(en)The invention relates to pesticide and bactericide, specifically to the benzopyrone compounds and its preparation method and use thereof. The benzopyrone compounds of the invention having general formula (I):

The present invention, having good pesticide activity and broad bactericide activity, applied for controlling various pests in plants such as army worm, diamond backmoth and aphid, carmine spider mite, two-spotted spider mite, ladybeetle, mites and mosquito larvae. Various disease in plants can be controlled by the invention and that of grape downy mildew, rice sheath and culm blight, rice blast, tomato early blight, tomato late blight, wheat leaf rust, wheat leaf blotch, wheat powdery mildew, cucumber powdery mildew, cucumber downy mildew, cucumber grey mold and so on.

1.ApplicationNumber: US-57352904-A
1.PublishNumber: US-7642364-B2
2.Date Publish: 20100105
3.Inventor: LIU CHANGLING
GUAN AIYING
ZHANG HONG
ZHANG MINGXING
LI ZHENGMING
LI MIAO
LI LIN
LI ZHINIAN
HOU CHUNQING

4.Inventor Harmonized: LIU CHANGLING(CN)
GUAN AIYING(CN)
ZHANG HONG(CN)
ZHANG MINGXING(CN)
LI ZHENGMING(CN)
LI MIAO(CN)
LI LIN(CN)
LI ZHINIAN(CN)
HOU CHUNQING(CN)

5.Country: US
6.Claims:
(en)The invention relates to pesticide and bactericide, specifically to the benzopyrone compounds and its preparation method and use thereof. The benzopyrone compounds of the invention having general formula (I):

The present invention, having good pesticide activity and broad bactericide activity, applied for controlling various pests in plants such as army worm, diamond backmoth and aphid, carmine spider mite, two-spotted spider mite, ladybeetle, mites and mosquito larvae. Various disease in plants can be controlled by the invention and that of grape downy mildew, rice sheath and culm blight, rice blast, tomato early blight, tomato late blight, wheat leaf rust, wheat leaf blotch, wheat powdery mildew, cucumber powdery mildew, cucumber downy mildew, cucumber grey mold and so on.

7.Description:
(en)FIELD OF THE INVENTION
The invention relates to insecticides and fungicides, specifically to benzopyrone compounds and its preparation method and use thereof.
BACKGROUND OF THE INVENTION
Benzopyrone and strobilurin (methoxyacrylate) compounds are natural products and known with biological active. Compounds of the following general formula have ever been published in JP04-182461:









The structure of compound JP51 in JP04-182461 is as follows:









Biological active data of the compound in JP04-182461 have not been disclosed. After synthesis and the biological evaluation, it was found that compound JP51 has low biological active.
SUMMARY OF THE INVENTION
The aim of the present invention is to provide benzopyrone compounds with biological activity against all sorts of plant diseases and insects at very low dosage, and the compounds can be applied in agriculture to control diseases and insects in plant.
Detailed description of the invention is as follows:
The present invention offered benzopyrone compounds having general formula (I):









wherein: A is selected from CH or N;
B is selected from O, S or NR 9 ; R 9 is selected from H or C 1 -C 12 alkyl;
R 1 and R 2 are respectively selected from H, C 1 -C 12 alkyl or C 1 -C 12 haloalkyl;
R 3 is selected from H, C 1 -C 12 alkyl, C 1 -C 12 haloalkyl or C 1 -C 12 alkoxy;
R 4 , R 5 , R 6 , R 7 , and R 8 may be the same or different, selected from H, halo, CN, NO 2 , C 1 -C 12 alkyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, C 1 -C 12 haloalkyl, C 1 -C 12 alkoxy, C 1 -C 12 alkylthio, C 1 -C 12 alkylsulfonyl, C 1 -C 12 alkylcarbonyl, C 1 -C 12 alkoxyC 1 -C 12 alkyl, C 1 -C 12 alkoxycarbonyl, C 1 -C 12 alkoxycarbonyl C 1 -C 12 alkyl, C 1 -C 12 haloalkoxyC 1 -C 12 alkyl, or amino C 1 -C 12 alkyl in which amino is substituted with 0-2 C 1 -C 12 alkyl, 0-3 substituted groups of aryl, aryloxyl, arylC 1 -C 12 alkyl, arylC 1 -C 12 alkoxy, aryloxyC 1 -C 12 alkyl, arylC 1 -C 12 alkoxylC 1 -C 12 alkyl, heteroaryl, heteroarylC 1 -C 12 alkyl, or heteroarylC 1 -C 12 alkoxyl, the 0-3 substituted groups may be selected from halo, NO 2 , C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy or C 1 -C 6 alkoxyC 1 -C 6 alkyl, and the groups having general formula are as follows:









