Pyrimidinylbenzimidazole and triazinylbenzimidazole derivatives and agricultural/horticultural bactericides

TECHNICAL FIELD

The present invention relates to novel pyrimidinylbenzimidazole and triazinylbenzimidazole derivatives and agricultural/horticultural fungicides containing said derivatives as the active ingredients.

BACKGROUND ART

As compounds related to the pyrimidinylbenzimidazole derivatives of the present invention, 4-aminopyrimidine derivatives disclosed as pharmaceuticals in U.S. Pat. No. 5,525,604 and European Patent No. 640,599 and pyrimidine derivatives disclosed as herbicides in International Publication No. WO94/17059, are mentioned, but no disclosure regarding agricultural/horticultural fungicides has been made. French Patent No. 1,476,529 discloses benzimidazolyl sulfonamide derivatives having insecticidal and fungicidal activities, but no disclosure regarding the present compounds has been made. Further, as compounds related to the triazinylbenzimidazole derivatives of the present invention, triazine derivatives disclosed in JP-A-47-36837, JP-A-49-17677 and Kogyo Kagaku Zassi (Journal of Industrial Chemistry) vol 73, No. 5, p1000 (1970) as coloring agents for textile goods, may be mentioned, but no disclosure regarding agricultural/horticultural fungicides has been made. Further, anilinopyrimidine derivatives as production intermediates therefor have not been known.

The present invention provides novel pyrimidinylbenzimidazole and triazinylbenzimidazole derivatives and agricultural/horticultural fungicides containing them as the active ingredients.

The present inventors have conducted extensive studies to create novel agricultural/horticultural fungicides and as a result, found that the pyrimidinylbenzimidazole and triazinylbenzimidazole derivatives of the present invention (hereinafter referred to as compounds of the present invention) are novel compounds which are not disclosed in any literatures and have outstanding effects as agricultural/horticultural fungicides, and the present invention has been accomplished.

DISCLOSURE OF THE INVENTION

Namely, the present invention resides in a pyrimidinylbenzimidazole or triazinylbenzimidazole derivative represented by the general formula [I]:

wherein A is N or CR

3

, each of R

1

and R

2

which are independent of each other, is a hydrogen atom, a halogen atom, a (C

1

-C

6

) alkyl group, a (C

2

-C

6

) alkenyl group, a (C

2

-C

6

) alkynyl group, a (C

3

-C

6

) cycloalkyl group, a (C

1

-C

4

) haloalkyl group, a (C

1

-C

6

) alkoxy group, a (C

2

-C

6

) alkenyloxy group, a (C

2

-C

6

) alkynyloxy group, a (C

3

-C

6

) cycloalkoxy group, a (C

1

-C

4

) haloalkoxy group, a cyano (C

1

-C

4

) alkyloxy group, a (C

1

-C

4

) alkoxy (C

1

-C

4

) alkyloxy group, a (C

3

-C

6

) cycloalkyl (C

1

-C

4

) alkoxy group, a benzyloxy group [said group may be substituted by a halogen atom, a (C

1

-C

4

) alkyl group or a (C

1

-C

4

) alkoxy group], a (C

1

-C

6

) alkylthio group, a (C

1

-C

4

) alkoxy (C

1

-C

4

) alkyl group, a phenoxy group [said group may be substituted by a halogen atom, a (C

1

-C

4

) alkyl group or a (C

1

-C

4

) alkoxy group], a (C

1

-C

4

) alkylcarbonyl group, a formyl group, a phenyl group, a di(C

1

-C

4

) alkylamino group, a cyano group or a (C

1

-C

6

) alkylsulfonyl group, R

3

is a hydrogen atom, a (C

1

-C

6

) alkyl group, a (C

1

-C

6

) alkoxy group or a halogen atom, X is a hydrogen atom, a halogen atom, a nitro group, a cyano group, a (C

1

-C

6

) alkyl group, a (C

2

-C

6

) alkenyl group, a (C

2

-C

6

) alkynyl group, a (C

3

-C

6

) cycloalkyl group, a benzyl group [said group may be substituted by a halogen atom, a (C

1

-C

4

) alkyl group or a (C

1

-C

4

) alkoxy group], a (C

1

-C

6

) alkoxy group, a (C

2

-C

6

) alkenyloxy group, a (C

2

-C

6

) alkynyloxy group, a (C

1

-C

6

) alkylthio group, a (C

1

-C

6

) alkylsulfonyl group, a phenoxy group, a (C

1

-C

4

) alkoxy (C

1

-C

4

) alkyl group, a (C

1

-C

4

) haloalkyl group, a (C

1

-C

4

) haloalkoxy group, a (C

1

-C

4

) alkylcarbonyl group, a (C

1

-C

4

) alkoxycarbonyl group, an amino group, a mono(C

1

-C

4

) alkylamino group, a di(C

1

-C

4

) alkylamino group, an anilino group or a phenyl group [said group may be substituted by a halogen atom, a (C

1

-C

4

) alkyl group or a (C

1

-C

4

) alkoxy group], Y is a halogen atom, a nitro group, a cyano group, a (C

1

-C

6

) alkyl group, a (C

2

-C

6

) alkenyl group, a (C

2

-C

6

) alkynyl group, a (C

1

-C

6

) alkoxy group, a (C

2

-C

6

) alkenyloxy group, a (C

2

-C

6

) alkynyloxy group, a (C

1

-C

4

) haloalkoxy group, a (C

1

-C

6

) alkylthio group, a (C

1

-C

4

) alkoxy (C

1

-C

4

) alkyl group, a (C

1

-C

4

) haloalkyl group, a (C

1

-C

4

) alkylcarbonyl group, a (C

1

-C

4

) alkoxycarbonyl group, a benzoyl group, an amino group, a mono(C

1

-C

4

) alkylamino group, a di(C

1

-C

4

) alkylamino group, a phenyl group [said group may be substituted by a halogen atom, a (C

1

-C

4

) alkyl group or a (C

1

-C

4

) alkoxy group] or a phenoxy group [said group may be substituted by a halogen atom, a (C

1

-C

4

) alkyl group or a (C

1

-C

4

) alkoxy group], and n is 0 or an integer of from 1 to 3}, an anilinopyrimidine or anilinotriazine derivative, as an intermediate therefor, represented by the general formula [XV]:

(wherein A is N or CR

3

, each of R

1

and R

2

which are independent of each other, is a hydrogen atom, a halogen atom, a (C

1

-C

6

) alkyl group, a (C

2

-C

6

) alkenyl group, a (C

2

-C

6

) alkynyl group, a (C

3

-C

6

) cycloalkyl group, a (C

1

-C

4

) haloalkyl group, a (C

1

-C

6

) alkoxy group, a (C

2

-C

6

) alkenyloxy group, a (C

2

-C

6

) alkynyloxy group, a (C

3

-C

6

) cycloalkoxy group, a (C

1

-C

4

) haloalkoxy group, a cyano (C

1

-C

4

) alkyloxy group, a (C

1

-C

4

) alkoxy (C

1

-C

4

) alkyloxy group, a (C

3

-C

6

) cycloalkyl (C

1

-C

4

) alkoxy group, a benzyloxy group [said group may be substituted by a halogen atom, a (C

1

-C

4

) alkyl group or a (C

1

-C

4

) alkoxy group], a (C

1

-C

6

) alkylthio group, a (C

1

-C

4

) alkoxy (C

1

-C

4

) alkyl group, a phenoxy group [said group may be substituted by a halogen atom, a (C

1

-C

4

) alkyl group or a (C

1

-C

4

) alkoxy group], a (C

1

-C

4

) alkylcarbonyl group, a formyl group, a phenyl group, a di(C

1

-C

4

) alkylamino group, a cyano group or a (C

1

-C

6

) alkylsulfonyl group, R

3

is a hydrogen atom, a (C

1

-C

6

) alkyl group, a (C

1

-C

6

) alkoxy group or a halogen atom, R

5

is an amino group, a nitro group or —NHCOX, X is a hydrogen atom, a halogen atom, a nitro group, a cyano group, a (C

1

-C

6

) alkyl group, a (C

2

-C

6

) alkenyl group, a (C

2

-C

6

) alkynyl group, a (C

3

-C

6

) cycloalkyl group, a benzyl group [said group may be substituted by a halogen atom, a (C

1

-C

4

) alkyl group or a (C

1

-C

4

) alkoxy group], a (C

1

-C

6

) alkoxy group, a (C

2

-C

6

) alkenyloxy group, a (C

2

-C

6

) alkynyloxy group, a (C

2

-C

6

) alkylthio group, a (C

1

-C

6

) alkylsulfonyl group, a phenoxy group, a (C

1

-C

4

) alkoxy (C

1

-C

4

) alkyl group, a (C

1

-C

4

) haloalkyl group, a (C

1

-C

4

) haloalkoxy group, a (C

1

-C

4

) alkylcarbonyl group, a (C

1

-C

4

) alkoxycarbonyl group, an amino group, a mono(C

1

-C

4

) alkylamino group, a di(C

1

-C

4

) alkylamino group, an anilino group or a phenyl group [said group may be substituted by a halogen atom, a (C

1

-C

4

) alkyl group or a (C

1

-C

4

) alkoxy group], Y is a halogen atom, a nitro group, a cyano group, a (C

1

-C

6

) alkyl group, a (C

2

-C

6

) alkenyl group, a (C

2

-C

6

) alkynyl group, a (C

1

-C

6

) alkoxy group, a (C

2

-C

6

) alkenyloxy group, a (C

2

-C

6

) alkynyloxy group, a (C

1

-C

4

) haloalkoxy group, a (C

1

-C

6

) alkylthio group, a (C

1

-C

4

) alkoxy (C

1

-C

4

) alkyl group, a (C

1

-C

4

) haloalkyl group, a (C

1

-C

4

) alkylcarbonyl group, a (C

1

-C

4

) alkoxycarbonyl group, a benzoyl group, an amino group, a mono(C

1

-C

4

) alkylamino group, a di(C

1

-C

4

) alkylamino group, a phenyl group [said group may be substituted by a halogen atom, a (C

1

-C

4

) alkyl group or a (C

1

-C

4

) alkoxy group] or a phenoxy group [said group may be substituted by a halogen atom, a (C

1

-C

4

) alkyl group or a (C

1

-C

4

) alkoxy group], and n is 0 or an integer of from 1 to 3}, and an agricultural/horticultural fungicide containing the pyrimidinylbenzimidazole or triazinylbenzimidazole derivative as the active ingredient.

Now, the symbols and terms used in the present specification will be explained below.

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

A notation such as (C

1

-C

6

) indicates that the carbon number of a substituent following this notation is from 1 to 6 in this case.

The (C

1

-C

6

) alkyl group is a linear or branched alkyl group and may, for example, be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl or 3,3-dimethylbutyl.

The (C

3

-C

6

) cycloalkyl may, for example, be cyclopropyl, cyclopentyl or cyclohexyl.

The (C

1

-C

4

) haloalkyl group is a linear or branched alkyl group substituted by a halogen atom and may, for example, be fluoromethyl, chloromethyl, difluoromethyl, dichloromethyl, trifluoromethyl or pentafluoroethyl.

The (C

2

-C

6

) alkenyl group is a linear or branched alkenyl group and may, for example, be vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-butenyl or 2-butenyl.

The (C

2

-C

6

) alkynyl group is a linear or branched alkynyl group and may, for example, be ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 4-methyl-1-pentynyl or 3-methyl-1-pentynyl.

The (C

1

-C

6

) alkoxy group is an alkyloxy group wherein the alkyl moiety has the above meaning and may, for example, be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isopentyloxy or n-hexyloxy.

The (C

2

-C

6

) alkenyloxy group is an alkenyloxy group wherein the alkenyl moiety has the above meaning, and may, for example, be allyloxy, isopropenyloxy or 2-butenyloxy.

The (C

2

-C

6

) alkynyloxy group is an alkynyloxy group wherein the alkynyl moiety has the above meaning, and may, for example, be 2-propynyloxy, 2-butynyloxy or 3-butynyloxy.

The (C

3

-C

6

) cycloalkoxy group is a cycloalkyloxy group wherein the cycloalkyl moiety has the above meaning, and may, for example, be cyclopropyloxy, cyclopentyloxy or cyclohexyloxy.

The (C

1

-C

4

) haloalkoxy group is a haloalkyloxy group wherein the haloalkyl moiety has the above meaning, and may, for example, be fluoromethoxy, difluoromethoxy, trifluoromethoxy or pentafluoroethoxy.

The (C

1

-C

6

) alkylthio group is an alkylthio group wherein the alkyl moiety has the above meaning, and may, for example, be methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio or n-hexylthio.

The (C

3

-C

6

) cycloalkyl (C

1

-C

4

) alkoxy group may, for example, be cyclopropylmethyloxy, cyclopentylmethyloxy or cyclohexylmethyloxy.

The (C

1

-C

4

) alkoxy (C

1

-C

4

) alkyl group is a group wherein the alkyl moiety and the alkoxy moiety have the above meanings, and may, for example, be a group such as methoxymethyl, ethoxymethyl, isopropoxymethyl, pentyloxymethyl, methoxyethyl or butoxyethyl.

The (C

1

-C

4

) alkoxy (C

1

-C

4

) alkyloxy group is a group wherein the alkyl moiety and the alkoxy moiety have the above meanings, and may, for example, be a group such as methoxymethyloxy, ethoxymethyloxy, isopropoxymethyloxy, pentyloxymethyloxy, methoxyethyloxy or butoxyethyloxy.

The cyano (C

1

-C

4

) alkyloxy group is a group wherein the alkyl moiety has the above meaning, and may, for example, be a group such as cyanomethyloxy, cyanoethyloxy or cyanopropyloxy.

The (C

1

-C

4

) alkylcarbonyl group is an alkylcarbonyl group wherein the alkyl moiety has the above meaning, and may, for example, be a group such as acetyl, propionyl, butyryl, isobutyryl, pivaloyl or hexanoyl.

The (C

1

-C

4

) alkoxycarbonyl group is an alkoxycarbonyl group wherein the alkoxy moiety has the above meaning, and may, for example, be methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl or n-hexyloxycarbonyl.

The mono (C

1

-C

4

) alkylamino group is a monoalkylamino group wherein the alkyl moiety has the above meaning, and may, for example, be methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, sec-butylamino, tert-butylamino or n-hexylamino.

The di (C

1

-C

4

) alkylamino group may, for example, be dimethylamino, diethylamino, dipropylamino or dibutylamino.

The (C

1

-C

6

) alkylsulfonyl group is an alkylsulfonyl group wherein the alkyl moiety has the above meaning, and may, for example, be methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl or n-hexylsulfonyl.

Now, specific examples of the compounds of the present invention represented by the general formula [I] will be disclosed in Tables 1 to 35. However, the compounds of the present invention are not limited to such compounds. Here, the compound numbers will be referred to in the subsequent description.

Symbols in the Tables have the following meanings respectively. Me represents methyl, Et represents ethyl, Pr represents n-propyl, Pr-i represents isopropyl, Bu represents n-butyl, Pr-c represents cyclopropyl, Pn-c represents cyclopentyl, Ph represents phenyl, and Bn represents benzyl. Further, Ph(2-Cl) represents 2-chlorophenyl, and Bn(4-Cl) represents 4-chlorobenzyl, for example.

TABLE 1

Compound

m.p. (° C.)

No.

X

Yn

A

R

1

R

2

or RI (n

D

20

)

I-1

H

H

CH

OMe

OMe

167-169

I-2

Cl

H

CH

OMe

OMe

90-91

I-3

Br

H

CH

OMe

OMe

87-90

I-4

SMe

H

CH

OMe

OMe

135-137

I-5

SO

2

Me

H

CH

OMe

OMe

114-117

I-6

Me

H

CH

OMe

OMe

132-134

I-7

Et

H

CH

OMe

OMe

102-104

I-8

Pr

H

CH

OMe

OMe

107-110

I-9

Pr-i

H

CH

OMe

OMe

70-73

I-10

Pr-c

H

CH

OMe

OMe

62-64

I-11

Bu

H

CH

OMe

OMe

I-12

Bn

H

CH

OMe

OMe

94-96

I-13

Bn(4-Cl)

H

CH

OMe

OMe

122-125

I-14

Bn(4-Me)

H

CH

OMe

OMe

88-90

I-15

Bn(4-OMe)

H

CH

OMe

OMe

I-16

CH═CH

2

H

CH

OMe

OMe

I-17

C≡CH

H

CH

OMe

OMe

I-18

OMe

H

CH

OMe

OMe

121-122

I-19

OCH

2

CH═CH

2

H

CH

OMe

OMe

I-20

OCH

2

C≡CH

H

CH

OMe

OMe

I-21

OCH

2

CF

3

H

CH

OMe

OMe

I-22

CH

2

OEt

H

CH

OMe

OMe

103-104

I-23

CH

2

Cl

H

CH

OMe

OMe

132-135

I-24

CH

2

I

H

CH

OMe

OMe

138-141

I-25

CCl

3

H

CH

OMe

OMe

128-131

I-26

CF

3

H

CH

OMe

OMe

79-80

I-27

C

2

F

5

H

CH

OMe

OMe

97-100

I-28

NH

2

H

CH

OMe

OMe

m.p.: Melting point

RI: Refractive index

TABLE 2

m.p. (° C.)

or

Compound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-29

NHMe

H

CH

OMe

OMe

135-138

I-30

N(Me)

2

H

CH

OMe

OMe

1.5642

I-31

NHPh

H

CH

OMe

OMe

I-32

CO

2

Et

H

CH

OMe

OMe

I-33

COMe

H

CH

OMe

OMe

I-34

Ph

H

CH

OMe

OMe

1.6219

I-35

Ph(4-Cl)

H

CH

OMe

OMe

141-144

I-36

Ph(4-Me)

H

CH

OMe

OMe

I-37

Ph(4-OMe)

H

CH

OMe

OMe

I-38

CN

H

CH

OMe

OMe

167-168

I-39

NO

2

H

CH

OMe

OMe

I-40

H

H

N

OMe

OMe

148-151

I-41

Cl

H

N

OMe

OMe

168-171

I-42

Br

H

N

OMe

OMe

I-43

SMe

H

N

OMe

OMe

I-44

SO

2

Me

H

N

OMe

OMe

I-45

Me

H

N

OMe

OMe

180-182

I-46

Et

H

N

OMe

OMe

I-47

Pr

H

N

OMe

OMe

127-128

I-48

Pr-i

H

N

OMe

OMe

135-141

I-49

Pr-c

H

N

OMe

OMe

I-50

Bu

H

N

OMe

OMe

I-51

Bn

H

N

OMe

OMe

I-52

Bn(4-Cl)

H

N

OMe

OMe

I-53

Bn(4-Me)

H

N

OMe

OMe

I-54

Bn(4-OMe)

H

N

OMe

OMe

I-55

CH═CH

2

H

N

OMe

OMe

I-56

C≡CH

H

N

OMe

OMe

I-57

OMe

H

N

OMe

OMe

I-58

OCH

2

CH═CH

2

H

N

OMe

OMe

I-59

OCH

2

C≡CH

H

N

OMe

OMe

I-60

OCH

2

CF

3

H

N

OMe

OMe

I-61

OPh

H

N

OMe

OMe

I-62

CH

2

OEt

H

N

OMe

OMe

TABLE 3

m.p.

(° C.)

Com-

or

pound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-63

CH

2

Cl

H

N

OMe

OMe

I-64

CH

2

I

H

N

OMe

OMe

I-65

CCl

3

H

N

OMe

OMe

I-66

CF

3

H

N

OMe

OMe

143-

146

I-67

C

2

F

5

H

N

OMe

OMe

I-68

NH

2

H

N

OMe

OMe

261-

264

I-69

NHMe

H

N

OMe

OMe

I-70

N(Me)

2

H

N

OMe

OMe

I-71

NHPh

H

N

OMe

OMe

I-72

CO

2

Et

H

N

OMe

OMe

I-73

COMe

H

N

OMe

OMe

I-74

Ph

H

N

OMe

OMe

I-75

Ph(4-Cl)

H

N

OMe

OMe

I-76

Ph(4-Me)

H

N

OMe

OMe

I-77

Ph(4-

H

N

OMe

OMe

OMe)

I-78

CN

H

N

OMe

OMe

I-79

NO

2

H

N

OMe

OMe

I-80

H

4-Me

CH

OMe

OMe

138-

141

I-81

H

4-Cl

CH

OMe

OMe

I-82

H

5-F

CH

OMe

OMe

175-

178

I-83

H

5-Cl

CH

OMe

OMe

181-

184

I-84

H

5-Br

CH

OMe

OMe

181-

184

I-85

H

5-Me

CH

OMe

OMe

168-

169

I-86

H

5-Bu-t

CH

OMe

OMe

138-

141

I-87

H

5-CF

3

CH

OMe

OMe

173-

174

I-88

H

5-OMe

CH

OMe

OMe

162-

164

I-89

H

5-OEt

CH

OMe

OMe

169-

171

I-90

H

5-OPr

CH

OMe

OMe

I-91

H

5-OCF

3

CH

OMe

OMe

138-

141

I-92

H

5-OCH

2

CH═CH

2

CH

OMe

OMe

I-93

H

5-OCH

2

C≡CH

CH

OMe

OMe

I-94

H

5-OPh

CH

OMe

OMe

I-95

H

5-OPh(4-Cl)

CH

OMe

OMe

I-96

H

5-OPh(4-Me)

CH

OMe

OMe

TABLE 4

m.p. (° C.)

or

Compound

RI

No.

X

Yn

A

R

1

R

2

(N

D

20

)

I-97

H

5-OPh(4-OMe)

CH

OMe

OMe

I-98

H

5-SMe

CH

OMe

OMe

I-99

H

5-CH

2

OMe

CH

OMe

OMe

I-100

H

5-COMe

CH

OMe

OMe

I-101

H

5-COPh

CH

OMe

OMe

223-226

I-102

H

5-CO

2

Et

CH

OMe

OMe

185-188

I-103

H

5-Ph

CH

OMe

OMe

162-165

I-104

H

5-Ph(4-Cl)

CH

OMe

OMe

I-105

H

5-Ph(4-Me)

CH

OMe

OMe

I-106

H

5-Ph(4-OMe)

CH

OMe

OMe

I-107

H

5-NO

2

CH

OMe

OMe

I-108

H

5-NH

2

CH

OMe

OMe

I-109

H

5-NHMe

CH

OMe

OMe

I-110

H

5-N(Me)

2

CH

OMe

OMe

I-111

H

5-CN

CH

OMe

OMe

249-252

I-112

H

6-F

CH

OMe

OMe

192-193

I-113

H

6-Cl

CH

OMe

OMe

199-202

I-114

H

6-Me

CH

OMe

OMe

134-136

I-115

H

6-CF

3

CH

OMe

OMe

192-193

I-116

H

6-OMe

CH

OMe

OMe

184-185

I-117

H

6-CO

2

Et

CH

OMe

OMe

184-187

I-118

H

6-COPh

CH

OMe

OMe

176-179

I-119

H

7-Me

CH

OMe

OMe

134-137

I-120

H

7-Cl

CH

OMe

OMe

I-121

H

5,6-Cl

2

CH

OMe

OMe

217-220

I-122

H

5,6-(Me)

2

CH

OMe

OMe

185-187

I-123

H

5,6-(OMe)

2

CH

OMe

OMe

I-124

H

4-Br,6-CF

3

CH

OMe

OMe

188-191

I-125

H

4-Cl,6-CF

3

CH

OMe

OMe

204-206

I-126

H

4,5,6-F

3

CH

OMe

OMe

I-127

H

4-Me

N

OMe

OMe

I-128

H

4-Cl

N

OMe

OMe

I-129

H

5-F

N

OMe

OMe

I-130

H

5-Cl

N

OMe

OMe

175-178

TABLE 5

m.p. (° C.)

