 and R 32 are as defined above; and

(2) reacting the compound prepared in (1) with a compound represented by HalCOOR 33 wherein Hal represents a halogen atom and R 33 is as defined above, in the presence of an alkali metal carbonate and an alkali metal iodide.

5. A process for preparing a compound represented by formula (IIa′)

wherein

R 2 , R 3 , R 4 , and R 5 , which may be the same or different, represent any one of the following (a) to (n):

(a) hydrogen atom;

(b) halogen atom;

(c) a hydroxyl group optionally protected by acetyl, chloroacetyl, dichloroacetyl, trichloroacetyl, benzoyl, 4-nitrobenzoyl, 3-oxobutyryl, benzyl, diphenylmethyl, triphenylmethyl, 4-methoxybenzyl, 3,4-dimethoxybenzyl, methoxymethyl, methoxyethoxymethyl, benzyloxymethyl, trimethylsilyl, tert-butyldimethylsilyl, triphenysilyl, 2-tetrahydropyranyl, or trimethylsilylethoxymethoxy;

(d) formyl;

(e) C 1-12 alkyl which may be substituted by a halogen atom;

(f) C 2-12 alkenyl which has one or more carbon-carbon double bonds and may be substituted by

(1) a halogen atom,

(2) cyano,

(3) —COR 9 wherein R 9 represents a hydrogen atom or C 1-6 alkyl,

(4) —COOR 10 wherein R 10 represents a hydrogen atom or C 1-6 alkyl,

(5) —CONR 11 R 12 wherein R 11 and R 12 , which may be the same or different, represent

(i) a hydrogen atom,

(ii) C 1-6 alkyl which may be substituted by amino optionally substituted by C 1-4 alkyl, phenyl optionally substituted by C 1-4 alkyl which may be substituted by a saturated five- to seven-membered heterocyclic ring containing one or two nitrogen atoms (the nitrogen atoms may be substituted by C 1-4 alkyl), or a saturated or unsaturated five- to seven-membered heterocyclic ring,

(iii) phenyl which may be substituted by carboxyl, or

(iv) a saturated or unsaturated five to seven-membered heterocyclic ring,

(6) a saturated or unsaturated five- to seven-membered heterocyclic ring which may be substituted by C 1-4 alkyl or may form a bicyclic ring fused with another ring;

(g) C 1-12 alkoxy which may be substituted by

(1) a halogen atom,

(2) a hydroxyl group,

(3) cyano,

(4) C 3-7 cycloalkyl,

(5) phenyl,

(6) C 1-4 alkoxy,

(7) phenoxy,

(8) amino which may be substituted by C 1-4 alkyl,

(9) —COR 13 wherein R 13 represents a hydrogen atom, C 1-6 alkyl, phenyl optionally substituted by halogen or C 1-4 alkoxy, or phenyl C 1-4 alkyl,

(10) —COOR 14 wherein R 14 represents a hydrogen atom or C 1-6 alkyl,

(11) —CONR 15 R 16 wherein R 15 and R 16 , which may be the same or different, represent a hydrogen atom or C 1-6 alkyl which may be substituted by a saturated or unsaturated five- to seven-membered heterocyclic ring, or

(12) a saturated or unsaturated five- to seven-membered heterocyclic ring which may be substituted by C 1-4 alkyl or phenyl C 1-4 alkyl;

(h) —CH═N—OR 16a wherein R 16a represents a hydrogen atom, C 1-6 alkyl, phenyl C 1-4 alkyl, or phenyl;

(i) —(CH 2 ) m OR 17 wherein m is an integer of 0 to 4, and R 17 represents a hydrogen atom, C 1-6 alkyl, or phenyl C 1-4 alkyl of which one or more hydrogen atoms on the benzene ring may be substituted by C 1-4 alkyl;

(j) —(CH 2 ) k —COR 18 wherein k is an integer of 1 to 4, and R 18 represents a hydrogen atom or C 1-4 alkyl;

(k) —(CH 2 ) j —COOR 19 wherein j is an integer of 0 to 4, and R 19 represents a hydrogen atom or C 1-6 alkyl;

(l) —(CH 2 ) p —NR 20 R 21 wherein p is an integer of 1 to 4, and R 20 and R 21 , which may be the same or different, represent

(1) a hydrogen atom,

(2) C 1-6 alkyl which may be substituted by amino optionally substituted by C 1-4 alkyl,

(3) phenyl C 1-4 alkyl,

(4) —COR 22 wherein R 22 represents a hydrogen atom or C 1-4 alkyl which may be substituted by carboxyl, or

(5) —SO 2 R 23 wherein R 23 represents C 1-4 alkyl or phenyl which may be substituted by a halogen atom;

(m) —(CH 2 ) q —CONR 24 R 25 wherein q is an integer of 0 to 4, and R 24 and R 25 which may be the same or different, represent a hydrogen atom, a saturated or unsaturated five- to seven-membered heterocyclic ring, or C 1-6 alkyl which may be substituted by a saturated or unsaturated five- to seven-membered heterocyclic ring, or alternatively R 24 and R 25 may form a saturated or unsaturated five- to seven-membered heterocyclic ring together with a nitrogen atom to which they are attached (the heterocyclic ring may further contain at least one oxygen, nitrogen, or sulfur atom, may form a bicyclic ring fused with another ring, or may be substituted by C 1-4 alkyl); and

(n) —NR 26 R 27 wherein R 26 and R 27 , which may be the same or different, represent a hydrogen atom or —COR 28 wherein R 28 represents a hydrogen atom, C 1-6 alkyl, or phenyl which may be substituted by C 1-4 alkyl or C 1-6 alkoxy optionally substituted by phenyl;

R 31 and R 32 , which may be the same or different, represent a hydrogen atom or C 1-6 alkyl which may be substituted by a halogen atom;

R 52 represents a hydrogen atom or a protective group for carboxyl selected from the group consisting of methyl, ethyl, tert-butyl, benzyl, 4-methoxybenzyl, diphenylmethyl, 4-nitrobenzyl, tert-butyldimethylsilyl, triphenylsilyl, 2-phenylsulfonylethyl, 2-methoxycarbonylethyl, 2-cyanoethyl, and 2-trimethylsilylethyl, and

Q represents

 wherein

R 33 represents

C 1-6 alkyl which may be substituted by C 1-6 alkoxy optionally substituted by C 1-6 alkoxy, phenyl optionally substituted by C 1-6 alkoxy, amino, or nitro, or a saturated or unsaturated five- to seven-membered heterocyclic ring optionally substituted by C 1-6 alkoxy, amino, or nitro,

phenyl which may be substituted by C 1-6 alkoxy, amino, or nitro, or

a saturated or unsaturated five- to seven-membered heterocyclic ring which may be substituted by C 1-6 alkoxy, amino, or nitro, or

R 33 may form C 1-4 alkylene together with R 31 or R 32 ,

which comprises:

reacting a compound represented by formula (V)

 wherein R 2 to R 5 and R 52 are as defined above,

 with a compound represented by formula (IV)

 wherein Hal represents a halogen atom, and Q, R 31 and R 32 are as defined above, in the presence of an inorganic base and an alkali metal iodide.