wherein: R 10 and R 11 are selected from H, C 1 -C 12 alkyl, aryl or aryl C 1 -C 12 alkyl; when R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are all H, B is not NR 9 ;
and stereoisomer.
The preferred compounds of general formula (I) of this invention are:
A is selected from CH or N;
B is selected from O, S or NR 9 ; R 9 is selected from H or C 1 -C 6 alkyl;
R 1 and R 2 are respectively selected from H, C 1 -C 6 alkyl or C 1 -C 6 haloalkyl;
R 3 is selected from H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl or C 1 -C 6 alkoxy;
R 4 , R 5 , R 6 , R 7 , and R 8 may be the same or different, selected from H, halo, CN, NO 2 , C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 1 -C 6 alkylsulfonyl, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkoxyC 1 -C 6 alkyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkoxycarbonylC 1 -C 6 alkyl, C 1 -C 6 haloalkoxyC 1 -C 6 alkyl, or amino C 1 -C 6 alkyl in which amino is substituted with 0-2 C 1 -C 12 alkyl, 0-3 substituted groups of aryl, aryloxyl, arylC 1 -C 6 alkyl, arylC 1 -C 6 alkoxy, aryloxyC 1 -C 6 alkyl, arylC 1 -C 6 alkoxylC 1 -C 6 alkyl, heteroaryl, heteroarylC 1 -C 6 alkyl, heteroarylC 1 -C 6 alkoxyl, the 0-3 substituted groups may be selected from halo, NO 2 , C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkoxy or C 1 -C 2 alkoxyC 1 -C 2 alkyl, and groups having formula are as follows:









wherein: R 10 and R 11 are respectively selected from H, C 1 -C 12 alkyl, aryl or arylC 1 -C 6 alkyl; when R 3 , R 4 ,R 5 , R 6 , R 7 , R 8 are all H, B is not NR 9 ;
Further more, the preferred compounds of general formula (I) of this invention are:
A is selected from CH or N;
B is selected from O or NH;
R 1 and R 2 are respectively selected from methyl;
R 3 is selected from H or methyl;
R 4 , R 5 , R 6 , R 7 , and R 8 may be the same or different, respectively selected from H, halo, CN, NO 2 , C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkoxyC 1 -C 6 alkyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkoxycarbonylC 1 -C 3 alkyl, C 1 -C 3 haloalkoxyC 1 -C 3 alkyl, or amino C 1 -C 3 alkyl in which amino is substituted with 0-2 C 1 -C 3 alkyl, phenyl, phenoxy, phenylC 1 -C 2 alkyl, phenylC 1 -C 2 alkoxy, phenoxyC 1 -C 2 alkyl, phenylmethyl, phenylmethoxyl, or phenylmethoxyC 1 -C 2 alkyl substituted with 0-2 halo, NO 2 , C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkoxy or C 1 -C 2 alkoxyC 1 -C 2 alkyl, and the substituted group having general formula is as follows:









wherein: R 10 and R 11 are respectively selected from H or C 1 -C 6 alkyl; when R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are all H, B is not NH.
Even more preferred compounds of formula (I) of this invention are:
A is selected from CH or N;
B is selected from O or NH;
R 1 and R 2 are selected from methyl;
R 3 is selected from H or methyl;
R 4 , R 5 , R 6 , R 7 , and R 8 may be the same or different, respectively selected from H, Cl, Br, F, CN, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkylcarbonyl, Cl -C 6 alkoxy, C 1 -C 6 alkoxyC 1 -C 3 alkyl, C 1 -C 3 haloalkoxyC 1 -C 3 alkyl, amino C 1 -C 3 alkyl in which amino is substituted with 0-2 C 1 -C 3 alkyl, phenyl, phenoxy, phenylmethyl, phenylmethoxyl, substituted with 0-2 halo, NO 2 , C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkoxy or C 1 -C 2 alkoxyC 1 -C 2 alkyl, and the substituted groups having general formula is as follows:









wherein: R 10 and R 11 are selected from methyl; when R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are all H, B is not NH.
The following is the meaning of terms in the general formula (I):
Halogen or halo is meant to include fluoro, chloro, bromo or iodo.
The alkyl includes either straight or branched chain alkyl such as methyl, ethyl, propyl, isopropyl or tert-butyl.
The haloalkyl refers to straight or branched chain alkyl , in which hydrogen atom may be all or partly substituted with halogen, such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, or trifluoromethyl.
The alkoxy refers to straight or branched chain alkyl, which is linked to the structure by oxygen atom.
The haloalkoxy refers to straight or branched chain alkoxy, in which hydrogen atom may be all or partly substituted with halogen_, such as chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, or trifluoroethoxy.
The alkenyl refers to an straight or branched, having double bonds at any position such as vinyl allyl. Substituted alkenyl includes arylvinyl which is substituted at any position with any group.
The alkynyl refers to straight or branched, having triple bonds at any position. such as ethynyl, propynyl. Substituted alkynyl includes arylethynyl which is substituted at any position with any group.
The aryl and aryl in arylalkyl, arylalkenyl, arylalkynyl, aryloxy, aryloxyalkyl include phenyl and naphthyl.
The substituent group in phenyl, phenoxy, phenylmethyl, phenylmethoxy are H, alkyl, alkoxy, haloalkyl, haloalkoxy, halo, NO 2 , CN and the like. The number of the substituent group can be from one to five.
The hetero aryl in this invention refers to five member ring or six member ring containing one or many N, O, S hetero atom such as furan, thiophene, pyrrole, pyrazole, imidazole, thiazole, triazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, benzofuran.
Because of the C═C and C═N link to different substituted group, the compounds of the invention may form geometrical isomer (the different isomers are respectively expressed with Z and E). Z isomer and E isomer and their mixture in any proportion are included in the invention.
The present invention is explained by the compounds of the following table I, but without being restricted thereby.