Com-

or

pound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-131

H

5-Br

N

OMe

OMe

>300

I-132

H

5-I

N

OMe

OMe

145-148

I-133

H

5-Me

N

OMe

OMe

177-180

I-134

H

5-Et

N

OMe

OMe

120-123

I-135

H

5-Pr

N

OMe

OMe

101-104

I-136

H

5-Pr-i

N

OMe

OMe

87-90

I-137

H

5-Bu-t

N

OMe

OMe

146-147

I-135

H

5-CH═CH

2

N

OMe

OMe

I-139

H

5-C≡CBu

N

OMe

OMe

I-140

H

5-CF

3

N

OMe

OMe

I-141

H

5-OMe

N

OMe

OMe

164-167

I-142

H

5-OEt

N

OMe

OMe

I-143

H

5-OPr

N

OMe

OMe

I-144

H

5-OCF

3

N

OMe

OMe

I-145

H

5-OCH

2

CH═CH

2

N

OMe

OMe

I-146

H

5-OCH

2

C≡CH

N

OMe

OMe

I-147

H

5-OPh

N

OMe

OMe

I-148

H

5-OPh(4-Cl)

N

OMe

OMe

I-149

H

5-OPh(4-Me)

N

OMe

OMe

I-150

H

5-OPh(4-OMe)

N

OMe

OMe

I-151

H

5-SMe

N

OMe

OMe

I-152

H

5-CH

2

OMe

N

OMe

OMe

I-153

H

5-COMe

N

OMe

OMe

I-154

H

5-COPh

N

OMe

OMe

I-155

H

5-CO

2

Et

N

OMe

OMe

I-156

H

5-Ph

N

OMe

OMe

I-157

H

5-Ph(4-Cl)

N

OMe

OMe

I-158

H

5-Ph(4-Me)

N

OMe

OMe

I-159

H

5-Ph(4-OMe)

N

OMe

OMe

I-160

H

5-NO

2

N

OMe

OMe

210-213

I-161

H

5-NH

2

N

OMe

OMe

I-162

H

5-NHMe

N

OMe

OMe

I-163

H

5-N(Me)

2

N

OMe

OMe

I-164

H

5-CN

N

OMe

OMe

TABLE 6

m.p. (° C.)

or

Compound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-165

H

6-F

N

OMe

OMe

I-166

H

6-Cl

N

OMe

OMe

I-167

H

6-Me

N

OMe

OMe

I-168

H

6-CF

3

N

OMe

OMe

I-169

H

6-OMe

N

OMe

OMe

I-170

H

6-NO

2

N

OMe

OMe

>300

I-171

H

6-CO

2

Et

N

OMe

OMe

I-172

H

6-COPh

N

OMe

OMe

I-173

H

7-Me

N

OMe

OMe

I-174

H

7-Cl

N

OMe

OMe

I-175

H

5,6-Cl

2

N

OMe

OMe

176-179

I-176

H

5,6-(Me)

2

N

OMe

OMe

193-196

I-177

H

5,6-(OMe)

2

N

OMe

OMe

I-178

H

4-Br,6-CF3

N

OMe

OMe

I-179

H

4-Cl,6-CF

3

N

OMe

OMe

I-180

H

4,5,6-F

3

N

OMe

OMe

I-181

Me

4-Me

CH

OMe

OMe

127-130

I-182

Me

4-Cl

CH

OMe

OMe

I-183

Me

5-F

CH

OMe

OMe

163-165

I-184

Me

5-Cl

CH

OMe

OMe

153-156

I-185

Me

5-Br

CH

OMe

OMe

180-183

I-186

Me

5-Me

CH

OMe

OMe

163-166

I-187

Me

5-Bu-t

CH

OMe

OMe

126-129

I-188

Me

5-CF

3

CH

OMe

OMe

129-132

I-189

Me

5-OMe

CH

OMe

OMe

190-193

I-190

Me

5-OEt

CH

OMe

OMe

211-214

I-191

Me

5-OPr

CH

OMe

OMe

I-192

Me

5-OCF

3

CH

OMe

OMe

137-139

I-193

Me

5-OPh

CH

OMe

OMe

I-194

Me

5-CO

2

Et

CH

OMe

OMe

173-176

I-195

Me

5-COPh

CH

OMe

OMe

169-171

I-196

Me

5-Ph

CH

OMe

OMe

164-166

I-197

Me

5-NH

2

CH

OMe

OMe

I-198

Me

5-N(Me)

2

CH

OMe

OMe

TABLE 7

m.p. (° C.)

or

Compound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-199

Me

5-CN

CH

OMe

OMe

211-214

I-200

Me

6-F

CH

OMe

OMe

162-163

I-201

Me

6-Cl

CH

OMe

OMe

165-166

I-202

Me

6-Me

CH

OMe

OMe

128-131

I-203

Me

6-CF

3

CH

OMe

OMe

162-165

I-204

Me

6-OMe

CH

OMe

OMe

158-161

I-205

Me

6-OEt

CH

OMe

OMe

I-206

Me

6-OPr

CH

OMe

OMe

I-207

Me

6-CO

2

Et

CH

OMe

OMe

184-187

I-208

Me

6-COPh

CH

OMe

OMe

179-182

I-209

Me

5,6-Cl

2

CH

OMe

OMe

204-206

I-210

Me

5,6-(Me)

2

CH

OMe

OMe

169-172

I-211

Me

5,6-(OMe)

2

CH

OMe

OMe

I-212

Me

4-Me

N

OMe

OMe

180-182

I-213

Me

4-Cl

N

OMe

OMe

I-214

Me

5-F

N

OMe

OMe

185-188

I-215

Me

5-Cl

N

OMe

OMe

173-176

I-216

Me

5-Br

N

OMe

OMe

>300

I-217

Me

5-I

N

OMe

OMe

161-164

I-218

Me

5-Me

N

OMe

OMe

192-195

I-219

Me

5-Et

N

OMe

OMe

113-116

I-220

Me

5-Pr

N

OMe

OMe

128-131

I-221

Me

5-Pr-i

N

OMe

OMe

124-125

I-222

Me

5-Bu-t

N

OMe

OMe

143-144

I-223

Me

5-CH═CH

2

N

OMe

OMe

I-224

Me

5-C≡CBu

N

OMe

OMe

111-114

I-225

Me

5-CF

3

N

OMe

OMe

167-170

I-226

Me

5-OMe

N

OMe

OMe

161-164

1-227

Me

5-OEt

N

OMe

OMe

I 228

Me

5-OPr

N

OMe

OMe

I-229

Me

5-OCF

3

N

OMe

OMe

128-131

I-230

Me

5-OPh

N

OMe

OMe

I-231

Me

5-SMe

N

OMe

OMe

I-232

Me

5-CO

2

Me

N

OMe

OMe

148-151

TABLE 8

m.p. (° C.)

or

Compound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-233

Me

5-CO

2

Et

N

OMe

OMe

I-234

Me

5-COMe

N

OMe

OMe

155-158

I-235

Me

5-COPh

N

OMe

OMe

163-166

I-236

Me

5-Ph

N

OMe

OMe

I-237

Me

5-NH

2

N

OMe

OMe

I-238

Me

5-N(Me)

2

N

OMe

OMe

I-239

Me

5-CN

N

OMe

OMe

188-191

I-240

Me

6-F

N

OMe

OMe

I-241

Me

6-Cl

N

OMe

OMe

I-242

Me

6-Me

N

OMe

OMe

130-133

I-243

Me

6-CF

3

N

OMe

OMe

I-244

Me

6-OMe

N

OMe

OMe

I-245

Me

6-OEt

N

OMe

OMe

I-246

Me

6-OPr

N

OMe

OMe

I-247

Me

6-CO

2

Et

N

OMe

OMe

I-248

Me

6-COPh

N

OMe

OMe

I-249

Me

5,6-Cl

2

N

OMe

OMe

I-250

Me

4,6-(Me)

2

N

OMe

OMe

172-175

I-251

Me

5,6-(Me)

2

N

OMe

OMe

165-168

I-252

Me

5,6-(OMe)

2

N

OMe

OMe

I-253

Cl

4-Me

CH

OMe

OMe

I-254

Cl

4-Cl

CH

OMe

OMe

I-255

Cl

5-F

CH

OMe

OMe

139-142

I-256

Cl

5-Cl

CH

OMe

OMe

159-161

I-257

Cl

5-Br

CH

OMe

OMe

I-258

Cl

5-Me

CH

OMe

OMe

145-148

I-259

Cl

5-CF

3

CH

OMe

OMe

136-139

I-260

Cl

5-OMe

CH

OMe

OMe

148-150

I-261

Cl

5-OEt

CH

OMe

OMe

187-190

I-262

Cl

5-OPr

CH

OMe

OMe

I-263

Cl

5-OCF

3

CH

OMe

OMe

102-105

I-264

Cl

5-OPh

CH

OMe

OMe

I-265

Cl

5-COPh

CH

OMe

OMe

I-266

Cl

5-Ph

CH

OMe

OMe

TABLE 9

m.p. (° C.)

or

Compound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-267

Cl

5-NH

2

CH

OMe

OMe

I-268

Cl

5-N(Me)

2

CH

OMe

OMe

I-269

Cl

5-CN

CH

OMe

OMe

I-270

Cl

6-F

CH

OMe

OMe

I-271

Cl

6-Cl

CH

OMe

OMe

163-164

I-272

Cl

6-Me

CH

OMe

OMe

98-101

I-273

Cl

5,6-(OMe)

2

CH

OMe

OMe

I-274

Cl

4-Me

N

OMe

OMe

I-275

Cl

4-Cl

N

OMe

OMe

I-276

Cl

5-F

N

OMe

OMe

I-277

Cl

5-Cl

N

OMe

OMe

146-149

I-278

Cl

5-Br

N

OMe

OMe

I-279

Cl

5-Me

N

OMe

OMe

159-162

I-280

Cl

5-CF

3

N

OMe

OMe

I-281

Cl

5-OMe

N

OMe

OMe

I-282

Cl

5-OEt

N

OMe

OMe

I-283

Cl

5-OPr

N

OMe

OMe

I-284

Cl

5-OCF

3

N

OMe

OMe

I-285

Cl

5-OPh

N

OMe

OMe

I-286

Cl

5-COPh

N

OMe

OMe

I-287

Cl

5-Ph

N

OMe

OMe

I-288

Cl

5-NH

2

N

OMe

OMe

I-289

Cl

5-N(Me)

2

N

OMe

OMe

I-290

Cl

5-CN

N

OMe

OMe

I-291

Cl

6-F

N

OMe

OMe

I-292

Cl

6-Cl

N

OMe

OMe

I-293

Cl

6-Me

N

OMe

OMe

I-294

Cl

5,6-(OMe)

2

N

OMe

OMe

I-295

CF

3

5-F

CH

OMe

OMe

133-136

I-296

CF

3

5-Cl

CH

OMe

OMe

114-116

I-297

CF

3

5-Br

CH

OMe

OMe

I-298

CF

3

5-Me

CH

OMe

OMe

93-96

I-299

CF

3

5-CF

3

CH

OMe

OMe

78-79

I-300

CF

3

5-OMe

CH

OMe

OMe

129-132

TABLE 10

m.p. (° C.)

or

Compound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-301

CF

3

5-OEt

CH

OMe

OMe

151-154

I-302

CF

3

5-OPr

CH

OMe

OMe

I-303

CF

3

5-N(Me)

2

CH

OMe

OMe

I-304

CF

3

5-CN

CH

OMe

OMe

I-305

CF

3

6-F

CH

OMe

OMe

I-306

CF

3

6-Cl

CH

OMe

OMe

I-307

CF

3

6-Me

CH

OMe

OMe

132-135

I-308

CF

3

5,6-(OMe)

2

CH

OMe

OMe

I-309

CF

3

5-F

N

OMe

OMe

170-173

I-310

CF

3

5-Cl

N

OMe

OMe

135-138

I-311

CF

3

5-Br

N

OMe

OMe

111-114

I-312

CF

3

5-Me

N

OMe

OMe

137-140

I-313

CF

3

5-Et

N

OMe

OMe

104-107

I-314

CF

3

5-Pr

N

OMe

OMe

89-92

I-315

CF

3

5-Pr-i

N

OMe

OMe

118-121

I-316

CF

3

5-Bu-t

N

OMe

OMe

113-116

I-317

CF

3

5-CF

3

N

OMe

OMe

I-318

CF

3

5-OMe

N

OMe

OMe

165-168

I-319

CF

3

5-OEt

N

OMe

OMe

I-32O

CF

3

5-OPr

N

OMe

OMe

I-321

CF

3

5-OCF

3

N

OMe

OMe

187-190

I-322

CF

3

5-SMe

N

OMe

OMe

I-323

CF

3

5-NHMe

N

OMe

OMe

I-324

CF

3

5-N(Me)

2

N

OMe

OMe

I-325

CF

3

5-CN

N

OMe

OMe

188-191

I-326

CF

3

5-CO

2

Me

N

OMe

OMe

126-129

I-327

CF

3

5-I

N

OMe

OMe

115-118

I-328

CF

3

6-F

N

OMe

OMe

I-329

CF

3

6-Cl

N

OMe

OMe

I-330

CF

3

6-Me

N

OMe

OMe

I-331

CF

3

5,6-(OMe)

2

N

OMe

OMe

I-332

Et

5-F

CH

OMe

OMe

135-138

I-333

Et

5-Cl

CH

OMe

OMe

137-140

I-334

Et

5-Me

CH

OMe

OMe

120-122

TABLE 11

m.p. (° C.)

or

Compound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-335

Et

5-CF

3

CH

OMe

OMe

117-118

I-336

Et

5-OMe

CH

OMe

OMe

118-120

I-337

Et

5-OEt

CH

OMe

OMe

I-338

Et

5-OPr

CH

OMe

OMe

I-339

Et

5-N(Me)

2

CH

OMe

OMe

I-340

Et

5-CN

CH

OMe

OMe

I-341

Et

6-F

CH

OMe

OMe

I-342

Et

6-Cl

CH

OMe

OMe

I-343

Et

6-Me

CH

OMe

OMe

I-344

Et

5,6-(OMe)

2

CH

OMe

OMe

I-345

Et

5-F

N

OMe

OMe

I-346

Et

5-Cl

N

OMe

OMe

125-128

I-347

Et

5-Me

N

OMe

OMe

I-348

Et

5-CF

3

N

OMe

OMe

I-349

Et

5-OMe

N

OMe

OMe

I-350

Et

5-OEt

N

OMe

OMe

I-351

Et

5-OPr

N

OMe

OMe

I-352

Et

5-N(Me)

2

N

OMe

OMe

I-353

Et

5-CN

N

OMe

OMe

I-354

Et

6-F

N

OMe

OMe

I-355

Et

6-Cl

N

OMe

OMe

I-356

Et

6-Me

N

OMe

OMe

I-357

Et

5,6-(OMe)

2

N

OMe

OMe

I-358

Pr

5-Cl

N

OMe

OMe

128-131

I-359

Pr-i

5-Cl

N

OMe

OMe

160-163

I-360

Pr-c

5-Cl

N

OMe

OMe

146-149

I-361

NH

2

5-F

CH

OMe

OMe

236-239

I-362

NH

2

5-Me

CH

OMe

OMe

>300

I-363

NH

2

5-CF

3

CH

OMe

OMe

268-271

I-364

NH

2

5-OMe

CH

OMe

OMe

232-235

I-365

NH

2

5-OEt

CH

OMe

OMe

239-242

I-366

NH

2

6-Me

CH

OMe

OMe

>300

I-367

NH

2

5,6-(OMe)

2

CH

OMe

OMe

I-368

NH

2

5-Cl

N

OMe

OMe

293-296

TABLE 12

m.p. (° C.)

Com-

or

pound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-369

NH

2

5-Me

N

OMe

OMe

272-275

I-370

NH

2

5-CF

3

N

OMe

OMe

I-371

NH

2

5-OMe

N

OMe

OMe

I-372

NH

2

5-OEt

N

OMe

OMe

I-373

NH

2

6-Me

N

OMe

OMe

I-374

NH

2

5,6-(OMe)

2

N

OMe

OMe

I-375

NHMe

5-Cl

N

OMe

OMe

238-241

I-376

N(Me)

2

5-Cl

N

OMe

OMe

66-69

I-377

CH

2

OMe

5-Cl

N

OMe

OMe

105-108

I-378

Ph

5-Cl

N

OMe

OMe

137-140

I-379

Bn

5-Cl

N

OMe

OMe

192-195

I-380

CN

5-Cl

CH

OMe

OMe

223-226

I-381

CN

5-Me

CH

OMe

OMe

229-231

I-382

CN

5-CF

3

CH

OMe

OMe

I-383

CN

5-OMe

CH

OMe

OMe

I-384

CN

5-Cl

N

OMe

OMe

I-385

CN

5-Me

N

OMe

OMe

I-386

CN

5-CF

3

N

OMe

OMe

I-387

CN

5-OMe

N

OMe

OMe

I-388

SMe

5-Cl

CH

OMe

OMe

184-187

I-389

SMe

5-Me

CH

OMe

OMe

155-158

I-390

SMe

5-CF

3

CH

OMe

OMe

I-391

SMe

5-OMe

CH

OMe

OMe

I-392

SMe

6-Cl

CH

OMe

OMe

I-393

SMe

6-Me

CH

OMe

OMe

I-394

SMe

5-Cl

N

OMe

OMe

135-138

I-395

SMe

5-Me

N

OMe

OMe

I-396

SMe

5-CF

3

N

OMe

OMe

I-397

SMe

5-OMe

N

OMe

OMe

I-398

SMe

6-Cl

N

OMe

OMe

I-399

SMe

6-Me

N

OMe

OMe

I-400

CCl

3

5-Cl

CH

OMe

OMe

132-134

I-401

CCl

3

5-Me

CH

OMe

OMe

I-402

CCl

3

5-OMe

CH

OMe

OMe

TABLE 13

m.p. (° C.)

or

Compound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-403

CCl

3

6-Cl

CH

OMe

OMe

I-404

CCl

3

6-Me

CH

OMe

OMe

136-139

I-405

CCl

3

5-Cl

N

OMe

OMe

123-126

I-406

CCl

3

5-Me

N

OMe

OMe

140-151

I-407

CCl

3

5-OMe

N

OMe

OMe

I-408

CCl

3

5-Br

N

OMe

OMe

I-409

CCl

3

6-Cl

N

OMe

OMe

I-410

CCl

3

6-Me

N

OMe

OMe

I-411

CF

2

Cl

5-Me

N

OMe

OMe

109-111

I-412

CF

2

Cl

5-Cl

N

OMe

OMe

86-89

I-413

CF

2

Cl

5-Br

N

OMe

OMe

I-414

CF

2

Cl

5-OMe

N

OMe

OMe

I-415

CH

2

Cl

5-Me

N

OMe

OMe

143-145

I-416

CH

2

Cl

5-Cl

N

OMe

OMe

160-161

I-417

CH

2

Cl

5-Br

N

OMe

OMe

I-418

CH

2

Cl

5-OMe

N

OMe

OMe

I-419

C

2

F

5

5-Me

N

OMe

OMe

I-420

C

2

F

5

5-Cl

N

OMe

OMe

I-421

C

2

F

5

5-Br

N

OMe

OMe

I-422

C

2

F

5

5-OMe

N

OMe

OMe

I-423

SO

2

Me

5-Cl

CH

OMe

OMe

149-152

I-424

SO

2

Me

5-Me

CH

OMe

OMe

176-177

I-425

SO

2

Me

6-Me

CH

OMe

OMe

I-426

SO

2

Me

5-Cl

N

OMe

OMe

I-427

SO

2

Me

5-Me

N

OMe

OMe

I-428

SO

2

Me

6-Me

N

OMe

OMe

I-429

OMe

5-Cl

CH

OMe

OMe

182-185

I-430

OMe

6-Cl

CH

OMe

OMe

178-180

I-431

OMe

5-Cl

N

OMe

OMe

I-432

OMe

6-Cl

N

OMe

OMe

I-433

H

H

N

OMe

OEt

I-434

H

5-Cl

N

OMe

OEt

I-435

H

5-Br

N

OMe

OEt

194-196

I-436

H

5-Me

N

OMe

OEt

TABLE 14

m.p. (° C.)

or

Compound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-437

Me

H

N

OMe

OEt

I-438

Me

5-Cl

N

OMe

OEt

153-156

I-439

Me

5-Br

N

OMe

OEt

143-145

I-440

Me

5-Me

N

OMe

OEt

155-156

I-441

Cl

5-Cl

N

OMe

OEt

I-442

Cl

5-Br

N

OMe

OEt

I-443

Cl

5-Me

N

OMe

OEt

I-444

CF

3

H

N

OMe

OEt

I-445

CF

3

5-Me

N

OMe

OEt

147-150

I-446

CF

3

5-Cl

N

OMe

OEt

149-151

I-447

CF

3

5-Br

N

OMe

OEt

138-139

I-448

CF

2

Cl

5-Cl

N

OMe

OEt

I-449

CF

2

Cl

5-Br

N

OMe

OEt

I-450

CF

2

Cl

5-Me

N

OMe

OEt

I-451

CH

2

Cl

5-Cl

N

OMe

OEt

I-452

CH

2

Cl

5-Br

N

OMe

OEt

I-453

CH

2

Cl

5-Me

N

OMe

OEt

I-454

C

2

F

5

5-Cl

N

OMe

OEt

I-455

C

2

F

5

5-Br

N

OMe

OEt

I-456

C

2

F

5

5-Me

N

OMe

OEt

I-457

H

H

CH

OEt

OEt

122-124

I-458

Cl

H

CH

OEt

OEt

79-82

I-459

Br

H

CH

OEt

OEt

I-460

SMe

H

CH

OEt

OEt

122-125

I-461

Me

H

CH

OEt

OEt

88-91

I-462

Et

H

CH

OEt

OEt

90-93

I-463

OMe

H

CH

OEt

OEt

87-89

I-464

OEt

H

CH

OEt

OEt

96-99

I-465

CF

3

H

CH

OEt

OEt

90-92

I-466

NH

2

H

CH

OEt

OEt

222-225

I-467

CN

H

CH

OEt

OEt

153-156

I-468

H

H

N

OEt

OEt

I-469

Cl

H

N

OEt

OEt

I-470

Br

H

N

OEt

OEt

TABLE 15

m.p. (° C.)

or

Compound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-471

SMe

H

N

OEt

OEt

I-472

Me

H

N

OEt

OEt

I-473

Et

H

N

OEt

OEt

I-474

OMe

H

N

OEt

OEt

I-475

OEt

H

N

OEt

OEt

I-476

CF

3

H

N

OEt

OEt

I-477

NH

2

H

N

OEt

OEt

I-478

CN

H

N

OEt

OEt

I-479

H

5-F

CH

OEt

OEt

156-159

I-480

H

5-Cl

CH

OEt

OEt

177-180

I-481

H

5-Br

CH

OEt

OEt

I-482

H

5-Me

CH

OEt

OEt

135-138

I-483

H

5-CF

3

CH

OEt

OEt

165-168

I-484

H

5-OMe

CH

OEt

OEt

I-485

H

5-OEt

CH

OEt

OEt

I-486

H

6-Cl

CH

OEt

OEt

164-167

I-487

H

5,6-(OMe)

2

CH

OEt

OEt

I-488

H

5-F

N

OEt

OEt

I-489

H

5-Cl

N

OEt

OEt

I-490

H

5-Br

N

OEt

OEt

170-173

I-491

H

5-Me

N

OEt

OEt

I-492

H

5-Bu-t

N

OEt

OEt

107-110

I-493

H

5-CF

3

N

OEt

OEt

I-494

H

5-OMe

N

OEt

OEt

I-495

H

5-OEt

N

OEt

OEt

I-496

H

6-Cl

N

OEt

OEt

I-497

H

5,6-(OMe)

2

N

OEt

OEt

I-498

Me

5-F

CH

OEt

OEt

131-133

I-499

Me

5-Cl

CH

OEt

OEt

171-174

I-500

Me

5-Br

CH

OEt

OEt

I-501

Me

5-Me

CH

OEt

OEt

119-122

I-502

Me

5-CF

3

CH

OEt

OEt

131-134

I-503

Me

5-OMe

CH

OEt

OEt

141-144

I-504

Me

5-OEt

CH

OEt

OEt

TABLE 16

m.p. (° C.)

or

Compound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-505

Me

5-OCF

3

CH

OEt

OEt

I-506

Me

5-CN

CH

OEt

OEt

I-507

Me

6-F

CH

OEt

OEt

133-134

I-508

Me

6-Cl

CH

OEt

OEt

146-149

I-509

Me

6-Me

CH

OEt

OEt

I-510

Me

6-CF

3

CH

OEt

OEt

138-141

I-511

Me

6-OMe

CH

OEt

OEt

135-138

I-512

Me

5,6-(OMe)

2

CH

OEt

OEt

I-513

Me

5-F

N

OEt

OEt

I-514

Me

5-Cl

N

OEt

OEt

175-178

I-515

Me

5-Br

N

OEt

OEt

169-172

I-516

Me

5-Me

N

OEt

OEt

141-144

I-517

Me

5-Bu-t

N

OEt

OEt

107-109

I-518

Me

5-CF

3

N

OEt

OEt

I-519

Me

5-OMe

N

OEt

OEt

I-520

Me

5-OEt

N

OEt

OEt

I-521

Me

5-OCF

3

N

OEt

OEt

I-522

Me

5-CN

N

OEt

OEt

I-523

Me

6-F

N

OEt

OEt

I-524

Me

6-Cl

N

OEt

OEt

I-525

Me

6-Me

N

OEt

OEt

I-526

Me

6-CF

3

N

OEt

OEt

I-527

Me

6-OMe

N

OEt

OEt

I-528

Me

5,6-(OMe)

2

N

OEt

OEt

I-529

Cl

5-Cl

CH

OEt

OEt

I-530

Cl

5-Me

CH

OEt

OEt

101-103

I-531

Cl

5-OMe

CH

OEt

OEt

153-156

I-532

Cl

5-OEt

CH

OEt

OEt

I-533

Cl

5,6-(OMe)

2

CH

OEt

OEt

I-534

Cl

5-Cl

N

OEt

OEt

130-133

I-535

Cl

5-Me

N

OEt

OEt

I-536

Cl

5-OMe

N

OEt

OEt

I-537

Cl

5-OEt

N

OEt

OEt

I-538

Cl

5,6-(OMe)

2

N

OEt

OEt

TABLE 17

m.p. (° C.)