As provided in table 1, where R 1 , R 2 ═CH 3 ; P is C(CH 3 )═NOCH 3 ; M is C 6 H 3 -3, 4-(OCH 3 ) 2 .














TABLE 1












Physical-

No.
A
B
R 3
R 4
R 5
R 6
R 7
R 8
property*
















1
CH
O
H
H
H
H
H
H
oil

2
CH
O
H
H
CH 3
H
H
H
140~143

3
CH
O
H
H
CH 3
H
H
CH 3
188–190

4
CH
O
H
H
C 6 H 5
H
H
CH 3
146–148

5
CH
O
H
CH 3
CH 3
H
H
H
120~122

6
CH
O
H
CH 3
CH 3
H
H
CH 3
174~176

7
CH
O
H
H
CF 3
H
H
H
164~166

8
CH
O
H
H
CH 3
H
H
P
oil

9
CH
O
H
H
CH 3
H
P
H
183~185

10
CH
O
H
H
CH 3
H
COCH 3
H
169~172

11
CH
O
H
H
CH 3
H
H
COCH 3
165~167

12
CH
O
H
Cl
CH 3
H
H
H
162–164

13
CH
O
H
H
CH 2 Cl
H
H
H

14
CH
O
H
Cl
CH 2 Cl
H
H
H

15
CH
O
H
Cl
CH 2 OCH 3
H
H
H

16
CH
O
H
Cl
CH 2 CH 3
H
H
H

17
CH
O
H
H
CH 2 CH 3
H
H
CH 3
154–156

18
CH
O
H
C 2 H 5
CH 3
H
H
H
132–135

19
CH
O
H
H
CH 2 OCH 3
H
H
H
140–142

20
CH
O
H
H
CH 2 OC 2 H 5
H
H
H

21
CH
O
H
Cl
CH 2 OC 2 H 5
H
H
H

22
CH
O
H
OCH 3
CH 2 OCH 3
H
H
H

23
CH
O
H
N(CH 3 ) 2
CH 3
H
H
H

24
CH
O
H
CN
H
H
H
H
166–168

25
CH
O
H
Cl
CH 3
H
H
CH 3
202–204

26
CH
O
H
H
CH(CH 3 ) 2
H
H
H
128–130

27
CH
O
H
C 3 H 7
CH 3
H
H
H
142–144

28
CH
O
H
H
tC 4 H 9
H
H
H

29
CH
O
H
H
4-Cl—C 6 H 4
H
H
H
149–152

30
CH
O
H
Cl
4-Cl—C 6 H 4
H
H
H

31
CH
O
H
H
4-Cl—C 6 H 4
H
H
CH 3

32
CH
O
H
Cl
C 6 H 5
H
H
H
142–144

33
CH
O
H
H
CH 2 CH 3
H
H
H
134–136

34
CH
O
H
H
CH 2 C 2 H 5
H
H
H
118–120

35
CH
O
H
H
CH 2 C 2 H 5
H
H
CH 3
146–148

36
CH
O
H
Cl
CH 2 C 2 H 5
H
H
H
118–120

37
CH
O
H
CH 3
CH 2 C 2 H 5
H
H
H
112–115

38
CH
O
H
H
4-F—C 6 H 4
H
H
H
132–134

39
CH
O
H
Cl
4-F—C 6 H 4
H
H
H

40
CH
O
H
H
4-F—C 6 H 4
H
H
CH 3

41
CH
O
H
H
4-CF 3 —C 6 H 4
H
H
H
161–162

42
CH
O
H
Cl
4-CF 3 —C 6 H 4
H
H
H

43
CH
O
H
Cl
CH 2 N(CH 3 ) 2
H
H
H

44
CH
O
H
OCH 3
C 2 H 5
H
H
H

45
CH
O
H
OCH 3
CH 3
H
H
H

46
CH
O
H
OC 2 H 5
CH 3
H
H
H

47
CH
O
H
H
CH 2 OCH 2 CF 3
H
H
H

48
CH
O
H
Cl
CH 2 OCH 2 CF 3
H
H
H

49
CH
O
H
F
CF 3
H
H
H

50
CH
O
H
F
CH 3
H
H
H
163–164

51
CH
O
H
H
CH 2 N(CH 3 ) 2
H
H
H

52
CH
O
H
H
C 6 H 5
H
H
H
130–133

53
CH
O
H
Cl
Cl
H
H
H

54
CH
O
H
F
Cl
H
H
H

55
CH
O
H
H
CH 2 OCH 2 C 6 H 5
H
P
H

56
CH
O
H
OCH 3
4-Cl—C 6 H 5
H
H
H

57
CH
O
H
F
4-Cl—C 6 H 5
H
H
H

58
CH
O
H
H
M
H
H
H
81–83

59
CH
O
H
Cl
M
H
H
H

60
CH
O
H
Cl
M
H
H
CH 3

61
CH
O
H
CH 3 S
CH 3
H
H
H

62
CH
O
H
CH 3 SO 2
CH 3
H
H
H

63
CH
O
H
F
F
H
H
H

64
CH
O
H
CH 3 SO 2
Cl
H
H
H

65
CH
O
H
H
4-NO 2 —C 6 H 5
H
H
H

66
CH
O
H
Cl
4-NO 2 —C 6 H 5
H
H
H

67
CH
O
H
H
4-NO 2 —C 6 H 5
H
H
CH 3

68
CH
O
H
PhCH 2
CH 3
H
H
H
159–162

69
CH
O
H
PhCH 2
CH 3
H
H
CH 3

70
CH
O
H
CF 3 CH 2 O
C 3 H 7
H
H
H

71
CH
NH
H
CH 3
CH 3
H
H
H

72
CH
NH
H
CH 3
CH 3
H
H
CH 3

73
CH
NH
H
OCH 3
CF 3
CH 3
H
H

74
CH
NH
H
OCH 3
CH 3
F
H
P

75
CH
NH
H
H
CF 3
H
H
CH 3

76
CH
NH
H
CH 3
CH 2 Cl
H
H
H

77
CH
NH
H
CH 3
CH 2 Cl
H
H
CH 3

78
CH
NH
H
Cl
CH 2 Cl
H
H
H

79
CH
NH
H
H
M
Cl
H
P

80
CH
NH
H
H
M
H
P
H

81
CH
NH
H
H
M
H
COCH 3
H

82
CH
NH
H
H
M
H
H
COCH 3

83
CH
NH
H
Cl
CH 2 OCH 3
H
H
H

84
CH
NH
H
H
4-C 6 H 5 Cl
H
H
H

85
CH
NH
H
H
4-C 6 H 5 Cl
H
H
CH 3

86
CH
NH
H
H
CH 2 OCH 3
H
H
CH 3

87
CH
NH
H
CH 3
CH 2 OCH 3
H
H
H

88
CH
NH
H
CH 3
CH 2 OCH 3
H
H
CH 3

89
CH
NH
H
H
CH 2 OCH 3
H
H
H

90
CH
NH
H
H
CH 2 OCH 3
H
H
P

91
CH
NH
H
H
CH 2 OCH 2 CF 3
H
P
H

92
CH
NH
H
H
CH 2 N(CH 3 ) 2
H
H
H

93
CH
NH
H
H
CH 2 OCH 2 CF 3
H
H
COCH 3

94
CH
NH
H
Cl
CH 2 OC 2 H 5
H
H
H

95
CH
NH
H
H
CH 2 OC 2 H 5
H
H
H

96
CH
NH
H
H
CH 2 OC 2 H 5
H
H
CH 3

97
CH
NH
H
H
CF 3
H
H
CH 3

98
CH
NH
H
CH 3
CF 3
H
H
H

99
CH
NH
H
CH 3
Cl
H
H
CH 3

100
N
O
H
Cl
CH 3
H
H
H
172–174

101
N
O
H
H
CH 3
H
H
H
150~152

102
N
O
H
H
CH 3
H
H
CH 3
178–180

103
N
O
H
CH 3
CH 3
H
H
H
112~118

104
N
O
H
F
CH 3
H
H
H

105
N
O
H
H
CF 3
H
H
Cl

106
N
O
H
CH 3
CH 3
H
H
CH 3
184~186

107
N
O
H
H
CH 3
H
P
CO 2 CH 3

108
N
O
H
H
CH 3
H
COCH 3
CO 2 CH 3

109
N
O
H
Cl
CH 3
H
H
CH 3
198–200

110
N
O
H
H
CH 2 Cl
H
H
CO 2 CH 3

111
N
O
H
H
H
H
H
H
106~110

112
N
O
H
H
CH 2 Cl
H
H
CF 3

113
N
O
H
H
3-CF 3 —C 6 H 4
H
H
CF 3

114
N
O
H
CH 3
3-CH 3 —C 6 H 4
H
H
CF 3

115
N
O
H
CH 3
4-CH 3 —C 6 H 4
H
H
CF 3

116
N
O
H
H
CH 2 Cl
H
H
H

117
N
O
H
Cl
CH 2 Cl
H
H
H

118
N
O
H
Cl
CH 2 F
H
H
H

119
N
O
H
H
CH 2 F
H
H
H

120
N
O
H
H
CH 2 Br
H
H
H

121
N
O
H
H
CH 2 OCH 3
H
H
CH 2 N(CH 3 ) 2

122
N
O
H
Cl
CH 2 OCH 3
H
H
CH 2 N(CH 3 ) 2

123
N
O
H
CH 3
CH 2 OCH 3
H
H
CH 2 N(CH 3 ) 2

124
N
O
H
H
CH 2 OCH 3
H
H
F

125
N
O
H
CH 3
CH 2 OCH 3
H
H
F

126
N
O
H
CH 3
CH 2 OCH 3
H
CO 2 CH 3
CH 2 N(CH 3 ) 2

127
N
O
H
H
CH 2 OCH 3
H
H
H

128