Com-

or

pound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-539

CF

3

5-Me

CH

OEt

OEt

I-540

CF

3

5-OMe

CH

OEt

OEt

I-541

CF

3

5,6-(OMe)

2

CH

OEt

OEt

I-542

CF

3

H

N

OEt

OEt

I-543

CF

3

5-Me

N

OEt

OEt

163-165

I-544

CF

3

5-OMe

N

OEt

OEt

140-143

I-545

CF

3

5-Cl

N

OEt

OEt

138-141

I-546

CF

3

5-Br

N

OEt

OEt

120-123

I-547

Et

5-Me

CH

OEt

OEt

I-548

Et

5-OMe

CH

OEt

OEt

I-549

Et

5,6-(OMe)

2

CH

OEt

OEt

I-550

CCl

3

5-Cl

N

OEt

OEt

110-113

I-551

CCl

3

5-Br

N

OEt

OEt

I-552

CCl

3

5-Me

N

OEt

OEt

I-553

CCl

3

5-OMe

N

OEt

OEt

I-554

CF

2

Cl

5-Cl

N

OEt

OEt

I-555

CF

2

Cl

5-Br

N

OEt

OEt

I-556

CF

2

Cl

5-Me

N

OEt

OEt

I-557

CH

2

Cl

5-Cl

N

OEt

OEt

I-558

CH

2

Cl

5-Br

N

OEt

OEt

I-559

CH

2

Cl

5-Me

N

OEt

OEt

I-560

C

2

F

5

5-Cl

N

OEt

OEt

I-561

C

2

F

5

5-Br

N

OEt

OEt

I-562

C

2

F

5

5-Me

N

OEt

OEt

I-563

CN

5-Cl

CH

OEt

OEt

170-172

I-564

CN

5-OMe

CH

OEt

OEt

I-565

CN

5,6-(OMe)

2

CH

OEt

OEt

I-566

CN

5-Me

N

OEt

OEt

I-567

CN

5-OMe

N

OEt

OEt

I-568

CN

5-Cl

N

OEt

OEt

I-569

SMe

5-Cl

CH

OEt

OEt

167-169

I-570

SMe

5-Me

CH

OEt

OEt

I-571

SMe

5-Cl

N

OEt

OEt

I-572

SMe

5-Me

N

OEt

OEt

TABLE 18

m.p. (° C.)

or

Compound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-573

SO

2

Me

5-Cl

CH

OEt

OEt

167-170

I-574

SO

2

Me

5-Me

CH

OEt

OEt

I-575

OMe

5-Cl

CH

OEt

OEt

143-146

I-576

H

H

CH

OPr

OPr

89-90

I-577

H

H

N

OPr

OPr

I-578

H

5-Cl

N

OPr

OPr

I-579

H

5-Br

N

OPr

OPr

I-580

Me

5-Cl

N

OPr

OPr

128-131

I-581

Me

5-Br

N

OPr

OPr

I-582

Me

5-Me

N

OPr

OPr

I-583

CF

3

5-Cl

N

OPr

OPr

71-74

I-584

CF

3

5-Br

N

OPr

OPr

I-585

CF

3

5-Me

N

OPr

OPr

I-586

H

H

CH

OPr-i

OPr-i

115-117

I-587

Me

5-Cl

CH

OPr-i

OPr-i

I-588

Me

5-Me

CH

OPr-i

OPr-i

I-589

H

H

N

OPr-i

OPr-i

I-590

H

5-Cl

N

OPr-i

OPr-i

I-591

H

5-Br

N

OPr-i

OPr-i

I-592

Me

5-Cl

N

OPr-i

OPr-i

85-88

I-593

Me

5-Br

N

OPr-i

OPr-i

I-594

Me

5-Me

N

OPr-i

OPr-i

I-595

CF

3

5-Cl

N

OPr-i

OPr-i

97-100

I-596

CF

3

5-Br

N

OPr-i

OPr-i

I-597

CF

3

5-Me

N

OPr-i

OPr-i

I-598

H

H

N

OCH

2

CH═CH

2

OCH

2

CH═CH

2

I-599

H

5-Cl

N

OCH

2

CH═CH

2

OCH

2

CH═CH

2

I-600

H

5-Br

N

OCH

2

CH═CH

2

OCH

2

CH═CH

2

I-601

Me

5-Cl

N

OCH

2

CH═CH

2

OCH

2

CH═CH

2

158-161

I-602

Me

5-Br

N

OCH

2

CH═CH

2

OCH

2

CH═CH

2

I-603

Me

5-Me

N

OCH

2

CH═CH

2

OCH

2

CH═CH

2

I-604

CF

3

5-Cl

N

OCH

2

CH═CH

2

OCH

2

CH═CH

2

I-605

CF

3

5-Br

N

OCH

2

CH═CH

2

OCH

2

CH═CH

2

I-606

CF

3

5-Me

N

OCH

2

CH═CH

2

OCH

2

CH═CH

2

TABLE 19

m.p.

(° C.)

Com-

or

pound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-607

H

H

N

OCH

2

C≡CH

OCH

2

C≡CH

I-608

H

5-Cl

N

OCH

2

C≡CH

OCH

2

C≡CH

I-609

H

5-Br

N

OCH

2

C≡CH

OCH

2

C≡CH

I-610

Me

5-Cl

N

OCH

2

C≡CH

OCH

2

C≡CH

I-611

Me

5-Br

N

OCH

2

C≡CH

OCH

2

C≡CH

I-612

Me

5-Me

N

OCH

2

C≡CH

OCH

2

C≡CH

I-613

CF

3

5-Cl

N

OCH

2

C≡CH

OCH

2

C≡CH

I-614

CF

3

5-Br

N

OCH

2

C≡CH

OCH

2

C≡CH

I-615

CF

3

5-Me

N

OCH

2

C≡CH

OCH

2

C≡CH

I-616

Me

5-Cl

CH

OCH

2

CN

OCH

2

CN

I-617

Me

5-Me

CH

OCH

2

CN

OCH

2

CN

I-618

H

5-Br

N

OCH

2

CN

OCH

2

CN

I-619

Me

5-Cl

N

OCH

2

CN

OCH

2

CN

I-620

Me

5-Br

N

OCH

2

CN

OCH

2

CN

I-621

Me

5-Me

N

OCH

2

CN

OCH

2

CN

I-622

CF

3

5-Cl

N

OCH

2

CN

OCH

2

CN

I-623

CF

3

5-Br

N

OCH

2

CN

OCH

2

CN

I-624

CF

3

5-Me

N

OCH

2

CN

OCH

2

CN

I-625

Me

5-Cl

CH

OCH

2

CH

2

OMe

OCH

2

CH

2

OMe

I-626

Me

5-Me

CH

OCH

2

CH

2

OMe

OCH

2

CH

2

OMe

I-627

H

5-Br

N

OCH

2

CH

2

OMe

OCH

2

CH

2

OMe

I-628

Me

5-Cl

N

OCH

2

CH

2

OMe

OCH

2

CH

2

OMe

I-629

Me

5-Br

N

OCH

2

CH

2

OMe

OCH

2

CH

2

OMe

I-630

Me

5-Me

N

OCH

2

CH

2

OMe

OCH

2

CH

2

OMe

I-631

CF

3

5-Cl

N

OCH

2

CH

2

OMe

OCH

2

CH

2

OMe

I-632

CF

3

5-Br

N

OCH

2

CH

2

OMe

OCH

2

CH

2

OMe

I-633

CF

3

5-Me

N

OCH

2

CH

2

OMe

OCH

2

CH

2

OMe

I-634

H

5-Br

N

OCH

2

Pr-c

OCH

2

Pr-c

I-635

Me

5-Cl

N

OCH

2

Pr-c

OCH

2

Pr-c

I-636

Me

5-Br

N

OCH

2

Pr-c

OCH

2

Pr-c

I-637

Me

5-Me

N

OCH

2

Pr-c

OCH

2

Pr-c

I-638

CF

3

5-Cl

N

OCH

2

Pr-c

OCH

2

Pr-c

I-639

CF

3

5-Br

N

OCH

2

Pr-c

OCH

2

Pr-c

I-640

CF

3

5-Me

N

OCH

2

Pr-c

OCH

2

Pr-c

TABLE 20

m.p.

(° C.)

Com-

or

pound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-641

Me

5-Me

CH

OCH

2

CH

2

Cl

OCH

2

CH

2

Cl

I-642

Me

5-Cl

CH

OCH

2

CH

2

Cl

OCH

2

CH

2

Cl

I-643

Me

5-Me

N

OCH

2

CH

2

Cl

OCH

2

CH

2

Cl

I-644

Me

5-Cl

N

OCH

2

CH

2

Cl

OCH

2

CH

2

Cl

I-645

CF

3

5-Me

N

OCH

2

CH

2

Cl

OCH

2

CH

2

Cl

I-646

CF

3

5-Cl

N

OCH

2

CH

2

Cl

OCH

2

CH

2

Cl

I-647

Me

5-Cl

N

OCH

2

CH

2

F

OCH

2

CH

2

F

I-648

Me

5-Me

N

OCH

2

CH

2

F

OCH

2

CH

2

F

I-649

CF

3

5-Me

N

OCH

2

CH

2

F

OCH

2

CH

2

F

I-650

CF

3

5-Cl

N

OCH

2

CH

2

F

OCH

2

CH

2

F

I-651

Me

5-Cl

N

OCH

2

CF

3

OCH

2

CF

3

I-652

Me

5-Me

N

OCH

2

CF

3

OCH

2

CF

3

I-653

CF

3

5-Me

N

OCH

2

CF

3

OCH

2

CF

3

I-654

CF

3

5-Cl

N

OCH

2

CF

3

OCH

2

CF

3

I-655

H

H

CH

OBn

OBn

I-656

H

H

N

OBn

OBn

I-657

H

H

N

OBn(4-Cl)

OBn(4-Cl)

I-658

H

H

N

OBn(4-Me)

OBn(4-Me)

I-659

H

H

N

OBn(4-

OBn(4-

OMe)

OMe)

I-660

H

H

CH

OMe

OPh

131-132

I-661

H

H

N

OMe

OPh

I-662

H

H

N

OMe

OPh(4-Cl)

I-663

H

H

N

OMe

OPh(4-Me)

I-664

H

H

N

OMe

OPh(4-OMe)

I-665

H

H

CH

OMe

OCHF

2

138-139

I-666

H

H

N

OMe

OCHF

2

I-667

H

H

CH

OMe

H

114-116

I-668

Me

H

CH

OMe

H

I-669

H

5-Cl

CH

OMe

H

173-176

I-670

H

5-Me

CH

OMe

H

140-142

I-671

Me

5-Cl

CH

OMe

H

127-130

I-672

Me

5-Me

CH

OMe

H

113-114

I-673

Me

5-CF

3

CH

OMe

H

I-674

Me

5-OMe

CH

OMe

H

TABLE 21

m.p. (° C.)

or

Compound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-675

Me

6-Cl

CH

OMe

H

126-130

I-676

Me

5,6-(OMe)

2

CH

OMe

H

I-677

Cl

5-Cl

CH

OMe

H

I-678

Cl

5-Me

CH

OMe

H

I-679

Cl

5-CF

3

CH

OMe

H

I-680

Cl

5-OMe

CH

OMe

H

I-681

Cl

5,6-(OMe)

2

CH

OMe

H

I-682

CF

3

5-Cl

CH

OMe

H

107-108

I-683

CF

3

5-Me

CH

OMe

H

76-79

I-684

CF

3

5-CF

3

CH

OMe

H

I-685

CF

3

5-OMe

CH

OMe

H

I-686

Et

5-Cl

CH

OMe

H

I-687

Et

5-Me

CH

OMe

H

I-688

Et

5-CF

3

CH

OMe

H

I-689

Et

5-OMe

CH

OMe

H

I-690

H

H

CH

OEt

H

104-107

I-691

Me

H

CH

OEt

H

I-692

H

5-Cl

CH

OEt

H

158-160

I-693

H

5-Me

CH

OEt

H

131-132

I-694

Me

5-Cl

CH

OEt

H

153-155

I-695

Me

5-Me

CH

OEt

H

109-111

I-696

Me

5-CF

3

CH

OEt

H

I-697

Me

5-OMe

CH

OEt

H

I-698

Me

5,6-(OMe)

2

CH

OEt

H

I-699

Me

6-Cl

CH

OEt

H

117-118

I-700

Cl

5-Me

CH

OEt

H

I-701

Cl

5-CF

3

CH

OEt

H

I-702

Cl

5-OMe

CH

OEt

H

I-703

Cl

5,6-(OMe)

2

CH

OEt

H

I-704

CF

3

5-Cl

CH

OEt

H

125-128

I-705

CF

3

5-Me

CH

OEt

H

86-87

I-706

CF

3

5-OMe

CH

OEt

H

I-707

Et

5-Cl

CH

OEt

H

I-708

Et

5-Me

CH

OEt

H

TABLE 22

m.p.

(° C.)

Com-

or

pound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-709

Et

5-CF

3

CH

OEt

H

I-710

Et

5-OMe

CH

OEt

H

I-711

H

H

CH

OPr

H

88-

86

I-712

Me

5-Me

CH

OPr

H

I-713

Me

5-Cl

CH

OPr

H

I-714

Me

5-OMe

CH

OPr

H

I-715

H

H

CH

OCH

2

CH═CH

2

H

I-716

Me

5-Me

CH

OCH

2

CH═CH

2

H

I-717

Me

5-Cl

CH

OCH

2

CH═CH

2

H

I-718

Me

5-OMe

CH

OCH

2

CH═CH

2

H

I-719

H

H

CH

OBn

H

I-720

Me

5-Me

CH

OBn

H

I-721

Me

5-Cl

CH

OBn

H

I-722

H

H

CH

OPh

H

257-

260

I-723

H

H

CH

OPh(4-Cl)

H

I-724

H

H

CH

OPh(4-Me)

H

I-725

H

H

CH

OPh(4-OMe)

H

I-726

H

H

CH

OMe

Me

107-

110

I-727

Me

H

CH

OMe

Me

I-728

H

5-Cl

CH

OMe

Me

I-729

H

5-Me

CH

OMe

Me

I-730

H

5-CF

3

CH

OMe

Me

I-731

Me

5-Cl

CH

OMe

Me

124-

127

I-732

Me

5-Me

CH

OMe

Me

I-733

Me

5-CF

3

CH

OMe

Me

I-734

Me

5-OMe

CH

OMe

Me

I-735

Me

6-Cl

CH

OMe

Me

I-736

Me

5,6-(OMe)

2

CH

OMe

Me

I-737

Cl

5-Cl

CH

OMe

Me

I-738

Cl

5-Me

CH

OMe

Me

I-739

Cl

5-OMe

CH

OMe

Me

I-740

Cl

5,6-(OMe)

2

CH

OMe

Me

I-741

CF

3

5-Cl

CH

OMe

Me

I-742

CF

3

5-Me

CH

OMe

Me

TABLE 23

m.p. (° C.)

or

Compound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-743

CF

3

5-OMe

CH

OMe

Me

I-744

Et

5-Cl

CH

OMe

Me

I-745

Et

5-Me

CH

OMe

Me

I-746

Et

5-OMe

CH

OMe

Me

I-747

H

H

N

OMe

Me

I-748

H

5-Cl

N

OMe

Me

I-749

H

5-Me

N

OMe

Me

I-750

H

5-CF

3

N

OMe

Me

I-751

Me

5-Cl

N

OMe

Me

I-752

Me

5-Me

N

OMe

Me

124-127

I-753

Me

5-CF

3

N

OMe

Me

I-754

Me

5-OMe

N

OMe

Me

I-755

Me

6-Cl

N

OMe

Me

I-756

Me

5,6-(OMe)

2

N

OMe

Me

I-757

Cl

5-Cl

N

OMe

Me

I-758

Cl

5-Me

N

OMe

Me

117-120

I-759

Cl

5-OMe

N

OMe

Me

I-760

Cl

5,6-(OMe)

2

N

OMe

Me

I-761

CF

3

5-Cl

N

OMe

Me

I-762

CF

3

5-Me

N

OMe

Me

117-120

I-763

CF

3

5-OMe

N

OMe

Me

I-764

Et

5-Cl

N

OMe

Me

I-765

Et

5-Me

N

OMe

Me

I-766

Et

5-OMe

N

OMe

Me

I-767

NH

2

5-Me

N

OMe

Me

>300

I-768

H

H

CH

OEt

Me

57-60

I-769

Me

H

CH

OEt

Me

92-94

I-770

CF

3

H

CH

OEt

Me

I-771

Cl

H

CH

OEt

Me

95-96

I-772

H

5-Me

CH

OEt

Me

105-108

I-773

Me

5-F

CH

OEt

Me

I-774

Me

5-Cl

CH

OEt

Me

I-775

Me

5-Me

CH

OEt

Me

108-110

I-776

Me

5-CF

3

CH

OEt

Me

TABLE 24

m.p. (° C.)

or

Compound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-777

Me

5-OMe

CH

OEt

Me

I-778

Me

5-CN

CH

OEt

Me

I-779

Me

6-Cl

CH

OEt

Me

I-780

Me

5,6-(OMe)

2

CH

OEt

Me

I-781

Cl

5-Cl

CH

OEt

Me

I-782

Cl

5-Me

CH

OEt

Me

I-783

Cl

5-CF

3

CH

OEt

Me

I-784

Cl

5-OMe

CH

OEt

Me

I-785

Cl

5,6-(OMe)

2

CH

OEt

Me

I-786

CF

3

5-Cl

CH

OEt

Me

I-787

CF

3

5-Me

CH

OEt

Me

117-118

I-788

CF

3

5-OMe

CH

OEt

Me

I-789

Et

5-Cl

CH

OEt

Me

I-790

Et

5-Me

CH

OEt

Me

I-791

Et

5-CF

3

CH

OEt

Me

I-792

Et

5-OMe

CH

OEt

Me

I-793

H

H

N

OEt

Me

I-794

H

5-Br

N

OEt

Me

I-795

Me

5-Cl

N

OEt

Me

I-796

Me

5-Br

N

OEt

Me

I-797

Me

5-Me

N

OEt

Me

I-798

Me

5-CF

3

N

OEt

Me

I-799

Cl

5-Cl

N

OEt

Me

I-800

Cl

5-Me

N

OEt

Me

I-801

CF

3

5-Cl

N

OEt

Me

I-802

CF

3

5-Br

N

OEt

Me

I-803

CF

3

5-Me

N

OEt

Me

I-804

H

H

CH

OPr

Me

47-50

I-805

H

5-OMe

CH

OPr

Me

100-102

I-806

Me

H

CH

OPr

Me

75-78

I-807

CF

3

H

CH

OPr

Me

I-808

H

5-Cl

CH

OPr

Me

I-809

H

5-Me

CH

OPr

Me

73-76

I-810

Me

5-F

CH

OPr

Me

TABLE 25

m.p. (° C.)

or

Compound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-811

Me

5-Cl

CH

OPr

Me

90-93

I-812

Me

5-Me

CH

OPr

Me

59-62

I-813

Me

5-OMe

CH

OPr

Me

99-101

I-814

Me

6-Cl

CH

OPr

Me

109-112

I-815

Me

5,6-(OMe)

2

CH

OPr

Me

I-816

Cl

5-Cl

CH

OPr

Me

I-817

Cl

5-Me

CH

OPr

Me

76-77

I-818

Cl

5-OMe

CH

OPr

Me

87-90

I-819

Cl

5,6-(OMe)

2

CH

OPr

Me

I-820

CF

3

5-Cl

CH

OPr

Me

I-821

CF

3

5-Me

CH

OPr

Me

I-822

CF

3

5-CF

3

CH

OPr

Me

I-823

CF

3

5-OMe

CH

OPr

Me

I-824

Et

5-Cl

CH

OPr

Me

I-825

Et

5-Me

CH

OPr

Me

I-826

Et

5-OMe

CH

OPr

Me

I-827

H

H

N

OPr

Me

I-828

H

5-Br

N

OPr

Me

I-829

Me

5-Cl

N

OPr

Me

I-830

Me

5-Br

N

OPr

Me

I-831

Me

5-Me

N

OPr

Me

104-107

I-832

Me

5-CF

3

N

OPr

Me

I-833

Cl

5-Cl

N

OPr

Me

I-834

Cl

5-Me

N

OPr

Me

I-835

CF

3

5-Cl

N

OPr

Me

I-836

CF

3

5-Br

N

OPr

Me

I-837

CF

3

5-Me

N

OPr

Me

I-838

NH

2

5-Me

N

OPr

Me

152-153

I-839

H

H

CH

OPr-i

Me

66-68

I-840

Me

H

CH

OPr-i

Me

1.5805

I-841

CF

3

H

CH

OPr-i

Me

I-842

H

5-Cl

CH

OPr-i

Me

I-843

H

5-Me

CH

OPr-i

Me

I-844

Me

5-F

CH

OPr-i

Me

TABLE 26

m.p. (° C.)

or

Compound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-845

Me

5-Cl

CH

OPr-i

Me

I-846

Me

5-Me

CH

OPr-i

Me

I-847

Me

5-OMe

CH

OPr-i

Me

I-848

Me

6-Cl

CH

OPr-i

Me

I-849

Me

5,6-(OMe)

2

CH

OPr-i

Me

I-850

Cl

5-Cl

CH

OPr-i

Me

I-851

Cl

5-Me

CH

OPr-i

Me

I-852

Cl

5-CF

3

CH

OPr-i

Me

I-853

Cl

5-OMe

CH

OPr-i

Me

I-854

Cl

5,6-(OMe)

2

CH

OPr-i

Me

I-855

CF

3

5-Cl

CH

OPr-i

Me

I-856

CF

3

5-Me

CH

OPr-i

Me

I-857

CF

3

5-OMe

CH

OPr-i

Me

I-858

Et

5-Cl

CH

OPr-i

Me

I-859

Et

5-Me

CH

OPr-i

Me

I-860

Et

5-OMe

CH

OPr-i

Me

I-861

H

H

N

OPr-i

Me

I-862

H

5-Br

N

OPr-i

Me

I-863

Me

5-Cl

N

OPr-i

Me

I-864

Me

5-Br

N

OPr-i

Me

I-865

Me

5-Me

N

OPr-i

Me

I-866

Me

5-CF

3

N

OPr-i

Me

I-867

Cl

5-Cl

N

OPr-i

Me

I-868

Cl

5-Me

N

OPr-i

Me

I-869

CF

3

5-Cl

N

OPr-i

Me

I-870

CF

3

5-Br

N

OPr-i

Me

I-871

CF

3

5-Me

N

OPr-i

Me

I-872

H

H

CH

OBu

Me

1.5795

I-873

Me

H

CH

OBu

Me

73-76

I-874

Me

5-Cl

CH

OBu

Me

I-875

Me

5-Me

CH

OBu

Me

I-876

Me

5-OMe

CH

OBu

Me

I-877

Cl

5-Cl

CH

OBu

Me

I-878

Cl

5-Me

CH

OBu

Me

TABLE 27

m.p. (° C.)