N
O
H
H
CH 2 OCH 3
H
H
P

129
N
O
H
H
3-CF 3 —C 6 H 4
H
P
H

130
N
O
H
H
3-CH 3 —C 6 H 4
H
COCH 3
H

131
N
O
H
H
4-CH 3 —C 6 H 4
H
H
COCH 3

132
N
O
H
Cl
CH 2 OC 2 H 5
H
H
H

133
N
O
H
H
CH 2 OC 2 H 5
H
H
H

134
N
O
H
H
CH 2 OC 2 H 5
H
H
CH 3

135
N
O
H
H
3-OCH 3 —C 6 H 4
H
H
CH 3

136
N
O
H
CH 3
4-OCH 3 —C 6 H 4
H
H
H

137
N
O
H
CH 3
2-OCH 3 —C 6 H 4
H
H
CH 3

138
N
O
H
H
CH 2 OC 2 H 5
H
H
Cl

139
N
O
H
H
CH 2 OC 2 H 5
H
H
P

140
N
O
H
H
M
H
P
H

141
N
O
H
H
3-CF 3 —C 6 H 4
H
COCH 3
H

142
N
O
H
H
3-CH 3 —C 6 H 4
H
H
COCH 3

143
N
O
H
H
4-CH 3 —C 6 H 4
H
H
H

144
N
O
H
H
2-Cl—C 6 H 4
H
H
H

145
N
O
H
H
3-Cl—C 6 H 4
H
H
CH 3

146
N
O
H
H
CH 2 OCH 2 CF 3
H
H
CH 3

147
N
O
H
CH 3
CH 2 OCH 2 CF 3
H
H
H

148
N
O
H
CH 3
—CH 2 OC 6 H 5
H
H
CH 3

149
N
O
H
H
—CH 2 OC 6 H 5
H
H
H

150
N
O
H
H
CH 2 OCH 2 C 6 H 5
H
H
P

151
N
O
H
H
CH 2 OCH 2 C 6 H 5
H
P
H

152
N
O
H
H
4-Cl—C 6 H 4
H
COCH 3
H

153
N
NH
H
H
CH 3
H
H
H
210–214

154
N
NH
H
CH 3
CH 3
H
H
CH 3
178~180

155
N
NH
H
H
2-Cl—C 6 H 4
H
H
CH 3

156
N
NH
H
CH 3
3-Cl—C 6 H 4
H
H
H

157
N
NH
H
CH 3
4-Cl—C 6 H 4
H
H
CH 3

158
N
NH
H
Cl
CH 2 Cl
H
H
H

159
N
NH
H
Cl
CH 3
H
H
H

160
N
NH
H
H
3-CF 3 —C 6 H 4
H
P
H

161
N
NH
H
H
3-CH 3 —C 6 H 4
H
COCH 3
H

162
N
NH
H
H
4-CH 3 —C 6 H 4
H
H
COCH 3

163
N
NH
H
H
CH 2 OCH 3
H
H
H

164
N
NH
H
H
4-F—C 6 H 4
H
H
H

165
N
NH
H
H
2-F—C 6 H 4
H
H
CH 3

166
N
NH
H
H
C 6 H 3 -3,5(Cl) 2
H
H
CH 3

167
N
NH
H
CH 3
2-OCH 3 —C 6 H 4
H
H
H

168
N
NH
H
CH 3
2-OCH 3 —C 6 H 4
H
H
CH 3

169
N
NH
H
Cl
CH 2 OCH 3
H
H
H

170
N
NH
H
H
CH 2 OCH 3
H
H
P

171
N
NH
H
H
3,5(Cl) 2 —C 6 H 3
H
P
H

172
N
NH
H
H
2,4(Cl) 2 —C 6 H 3
H
H
H

173
N
NH
H
H
3,4(Cl) 2 —C 6 H 3
H
H
H

174
N
NH
H
Cl
CH 2 OC 2 H 5
H
H
H

175
N
NH
H
H
CH 2 OC 2 H 5
H
H
H

176
N
NH
H
H
CH 2 OC 2 H 5
H
H
CH 3

177
N
NH
H
H
CF 3
H
H
CH 3

178
N
NH
H
CH 3
CF 3
H
H
H

179
N
NH
H
CH 3
Cl
H
H
CH 3

180
N
NH
H
H
Cl
H
H
H

181
N
NH
H
H
CH 3
H
H
Cl

182
N
NH
H
H
C 6 H 5
H
H
Cl

183
N
NH
H
CH 3
CH 3
H
H
F

184
N
NH
H
CH 3
CH 3
H
H
H

185
N
NH
H
H
CF 3
H
H
Cl

186
N
NH
H
CH 3
4-F—C 6 H 4
H
H
CH 3

187
N
NH
H
H
2-F—C 6 H 4
H
P
CO 2 CH 3

188
N
NH
H
H
2-Cl—C 6 H 4
H
COCH 3
CO 2 CH 3

189
N
NH
H
H
3-Cl—C 6 H 4
H
H
CO 2 CH 3

190
N
NH
H
H
4-Cl—C 6 H 4
H
H
CO 2 CH 3

191
N
NH
H
H
CH 2 Cl
H
CH 3
H

192
N
NH
H
H
CH 2 Cl
H
CO 2 C 2 H 5
CF 3

193
N
NH
H
H
CH 2 Cl
H
H
CF 3

194
N
NH
H
CH 3
M
H
CO 2 C 2 H 5
CF 3

195
N
NH
H
CH 3
CH 2 Cl
H
H
CF 3

196
N
NH
H
H
CH 2 Cl
H
H
H

197
N
NH
H
H
CH 2 Cl
H
H
P

198
N
NH
H
H
CH 2 Cl
H
P
H

199
N
NH
H
H
CH 2 Cl
H
COCH 3
H

200
N
NH
H
CH 3
3,5-diCl—C 6 H 3
H
CO 2 CH 3
H

201
CH
O
CH 3
H
H
H
H
H

202
CH
O
CH 3
H
CH 3
H
H
H

203
CH
O
CH 3
H
CH 3
H
H
CH 3

204
CH
O
CH 3
H
C 6 H 5
H
H
CH 3

205
CH
O
CH 3
CH 3
CH 3
H
H
H

206
CH
O
CH 3
CH 3
CH 3
H
H
CH 3

207
CH
O
CH 3
H
CF 3
H
H
H

208
CH
O
CH 3
H
CH 3
H
H
P

209
CH
O
CH 3
H
CH 3
H
P
H

210
CH
O
CH 3
H
CH 3
H
COCH 3
H

211
CH
O
CH 3
H
CH 3
H
H
COCH 3

212
CH
O
CH 3
H
CH 2 Cl
H
H
H

213
CH
O
CH 3
Cl
CH 2 Cl
H
H
H

214
CH
O
CH 3
H
CH 2 Cl
H
H
CF 3

215
CH
O
CH 3
H
CH 2 Cl
H
H
CH 3

216
CH
O
CH 3
CH 3
CH 2 OCH 3
H
H
H

217
CH
O
CH 3
CH 3
CH 2 OCH 3
H
H
CH 3

218
CH
O
CH 3
OCH 3
CH 2 Cl
H
H
H

219
CH
O
CH 3
H
CH 2 Cl
H
H
P

220
CH
O
CH 3
H
CH 2 Cl
H
P
H

221
CH
O
CH 3
H
CH 2 Cl
H
COCH 3
H

222
CH
O
CH 3
H
CH 2 Cl
H
H
COCH3

223
CH
O
CH 3
H
CH 2 OCH 2 CF 3
H
H
H

224
CH
O
CH 3
Cl
CH 2 OC 2 H 5
H
H
H

225
CH
O
CH 3
Cl
CH 2 OCH 3
H
H
CH 3

226
CH
O
CH 3
H
CH 2 OCH 3
H
H
CH 3

227
CH
O
CH 3
CH 3
3-CF 3 —C 6 H 4
H
H
H

228
CH
O
CH 3
CH 3
3-CH 3 —C 6 H 4
H
H
CH 3

229
CH
O
CH 3
H
4-CH 3 —C 6 H 4
H
H
H

230
CH
O
CH 3
H
2-Cl —C 6 H 4
H
H
P

231
CH
O
CH 3
H
3-Cl —C 6 H 4
H
P
H

232
CH
O
CH 3
H
CF 3
H
COCH 3
H

233
CH
O
CH 3
Cl
CH 2 OCH 3
H
H
COCH 3

234
CH
O
CH 3
OCH 3
CH 2 OC 2 H 5
H
H
H

235
CH
O
CH 3
C 2 H 5
CH 2 OC 2 H 5
H
CH 3
H

236
CH
O
CH 3
H
CH 2 OC 2 H 5
H
H
CH 3

237
CH
O
CH 3
Cl
CH 2 OC 2 H 5
H
CO 2 C 2 H 5
CH 3

238
CH
O
CH 3
CH 3
2-F—C 6 H 4
H
H
H

239
CH
O
CH 3
CH 3
3-F—C 6 H 4
H
H
CH 3

240
CH
O
CH 3
H
4-F—C 6 H 4
H
H
H

241
CH
O
CH 3
H
CH 2 OC 2 H 5
H
H
P

242
CH
O
CH 3
H
CH 2 OC 2 H 5
H
P
H

243
CH
O
CH 3
H
CH 2 OC 2 H 5
H
COCH 3
H

244
CH
O
CH 3
H
CH 2 OC 2 H 5
H
H
COCH 3

245
CH
O
CH 3
H
CH 2 OCH 2 CF 3
H
H
H

246
CH
O
CH 3
Cl
CH 2 OCH 2 CF 3
H
H
H

247
CH
O
CH 3
H
CF 3
H
H
CH 3

248
CH
O
CH 3
H
CH 2 OCH 2 CF 3
H
H
CH 3

249
CH
O
CH 3
CH 3
CH 2 OCH 2 CF 3
H
H
H

250
CH
O
CH 3
CH 3
—CH 2 OPh
H
H
CH 3

251
CH
O
CH 3
H
—CH 2 OPh
H
H
H

252
CH
O
CH 3