Com-

or

pound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-879

Cl

5-OMe

CH

OBu

Me

I-880

CF

3

5-Cl

CH

OBu

Me

I-881

CF

3

5-Me

CH

OBu

Me

I-882

CF

3

5-OMe

CH

OBu

Me

I-883

H

H

CH

OCH

2

CH═CH

2

Me

55-58

I-884

H

5-Me

CH

OCH

2

CH═CH

2

Me

I-885

Me

H

CH

OCH

2

CH═CH

2

Me

84-87

I-886

Me

5-Cl

CH

OCH

2

CH═CH

2

Me

I-887

Me

5-Me

CH

OCH

2

CH═CH

2

Me

I-888

Me

5-OMe

CH

OCH

2

CH═CH

2

Me

I-889

Cl

5-Cl

CH

OCH

2

CH═CH

2

Me

I-890

Cl

5-Me

CH

OCH

2

CH═CH

2

Me

I-891

CF

3

5-Cl

CH

OCH

2

CH═CH

2

Me

I-892

CF

3

5-Me

CH

OCH

2

CH═CH

2

Me

I-893

CF

3

5-OMe

CH

OCH

2

CH═CH

2

Me

I-894

H

H

CH

OCH

2

C≡CH

Me

145-148

I-895

H

5-Me

CH

OCH

2

C≡CH

Me

183-186

I-896

Me

H

CH

OCH

2

C≡CH

Me

147-149

I-897

Me

5-Cl

CH

OCH

2

C≡CH

Me

I-898

Me

5-Me

CH

OCH

2

C≡CH

Me

147-150

I-899

Me

5-OMe

CH

OCH

2

C≡CH

Me

I-900

Cl

5-Cl

CH

OCH

2

C≡CH

Me

I-901

Cl

5-Me

CH

OCH

2

C≡CH

Me

I-902

CF

3

5-Cl

CH

OCH

2

C≡CH

Me

I-903

CF

3

5-Me

CH

OCH

2

C≡CH

Me

113-116

I-904

NH

2

5-Me

CH

OCH

2

C≡CH

Me

225-228

I-905

H

H

CH

OBn

Me

I-906

H

H

CH

OPn-c

Me

1.5965

I-907

Me

H

CH

OPn-c

Me

1.5941

I-908

Me

5-Cl

CH

OPn-c

Me

I-909

Me

5-Cl

N

OPn-c

Me

I-910

H

H

CH

SMe

Me

I-911

Me

H

CH

SMe

Me

139-142

I-912

Me

5-Me

CH

SMe

Me

TABLE 28

m.p. (° C.)

or

Compound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-913

Me

5-Cl

CH

SMe

Me

I-914

H

H

N

SMe

Me

I-915

Me

5-Me

N

SMe

Me

134-137

I-916

Me

5-Cl

N

SMe

Me

I-917

H

H

CH

OMe

Et

I-918

Me

5-Me

CH

OMe

Et

I-919

Me

5-Cl

CH

OMe

Et

I-920

Me

5-CF

3

CH

OMe

Et

I-921

Me

5-OMe

CH

OMe

Et

I-922

Cl

5-Me

CH

OMe

Et

I-923

Cl

5-Cl

CH

OMe

Et

I-924

H

H

CH

OEt

Et

I-925

Me

5-Me

CH

OEt

Et

I-926

Me

5-Cl

CH

OEt

Et

I-927

Me

5-CF

3

CH

OEt

Et

I-928

Me

5-OMe

CH

OEt

Et

I-929

Cl

5-Me

CH

OEt

Et

I-930

Cl

5-Cl

CH

OEt

Et

I-931

H

H

CH

OPr

Et

I-932

Me

5-Me

CH

OPr

Et

I-933

Me

5-Cl

CH

OPr

Et

I-934

Me

5-CF

3

CH

OPr

Et

I-935

Me

5-OMe

CH

OPr

Et

I-936

Cl

5-Me

CH

OPr

Et

I-937

Cl

5-Cl

CH

OPr

Et

I-938

H

H

N

OMe

Et

I-939

H

5-Br

N

OMe

Et

125-128

I-940

Me

5-Me

N

OMe

Et

I-941

Me

5-Cl

N

OMe

Et

134-137

I-942

Me

5-Br

N

OMe

Et

134-141

I-943

Cl

5-Me

N

OMe

Et

I-944

Cl

5-Cl

N

OMe

Et

I-945

CF

3

5-Me

N

OMe

Et

86-89

I-946

CF

3

5-Cl

N

OMe

Et

79-82

TABLE 29

m.p. (° C.)

or

Compound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-947

CF

3

5-Br

N

OMe

Et

97-100

I-948

H

H

N

OEt

Et

I-949

H

5-Br

N

OEt

Et

79-82

I-950

Me

5-Me

N

OEt

Et

I-951

Me

5-Cl

N

OEt

Et

I-952

Me

5-Br

N

OEt

Et

96-98

I-953

Cl

5-Me

N

OEt

Et

I-954

Cl

5-Cl

N

OEt

Et

I-955

CF

3

5-Me

N

OEt

Et

I-956

CF

3

5-Cl

N

OEt

Et

66-67

I-957

CF

3

5-Br

N

OEt

Et

97-100

I-958

H

H

CH

OMe

Pr

78-80

I-959

Me

H

CH

OMe

Pr

1.5892

I-960

Cl

H

CH

OMe

Pr

1.6009

I-961

H

5-Cl

CH

OMe

Pr

I-962

H

5-Me

CH

OMe

Pr

116-119

I-963

Me

5-F

CH

OMe

Pr

I-964

Me

5-Cl

CH

OMe

Pr

113-116

I-965

Me

5-Me

CH

OMe

Pr

105-107

I-966

Me

5-OMe

CH

OMe

Pr

I-967

Me

6-Cl

CH

OMe

Pr

68-71

I-968

Cl

5-Cl

CH

OMe

Pr

I-969

Cl

5-Me

CH

OMe

Pr

I-970

Cl

5-OMe

CH

OMe

Pr

I-971

CF

3

5-Cl

CH

OMe

Pr

I-972

CF

3

5-Me

CH

OMe

Pr

I-973

CF

3

5-OMe

CH

OMe

Pr

I-974

H

H

CH

OEt

Pr

I-975

H

5-Cl

CH

OEt

Pr

I-976

H

5-Me

CH

OEt

Pr

I-977

Me

5-F

CH

OEt

Pr

I-978

Me

5-Cl

CH

OEt

Pr

I-979

Me

5-Me

CH

OEt

Pr

I-980

Me

5-CF

3

CH

OEt

Pr

TABLE 30

m.p. (° C.)

or

Compound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-981

Me

5-OMe

CH

OEt

Pr

I-982

Cl

5-Cl

CH

OEt

Pr

I-983

Cl

5-Me

CH

OEt

Pr

I-984

Cl

5-CF

3

CH

OEt

Pr

I-985

Cl

5-OMe

CH

OBt

Pr

I-986

CF

3

5-Cl

CH

OEt

Pr

I-987

CF

3

5-Me

CH

OEt

Pr

I-988

CF

3

5-OMe

CH

OEt

Pr

I-989

H

H

CH

OPr

Pr

I-990

Me

5-Me

CH

OPr

Pr

I-991

Me

5-Cl

CH

OPr

Pr

I-992

Me

5-OMe

CH

OPr

Pr

I-993

Cl

5-Me

CH

OPr

Pr

I-994

Cl

5-Cl

CH

OPr

Pr

I-995

H

H

N

OMe

Pr

I-996

H

5-Br

N

OMe

Pr

I-997

Me

5-Cl

N

OMe

Pr

I-998

Me

5-Br

N

OMe

Pr

I-999

Me

5-Me

N

OMe

Pr

112-115

I-1000

Cl

5-Cl

N

OMe

Pr

I-1001

Cl

5-Me

N

OMe

Pr

I-1002

CF

3

5-Cl

N

OMe

Pr

I-1003

CF

3

5-Br

N

OMe

Pr

I-1004

CF

3

5-Me

N

OMe

Pr

92-95

I-1005

H

H

N

OEt

Pr

I-1006

H

5-Br

N

OEt

Pr

I-1107

Me

5-Cl

N

OEt

Pr

I-1008

Me

5-Br

N

OEt

Pr

I-1009

Me

5-Me

N

OEt

Pr

I-1010

Cl

5-Cl

N

OEt

Pr

I-1011

Cl

5-Me

N

OPr

Pr

I-1012

CF

3

5-Cl

N

OPr

Pr

I-1013

CF

3

5-Br

N

OPr

Pr

I-1014

CF

3

5-Me

N

OPr

Pr

TABLE 31

m.p. (° C.)

or

Compound

RI

No.

X

Yn

A

R

1

R

2

(n

D

20

)

I-1015

H

H

N

OMe

Pr-c

I-1016

H

5-Br

N

OMe

Pr-c

154-157

I-1017

Me

5-Cl

N

OMe

Pr-c

116-119

I-1018

Me

5-Br

N

OMe

Pr-c

121-124

I-1019

Me

5-Me

N

OMe

Pr-c

167-170

I-1020

CF

3

5-Cl

N

OMe

Pr-c

101-104

I-1021

CF

3

5-Br

N

OMe

Pr-c

119-122

I-1022

CF

3

5-Me

N

OMe

Pr-c

116-119

I-1023

H

H

N

OEt

Pr-c

I-1024

H

5-Br

N

OEt

Pr-c

137-140

I-1025

Me

5-Cl

N

OEt

Pr-c

130-133

I-1026

Me

5-Br

N

OEt

Pr-c

124-127

I-1027

Me

5-Me

N

OEt

Pr-c

131-133

I-1028

CF

3

5-Cl

N

OEt

Pr-c

82-85

I-1029

CF

3

5-Br

N

OEt

Pr-c

105-108

I-1030

CF

3

5-Me

N

OEt

Pr-c

79-82

I-1031

H

H

N

SMe

Pr-c

I-1032

H

5-Br

N

SMe

Pr-c

I-1033

Me

5-Cl

N

SMe

Pr-c

I-1034

Me

5-Br

N

SMe

Pr-c

I-1035

Me

5-Me

N

SMe

Pr-c

I-1036

CF

3

5-Cl

N

SMe

Pr-c

I-1037

CF

3

5-Br

N

SMe

Pr-c

I-1038

CF

3

5-Me

N

SMe

Pr-c

I-1039

Me

H

CH

SMe

SMe

129-131

I-1040

H

5-Cl

N

SMe

SMe

I-1041

H

5-Br

N

SMe

SMe

I-1042

Me

H

N

SMe

SMe

176-179

I-1043

Me

5-Cl

N

SMe

SMe

186-189

I-1044

Me

5-Br

N

SMe

SMe

I-1045

Me

5-Me

N

SMe

SMe

I-1046

CF

3

5-Cl

N

SMe

SMe

144-146

I-1047

CF

3

5-Br

N

SMe

SMe

I-1048

CF

3

5-Me

N

SMe

Me

106-109

TABLE 32

m.p.

Compound

(° C.) or

No.

X

Yn

A

R

1

R

2

RI (n

D

20

)

I-1049

H

5-Br

N

OMe

SMe

I-1050

Me

5-Cl

N

OMe

SMe

I-1051

Me

5-Br

N

OMe

SMe

I-1052

Me

5-Me

N

OMe

SMe

I-1053

CF

3

5-Cl

N

OMe

SMe

I-1054

CF

3

5-Br

N

OMe

SMe

I-1055

CF

3

5-Me

N

OMe

SMe

I-1056

H

H

CH

OMe

Ph

160-162

I-1057

H

H

N

OMe

Ph

I-1058

Me

5-Me

N

OMe

Ph

165-168

I-1059

CF

3

6-Me

N

OMe

Ph

150-153

I-1060

H

H

CH

Cl

Ph

176-179

I-1061

H

H

N

Cl

Ph

I-1062

H

H

CH

Cl

Cl

165-168

I-1063

Me

H

CH

Cl

Cl

170-172

I-1064

Me

5,6-Cl

2

CH

Cl

Cl

202-205

I-1065

H

H

N

Cl

Cl

I-1066

Me

H

N

Cl

Cl

>300

I-1067

H

H

CH

Cl

Me

187-190

I-1068

Me

H

CH

Cl

Me

122-125

I-1069

H

H

CH

Cl

N(Me)

2

205-208

I-1070

H

H

N

Cl

N(Me)

2

I-1071

Me

5-Cl

N

N(Me)

2

N(Me)

2

203-206

I-1072

H

H

CH

OMe

N(Me)

2

129-132

I-1073

H

H

CBr

OMe

OMe

>300

I-1074

H

H

CMe

OMe

OMe

152-155

I-1075

H

H

CMe

Cl

Cl

184-187

I-1076

H

H

COMe

H

H

131-134

I-1077

Me

5-Me

COMe

H

H

I-1078

Me

5-Cl

COMe

H

H

I-1079

H

H

CH

Me

Me

131-132

I-1080

Me

5-Cl

CH

Me

Me

138-140

I-1081

Me

5-CF

3

CH

Me

Me

I-1082

H

H

CH

Me

CF

3

107-110

TABLE 33

Compound

m.p. (° C.)

No.

X

Yn

A

R

1

R

2

or RI (n

D

20

)

I-1083

Me

5-Cl

CH

Me

CF

3

I-1084

Me

5-Cl

N

Me

CF

3

I-1085

H

H

CH

Me

Et

60-63

I-1086

H

5-Me

CH

Me

Et

55-58

I-1087

Me

5-Me

CH

Me

Et

109-112

I-1088

Me

5-Cl

CH

Me

Et

76-79

I-1089

Me

5-OMe

CH

Me

Et

I-1090

Me

6-Cl

CH

Me

Et

84-87

I-1091

Cl

5-Cl

CH

Me

Et

I-1092

Cl

5-Me

CH

Me

Et

I-1093

H

H

CH

Et

Et

58-61

I-1094

H

5-Me

CH

Et

Et

68-71

I-1095

Me

5-Me

CH

Et

Et

76-79

I-1096

Me

5-Cl

CH

Et

Et

78-80

I-1097

Me

5-OMe

CH

Et

Et

I-1098

Me

6-Cl

CH

Et

Et

80-83

I-1099

Cl

5-Cl

CH

Et

Et

I-1100

Cl

5-Me

CH

Et

Et

I-1101

H

H

CH

Me

Pr-c

124-125

I-1102

H

5-Me

CH

Me

Pr-c

I-1103

Me

5-Me

CH

Me

Pr-c

153-156

I-1104

Me

5-Cl

CH

Me

Pr-c

119-122

I-1105

Me

5-OMe

CH

Me

Pr-c

I-1106

Me

6-Cl

CH

Me

Pr-c

110-113

I-1107

Cl

5-Cl

CH

Me

Pr-c

I-1108

Cl

5-Me

CH

Me

Pr-c

I-1109

H

H

CH

Et

Pr-c

I-1110

Me

5-Me

CH

Et

Pr-c

I-1111

Me

5-Cl

CH

Et

Pr-c

I-1112

Me

5-OMe

CH

Et

Pr-c

I-1113

Me

6-Cl

CH

Et

Pr-c

I-1114

Cl

5-Cl

CH

Et

Pr-c

I-1115

Cl

5-Me

CH

Et

Pr-c

I-1116

H

H

CH

Et

Et

TABLE 34

Compound

m.p. (° C.)

No.

X

Yn

A

R

1

R

2

or RI (n

D

20

)

I-1117

Me

5-Me

CH

Et

Et

I-1118

Me

5-Cl

CH

Et

Et

I-1119

Me

5-OMe

CH

Et

Et

I-1120

Me

6-Cl

CH

Et

Et

I-1121

Cl

5-Cl

CH

Et

Et

I-1122

Cl

5-Me

CH

Et

Et

I-1123

H

H

CH

C≡CMe

Me

134-136

I-1124

Me

5-Me

CH

C≡CMe

Me

I-1125

Me

5-Cl

CH

C≡CMe

Me

I-1126

Me

5-Me

N

C≡CMe

Me

I-1127

Me

5-Cl

N

C≡CMe

Me

I-1128

Cl

5-Cl

CH

C≡CMe

Me

I-1129

Cl

5-Me

CH

C≡CMe

Me

I-1130

H

H

CH

CH═CH

2

Me

I-1131

Me

5-Me

CH

CH═CH

2

Me

I-1132

Me

5-Cl

CH

CH═CH

2

Me

I-1133

Me

5-Me

N

CH═CH

2

Me

I-1134

Cl

5-Cl

CH

CH═CH

2

Me

I-1135

Cl

5-Me

CH

CH═CH

2

Me

I-1136

H

H

CH

CHO

Me

I-1137

Me

5-Cl

CH

CHO

Me

I-1138

Me

5-Cl

N

CHO

Me

I-1139

H

H

CH

COMe

Me

I-1140

Me

5-Cl

CH

COMe

Me

I-1141

Me

5-Cl

N

COMe

Me

I-1142

H

H

CH

CH

2

OMe

Me

I-1143

Me

5-Cl

CH

CH

2

OMe

Me

I-1144

Me

5-Me

CH

CH

2

OMe

Me

I-1145

H

H

N

CH

2

OMe

OMe

I-1146

Me

H

CH

CN

CN

I-1147

Me

H

CH

CN

Me

187-189

I-1148

Me

H

N

CN

CN

I-1149

Me

H

N

CN

Me

I-1150

Me

H

CH

SO

2

Me

SO

2

Me

TABLE 35

Compound

m.p. (° C.)

No.

X

Yn

A

R

1

R

2

or RI (n

D

20

)

I-1151

Me

H

N

SO

2

Me

SO

2

Me

I-1152

Me

H

CH

SO

2

Me

Me

183-186

Typical processes for producing pyrimidinylbenzimidazole and triazinylbenzimidazole derivatives represented by the general formula [I] as the compounds of the present invention, will be exemplified below.

(wherein X, Y, R

1

, R

2

, A and n have the same meanings as mentioned above respectively, and L is a leaving group such as a halogen atom, a (C

1

-C

6

) alkylsulfonyl group or a benzylsulfonyl group.)

The compound of the present invention represented by the general formula [I] can be produced by reacting a benzimidazole derivative represented by the general formula [II] and a pyrimidine derivative or triazine derivative represented by the general formula [III] in the presence of a base in a solvent. Here, as the base, a carbonate, hydrogencarbonate, acetate, alcoholate, hydroxide, hydride or oxide of an alkali metal or alkaline earth metal, particularly sodium, potassium, magnesium or calcium, may, for example, be used. The solvent which can be used in the present reaction may be one which does not inhibit the progress of the present reaction, and an ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, monoglyme or diglyme, a halogenated hydrocarbon such as dichloroethane, chloroform, carbon tetrachloride or tetrachloroethane, an aromatic hydrocarbon such as benzene, chlorobenzene, nitrobenzene or toluene, or N,N-dimethylformamide, N,N-dimethylacetoamide, 1,3-dimethyl-2-imidazolinone or dimethylsulfoxide, may, for example, be used. These inert solvents may be used alone or as mixed. The reaction temperature may be selected within a range of from −20° C. to the boiling point of the inert solvent to be used, and preferably within a range of from 0° C. to 80° C. The reaction time varies depending upon e.g. the reaction temperature and the reaction amount, but may be selected within a range of from 1 hour to 48 hours in general. After completion of the reaction, the desired product is isolated from the reaction system by a conventional method and may be purified by e.g. column chromatography or recrystallization, as the case requires.

Here, the benzimidazole derivative represented by the general formula [II] may be a commercially available product or may be produced by a known method [e.g. a method as disclosed in Angewandte Chemie, vol 85, p866 (1973); Journal of the American Chemical Society, vol 69, p2459 (1947); Journal of the American Chemical Society, vol 82, p3138 (1960); Organic Syntheses, vol 2, p65 (1943); or Organic Syntheses, vol 4, p569 (1963)].

(wherein X, Y, R

1

, R

2

, A and n have the same meanings as mentioned above respectively.)

The anilide derivative represented by the general formula [V] can be produced by reacting an anilinopyrimidine derivative or anilinotriazine derivative represented by the general formula [IV] with an acylating agent in an inert solvent. The reaction is carried out preferably in the presence of a base. As the acylating agent, an acid halide such as acetyl chloride, propionyl chloride or benzoyl chloride, or an acid anhydride such as trifluoroacetic anhydride, propionic anhydride or benzoic anhydride may be mentioned. The inert solvent which can be used in the present reaction may be one which does not inhibit the progress of the present reaction, and for example, e.g. a ketone such as acetone, methyl ethyl ketone or cyclohexanone, an ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, monoglyme or diglyme, an ester such as ethyl acetate or methyl acetate, a halogenated hydrocarbon such as dichloroethane, chloroform, carbon tetrachloride or tetrachloroethane, an aromatic hydrocarbon such as benzene, chlorobenzene, nitrobenzene or toluene, a nitrile such as acetonitrile, or N,N-dimethylformamide, N,N-dimethylacetoamide, 1,3-dimethyl-2-imidazolinone, dimethylsulfoxide, pyridine or water, may be used. These inert solvents may be used alone or as mixed. As the base to be used in the present reaction, an inorganic base or an organic base may be used. For example, as an inorganic base, a carbonate or hydroxide of an alkali metal or alkaline earth metal, such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide or calcium hydroxide, or a hydride of an alkali metal such as lithium hydride or sodium hydride, may be used, and as an organic base, triethylamine, diisopropylethylamine or pyridine may, for example, be used. The reaction temperature may be selected within a range of from −20° C. to the boiling point of the inert solvent to be used, and preferably within a range of from 0° C. to 50° C. The reaction time varies depending upon e.g. the reaction temperature and the reaction amount, but may be selected within a range of from several minutes to 48 hours in general.