H
CH 2 OCH 2 Ph
H
H
P

253
CH
O
CH 3
H
CH 2 OCH 2 Ph
H
P
H

254
CH
O
CH 3
H
4-Cl—C 6 H 5
H
COCH 3
H

255
CH
O
CH 3
H
4-Cl—C 6 H 5
H
H
COCH 3

256
CH
O
CH 3
H
M
H
CO 2 C 2 H 5
H

257
CH
O
CH 3
H
M
H
H
H

258
CH
O
CH 3
Cl
M
H
H
CH 3

259
CH
O
CH 3
H
M
H
H
CH 3

260
CH
O
CH 3
CH 3
M
H
H
H

261
CH
NH
CH 3
Cl
H
H
H
H

262
CH
NH
CH 3
Cl
CH 3
H
H
H

263
CH
NH
CH 3
H
CH 3
H
H
CH 3

264
CH
NH
CH 3
H
C 6 H 5
H
H
CH 3

265
CH
NH
CH 3
CH 3
CH 3
H
H
H

266
CH
NH
CH 3
CH 3
CH 3
H
H
CH 3

267
CH
NH
CH 3
OCH 3
CF 3
H
H
H

268
CH
NH
CH 3
OCH 3
CH 3
H
H
P

269
CH
NH
CH 3
H
CH 3
H
P
H

270
CH
NH
CH 3
H
CH 3
H
COCH 3
H

271
CH
NH
CH 3
H
CH 3
H
H
COCH 3

272
CH
NH
CH 3
H
CH 2 Cl
H
H
H

273
CH
NH
CH 3
H
M
H
H
H

274
CH
NH
CH 3
H
CH 2 Cl
H
H
CH 3

275
CH
NH
CH 3
H
CF 3
H
H
CH 3

276
CH
NH
CH 3
CH 3
CH 2 Cl
H
H
H

277
CH
NH
CH 3
CH 3
CH 2 Cl
H
H
CH 3

278
CH
NH
CH 3
Cl
CH 2 Cl
H
H
H

279
CH
NH
CH 3
H
M
H
H
P

280
CH
NH
CH 3
H
M
H
P
H

281
CH
NH
CH 3
H
M
H
COCH 3
H

282
CH
NH
CH 3
H
M
H
H
COCH 3

283
CH
NH
CH 3
Cl
CH 2 OCH 3
H
H
H

284
CH
NH
CH 3
H
4-C 6 H 5 Cl
H
H
H

285
CH
NH
CH 3
H
4-C 6 H 5 Cl
H
H
CH 3

286
CH
NH
CH 3
H
CH 2 OCH 3
H
H
CH 3

287
CH
NH
CH 3
CH 3
CH 2 OCH 3
H
H
H

288
CH
NH
CH 3
CH 3
CH 2 OCH 3
H
H
CH 3

289
CH
NH
CH 3
H
CH 2 OCH 3
H
H
H

290
CH
NH
CH 3
H
CH 2 OCH 3
H
H
P

291
CH
NH
CH 3
H
CH 2 OCH 2 CF 3
H
P
H

292
CH
NH
CH 3
H
CH 2 OCH 2 CF 3
H
COCH 3
H

293
CH
NH
CH 3
H
CH 2 OCH 2 CF 3
H
H
COCH 3

294
CH
NH
CH 3
Cl
CH 2 OC 2 H 5
H
H
H

295
CH
NH
CH 3
H
CH 2 OC 2 H 5
H
H
H

296
CH
NH
CH 3
H
CH 2 OC 2 H 5
H
H
CH 3

297
CH
NH
CH 3
H
CF 3
H
H
CH 3

298
CH
NH
CH 3
CH 3
CF 3
H
H
H

299
CH
NH
CH 3
CH 3
Cl
H
H
CH 3

300
CH
NH
CH 3
H
Cl
H
H
H

301
N
O
CH 3
H
CH 3
H
H
H

302
N
O
CH 3
H
C 6 H 5
H
H
Cl

303
N
O
CH 3
CH 3
CH 3
H
H
H

304
N
O
CH 3
CH 3
CH 3
H
H
H

305
N
O
CH 3
H
CF 3
H
H
Cl

306
N
O
CH 3
CH 3
CH 3
H
H
CH 3

307
N
O
CH 3
H
CH 3
H
P
CO 2 CH 3

308
N
O
CH 3
H
CH 3
H
COCH 3
CO 2 CH 3

309
N
O
CH 3
H
CH 3
H
H
CO 2 CH 3

310
N
O
CH 3
H
CH 2 Cl
H
H
CO 2 CH 3

311
N
O
CH 3
H
H
H
H
H

312
N
O
CH 3
H
CH 2 Cl
H
H
CF 3

313
N
O
CH 3
H
3-CF 3 —C 6 H 4
H
H
CF 3

314
N
O
CH 3
CH 3
3-CH 3 —C 6 H 4
H
H
CF 3

315
N
O
CH 3
CH 3
4-CH 3 —C 6 H 4
H
H
CF 3

316
N
O
CH 3
H
CH 2 Cl
H
H
H

317
N
O