Then, the anilide derivative represented by the general formula [V] is subjected to a cyclization reaction without a solvent or in a solvent, in the presence of a catalyst as the case requires, to produce the compound of the present invention represented by the general formula [I]. As the catalyst to be used here, an inorganic acid such as sulfuric acid or hydrochloric acid or an organic acid such as para-toluenesulfonic acid may, for example, be used. As the solvent which can be used in the present reaction, the solvent exemplified in Process 1 may be used. The reaction temperature may be selected within a range of from 0° C. to the boiling point of the solvent to be used, and preferably within a range of from room temperature to the boiling point of the solvent. The reaction time varies depending upon e.g. the reaction temperature and the reaction amount, but may be selected within a range of from 1 hour to 48 hours in general. After the completion of the reaction, the desired product is isolated from the reaction system by a conventional method and may be purified by e.g. column chromatography or recrystallization, as the case requires.

(wherein X, Y, R

1

, R

2

, A and n have the same meanings as mentioned above respectively.)

The compound of the present invention represented by the general formula [I] can be produced directly by heating an anilinopyrimidine derivative or anilinotriazine derivative represented by the general formula [IV] in a carboxylic acid represented by the general formula [VI], in the presence of an acid anhydride as the case requires. The reaction temperature may be selected within a range of from 0° C. to the boiling point of the carboxylic acid to be used, preferably within a range of from room temperature to the boiling point of the carboxylic acid. The reaction time may be selected within a range of from 1 hour to 48 hours in general. After the completion of the reaction, the desired product is isolated from the reaction system by a conventional method and may be purified by e.g. column chromatography or recrystallization, as the case requires.

(wherein Y, R

1

, R

2

, A and n have the same meanings as mentioned above respectively.)

The compound represented by the general formula [I-a] can be produced by reacting an anilinopyrimidine derivative or anilinotriazine derivative represented by the general formula [IV] and a reagent [VII] such as BrCN or H

2

NCN by a method known from a literature [e.g. a method as disclosed in Journal of the American Chemical Society, vol 69, p2459 (1947); or Angewandte Chemie, vol 85, p866 (1973)] in a solvent. As the solvent which can be used in the present reaction, the solvent as exemplified in Process 1 may be used. The reaction temperature may be selected within a range of from −20° C. to the boiling point of the reaction mixture to be used, preferably within a range of from 0° C. to the boiling point of the reaction mixture. The reaction time varies depending upon e.g. the reaction temperature or the reaction amount, and may be selected within a range of from 1 hour to 48 hours in general. After the completion of the reaction, the desired product is isolated from the reaction system by a conventional method and may be purified by e.g. column chromatography or recrystallization, as the case requires.

(wherein X′ is a halogen atom, and Y, R

1

, R

2

, A and n have the same meanings as mentioned above respectively.)

The compound represented by the general formula [I-d] can be produced by diazotizing a 2-aminobenzimidazole derivative represented by the general formula [I-a] by a known method [e.g. Sandmeyer method, Schwechten method or Gattermann method] in a solvent at a reaction temperature which are conventionally employed, followed by halogenation. After the completion of the reaction, the desired product is isolated from the reaction system by a conventional method and may be purified by e.g. column chromatography or recrystallization, as the case requires.

(wherein Y, R

1

, R

2

, A and n have the same meanings as mentioned above respectively, and R

4

is a C

1

-C

6

alkyl group.)

The compound represented by the general formula [I-e] can be produced by oxidizing a pyrimidinylbenzimidazole derivative or triazinylbenzimidazole derivative represented by the general formula [I-b] by a known method. After the completion of the reaction, the desired product is isolated from the reaction system by a conventional method and may be purified by e.g. column chromatography or recrystallization, as the case requires. The oxidizing agent which can be used in the present reaction may, for example, be hydrogen peroxide or an organic peracid such as m-chloroperbenzoic acid. As the solvent which can be used, the solvent as exemplified in Process 1 may be used. The reaction temperature may be selected within a range of from −20° C. to the boiling point of the reaction mixture to be used, preferably within a range of from 5° C. to the boiling point of the reaction mixture. After the completion of the reaction, the desired product is isolated from the reaction system by a conventional method and may be purified by e.g. column chromatography or recrystallization, as the case requires.

(wherein Y, R

1

, R

2

, A, L and n have the same meanings as mentioned above respectively, and X″ is a (C

1

-C

6

) alkoxy, (C

2

-C

6

) alkenyloxy, (C

2

-C

6

) alkynyloxy, (C

1

-C

6

) alkylthio or (C

1

-C

6

) alkylamino group.)

The compound of the present invention represented by the general formula [I-f] can be produced by reacting a pyrimidinylbenzimidazole derivative or triazinylbenzimidazole derivative represented by the general formula [I-c] and an alcohol, mercaptan or amine represented by the general formula [XVI] in the presence of a base without a solvent or in a solvent. As the base and the solvent which can be used in the present reaction, the base and the solvent as exemplified in Process 1 may be used. The reaction temperature may be selected within a range of from −20° C. to the boiling point of the reaction mixture to be used, preferably within a range of from room temperature to the boiling point of the reaction mixture. After the completion of the reaction, the desired product is isolated from the reaction system by a conventional method and may be purified by e.g. column chromatography or recrystallization, as the case requires.

(wherein X, Y, A, L and n have the same meanings as mentioned above respectively, and Z is a (C

1

-C

6

) alkoxy, (C

2

-C

6

) alkenyloxy, (C

2

-C

6

) alkynloxy, (C

1

-C

6

) alkylthio or di (C

1

-C

6

) alkylamino group.)

The compound of the present invention represented by the general formula [I-h] can be produced by reacting a pyrimidinylbenzimidazole derivative or triazinylbenzimidazole derivative represented by the general formula [I-g] and an alcohol, mercaptan or amine represented by the general formula [VIII] in the presence of a base without a solvent or in a proper solvent. As the base and the solvent which can be used in the present reaction, the base and the solvent as exemplified in Process 1 may be used. The reaction temperature may be selected within a range of from −20° C. to the boiling point of the reaction mixture to be used, preferably within a range of from room temperature to the boiling point of the reaction mixture. After the completion of the reaction, the desired product is isolated from the reaction system by a conventional method and may be purified by e.g. column chromatography or recrystallization, as the case requires.

(wherein Y, R

1

, R

2

, A and n have the same meanings as mentioned above respectively.)

The compound of the present invention represented by the general formula [I-i] can be produced by reducing an anilinotriazine derivative represented by the general formula [IX] with iron powder in acetic acid or in a mixed solvent of acetic anhydride and acetic acid. The reaction temperature may be selected within a range of from −20° C. to the boiling point of the reaction mixture to be used, preferably within a range of from room temperature to the boiling point of the reaction mixture. After the completion of the reaction, the desired product is isolated from the reaction system by a conventional method and may be purified by e.g. column chromatography or recrystallization, as the case requires.

Now, processes for synthesizing the production intermediates for the compounds of the present invention will be explained in detail below.

Process 10

Synthesis of Production Intermediate Represented by the General Formula [IV]

The compound [IV] may be synthesized, for example, in accordance with the following process, but the process is not limited thereto.

(wherein Y, R

1

, R

2

, A, L and n have the same meanings as mentioned above respectively.)

A formanilide derivative represented by the general formula [X] and a pyrimidine derivative or triazine derivative represented by the general formula [III] are reacted in the presence of a base in an inert solvent at a reaction temperature within a range of from −20° C. to the boiling point of the solvent, preferably within a range of from room temperature to 80° C., followed by hydrolysis with e.g. an acid such as hydrochloric acid, hydrobromic acid or sulfuric acid or an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide by a generally known method to obtain [XI]. Then, the obtained [XI] is reduced with a reducing agent such as iron, tin chloride, or a hydrogen atom accompanied with another catalyst such as palladium carbon or Raney Nickel, by a generally known method to produce an anilinopyrimidine derivative or anilinotriazine derivative represented by the general formula [IV].

Process 11

Synthesis of Production Intermediate Represented by the General Formula [XI-b]

The compound [XI-b] may be synthesized, for example, in accordance with the following process, but the process is not limited thereto.

(wherein Y, Z and n have the same meanings as mentioned above respectively.)

A nitroaniline derivative represented by the general formula [XII] and cyanuric chloride represented by [XIII] are reacted in the presence of a base without a solvent or in a proper solvent to produce an anilinotriazine derivative represented by the general formula [XI-a], which is successively reacted with an alcohol, mercaptan or amine represented by the general formula [VIII] in the presence of a base without a solvent or in a proper solvent to produce an anilinotriazine derivative represented by the general formula [XI-b]. As the base and the solvent which can be used in the present reaction, the base and the solvent as exemplified in Process 1 may be used. The reaction temperature may be selected within a range of from −20° C. to the boiling point of the reaction mixture to be used, preferably within a range of from room temperature to the boiling point of the reaction mixture. After the completion of the reaction, the desired product is isolated from the reaction system by a conventional method and may be purified by e.g. column chromatography or recrystallization, as the case requires.

Process 12

Synthesis of Production Intermediates Represented by the General Formulae [XI-c] and [XI-d]

The compounds [XI-c] and [XI-d] may be synthesized, for example, in accordance with the following process, but the process is not limited thereto.

(wherein R

1

, Y, L, Z and n have the same meanings as mentioned above respectively.)

A formanilide derivative represented by the general formula [X] and a triazine derivative represented by [XIV] are reacted in the presence of a base without a solvent or in a proper solvent, followed by hydrolysis with e.g. an acid such as hydrochloric acid, hydrobromic acid or sulfuric acid or an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, by a generally known method to produce an anilinotriazine derivative represented by the general formula [XI-c], which is successively reacted with an alcohol, mercaptan or amine represented by the general formula [VIII] in the presence of a base without a solvent or in a proper solvent to produce an anilinotriazine derivative represented by the general formula [XI-d]. As the base and the solvent which can be used in the present reaction, the base and the solvent as exemplified in Process 1 may be used. The reaction temperature may be selected within a range of from −20° C. to the boiling point of the reaction mixture to be used, preferably within a range of from room temperature to the boiling point of the reaction mixture. After the completion of the reaction, the desired product is isolated from the reaction system by a conventional method and may be purified by e.g. column chromatography or recrystallization, as the case requires.

Here, the anilinopyrimidine and anilinotriazine derivatives represented by the general formulae [IV], [V] and [XI] are also novel compounds, and specific examples in thereof will be disclosed in Tables 36 to 65.

TABLE 36

Compound

m.p. (° C.)

No.

X

Yn

A

R

1

R

2

or RI (n

D

20

)

1-1

H

H

CH

OMe

OMe

1-2

Me

H

CH

OMe

OMe

1-3

Et

H

CH

OMe

OMe

1-4

Pr

H

CH

OMe

OMe

1-5

Pr-i

H

CH

OMe

OMe

1-6

Pr-c

H

CH

CMe

OMe

1-7

Bu

H

CH

OMe

OMe

1-8

Bn

H

CH

OMe

OMe

169-172

1-9

Bn(4-Cl)

H

CH

OMe

OMe

187-200

1-10

Bn(4-Me)

H

CH

OMe

OMe

157-158

1-11

Bn(4-OMe)

H

CH

OMe

OMe

1-12

CH═CH

2

H

CH

OMe

OMe

147-149

1-13

C≡CH

H

CH

OMe

OMe

1-14

CH

2

OEt

H

CH

OMe

OMe

1-15

CH

2

Cl

H

CH

OMe

OMe

125-126

1-16

CH

2

CH

2

Cl

H

CH

OMe

OMe

162-165

1-17

CH

2

I

H

CH

OMe

OMe

1-18

CCl

3

H

CH

OMe

OMe

1-19

CF

3

H

CH

OMe

OMe

1-20

C

2

F

5

H

CH

OMe

OMe

82-85

1-21

Ph

H

CH

OMe

OMe

148-152

1-22

Ph(4-Cl)

H

CH

OMe

OMe

1-23

Ph(4-Me)

H

CH

OMe

OMe

1-24

Ph(4-OMe)

H

CH

OMe

OMe

1-25

H

H

N

OMe

OMe

1-26

Me

H

N

OMe

OMe

TABLE 37

Compound

m.p. (° C.)

No.

X

Yn

A

R

1

R

2

or RI (n

D

20

)

1-27

Et

H

N

OMe

OMe

1-28

Pr

H

N

OMe

OMe

1-29

Pr-i

H

N

OMe

OMe

1-30

Pr-c

H

N

OMe

OMe

1-31

Bu

H

N

OMe

OMe

1-32

Bn

H

N

OMe

OMe

1-33

Bn(4-Cl)

H

N

OMe

OMe

1-34

Bn(4-Me)

H

N

OMe

OMe

1-35

Bn(4-OMe)

H

N

OMe

OMe

1-36

CH═CH

2

H

N

OMe

OMe

1-37

C≡CH

H

N

OMe

OMe

1-38

CH

2

OEt

H

N

OMe

OMe

1-39

CH

2

Cl

H

N

OMe

OMe

1-40

CH

2

I

H

N

OMe

OMe

1-41

CCl

3

H

N

OMe

OMe

1-42

CF

3

H

N

OMe

OMe

1-43

C

2

F

5

H

N

OMe

OMe

1-44

Ph

H

N

OMe

OMe

1-45

Ph(4-Cl)

H

N

OMe

OMe

1-46

Ph(4-Me)

H

N

OMe

OMe

1-47

Ph(OMe)

H

N

OMe

OMe

1-48

H

6-Me

CH

OMe

OMe

1-49

H

6-Cl

CH

OMe

OMe

1-50

H

5-F

CH

OMe

OMe

1-51

H

5-Cl

CH

OMe

OMe

1-52

H

5-Br

CH

OMe

OMe

1-53

H

5-Me

CH

OMe

OMe

1-54

H

5-Bu-t

CH

OMe

OMe

1-55

H

5-CF

3

CH

OMe

OMe

1-56

H

5-OMe

CH

OMe

OMe

1-57

H

5-OEt

CH

OMe

OMe

1-58

H

5-OPr

CH

OMe

OMe

1-59

H

5-OCF

3

CH

OMe

OMe

TABLE 38

Compound

m.p. (° C.)

No.

X

Yn

A

R

1

R

2

or RI (n

D

20

)

1-60

H

5-OCH

2

CH═CH

2

CH

OMe

OMe

1-61

H

5-OCH

2

C≡CH

CH

OMe

OMe

1-62

H

5-OPh

CH

OMe

OMe

1-63

H

5-OPh(4-Cl)

CH

OMe

OMe

1-64

H

5-OPh(4-Me)

CH

OMe

OMe

1-65

H

5-OPh(4-OMe)

CH

OMe

OMe

1-66

H

5-SMe

CH

OMe

OMe

1-67

H

5-CH

2

OMe

CH

OMe

OMe

1-68

H

5-COMe

CH

OMe

OMe

1-69

H

5-COPh

CH

OMe

OMe

1-70

H

5-CO

2

Et

CH

OMe

OMe

1-71

H

5-Ph

CH

OMe

OMe

1-72

H

5-Ph(4-Cl)

CH

OMe

OMe

1-73

H

5-Ph(4-Me)

CH

OMe

OMe

1-74

H

5-Ph(4-OMe)

CH

OMe

OMe

1-75

H

5-NO

2

CH

OMe

OMe

1-76

H

5-NH

2

CH

OMe

OMe

1-77

H

5-NHMe

CH

OMe

OMe

1-78

H

5-NMe

2

CH

OMe

OMe

1-79

H

5-CN

CH

OMe

OMe

1-80

H

4-F

CH

OMe

OMe

1-81

H

4-Cl

CH

OMe

OMe

1-82

H

4-Me

CH

OMe

OMe

1-83

H

4-CF

3

CH

OMe

OMe

1-84

H

4-OMe

CH

OMe

OMe

1-85

H

4-CO

2

Et

CH

OMe

OMe

1-86

H

4-COPh

CH

OMe

OMe

1-87

H

3-Me

CH

OMe

OMe

1-88

H

3-Cl

CH

OMe

OMe

1-89

H

4,5-Cl

2

CH

OMe

OMe

1-90

H

4,5-Me

2

CH

OMe

OMe

1-91

H

4,5-(OMe)

2

CH

OMe

OMe

1-92

H

4-CF

3

, 6-Br

CH

OMe

OMe

TABLE 39

Compound

m.p. (° C.)

No.

X

Yn

A

R

1

R

2

or RI (n

D

20

)

1-93

H

4-CF

3

, 6-Cl

CH

OMe

OMe

1-94

H

4,5,6-F

3

CH

OMe

OMe

1-95

H

6-Me

N

OMe

OMe

1-96

H

6-Cl

N

OMe

OMe

1-97

H

5-F

N

OMe

OMe

1-98

H

5-Cl

N

OMe

OMe

1-99

H

5-Br

N

OMe

OMe

1-100

H

5-Me

N

OMe

OMe

1-101

H

5-CF

3

N

OMe

OMe

1-102

H

5-OMe

N

OMe

OMe

1-103

H

5-OEt

N

OMe

OMe

1-104

H

5-OPr

N

OMe

OMe

1-105

H

5-OCF

3

N

OMe

OMe

1-106

H

5-OCH

2

CH═CH

2

N

OMe

OMe

1-107

H

5-OCH

2

C≡CH

N

OMe

OMe

1-108

H

5-OPh

N

OMe

OMe

1-109

H

5-SMe

N

OMe

OMe

1-110

H

5-COPh

N

OMe

OMe

1-111

H

5-CO

2

Et

N

OMe

OMe

1-112

H

5-Ph

N

OMe

OMe

1-113

H

5-Ph(4-Cl)

N

OMe

OMe

1-114

H

5-Ph(4-Me)

N

OMe

OMe

1-115

H

5-Ph(4-OMe)

N

OMe

OMe

1-116

H

5-NO

2

N

OMe

OMe

1-117

H

5-NH

2

N

OMe

OMe

1-118

H

5-NHMe

N

OMe

OMe

1-119

H

5-NMe

2

N

OMe

OMe

1-120

H

5-CN

N

OMe

OMe

1-121

H

4-F

N

OMe

OMe

1-122

H

4-Cl

N

OMe

OMe

1-123

H

4-Me

N

OMe

OMe

1-124

H

4-CF

3

N

OMe

OMe

1-125

H

4-OMe

N

OMe

OMe

TABLE 40

Compound

m.p. (° C.)

No.

X

Yn

A

R

1

R

2

or RI (n

D

20

)

1-126

H

4-NO

2

N

OMe

OMe

1-127

H

4-CO

2

Et

N

OMe

OMe

1-128

H

4-COPh

N

OMe

OMe

1-129

H

3-Me

N

OMe

OMe

1-130

H

3-Cl

N

OMe

OMe

1-131

H

4,5-Cl

2

N

OMe

OMe

1-132

H

4,5-Me

2

N

OMe

OMe

1-133

H

4,5-(OMe)

2

N

OMe

OMe

1-134

H

4-CF

3

, 6-Br

N

OMe

OMe

1-135

H

4-CF

3

, 6-Cl

N

OMe

OMe

1-136

H

4,5,6-F

3

N

OMe

OMe

1-137

Me

6-Me

CH

OMe

OMe

1-138

Me

6-Cl

CH

OMe

OMe

1-139

Me

6-F

CH

OMe

OMe

1-140

Me

5-Cl

CH

OMe

OMe

1-141

Me

5-Br

CH

OMe

OMe

1-142

Me

5-Me

CH

OMe

OMe

1-143

Me

5-Bu-t

CH

OMe

OMe

1-144

Me

5-CF

3

CH

OMe

OMe

1-145

Me

5-OMe

CH

OMe

OMe

1-146

Me

5-COPh

CH

OMe

OMe

1-147

Me

5-Ph

CH

OMe

OMe

1-148

Me

5-NH

2

CH

OMe

OMe

1-149

Me

5-NMe

2

CH

OMe

OMe

1-150

Me

5-CN

CH

OMe

OMe

1-151

Me

4-F

CH

OMe

OMe

1-152

Me

4-Cl

CH

OMe

OMe

1-153

Me

4-Me

CH

OMe

OMe

1-154

Me

4-CF

3

CH

OMe

OMe

1-155

Me

4-OMe

CH

OMe

OMe

1-156

Me

4-COPh

CH

OMe

OMe

1-157

Me

4,5-Cl

2

CH

OMe

OMe

1-158

Me

4,5-Me

2

CH

OMe

OMe

TABLE 41

Compound

m.p. (° C.)

No.

X

Yn

A

R

1

R

2

or RI (n

D

20

)

1-159

Me

4,5-(OMe)

2

CH

OMe

OMe

1-160

Me

6-Me

N

OMe

OMe

1-161

Me

6-Cl

N

OMe

OMe

1-162

Me

5-F

N

OMe

OMe

1-163

Me

5-Cl

N

OMe

OMe

1-164

Me

5-Br

N

OMe

OMe

1-165

Me

5-Me

N

OMe

OMe

180-183

1-166

Me

5-Et

N

OMe

OMe

1-167

Me

5-Pr

N

OMe

OMe

1-168

Me

5-Pr-i

N

OMe

OMe

1-169

Me

5-Bu-t

N

OMe

OMe

1-170

Me

5-CH═CH

2

N

OMe

OMe

1-171

Me

5-C≡CBu

N

OMe

OMe

1-172

Me

5-CF

3

N

OMe

OMe

1-173

Me

5-OMe

N

OMe

OMe

1-174

Me

5-SMe

N

OMe

OMe

1-175

Me

5-COPh

N

OMe

OMe

1-176

Me

5-Ph

N

OMe

OMe

1-177

Me

5-NH

2

N

OMe

OMe

1-178

Me

5-NMe

2

N

OMe

OMe

1-179

Me

5-CN

N

OMe

OMe

1-180

Me

4-F

N

OMe

OMe

1-181

Me

4-Cl

N

OMe

OMe

1-182

Me

4-Me

N

OMe

OMe

1-183

Me

4-CF

3

N

OMe

OMe

1-184

Me

4-OMe

N

OMe

OMe

1-185

Me

4-OEt

N

OMe

OMe

1-186

Me

4-OPr

N

OMe

OMe

1-187

Me

4-CO

2

Et

N

OMe

OMe

1-188

Me

4-COPh

N

OMe

OMe

1-189

Me

4,5-Cl

2

N

OMe

OMe

1-190

Me

4,6-Me

2

N

OMe

OMe

1-191

Me

4,5-Me

2

N

OMe

OMe

TABLE 42

Compound

m.p. (° C.)

No.

X

Yn

A

R

1

R

2

or RI (n

D

20

)

1-192

Me

4,5-(OMe)

2

N

OMe

OMe

1-193

CF

3

5-F

CH

OMe

OMe

158-160

1-194

CF

3

5-Cl

CH

OMe

OMe

150-151

1-195

CF

3

5-Br

CH

OMe

OMe

1-196

CF

3

5-Me

CH

OMe

OMe

144-147

1-197

CF

3

5-CF

3

CH

OMe

OMe

168-171

1-198

CF

3

5-OMe

CH

OMe

OMe

1-199

CF

3

5-OEt

CH

OMe

OMe

122-125

1-200

CF

3

5-OPr

CH

OMe

OMe

1-201

CF

3

5-NMe

2

CH

OMe

OMe

1-202

CF

3

5-CN

CH

OMe

OMe

1-203

CF

3

4-F

CH

OMe

OMe

1-204

CF

3

4-Cl

CH

OMe

OMe

1-205

CF

3

4-Me

CH

OMe

OMe

1-206

CF

3

4,5-(OMe)

2

CH

OMe

OMe

1-207

CF

3

5-F

N

OMe

OMe

202-205

1-208

CF

3

5-Cl

N

OMe

OMe

1-209

CF

3

5-Br

N

OMe

OMe

1-210

CF

3

5-Me

N

OMe

OMe

195-198

1-211

CF

3

5-Et

N

OMe

OMe

182-185

1-212

CF

3

5-Pr

N

OMe

OMe

141-144

1-213

CF

3

5-Pr-i

N

OMe

OMe

193-196

1-214

CF

3

5-Bu-t

N

OMe

OMe

215-218

1-215

CF

3

5-CF

3

N

OMe

OMe

1-216

CF

3

5-OMe

N

OMe

OMe

183-185

1-217

CF

3

5-OEt

N

OMe

OMe

1-218

CF

3

5-OPr

N

OMe

OMe

1-219

CF

3

5-OCF

3

N

OMe

OMe

188-191

1-220

CF

3

5-SMe

N

OMe

OMe

1-221

CF

3

5-NHMe

N

OMe

OMe

1-222

CF

3

5-NMe

2

N

OMe

OMe

1-223

CF

3

5-CN

N

OMe

OMe

1-224

CF

3

5-CO

2

Me

N

OMe

OMe

186-189

TABLE 43

Compound

m.p. (° C.)

No.

X

Yn

A

R

1

R

2

or RI (n

D

20

)

1-225

CF

3

5-I

N

OMe

OMe

169-172

1-226

CF

3

4-F

N

OMe

OMe

1-227

CF

3

4-Cl

N

OMe

OMe

1-228

CF

3

6-Me

N

OMe

OMe

1-229

CF

3

4,5-(OMe)

2

N

OMe

OMe

1-230

Et

5-F

CH

OMe

OMe

1-231

Et

5-Cl

CH

OMe

OMe

1-232

Et

5-Me

CH

OMe

OMe

1-233

Et

5-CF

3

CH

OMe

OMe

1-234

Et

5-OMe

CH

OMe

OMe

1-235

Et

5-CN

CH

OMe

OMe

1-236

Et

4-F

CH

OMe

OMe

1-237

Et

4-Cl

CH

OMe

OMe

1-238

Et

4-Me

CH

OMe

OMe

1-239

Et

4,5-(OMe)

2

CH

OMe

OMe

1-240

Et

5-F

N

OMe

OMe

1-241

Et

5-Cl

N

OMe

OMe

1-242

Et

5-Me

N

OMe

OMe

1-243

Et

5-CF

3

N

OMe

OMe

1-244

Et

5-OMe

N

OMe

OMe

1-245

Et

5-CN

N

OMe

OMe

1-246

Et

4-F

N

OMe

OMe

1-247

Et

4-Cl

N

OMe

OMe

1-248

Et

4-Me

N

OMe

OMe

1-249

Et

4,5-(OMe)

2

N

OMe

OMe

1-250

Pr

5-Cl

N

OMe

OMe

137-140

1-251

Pr-i

5-Cl

N

OMe

OMe

149-152

1-252

Pr-c

5-Cl

N

OMe

OMe

181-184

1-253

CH

2

OMe

5-Cl

N

OMe

CMe

1-254

Ph

5-Cl

N

OMe

OMe

176-179

1-255

Ph

5-Br

N

OMe

OMe

1-256

Ph(4-Cl)

5-Cl

N

OMe

OMe

1-257

Ph(4-Me)

5-Cl

N

OMe

OMe

TABLE 44

Compound

m.p. (° C.)

No.

X

Yn

A

R

1

R

2

or RI (n

D

20

)

1-258

Ph(4-OMe)

5-Cl

N

OMe

OMe

1-259

Bn

5-Cl

N

OMe

OMe

1-260

CF

2

Cl

5-Me

N

OMe

OMe

1-261

CF

2

Cl

5-Cl

N

OMe

OMe

1-262

CF

2

Cl

5-Br

N

OMe

OMe

1-263

CF

2

Cl

5-OMe

N

OMe

OMe

1-264

CH

2

Cl

5-Me

N

OMe

OMe

1-265

CH

2

Cl

5-Cl

N

OMe

OMe

1-266

CH

2

Cl

5-Br

N

OMe

OMe

1-267

CH

2

Cl

5-OMe

N

OMe

OMe

1-268

C

2

F

5

5-Me

N

OMe

OMe

1-269

C

2

F

5

5-Cl

N

OMe

OMe

1-270

C

2

F

5

5-Br

N

OMe

OMe

1-271

C

2

F

5

5-OMe

N

OMe

OMe

1-272

Ph(4-Cl)

5-OMe

CH

OMe

OMe

187-200

1-273

CH

2

OMe

5-Cl

N

OMe

OMe

183-186

1-274

CF

3

5-Me

N

OMe

OEt

1-275

CF

3

5-Cl

N

OMe

OEt

1-276

CF

3

5-Br

N

OMe

OEt

1-277

CF

2

Cl

5-Cl

N

OMe

OEt

1-278

CF

2

Cl

5-Br

N

OMe

OEt

1-279

CF

2

Cl

5-Me

N

OMe

OEt

1-280

CH

2

Cl

5-Cl

N

OMe

OEt

1-281

CH

2

Cl

5-Br

N

OMe

OEt

1-282

CH

2

Cl

5-Me

N

OMe

OEt

1-283

C

2

F

5

5-Cl

N

OMe

OEt

1-284

C

2

F

5

5-Br

N

OMe

OEt

1-285

C

2

F

5

5-Me

N

OMe

OEt

1-286

Me

5-F

CH

OEt

OEt

1-287

Me

5-Cl

CH

OEt

OEt

1-288

Me

5-Br

CH

OEt

OEt

1-289

Me

5-Me

CH

OEt

OEt

1-290

Me

5-CF

3

CH

OEt

OEt

TABLE 45

Compound

m.p. (° C.)

No.

X

Yn

A

R

1

R

2

or RI (n

D

20

)

1-291

Me

5-F

N

OEt

OEt

1-292

Me

5-Cl

N

OEt

OEt

1-293

Me

5-Br

N

OEt

OEt

1-294

Me

5-Me

N

OEt

OEt

1-295

Me

5-CF

3

N

OEt

OEt

1-296

CF

3

5-F

CH

OEt

OEt

1-297

CF

3

5-Cl

CH

OEt

OEt

1-298

CF

3

5-Br

GH

OEt

OEt

1-299

CF

3

5-Me

CH

OEt

OEt

1-300

CF

3

5-CF

3

CH

OEt

OEt

1-301

CF

3

5-OMe

N

OEt

OEt

159-161

1-302

CF

3

5-Cl

N

OEt

OEt

194-197

1-303

CF

3

5-Br

N

OEt

OEt

191-194

1-304

CF

3

5-Me

N

OEt

OEt

201-204

1-305

CF

3

5-CF

3

N

OEt

OEt

1-306

Ph

H

N

OEt

OEt

1-307

Ph(4-Cl)

H

N

OEt

OEt

1-308

Ph(4-Me)

H

N

OEt

OEt

1-309

Ph(4-OMe)

H

N

OEt

OEt

1-310

Ph

5-Cl

N

OEt

OEt

1-311

Ph(4-Cl)

5-Cl

N

OEt

OEt

1-312

Ph(4-Me)

5-Cl

N

OEt

OEt

1-313

Ph(4-OMe)

5-Cl

N

OEt

OEt

1-314

Ph

5-Br

N

OEt

OEt

1-315

Ph(4-Cl)

5-Br

N

OEt

OEt

1-316

Ph(4-Me)

5-Br

N

OEt

OEt

1-317

Ph(4-OMe)

5-Br

N

OEt

OEt

1-318

H

H

CH

OPr

OPr

1-319

Me

5-Cl

N

OPr

OPr

1-320

Me

5-Br

N

OPr

OPr

1-321

Me

5-Me

N

OPr

OPr

1-322

CF

3

5-Cl

N

OPr

OPr

150-153

1-323

CF

3

5-Br

N

OPr

OPr

TABLE 46

Compound

m.p. (° C.)

No.

X

Yn

A

R

1

R

2

or RI (n

D

20

)

1-324

CF

3

5-Me

N

OPr

OPr

1-325

H

H

CH

OPr-i

OPr-i

1-326

Me

5-Cl

CH

OPr-i

OPr-i

1-327

Me

5-Me

CH

OPi-i

OPr-i

1-328

Me

5-Cl

N

OPr-i

OPr-i

1-329

Me

5-Br

N

OPr-i

OPr-i

1-330

Me

5-Me

N

OPr-i

OPr-i

1-331

CF

3

5-Cl

N

OPr-i

OPr-i

198-201

1-332

CF

3

5-Br

N

OPr-i

OPr-i

1-333

CF

3

5-Me

N

OPr-i

OPr-i

1-334

Me

5-Cl

N

OCH

2

CH═CH

2

OCH

2

CH═CH

2

1-335

Me

5-Br

N

OCH

2

CH═CH

2

OCH

2

CH═CH

2

1-336

Me

5-Me

N

OCH

2

CH═CH

2

OCH

2

CH═CH

2

1-337

CF

3

5-Cl

N

OCH

2

CH═CH

2

OCH

2

CH═CH

2

121-124

1-338

CF

3

5-Br

N

OCH

2

CH═CH

2

OCH

2

CH═CH

2

1-339

CF

3

5-Me

N

OCH

2

CH═CH

2

OCH

2

CH═CH

2

1-340

Me

5-Cl

N

OCH

2

C≡CH

OCH

2

C≡CH

1-341

Me

5-Br

N

OCH

2

C≡CH

OCH

2

C≡CH

1-342

Me

5-Me

N

OCH

2

C≡CH

OCH

2

C≡CH

1-343

CF

3

5-Cl

N

OCH

2

C≡CH

OCH

2

C≡CH

1-344

CF

3

5-Br

N

OCH

2

C≡CH

OCH

2

C≡CH

1-345

CF

3

5-Me

N

OCH

2

C≡CH

OCH

2

C≡CH

1-346

Me

5-Cl

CH

OCH

2

CN

OCH

2

CN

1-347

Me

5-Me

CH

OCH

2

CN

OCH

2

CN

1-348

Me

5-Cl

N

OCH

2

CN

OCH

2

CN

1-349

Me

5-Br

N

OCH

2

CN

OCH

2

CN

1-350

Me

5-Me

N

OCH

2

CN

OCH

2

CN

1-351

CF

3

5-Cl

N

OCH

2

CN

OCH

2

CN

1-352

CF

3

5-Br

N

OCH

2

CN

OCH

2

CN

1-353

CF

3

5-Me

N

OCH

2

CN

OCH

2

CN

1-354

Me

5-Cl

CH

OCH

2

CH

2

OMe

OCH

2

CH

2

OMe

1-355

Me

5-Me

CH

OCH

2

CH

2

OMe

OCH

2

CH

2

OMe

1-356

H

5-Br

N

OCH

2

CH

2

OMe

OCH

2

CH

2

OMe

TABLE 47

Compound

m.p. (° C.)

No.

X

Yn

A

R

1

R

2

or RI (n

D

20

)

1-357

Me

5-Cl

N

OCH

2

CH

2

OMe

OCH

2

CH

2

OMe

1-358

Me

5-Br

N

OCH

2

CH

2

OMe

OCH

2

CH

2

OMe

1-359

Me

5-Me

N

OCH

2

CH

2

OMe

OCH

2

CH

2

OMe

1-360

CF

3

5-Cl

N

OCH

2

CH

2

OMe

OCH

2

CH

2

OMe

1-361

CF

3

5-Br

N

OCH

2

CH

2

OMe

OCH

2

CH

2

OMe

1-362

CF

3

5-Me

N

OCH

2

CH

2

OMe

OCH

2

CH

2

OMe

1-363

H

5-Br

N

OCH

2

Pr-c

OCH

2

Pr-c

1-364

Me

5-Cl

N

OCH

2

Pr-c

OCH

2

Pr-c

1-365

Me

5-Br

N

OCH

2

Pr-c

OCH

2

Pr-c

1-366

Me

5-Me

N

OCH

2

Pr-c

OCH

2

Pr-c

1-367

CF

3

5-Cl

N

OCH

2

Pr-c

OCH

2

Pr-c

1-368

CF

3

5-Br

N

OCH

2

Pr-c

OCH

2

Pr-c

1-369

CF

3

5-Me

N

OCH

2

Pr-c

OCH

2

Pr-c

1-370

H

H

CH

OBn

OBn

1-371

H

H

N

OBn

OBn

1-372

H

H

N

OBn(4-Cl)

OBn(4-Cl)

1-373

H

H

N

OBn(4-Me)

OBn(4-Me)

1-374

H

H

N

OBn(4-OMe)

OBn(4-OMe)

1-375

H

H

CH

OMe

OPh

1-376

H

H

N

OMe

OPh

1-377

H

H

N

OMe

OPh(4-Cl)

1-378

H

H

N

OMe

OPh(4-Me)

1-379

H

H

N

OMe

OPh(4-OMe)

1-380

H

H

CH

OMe

OCHF

2

1-381

H

H

N

OMe

OCHF

2

1-382

Me

5-Cl

CH

OMe

H

1-383

Me

5-Me

CH

OMe

H

1-384

Me

5-CF

3

CH

OMe

H

1-385

Me

5-OMe

CH

OMe

H

1-386

CF

3

5-Cl

CH

OMe

H

125-128

1-387

CF

3

5-Me

CH

OMe

H

130-133

1-388

CF

3

5-CF

3

CH

OMe

H

1-389

CF

3

5-OMe

CH

OMe

H

153-156

TABLE 48

Compound

m.p. (° C.)

No.

X

Yn

A

R

1

R

2

or RI (n

D

20

)

1-390

CF

3

5-Cl

CH

OEt

H

1-391

CF

3

5-Me

CH

OEt

H

125-127

1-392

CF

3

5-OMe

CH

OEt

H

1-393

Me

5-Cl

CH

OMe

Me

1-394

Me

5-Me

CH

OMe

Me

1-395

Me

5-CF

3

CH

OMe

Me

1-396

CF

3

5-Cl

CH

OMe

Me

1-397

CF

3

5-Me

CH

OMe

Me

1-398

CF

3

5-OMe

CH

OMe

Me

1-399

Me

5-Cl

N

OMe

Me

1-400

Me

5-Me

N

OMe

Me

1-401

Me

5-CF

3

N

OMe

Me

1-402

CF

3

5-Cl

N

OMe

Me

1-403

CF

3

5-Me

N

OMe

Me

192-195

1-404

CF

3

5-OMe

N

OMe

Me

1-405

CF

3

5-Cl

N

OMe

Pr

1-406

CF

3

5-Br

N

OMe

Pr

1-407

CF

3

5-Me

N

OMe

Pr

149-152

1-408

CF

3

5-Cl

N

OMe

Pr-c

1-409

CF

3

5-Br

N

OMe

Pr-c

1-410

CF

3

5-Me

N

OMe

Pr-c

103-106

1-411

CF

3

5-Cl

N

OEt

Pr-c

1-412

CF

3

5-Me

N

OEt

Pr-c

1-413

CF

3

5-CF

3

N

OEt

Pr-c

1-414

Me

5-Cl

CH

OEt

Me

1-415

Me

5-Me

CH

OEt

Me

1-416

Me

5-CF

3

CH

OEt

Me

1-417

Me

5-OMe

CH

OEt

Me

1-418

CF

3

5-Cl

CH

OEt

Me

1-419

CF

3

5-Me

CH

OEt

Me

1-420

CF

3

5-OMe

CH

OEt

Me

136-139

1-421

Me

5-Cl

N

OEt

Me

1-422

Me

5-Br

N

OEt

Me

TABLE 49

m.p.

Compound

(° C.) or

No.

X

Yn

A

R

1

R

2

RI (n

D

20

)

1-423

Me

5-Me

N

OEt

Me

1-424

Me

5-CF

3

N

OEt

Me

1-425

CF

3

5-Cl

N

OEt

Me

1-426

CF

3

5-Br

N

OEt

Me

1-427

CF

3

5-Me

N

OEt

Me

1-428

CF

3

5-Cl

CH

OCH

2

CH═CH

2

Me

1-429

CF

3

5-Me

CH

OCH

2

CH═CH

2

Me

1-430

CF

3

5-OMe

CH

OCH

2

CH═CH

2

Me

1-431

CF

3

5-Cl

N

OCH

2

CH═CH

2

Me

1-432

CF

3

5-Me

N

OCH

2

CH═CH

2

Me

175-178

1-433

CF

3

5-OMe

N

OCH

2

CH═CH

2

Me

1-434

CF

3

5-Me

CH

SMe

Me

1-435

CF

3

5-Cl

CH

SMe

Me

1-436

CF

3

5-Me

N

SMe

Me

196-199

1-437

CF

3

5-Cl

N

SMe

Me

157-160

1-438

CF

3

5-Cl

N

OMe

Et

1-439

CF

3

5-Br

N

OMe

Et

1-440

CF

3

5-Me

N

OMe

Et

1-441

CF

3

5-Cl

N

OEt

Et

1-442

CF

3

5-Br

N

OEt

Et

1-443

CF

3

5-Me

N

OEt

Et

1-444

Me

5-Cl

N

SMe

SMe

1-445

Me

5-Br

N

SMe

SMe

1-446

Me

5-Me

N

SMe

SMe

1-447

CF

3

5-Cl

N

SMe

SMe

1-448

CF

3

5-Br

N

SMe

SMe

1-449

CF

3

5-Me

N

SMe

SMe

1-450

Me

5-Cl

N

OMe

SMe

1-451

Me

5-Br

N

OMe

SMe

1-452

CF

3

5-Cl

N

OMe

SMe

1-453

CF

3

5-Br

N

OMe

SMe

1-454

CF

3

5-Me

N

OMe

SMe

1-455

Me

5-Me

N

OMe

Ph

TABLE 50

m.p.

Compound

(° C.) or

No.

X

Yn

A

R

1

R

2

RI (n

D

20

)

1-456

CF

3

5-Me

N

OMe

Ph

219-222

1-457

Me

H

CH

Cl

Cl

1-458

Me

4,5-Cl

2

CH

Cl

Cl

1-459

Me

H

N

Cl

Cl

1-460

Me

H

CH

Cl

Me

1-461

Me

5-Cl

N

NMe

2

NMe

2

1-462

CF

3

5-Cl

N

NMe

2

NMe

2

219-222

1-463

H

H

CH

OMe

NMe

2

1-464

H

H

CBr

OMe

OMe

1-465

H

H

CMe

Cl

Cl

1-466

Me

5-Me

COMe

H

H

1-467

Me

5-Cl

COMe

H

H

1-468

Me

5-Cl

CH

Me

Me

1-469

Me

5-CF

3

CH

Me

Me

1-470

Me

5-Cl

CH

Me

CF

3

1-471

Me

5-Me

CH

Me

Et

1-472

Me

5-Cl

CH

Me

Et

1-473

CF

3

5-Me

CH

Me

Et

1-474

CF

3

5-Cl

CH

Me

Et

1-475

Me

5-Me

CH

Me

Pr-c

1-476

Me

5-Cl

CH

Me

Pr-c

1-477

CF

3

5-Me

CH

Me

Pr-c

1-478

CF

3

5-Cl

CH

Me

Pr-c

1-479

CF

3

5-Cl

CH

C≡CMe

Me

1-480

CF

3

5-Cl

N

C≡CMe

Me

1 481

CF

3

5-Cl

CH

CH═CH

2

Me

1-482

CF

3

5-Cl

N

CH═CH

3

Me

1-483

Me

5-Cl

CH

CHO

Me

1-484

Me

5-Cl

N

CHO

Me

1-485

Me

5-Cl

CH

COMe

Me

1-486

Me

5-Cl

N

COMe

Me

1-487

Me

5-Cl

CH

CH

2

OMe

Me

1-488

Me

5-Me

CH

CH

2

OMe

Me

TABLE 51

Compound

m.p. (° C.)

No.

X

Yn

A

R

1

R

2

or RI (n

D

20

)

1-489

Me

H

CH

CN

CN

1-490

Me

H

CH

CN

Me

1-491

Me

H

N

CN

CN

1-492

Me

H

N

CN

Me

1-493

Me

H

CH

SO

2

Me

SO

2

Me

1-494

Me

H

N

SO

2

Me

SO

2

Me

1-495

Me

H

CH

SO

2

Me

Me

TABLE 52

Compound

m.p. (° C.)

No.

Yn

A

R

1

R

2

or RI (n

D

20

)

2-1

3-Me

CH

OMe

OMe

2-2

3-Cl

CH

OMe

OMe

2-3

4-F

CH

OMe

OMe

194-196

2-4

4-Cl

CH

OMe

OMe

188-190

2-5

4-Br

CH

OMe

OMe

191-194

2-6

4-Me

CH

OMe

OMe

158-161

2-7

4-Bu-t

CH

OMe

OMe

2-8

4-CF

3

CH

OMe

OMe

178-180

2-9

4-OMe

CH

OMe

OMe

189-190

2-10

4-OEt

CH

OMe

OMe

178-180

2-11

4-OPr

CH

OMe

OMe

2-12

4-OCF

3

CH

OMe

OMe

144-147

2-13

4-OCH

2

CH═CH

2

CH

OMe

OMe

2-14

4-OCH

2

C≡CH

CH

OMe

OMe

2-15

4-OPh

CH

OMe

OMe

2-16

4-OPh(4-Cl)

CH

OMe

OMe

2-17

4-OPh(4-Me)

CH

OMe

OMe

2-18

4-OPh(4-OMe)

CH

OMe

OMe

2-19

4-SMe

CH

OMe

OMe

2-20

4-CH

2

OMe

CH

OMe

OMe

2-21

4-COMe

CH

OMe

OMe

2-22

4-COPh

CH

OMe

OMe

2-23

4-CO

2

Et

CH

OMe

OMe

2-24

4-Ph

CH

OMe

OMe

TABLE 53

Compound

m.p. (° C.)

No.

Yn

A

R

1

R

2

or RI (n

D

20

)

2-25

4-Ph(4-Cl)

CH

OMe

OMe

2-26

4-Ph(4-Me)

CH

OMe

OMe

2-27

4-Ph(4-OMe)

CH

OMe

OMe

2-28

4-NO

2

CH

Ome

OMe

2-29

4-NH2

CH

OMe

OMe

2-30

4-NHMe

CH

OMe

OMe

2-31

4-NMe

2

CH

OMe

OMe

2-32

4-CN

CH

OMe

OMe

241-244

2-33

5-F

CH

OMe

OMe

2-34

5-Cl

CH

OMe

OMe

2-35

5-Me

CH

OMe

OMe

2-36

5-CF

3

CH

OMe

OMe

2-37

5-OMe

CH

OMe

OMe

2-38

5-CO

2

Me

CH

OMe

OMe

2-39

5-COPh

CH

OMe

OMe

2-40

6-Me

CH

OMe

OMe

136-139

2-41

6-Cl

CH

OMe

OMe

2-42

4,5-Cl

2

CH

OMe

OMe

2-43

4,5-Me

2

CH

OMe

OMe

2-44

4,5-(OMe)

2

CH

OMe

OMe

2-45

4,6-Me

2

CH

OMe

OMe

139-142

2-46

3-Br, 5-CF

3

CH

OMe

OMe

2-47

3-Cl, 5-CF

3

CH

OMe

OMe

2-48

3,4,5-F

3

CH

OMe

OMe

2-49

H

N

OMe

OMe

177-180

2-50

3-Me

N

OMe

OMe

2-51

3-Cl

N

OMe

OMe

2-52

4-F

N

OMe

OMe

184-187

2-53

4-Cl

N

OMe

OMe

206-208

2-54

4-Br

N

OMe

OMe

2-55

4-I

N

OMe

OMe

218-221

TABLE 54

Compound

m.p. (° C.)

No.

Yn

A

R

1

R

2

or RI (n

D

20

)

2-56

4-Me

N

OMe

OMe

189-191

2-57

4-Et

N

OMe

OMe

146-149

2-58

4-Pr

N

OMe

OMe

170-173

2-59

4-CF

3

N

OMe

OMe

2-60

4-Bu-t

N

OMe

OMe

118-121

2-61

4-C≡CBu-t

N

OMe

OMe

117-120

2-62

4-OMe

N

OMe

OMe

197-199

2-63

4-OEt

N

OMe

OMe

2-64

4-OPr

N

OMe

OMe

2-65

4-OCF

3

N

OMe

OMe

119-122

2-66

4-OCH

2

CH═CH

2

N

OMe

OMe

2-67

4-OCH

2

C≡CH

N

OMe

OMe

2-68

4-OPh

N

OMe

OMe

2-69

4-SMe

N

OMe

OMe

2-70

4-COPh

N

OMe

OMe

221-224

2-71

4-CO

2

Me

N

OMe

OMe

289-292

2-72

4-Ph

N

OMe

OMe

2-73

4-Ph(4-Cl)

N

OMe

OMe

2-74

4-Ph(4-Me)

N

OMe

OMe

2-75

4-Ph(4-OMe)

N

OMe

OMe

2-76

4-NO

2

N

OMe

OMe

2-77

4-NH

2

N

OMe

OMe

2-78

4-NHMe

N

OMe

OMe

2-79

4-NMe

2

N

OMe

OMe

155-158

2-80

4-CN

N

OMe

OMe

189-201

2-81

5-F

N

OMe

OMe

2-82

5-Cl

N

OMe

OMe

2-83

5-Me

N

OMe

OMe

151-154

2-84

5-CF

3

N

OMe

OMe

2-85

5-OMe

N

OMe

OMe

2-86

5-NO

2

N

OMe

OMe

TABLE 55

Compound

m.p. (° C.)

No.

Yn

A

R

1

R

2

or RI (n

D

20

)

2-87

5-CO

2

Et

N

OMe

OMe

2-88

5-COPh

N

OMe

OMe

2-89

6-Me

N

OMe

OMe

2-90

6-Cl

N

OMe

OMe

2-91

4,5-Cl

2

N

OMe

OMe

2-92

4,5-Me

2

N

OMe

OMe

2-93

4,5-(OMe)

2

N

OMe

OMe

2-94

3-Br, 5-CF

3

N

OMe

OMe

2-95

3-Cl, 5-CF

3

N

OMe

OMe

2-96

3,4,5-F

3

N

OMe

OMe

2-97

4-Me

N

OMe

OEt

173-175

2-98

4-Cl

N

OMe

OEt

130-132

2-99

4-Br

N

OMe

OEt

2-100

H

CH

OEt

OEt

92-95

2-101

4-F

CH

OEt

OEt

131-134

2-102

4-Cl

CH

OEt

OEt

147-149

2-103

4-Br

CH

OEt

OEt

2-104

4-Me

CH

OEt

OEt

147-150

2-105

4-CF

3

CH

OEt

OEt

134-137

2-106

4-F

N

OEt

OEt

2-107

4-Cl

N

OEt

OEt

2-108

4-Br

N

OEt

OEt

2-109

4-Me

N

OEt

OEt

2-110

4-CF

3

N

OEt

OEt

2-111

4-Cl

N

OPr

OPr

2-112

4-Cl

CH

OPr-i

OPr-i

2-113

4-Me

CH

OPr-i

OPr-i

2-114

4-Cl

N

OPr-i

OPr-i

2-115

4-Br

N

OPr-i

OPr-i

2-116

4-Cl

N

OCH

2

CH═CH

2

OCH

2

CH═CH

2

2-117

4-Br

N

OCH

2

CH═CH

2

OCH

2

CH═CH

2

TABLE 56

m.p.

Compound

(° C.) or

No.

Yn

A

R

1

R

2

RI (n

D

20

)

2-118

4-Cl

N

OCH

2

C≡CH

OCH

2

C≡CH

2-119

4-Br

N

OCH

2

C≡CH

OCH

2

C≡CH

2-120

4-Cl

N

OCH

2

CN

OCH

2

CN

2-121

4-Br

N

OCH

2

CN

OCH

2

CN

2-122

4-Br

N

OCH

2

CH

2

OMe

OCH

2

CH

2

OMe

2-123

4-Cl

N

OCH

2

CH

2

OMe

OCH

2

CH

2

OMe

2-124

4-Br

N

OCH

2

Pr-c

OCH

2

Pr-c

2-125

4-Cl

N

OCH

2

Pr-c

OCH

2

Pr-c

65-68

2-126

H

CH

OBn

OBn

2-127

H

N

OBn

OBn

2-128

H

N

OBn(4-Cl)

OBn(4-Cl)

2-129

H

N

OBn(4-Me)

OBn(4-Me)

2-130

H

N

OBn(4-OMe)

OBn(4-OMe)

2-131

H

CH

OMe

OPh

2-132

H

N

OMe

OPh

2-133

H

N

OMe

OPh(4-Cl)

2-134

H

N

OMe

OPh(4-Me)

2-135

H

N

OMe

OPh(4-OMe)

2-136

H

CH

OMe

OCHF

2

2-137

H

N

OMe

OCHF

2

2-138

4-Cl

CH

OMe

H

136-139

2-139

4-Me

CH

OMe

H

136-139

2-140

4-Cl

CH

OEt

H

118-119

2-141

4-Me

CH

OEt

H

99-100

2-142

4-Cl

CH

OMe

Me

2-143

4-Me

CH

OMe

Me

2-144

4-CF

3

CH

OMe

Me

155-158

2-145

4-Cl

N

OMe

Me

2-146

4-Me

N

OMe

Me

2-147

4-Cl

N

OMe

Pr

2-148

4-Me

N

OMe

Pr

116-119

TABLE 57

Compound

m.p. (° C.)

No.

Yn

A

R

1

R

2

or RI (n

D

20

)

2-149

4-Cl

N

OMe

Pr-c

2-150

4-Br

N

OMe

Pr-c

20151

4-Me

N

OMe

Pr-c

130133

2-152

4-Cl

N

OEt

Pr-c

2-153

4-Me

N

OEt

Pr-c

2-154

4-Cl

N

OMe

Et

109-112

2-155

4-Br

N

OMe

Et

113-116

2-156

4-Me

N

OMe

Et

2-157

4-Cl

N

OEt

Et

2-158

4-Br

N

OEt

Et

2-159

4-Me

N

OEt

Et

2-160

4-Me

N

OPr

Me

175-178

2-161

4-Cl

N

OPr

Me

2-162

4-Me

CH

Me

Et

75-78

2-163

4-Cl

CH

Me

Et

2-164

4-Me

CH

Et

Et

64-67

2-165

4-Cl

CH

Et

Et

2-166

4-Me

N

Me

SMe

174-177

2-167

4-Cl

N

SMe

SMe

179-182

2-168

4-Br

N

SMe

SMe

2-169

4-Me

N

SMe

SMe

2-170

4-Cl

N

OMe

SMe

2-171

4-Me

N

OMe

SMe

2-172

4-Me

N

OMe

Ph

165-168

2-173

4-Cl

N

NMe

2

NMe

2

>300

2-174

H

CBr

OMe

OMe

2-175

H

CMe

Cl

Cl

2-176

4-Me

COMe

H

H

2-177

4-Cl

COMe

H

H

2-178

4-Me

N

Cl

Ph

106-109

2-179

4-Cl

N

Cl

Ph

TABLE 58

Compound

m.p. (° C.)

No.

Yn

A

R

1

R

2

or RI (n

D

20

)

2-180

4-Cl

CH

C≡CMe

Me

2-181

4-Cl

N

C≡CMe

Me

2-182

4-Cl

CH

CH═CH

2

Me

2-183

4-Cl

N

CH═CH

2

Me

2-184

4-Cl

CH

CHO

Me

2-185

4-Cl

N

CHO

Me

2-186

4-Cl

CH

COMe

Me

2-187

4-Cl

N

COMe

Me

2-188

4-Cl

CH

CH

2

OMe

Me

2-189

4-Me

CH

CH

2

OMe

Me

2-190

H

CH

CN

CN

2-191

H

CH

CN

Me

2-192

H

N

CN

CN

2-193

H

N

CN

Me

2-194

H

CH

SO

2

Me

SO

2

Me

2-195

H

N

SO

2

Me

SO

2

Me

2-196

H

CH

SO

2

Me

Me

TABLE 59

Compound

m.p. (° C.)

No.

Yn

A

R

1

R

2

or RI (n

D

20

)

3-1

3-Me

CH

OMe

OMe

3-2

3-Cl

CH

OMe

OMe

3-3

4-F

CH

OMe

OMe

120-123

3-4

4-Cl

CH

OMe

OMe

3-5

4-Br

CH

OMe

OMe

117-118

3-6

4-Me

CH

OMe

OMe

128-129

3-7

4-Bu-t

CH

OMe

OMe

3-8

4-CF

3

CH

OMe

OMe

113-115

3-9

4-OMe

CH

OMe

OMe

3-10

4-OEt

CH

OMe

OMe

129-132

3-11

4-OPr

CH

OMe

OMe

3-12

4-OCF

3

CH

OMe

OMe

85-88

3-13

4-OCH

2

CH═CH

2

CH

OMe

OMe

3-14

4-OCH

2

C≡CH

CH

OMe

OMe

3-15

4-OPh

CH

OMe

OMe

3-16

4-OPh(4-Cl)

CH

OMe

OMe

3-17

4-OPh(4-Me)

CH

OMe

OMe

3-18

4-OPh(4-OMe)

CH

OMe

OMe

3-19

4-SMe

CH

OMe

OMe

3-20

4-CH

2

OMe

CH

OMe

OMe

3-21

4-COMe

CH

OMe

OMe

3-22

4-COPh

CH

OMe

OMe

3-23

4-CO

2

Et

CH

OMe

OMe

3-24

4-Ph

CH

OMe

OMe

130-132

TABLE 60

m.p. (° C.)

or

Compound

RI

No.

Yn

A

R

1

R

2

(n

D

20

)

3-25

4-Ph(4-Cl)

CH

OMe

OMe

3-26

4-Ph(4-Me)

CH

OMe

OMe

3-27

4-Ph(4-OMe)

CH

OMe

OMe

3-28

4-NO

2

CH

OMe

OMe

3-29

4-NH

2

CH

OMe

OMe

3-30

4-NHMe

CH

OMe

OMe

3-31

4-NMe

2

CH

OMe

OMe

3-32

4-CN

CH

OMe

OMe

166-169

3-33

5-F

CH

OMe

OMe

3-34

5-Cl

CH

OMe

OMe

124-125

3-35

5-Me

CH

OMe

OMe

91-94

3-36

5-CF

3

CH

OMe

OMe

3-37

5-OMe

CH

OMe

OMe

3-38

5-CO

2

Me

CH

OMe

OMe

3-39

5-COPh

CH

OMe

OMe

3-40

6-Me

CH

OMe

OMe

3-41

6-Cl

CH

OMe

OMe

3-42

4,5-Cl

2

CH

OMe

OMe

3-43

4,6-Me

2

CH

OMe

OMe

145-147

3-44

4,5-Me

2

CH

OMe

OMe

3-45

4,5-(OMe)

2

CH

OMe

OMe

3-46

3-Br,5-CF

3

CH

OMe

OMe

3-47

3-Cl,5-CF

3

CH

OMe

OMe

3-48

3,4,5-F

3

CH

OMe

OMe

3-49

H

N

OMe

OMe

152-155

3-50

3-Me

N

OMe

OMe

3-51

3-Cl

N

OMe

OMe

3-52

4-F

N

OMe

OMe

183-186

3-53

4-Cl

N

OMe

OMe

202-205

3-54

4-Br

N

OMe

OMe

200-203

3-55

4-I

N

OMe

OMe

191-194

TABLE 61

m.p. (° C.)

or

Compound

RI

No.

Yn

A

R

1

R

2

(n

D

20

)

3-56

4-Me

N

OMe

OMe

180-183

3-57

4-Et

N

OMe

OMe

123-126

3-58

4-Pr

N

OMe

OMe

136-139

3-59

4-CF

3

N

OMe

OMe

177-180

3-60

4-Bu-t

N

OMe

OMe

140-143

3-61

4-C-≡CBu-t

N

OMe

OMe

161-164

3-62

4-OMe

N

OMe

OMe

182-185

3-63

4-OEt

N

OMe

OMe

3-64

4-OPr

N

OMe

OMe

3-65

4-OCF

3

N

OMe

OMe

3-66

4-OCH

2

CH═CH

2

N

OMe

OMe

3-67

4-OCH

2

C≡CH

N

OMe

OMe

3-68

4-OPh

N

OMe

OMe

3-69

4-SMe

N

OMe

OMe

3-70

4-COPh

N

OMe

OMe

175-178

3-71

4-CO

2

Me

N

OMe

OMe

197-200

3-72

4-Ph

N

OMe

OMe

3-73

4-Ph(4-Cl)

N

OMe

OMe

3-74

4-Ph(4-Me)

N

OMe

OMe

3-75

4-Ph(4-OMe)

N

OMe

OMe

3-76

4-NO

2

N

OMe

OMe

3-77

4-NH

2

N

OMe

OMe

3-78

4-NHMe

N

OMe

OMe

3-79

4-NMe

2

N

OMe

OMe

115-118

3-80

4-CN

N

OMe

OMe

215-218

3-81

5-F

N

OMe

OMe

3-82

5-Cl

N

OMe

OMe

3-83

5-Me

N

OMe

OMe

131-134

3-84

5-CF

3

N

OMe

OMe

3-85

5-OMe

N

OMe

OMe

3-86

5-NO

2

N

OMe

OMe

TABLE 62

m.p. (° C.)

or

Compound

RI

No.

Yn

A

R

1

R

2

(n

D

20

)

3-87

5-CO

2

Et

N

OMe

OMe

3-88

5-COPh

N

OMe

OMe

3-89

6-Me

N

OMe

OMe

3-90

6-Cl

N

OMe

OMe

3-91

4,5-Cl

2

N

OMe

OMe

3-92

4,5-Me

2

N

OMe

OMe

3-93

4,5-(OMe)

2

N

OMe

OMe

3-94

3-Br,5-CF

3

N

OMe

OMe

3-95

3-Cl,5-CF

3

N

OMe

OMe

3-96

3,4,5-F

3

N

OMe

OMe

3-97

4-Me

N

OMe

OEt

134-137

3-98

4-Cl

N

OMe

OEt

132-135

3-99

4-Br

N

OMe

OEt

140-142

3-100

H

CH

OEt

OEt

146-148

3-101

4-F

CH

OEt

OEt

3-102

4-Cl

CH

OEt

OEt

3-103

4-Br

CH

OEt

OEt

3-104

4-Me

CH

OEt

OEt

3-105

4-CF

3

CH

OEt

OEt

167-170

3-106

4-F

N

OEt

OEt

3-107

4-Cl

N

OEt

OEt

163-166

3-108

4-Br

N

OEt

OEt

172-175

3-109

4-Me

N

OEt

OEt

158-161

3-110

4-Bu-t

N

OEt

OEt

128-129

3-111

4-OMe

N

OEt

OEt

128-129

3-112

4-CF

3

N

OEt

OEt

3-113

4-Cl

N

OPr

OPr

145-148

3-114

4-Cl

CH

OPr-i

OPr-i

3-115

4-Me

CH

OPr-i

OPr-i

3-116

4-Cl

N

OPr-i

OPr-i

179-182

3-117

4-Br

N

OPr-i

OPr-i

TABLE 63

m.p. (° C.)

or

Compound

RI

No.

Yn

A

R

1

R

2

(n

D

20

)

3-118

4-Cl

N

OCH

2

CH═CH

2

OCH

2

CH═CH

2

3-119

4-Br

N

OCH

2

CH═CH

2

OCH

2

CH═CH

2

3-120

4-Cl

N

OCH

2

C≡CH

OCH

2

C≡CH

3-121

4-Br

N

OCH

2

C≡CH

OCH

2

C≡CH

3-122

4-Cl

N

OCH

2

CN

OCH

2

CN

3-123

4-Br

N

OCH

2

CN

OCH

2

CN

3-124

4-Br

N

OCH

2

CH

2

OMe

OCH

2

CH

2

OMe

3-125

4-Cl

N

OCH

2

CH

2

OMe

OCH

2

CH

2

OMe

3-126

4-Br

N

OCH

2

Pr-c

OCH

2

Pr-c

3-127

4-Cl

N

OCH

2

Pr-c

OCH

2

Pr-c

156-159

3-128

H

CH

OBn

OBn

3-129

H

N

OBn

OBn

3-130

H

N

OBn(4-Cl)

OBn(4-Cl)

3-131

H

N

OBn(4-Me)

OBn(4-Me)

3-132

H

N

OBn(4-OMe)

OBn(4-OMe)

3-133

H

CH

OMe

OPh

3-134

H

N

OMe

OPh

3-135

H

N

OMe

OPh(4-Cl)

3-136

H

N

OMe

OPh(4-Me)

3-137

H

N

OMe

OPh(4-OMe)

3-138

H

CH

OMe

OCHF

2

3-139

H

N

OMe

OCHF

2

3-140

4-Cl

CH

OMe

H

136-139

3-141

4-Me

CH

OMe

H

126-129

3-142

4-Cl

CH

OEt

H

113-115

3-143

4-Me

CH

OEt

H

103-105

3-144

4-Cl

CH

OMe

Me

3-145

4-Me

CH

OMe

Me

3-146

4-CF

3

CH

OMe

Me

134-137

3-147

4-Cl

N

OMe

Me

3-148

4-Me

N

OMe

Me

202-205

TABLE 64

m.p. (° C.)

or

Compound

RI

No.

Yn

A

R

1

R

2

(n

D

20

)

3-149

4-Cl

N

OMe

Pr

3-150

4-Me

N

OMe

Pr

133-136

3-151

4-Cl

N

OMe

Pr-c

3-152

4-Br

N

OMe

Pr-c

163-165

3-153

4-Me

N

OMe

Pr-c

56-59

3-154

4-Cl

N

OEt

Pr-c

163-166

3-155

4-Me

N

OEt

Pr-c

105-108

3-156

4-Cl

N

OMe

Et

155-158

3-157

4-Br

N

OMe

Et

162-165

3-158

4-Me

N

OMe

Et

171-174

3-159

4-Cl

N

OEt

Et

3-160

4-Br

N

OEt

Et

3-161

4-Me

N

OEt

Et

3-162

4-Me

N

OPr

Me

3-163

4-Cl

N

OPr

Me

3-164

4-Me

CH

Me

Et

92-95

3-165

4-Cl

CH

Me

Et

3-166

4-Me

CH

Et

Et

91-94

3-167

4-Cl

CH

Et

Et

3-168

4-Me

N

Me

SMe

180-183

3-169

4-Cl

N

SMe

SMe

192-195

3-170

4-Br

N

SMe

SMe

3-171

4-Me

N

SMe

SMe

3-172

4-Cl

N

OMe

SMe

3-173

4-Me

N

OMe

SMe

3-174

4-Me

N

OMe

Ph

170-173

3-175

4-Cl

N

NMe

2

NMe

2

176-179

3-176

H

CBr

OMe

OMe

3-177

H

CMe

Cl

Cl

3-178

4-Me

COMe

H

H

3-179

4-Cl

COMe

H

H

TABLE 65

m.p. (° C.)

or

Compound

RI

No.

Yn

A

R

1

R

2

(n

D

20

)

3-180

4-Me

N

Cl

Ph

3-181

4-Cl

N

Cl

Ph

3-182

4-Cl

CH

C≡CMe

Me

3-183

4-Cl

N

C≡CMe

Me

3-184

4-Cl

CH

CH═CH

2

Me

3-185

4-Cl

N

CH═CH

2

Me

3-186

4-Cl

CH

CHO

Me

3-187

4-Cl

N

CHO

Me

3-188

4-Cl

CH

COMe

Me

3-189

4-Cl

N

COMe

Me

3-190

4-Cl

CH

CH

2

OMe

Me

3-191

4-Me

CH

CH

2

OMe

Me

3-192

H

CH

CN

CN

3-193

H

CH

CN

Me

3-194

H

N

CN

CN

3-195

H

N

CN

Me

3-196

H

CH

SO

2

Me

SO

2

Me

3-197

H

N

SO

2

Me

SO

2

Me

3-198

H

CH

SO

2

Me

Me

BEST MODE FOR CARRYING OUT THE INVENTION

Now, the processes for producing the compound of the present invention, formulation methods and applications will be specifically described with reference to Examples.

PREPARATION EXAMPLE 1

1-(4-methoxypyrimidin-2-yl)-benzimidazole (Compound Number I-667)

Benzimidazole (0.50 g) was dissolved in dimethylformamide (10 ml), and sodium hydride (60% purity, oily) (0.18 g) was added thereto at room temperature. After stirring for 1 hour, 2-chloro-4-methoxypyrimidine (0.62 g) was added at room temperature, followed by stirring for 3 hours. Ice water was added, followed by extraction with ethyl acetate, washing with a saturated sodium chloride aqueous solution and drying over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 0.40 g of the desired product as a white powder (m.p. 114-116° C.).

PREPARATION EXAMPLE 2

1-(4,6-Dimethoxypyrimidin-2-yl)-2-methylthiobenzimidazole (Compound Number I-4)

2-Methylthiobenzimidazole (0.50 g) was dissolved in dimethylformamide (10 ml), and sodium hydride (60% purity, oily) (0.13 g) was added thereto at room temperature. After stirring for 1 hour, 2-methylsulfonyl-4,6-dimethoxypyrimidine (0.67 g) was added at room temperature, followed by stirring for 8 hours. Ice water was added, followed by extraction with ethyl acetate, washing with a saturated sodium chloride aqueous solution and drying over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 0.80 g of the desired product as a white powder (m.p. 135-137° C.)

PREPARATION EXAMPLE 3

1-(4,6-Dimethoxypyrimidin-2-yl)-2-methylsulfonylbenzimidazole (Compound Number I-5)

1-(4,6-dimethoxypyrimidin-2-yl)-2-methylthiobenzimidazole (0.70 g) and m-chloroperbenzoic acid (1.30 g) were dissolved in chloroform (30 ml), followed by stirring at room temperature for 3 hours. The reaction liquid was washed with a 5% aqueous potassium carbonate solution and water, and the organic solvent layer was dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 0.50 g of the desired product as a white powder (m.p. 114-117° C.).

PREPARATION EXAMPLE 4

1-(4,6-Dimethoxypyrimidin-2-yl)-2-methoxybenzimidazole (Compound Number I-18)

1-(4,6-dimethoxypyrimidin-2-yl)-2-methylsulfonylbenzimidazole (0.40 g) was dissolved in tetrahydrofuran (20 ml), and sodium methylate (0.50 g) was added thereto under cooling with ice, followed by stirring for 1 hour. Ice water was added, followed by extraction with ethyl acetate, washing with a saturated sodium chloride aqueous solution and drying over anhydrous magnesium sulfate. The solvent was distilled off, and the mixture was purified by silica gel column chromatography to obtain 0.40 g of the desired product as a white powder (m.p. 121-122° C.).

PREPARATION EXAMPLE 5

1-(4,6-Dimethoxypyrimidin-2-yl)-2,5-dimethylbenzimidazole (Compound Number I-186)

In N′-(4,6-dimethoxypyrimidin-2-yl)-4-methylbenzene-1,2-diamine (2.50 g) was dissolved in acetic acid (20 ml) and acetic anhydride (10 ml), followed by reflux for 4 hours. Water was added, and the crystals were collected by filtration, washed with water and dried. Recrystallization from ethanol was carried out to obtain 1.90 g of the desired product as white feather-like crystals (m.p. 163-166° C.)

PREPARATION EXAMPLE 6

2-Amino-1-(4,6-dimethoxypyrimidin-2-yl)-5-methylbenzimidazole (Compound Number I-362)

N′-(4,6-dimethoxypyrimidin-2-yl)-4-methylbenzene-1,2-diamine (2.00 g) was dissolved in ethanol, and cyanogen bromide (1.00 g) was added thereto at room temperature, followed by stirring at 60° C. for 1 hour. Water was added, and the crystals were collected by filtration, washed with water and dried to obtain 2.03 g of the desired product as a white powder (m.p. at least 300° C.).

PREPARATION EXAMPLE 7

2-Chloro-1-(4,6-dimethoxypyrimidin-2-yl)-5-methylbenzimidazole (Compound Number I-258)

2-Amino-1-(4,6-dimethoxypyrimidin-2-yl)-5-methylbenzimidazole (1.67 g) and copper(II)chloride (0.94 g) were suspended in acetonitrile (30 ml), and tert-butyl nitrite (0.90 g) was added thereto at room temperature, followed by reflux for 30 minutes. Water was added, followed by extraction with ethyl acetate, washing with a saturated sodium chloride aqueous solution and drying over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 1.48 g of the desired product as white feather-like crystals (m.p. 145-148° C.).

PREPARATION EXAMPLE 8

1-(4,6-Dimethoxypyrimidin-2-yl)-5-methyl-2-trifluoromethylbenzimidazole (Compound Number I-298)

2-(4,6-dimethoxypyrimidin-2-yl)amino-5-methyltrifluoroacetic anilide (0.60 g) and para-toluenesulfonic acid (0.05 g) were dissolved in toluene (30 ml), followed by reflux for 5 hours. Water and ethyl acetate were added, and the organic layer was washed with a saturated sodium hydrogencarbonate solution and a saturated sodium chloride aqueous solution and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 0.56 g of the desired product as a white powder (m.p. 93-96° C.).

PREPARATION EXAMPLE 9

1-(4,6-Dichloro-[1,3,5]triazin-2-yl)-2-methylbenzimidazole (Compound Number I-1066)

2-Methylbenzimidazole (5.0 g) was dissolved in tetrahydrofuran (50 ml), and sodium hydride (60% purity, oily) (1.6 g) was added thereto at room temperature. After stirring for 1 hour, cyanuric chloride (7.0 g) was added at room temperature, followed by stirring for 3 hours. Ice water was added, followed by extraction with ethyl acetate, washing with a saturated sodium chloride aqueous solution and drying over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 2.6 g of the desired product as a white powder (m.p. at least 300° C.).

PREPARATION EXAMPLE 10

1-(4,6-Dimethylthio-[1,3,5]triazin-2-yl)-2-methylbenzimidazole (Compound Number I-1042)

1-(4,6-dichloro-[1,3,5]triazin-2)-2-methylbenzimidazole (0.5 g) was dissolved in methanol (10 ml), and a 15% aqueous methyl mercaptan sodium salt solution (0.25 g) was added at room temperature, followed by stirring for 1 hour. After the completion of the reaction, the reaction liquid was poured into ice water, and the crystals thus deposited were collected by filtration, washed with water and dried to obtain 0.46 g of the desired product as a white powder (m.p. 176-179° C.).

PREPARATION EXAMPLE 11

5-Chloro-1-(4,6-dimethoxy-[1,3,5]triazin-2-yl)-2-methylbenzimidazole (Compound Number I-215)

4-Chloro-N′-(4,6-dimethoxy-[1,3,5]triazin-z-2-yl)benzene-1,2-diamine (0.5 g) was dissolved in acetic acid (10 ml), and acetic anhydride (10 ml) followed by reflux for 4 hours. Water was added, and the crystals were collected by filtration, washed with water and dried. Recrystallization from ethanol was carried out to obtain 0.47 g of the desired product as white feather-like crystals (m.p. 173-176° C.).

PREPARATION EXAMPLE 12

5-Chloro-1-(4,6-dimethoxy-[1,3,5]triazin-2-yl)-2-methylbenzimidazole (Compound Number I-215)

2-Nitro-4-chloro-N-(4,6-dimethoxy-[1,3,5]triazin-2-yl)aniline (0.5 g) and iron powder (0.3 g) were dissolved in acetic acid (10 ml) and acetic anhydride (5 ml), followed by reflux for 4 hours. The reaction mixture was cooled to room temperature, followed by filtration. The filtrate was concentrated under reduced pressure, water was added to the residue, and the crystals were collected by filtration, washed with water and dried. Recrystallization from ethanol was carried out to obtain 0.39 g of the desired product as white feather-like crystals (m.p. 173-176° C.)

PREPARATION EXAMPLE 13

2-Amino-5-chloro-1-(4,6-dimethoxy-[1,3,5]triazin-2-yl)benzimidazole (Compound Number I-368)

4-Chloro-N′-(4,6-dimethoxy-[1,3,5]triazin-2-yl)benzene-1,2-diamine (1.5 g) was dissolved in ethanol (50 ml), and cyanogen bromide (0.6 g) was added thereto at room temperature, followed by stirring at 60° C. for 1 hour. Water was added, and the crystals were collected by filtration, washed with water and dried to obtain 1.2 g of the desired product as a pink powder (m.p. 293-2960° C.)

PREPARATION EXAMPLE 14

2,5-Dichloro-1-(4,6-dimethoxy-[1,3,5]triazin-2-yl)benzimidazole (Compound Number I-277)

2-Amino-5-chloro-1-(4,6-dimethoxy-[1,3,5]triazin-2-yl)benzimidazole (1.1 g) and copper(II)chloride (0.6 g) were suspended in acetonitrile (50 ml), and tert-butyl nitrite (0.5 g) was added thereto at room temperature, followed by reflux for 30 minutes. Water was added, followed by extraction with ethyl acetate, washing with a saturated sodium chloride aqueous solution and drying over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 0.5 g of the desired product as white feather-like crystals (m.p. 146-149° C.).

PREPARATION EXAMPLE 15

1-(4,6-Dimethoxy-[1,3,5]triazin-2-yl)-5-methyl-2-trifluoromethylbenzimidazole (Compound Number I-312)

2-(4,6-dimethoxy-[1,3,5]triazin-2-yl)amino-5-methyltrifluoroacetic anilide (1.0 g) and para-toluenesulfonic acid (0.05 g) were dissolved in chlorobenzene (30 ml), followed by reflux for 5 hours. Water and ethyl acetate were added, and the organic layer was washed with a saturated sodium hydrogencarbonate solution and a saturated sodium chloride aqueous solution and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 0.23 g of the desired product as a white powder (m.p. 137-140° C.).

Now,

1

H-NMR(CDCl

3

/TMS, δ (ppm)) data of some among examples of the compounds of the present invention, will be shown below.

TABLE 66

Compound

No.

1

H-NMR δ (ppm), solvent CDCl

3

I-30

2.99(6H,s);4.03(6H,s);5.99(1H,8);7.03-7.09(1H,m);7.17-7.22(1H,m);

7.48-7.51(1H,m);7.84-7.85(1H,m);8.01(1H,s)

I-34

3.64(6H,s);5.92(1H,s);7.42-7.36(5H,m);7.56-7.60(2H,m);

7.58-7.88(1H,m);8.20-8.23(1H,m)

I-840

1.41(6H,d,J=6.3Hz);2.52(3H,s);2.98(3H,s);5.39-5.47(1H,m);

6.46(1H,s);7.26-7.33(2H,m);7.69-7.72(1H,m);8.25-8.28(1H,m)

I-872

1.01(3H,t,J=7.5Hz);1.49-1.57(2H,m);1.80-1.87(2H,m);2.51(3H,s);

4.50(2H,t,J=6.57Hz);6.45(1H,s);7.33-7.43(2H,m);7.82-7.85(1H,m);

8.55-8.59(1H,m);9.05(1H,s)

I-906

1.66-2.11(8H,m);2.45(3H,8);5.51-5.56(1H,m);6.36(1H,s);

7.28-7.41(2H,m);7.81-7.83(1H,m);8.45-8.52(1H,m);9.05(1H,s)

I-907

1.65-2.04(8H,m);2.51(3H,s);3.98(3H,s);5.51-5.55(1H,m);6.46(1H,s);

7.26-7.34(2H,m);7.68-7.73(1H,m);8.25-8.31(1H,m)

I-959

1.03(3H,t,J=7.41Hz);1.81-1.89(2H,m);2.76(2H,t,J=7.14Hz);

3.00(3H,s);4.08(3H,s);6.51(1H,s);7.27-7.33(2H,m);7.70-7.73(1H,m);

8.28-8.34(1H,m)

I-960

1.03(3H,t,J=7.29Hz);1.81-1.89(2H,m);2.77(2H,t,J=7.29Hz);

4.07(3H,s);6.58(1H,s);7.30-7.37(2H,m);7.71-7.74(1H,m);

8.00-8.05(1H,m)

Now, Preparation Examples of intermediates for the synthesis of the compounds of the present invention will be shown below.

PREPARATION EXAMPLE 16

N-(4,6-Dimethoxypyrimidin-2-yl)-4-methyl-2-nitroaniline (Compound Number 2-6)

N-formyl-4-methyl-2-nitroaniline (25.00 g) was dissolved in dimethylformamide (400 ml), and sodium hydride (60% purity, oily) (6.11 g) was added thereto at room temperature. After stirring for 10 minutes, 2-methylsulfonyl-4,6-dimethoxypyrimidine (30.28 g) was added at room temperature, followed by stirring for 3 hours. A 10% NaOH aqueous solution was added thereto, and the crystals were collected by filtration, washed with water and dried to obtain 37.50 g of the desired product as a yellow powder (m.p. 158-161° C.).

PREPARATION EXAMPLE 17

N′-(4,6-Dimethoxypyrimidin-2-yl)-4-methylbenzene-1,2-diamine (Compound Number 3-6)

N-(4,6-dimethoxypyrimidin-2-yl)-4-methyl-2-nitroaniline (37.50 g) was dissolved in ethyl acetate (600 ml), and 10% palladium carbon (3.75 g) was added thereto. Stirring was carried out at room temperature under normal pressure in an atmosphere of hydrogen for 4 hours, followed by filtration. The solvent of the filtrate was distilled off to obtain 32.70 g of the desired product as a white powder (m.p. 128-129° C.).

PREPARATION EXAMPLE 18

2-(4,6-Dimethoxypyrimidin-2-yl)amino-5-methyltrifluoroacetic Anilide (Compound Number 1-196)

N′-(4,6-dimethoxypyrimidin-2-yl)-4-methylbenzene-1,2-diamine (0.80 g) was dissolved in pyridine (10 ml), and trifluoroacetic anhydride (0.97 g) was added thereto under cooling with ice salt. After stirring for 1 hour, diluted hydrochloric acid was added thereto, followed by extraction with ethyl acetate, washing with diluted hydrochloric acid and a saturated sodium chloride aqueous solution and drying over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 0.88 g of the desired product as a white powder (m.p. 144-147° C.)

PREPARATION EXAMPLE 19

N-(4,6-Dimethoxy-[1,3,5]triazin-2-yl)-4-methyl-2-nitroaniline (Compound Number 2-56)

N-formyl-4-methyl-2-nitroaniline (7.2 g) was dissolved in tetrahydrofuran (50 ml), and sodium hydride (60% purity, oily) (2.0 g) was added thereto at room temperature. After stirring for 10 minutes, 2-chloro-4,6-dimethoxy-[1,3,5]triazine (7.0 g) was added at room temperature, followed by stirring for 3 hours. A 10% aqueous sodium hydroxide solution was added thereto, and the crystals were collected by filtration, washed with water and dried to obtain 10.0 g of the desired product as a yellow powder (m.p. 189-191° C.).

SYNTHESIS EXAMPLE 20

N′-(4,6-Dimethoxy-[1,3,5]triazin-2-yl)-4-methylbenzene-1,2-diamine (Compound Number 3-56)

N-(4,6-dimethoxy-[1,3,5]triazin-2-yl)-4-methyl-2-nitroaniline (10 g) was dissolved in ethyl acetate (50 ml) and water (50 ml), and 10 g of iron power and acetic acid (2 ml) were added thereto, followed by reflux for 2 hours. Insoluble matters were removed by filtration, and the ethyl acetate layer was washed with a saturated sodium chloride aqueous solution and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 8.8 g of the desired product as a white powder (m.p. 180-183° C.)

PREPARATION EXAMPLE 21

2-(4,6-Dimethoxy-[1,3,5]triazin-2-yl)amino-5-methyltrifluoroacetic Anilide (Compound Number 1-210)

N′-(4,6-dimethoxy-[1,3,5]triazin-2-yl)-4-methylbenzene-1,2-diamine (1.0 g) was dissolved in pyridine (50 ml), and trifluoroacetic anhydride (0.8 g) was added thereto under cooling with ice salt. After stirring for 1 hour, diluted hydrochloric acid was added thereto, followed by extraction with ethyl acetate, washing with diluted hydrochloric acid and a saturated sodium chloride aqueous solution and drying over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 1.3 g of the desired product as a white powder (m.p. 195-198° C.).

PREPARATION EXAMPLE 22

4-Chloro-N-(4,6-dimethoxy-[1,3,5]triazin-2-yl)-2-nitroaniline (Compound Number 2-53)

4-Chloro-2-nitroaniline (5.0 g) and sodium hydrogencarbonate (3.6 g) were dissolved in tetrahydrofuran (50 ml), and cyanuric chloride (8.0 g) was added thereto, followed by stirring for 8 hours. To the reaction solution, 28% sodium methylate (11.2 g) was added, followed by ref lux for 1 hour. Water was added thereto, followed by extraction with ethyl acetate, washing with a saturated sodium chloride aqueous solution and drying over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was subjected to recrystallization from ethanol to obtain 6.3 of the desired product as a yellow powder (m.p. 206-208° C.).

The agricultural/horticultural fungicides of the present invention contain triazinylbenzimidazole derivatives represented by the general formula [I] as the active ingredients. When the compounds of the present invention are used for agricultural/horticultural fungicides, the active ingredient can be used in appropriate formulations depending on the purpose. The active ingredient is usually diluted with an inert liquid or solid carrier and is used in an appropriate dosage form such as a dust, a wettable powder, an emulsifiable concentrate or a granule by blending it with a surfactant and other ingredients, depending on its use.

Preferable examples of carriers include solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate and urea and liquid carriers such as isopropyl alcohol, xylene, cyclohexanone and methylnaphthalene. Examples of surfactants and dispersants include dinaphthylmethanesulfonates, alcohol-sulfuric acid ester salts, alkylarylsulfonates, lignin sulfonate, polyoxyethylene glycol ether, polyoxyethylene oalkyl aryl ethers and polyoxyethylene sorbitan monoalkylate. Examples of adjuvants include carboxymethyl cellulose and the like. These formulations are applied after diluted to appropriate concentrations or directly.

The agricultural/horticultural fungicides of the present invention can be used for foliage treatment, soil treatment or submerged treatment. The blending proportion of the active ingredient is suitably selected depending on the case. However, the preferable proportion is from 0.1 to 20% (by weight) in the cases of a dust or a granule, and from 5 to 80% (by weight) in the cases of an emulsifiable concentrate or a wettable powder.

The dose of the agricultural/horticultural fungicides of the present invention depends on the type of the compound to be used, the disease to be controlled, the tendency of disease development, the degrees of the damage, the environmental conditions and the type of the formulation to be used. For example, for direct use as a dust or a granule, the dose of the active ingredient is selected suitably within a range of from 0.1 g to 5 kg, preferably from 1 g to 1 kg, per 10 are. For use in a liquid state as an emulsifiable concentrate or a wettable powder, the dose is selected suitably within a range of from 0.1 ppm to 10,000 ppm, preferably from 1 to 3,000 ppm.

The compounds of the present invention in the above formulations can control plant diseases caused by Oomycetes, Ascomycetes, Deuteromycetes and Basidiomycetes. Specific but non-restrictive examples of microorganisms are given below. Pseudoperonospora genus such as

Pseudoperonospora cubensis

, Erysiphe genus such as

Erysiphe graminis

, Venturia genus such as

Venturia inaequalis

, Pyricularia genus such as

Pyricularia oryzae

, Botrytis genus such as

Botrytis cinerea

, Rhizoctonia genus such as

Rhizoctonia solani

and Puccinia genus such as

Puccinia recondita.

The compounds of the present invention can be used in combination with insecticides, other fungicides, herbicides, plant growth regulators or fertilizers, as the case requires. Now, typical formulations of the agricultural/horticultural fungicides of the present invention will be described with reference to Formulation Examples. Hereinafter, “%” means “% by weight”.

FORMULATION EXAMPLE 1

Dust

2% of Compound (I-45), 5% of diatomaceous earth and 93% of clay were uniformly mixed and pulverized to give a dust.

FORMULATION EXAMPLE 2

Wettable Powder

50% of Compound (I-170), 45% of diatomaceous earth, 2% of sodium dinaphthylmethanedisulfonate and 3% of sodium lignin sulfonate were uniformly mixed and pulverized to give a wettable powder.

FORMULATION EXAMPLE 3

Emulsifiable Concentrate

30% of Compound (I-309), 20% of cyclohexanone, 11% of polyoxyethylene alkyl aryl ether, 4% of calcium alkylbenzenesulfonate and 35% of methylnaphthalene were uniformly dissolved to give an emulsifiable concentrate.

FORMULATION EXAMPLE 4

Granule

5% of Compound (I-121), 2% of the sodium salt of the lauryl alcohol sulfuric ester, 5% of sodium lignin sulfonate, 2% of carboxymethyl cellulose and 86% of clay were uniformly mixed and pulverized. The resulting mixture was kneaded with 20% of water, granulated to 14 to 32 mesh by means of an extrusion granulator and dried to give a granule.

Now, the effects of the agricultural/horticultural fungicides of the present invention will be described with reference to specific Test Example.

TEST EXAMPLE 1

Test for Preventive Effect on Wheat Powdery Mildew

9 Wheat seeds (variety: Norin-61-go) were sown in each 9 cm×9 cm polyvinyl chloride pot, grown in a greenhouse for 8 days, then treated with 10 ml per pot of aqueous solutions of wettable powders prepared in accordance with Formulation Example 2, at a concentration of 500 ppm in terms of the active ingredients and dried in the air. Then, the seedlings were inoculated with

Erysiphe graminis

spores by sprinkle over the plant and placed in a greenhouse of from 20 to 25° C. 10 days after the inoculation, the total diseases area of the first leaves in each pot was observed and evaluated on the basis of the standards shown in Table 67. The results are shown in Tables 68 and 69.

TABLE 67

Evaluation

A

No diseased area

B

Diseased area of less than 25%

C

Diseased area of at least 25% but less than 50%

D

Diseased area of at least 50%

TABLE 68

Com-

Biological

Com-

Biological

Com-

Biological

pound

effective-

pound

effective-

pound

effective-

No.

ness

No.

ness

No

ness

I-1

A

I-189

A

I-307

A

I-2

A

I-192

B

I-309

A

I-3

A

I-195

B

I-310

A

I-6

B

I-199

B

I-311

A

I-7

A

I-200

A

I-312

A

I-10

B

I-201

A

I-313

A

I-22

A

I-202

B

I-314

A

I-23

A

I-203

B

I-315

B

I-25

A

I-204

A

I-316

B

I-26

A

I-208

B

I-318

A

I-27

B

I-209

B

I-321

A

I-29

B

I-212

B

I-327

A

I-30

B

I-214

A

I-332

B

I-35

B

I-215

A

I-333

A

I-38

B

I-216

A

I-334

A

I-40

B

I-217

A

I-335

A

I-41

A

I-218

A

I-336

A

I-45

A

I-219

A

I-346

A

I-66

A

I-220

B

I-358

A

I-82

A

I-221

B

I-359

A

I-83

B

I-222

B

I-360

B

I-84

A

I-225

A

I-362

A

I-85

A

I-226

A

I-364

A

I-87

A

I-229

A

I-366

A

I-88

B

I-232

B

I-368

B

I-91

B

I-234

A

I-369

B

I-111

B

I-235

A

I-375

A

I-112

B

I-239

A

I-376

B

I-113

B

I-242

A

I-377

A

I-114

B

I-250

B

I-378

A

I-116

B

I-251

A

I-379

A

I-122

B

I-255

A

I-380

A

I-130

A

I-256

A

I-381

A

I-131

A

I-258

A

I-388

A

I-132

A

I-259

A

I-389

B

I-133

A

I-260

A

I-394

A

I-134

A

I-261

B

I-400

A

I-135

A

I-263

A

I-404

B

I-136

B

I-271

A

I-405

A

I-141

A

I-272

A

I-406

A

I-175

A

I-277

B

I-423

A

I-176

A

I-279

A

I-424

A

I-181

B

I-295

A

I-438

A

I-183

B

I-296

A

I-457

B

I-184

A

I-298

A

I-458

A

I-185

A

I-299

A

I-461

A

I-186

A

I-300

A

I-462

B

I-188

A

I-301

A

I-465

B

TABLE 69

Com-

Biological

Com-

Biological

Com-

Biological

pound

effective-

pound

effective-

pound

effective-

No.

ness

No.

ness

No

ness

I-479

A

I-752

A

I-1088

A

I-480

A

I-758

A

I-1090

B

I-482

A

I-762

A

I-1093

A

I-483

A

I-767

B

I-1094

A

I-486

A

I-768

A

I-1095

A

I-490

A

I-769

A

I-1096

A

I-498

A

I-771

A

I-1098

A

I-499

A

I-772

A

I-1103

B

I-501

A

I-775

A

I-1104

B

I-502

A

I-804

A

I-1106

B

I-503

A

I-805

B

I-1123

B

I-507

A

I-806

B

I-1147

B

I-508

B

I-809

B

I-510

A

I-818

B

I-511

A

I-831

B

I-514

A

I-839

A

I-515

A

I-840

B

I-516

A

I-872

B

I-530

A

I-883

A

I-531

A

I-885

B

I-534

A

I-894

B

I-543

A

I-895

B

I-544

A

I-903

B

I-545

A

I-904

B

I-546

A

I-915

A

I-550

A

I-958

B

I-573

B

I-959

A

I-580

A

I-960

A

I-592

A

I-962

A

I-595

B

I-964

B

I-601

A

I-965

A

I-667

B

I-967

A

I-669

B

I-999

A

I-670

B

I-1004

A

I-671

B

I-1019

A

I-672

B

I-1022

A

I-675

B

I-1043

A

I-682

A

I-1046

A

I-683

A

I-1048

A

I-690

A

I-1058

A

I-692

B

I-1059

A

I-693

A

I-1064

B

I-694

B

I-1071

A

I-695

A

I-1079

B

I-704

B

I-1082

B

I-705

A

I-1085

A

I-726

B

I-1086

B

I-731

B

I-1087

A

The agricultural/horticultural fungicides of the present invention have a broad disease control spectrum, and have an excellent effect particularly on wheat powdery mildew. Further, they have high controlling effects on cucumber downy mildew, apple scab, rice blast, cucumber gray mold, rice sheath blight and wheat brown leaf rust, and are excellent in residual effectiveness and rain-fastness without damaging crops, and thus they are useful as agricultural/horticultural fungicides.

Number	Date	Country	Kind
10-343614	Nov 1998	JP
11-039566	Feb 1999	JP

Number	Name	Date	Kind
4659363	Hubele et al.	Apr 1987	A
4694009	Hubele et al.	Sep 1987	A
4698091	Brunner et al.	Oct 1987	A
4802909	Rempfler et al.	Feb 1989	A
4973690	Rempfler et al.	Nov 1990	A
4999046	Rempfler	Mar 1991	A
5179098	Clough et al.	Jan 1993	A
5714509	Luo et al.	Feb 1998	A
5739129	Aquino et al.	Apr 1998	A

Number	Date	Country
151 404	Oct 1981	DE
0 945 443	Sep 1999	EP
1 476 529	Apr 1967	FR
56-65804	Jun 1981	JP
WO 9905138	Feb 1999	WO
WO-01 25220	Apr 2001	WO

Pyrimidinylbenzimidazole and triazinylbenzimidazole derivatives and agricultural/horticultural bactericides

Information

Patent Number

Date Filed

Date Issued

Inventors

Original Assignees

Examiners

Agents

CPC

US Classifications

Field of Search

US

International Classifications

Abstract

Description

Claims

Priority Claims (2)

PCT Information

US Referenced Citations (9)

Foreign Referenced Citations (6)

Non-Patent Literature Citations (2)