CH 3
H
CH 2 Cl
H
H
P

318
N
O
CH 3
H
CH 2 Cl
H
P
H

319
N
O
CH 3
H
CH 2 Cl
H
COCH 3
H

320
N
O
CH 3
H
CH 2 Cl
H
H
COCH3

321
N
O
CH 3
H
CH 2 OCH 3
H
H
CH 2 N(CH 3 ) 2

322
N
O
CH 3
Cl
CH 2 OCH 3
H
H
CH 2 N(CH 3 ) 2

323
N
O
CH 3
CH 3
CH 2 OCH 3
H
H
CH 2 N(CH 3 ) 2

324
N
O
CH 3
H
CH 2 OCH 3
H
H
F

325
N
O
CH 3
CH 3
CH 2 OCH 3
H
H
F

326
N
O
CH 3
CH 3
CH 2 OCH 3
H
CO 2 CH 3
CH 2 N(CH 3 ) 2

327
N
O
CH 3
H
CH 2 OCH 3
H
H
H

328
N
O
CH 3
H
CH 2 OCH 3
H
H
P

329
N
O
CH 3
H
3-CF 3 —C 6 H 4
H
P
H

330
N
O
CH 3
H
3-CH 3 —C 6 H 4
H
COCH 3
H

331
N
O
CH 3
H
4-CH 3 —C 6 H 4
H
H
COCH 3

332
N
O
CH 3
Cl
CH 2 OC 2 H 5
H
H
H

333
N
O
CH 3
H
CH 2 OC 2 H 5
H
H
H

334
N
O
CH 3
H
CH 2 OC 2 H 5
H
H
CH 3

335
N
O
CH 3
H
3-OCH 3 —C 6 H 4
H
H
CH 3

336
N
O
CH 3
CH 3
4-OCH 3 —C 6 H 4
H
H
H

337
N
O
CH 3
CH 3
2-OCH 3 —C 6 H 4
H
H
CH 3

338
N
O
CH 3
H
CH 2 OC 2 H 5
H
H
Cl

339
N
O
CH 3
H
CH 2 OC 2 H 5
H
H
P

340
N
O
CH 3
H
M
H
P
H

341
N
O
CH 3
H
3-CF 3 —C 6 H 4
H
COCH 3
H

342
N
O
CH 3
H
3-CH 3 —C 6 H 4
H
H
COCH 3

343
N
O
CH 3
H
4-CH 3 —C 6 H 4
H
H
H

344
N
O
CH 3
H
2-Cl—C 6 H 4
H
H
H

345
N
O
CH 3
H
3-Cl—C 6 H 4
H
H
CH 3

346
N
O
CH 3
H
CH 2 OCH 2 CF 3
H
H
CH 3

347
N
O
CH 3
CH 3
CH 2 OCH 2 CF 3
H
H
H

348
N
O
CH 3
CH 3
—CH 2 OPh
H
H
CH 3

349
N
O
CH 3
H
—CH 2 OPh
H
H
H

350
N
O
CH 3
H
CH 2 OCH 2 Ph
H
H
P

351
N
O
CH 3
H
CH 2 OCH 2 Ph
H
P
H

352
N
O
CH 3
H
4-Cl—C 6 H 4
H
COCH 3
H

353
N
NH
CH 3
H
CH 3
H
H
H

354
N
NH
CH 3
CH 3
CH 3
H
H
CH 3

355
N
NH
CH 3
H
2-Cl—C 6 H 4
H
H
CH 3

356
N
NH
CH 3
CH 3
3-Cl—C 6 H 4
H
H
H

357
N
NH
CH 3
CH 3
4-Cl—C 6 H 4
H
H
CH 3

358
N
NH
CH 3
H
CH 2 Cl
H
H
H

359
N
NH
CH 3
H
M
H
H
P

360
N
NH
CH 3
H
3-CF 3 —C 6 H 4
H
P
H

361
N
NH
CH 3
H
3-CH 3 —C 6 H 4
H
COCH 3
H

362
N
NH
CH 3
H
4-CH 3 —C 6 H 4
H
H
COCH 3

363
N
NH
CH 3
H
CH 2 OCH 3
H
H
H

364
N
NH
CH 3
H
4-F—C 6 H 4
H
H
H

365
N
NH
CH 3
H
2-F—C 6 H 4
H
H
CH 3

366
N
NH
CH 3
H
C 6 H 3 -3,5(Cl) 2
H
H
CH 3

367
N
NH
CH 3
CH 3
2-OCH 3 —C 6 H 4
H
H
H

368
N
NH
CH 3
CH 3
2-OCH 3 —C 6 H 4
H
H
CH 3

369
N
NH
CH 3
Cl
CH 2 OCH 3
H
H
H

370
N
NH
CH 3
H
CH 2 OCH 3
H
H
P

371
N
NH
CH 3
H
C 6 H 3 -3,5(Cl) 2
H
P
H

372
N
NH
CH 3
H
CH 2 OCH 2 CF 3
H
COCH 3
H

373
N
NH
CH 3
H
CH 2 OCH 2 CF 3
H
H
COCH 3

374
N
NH
CH 3
Cl
CH 2 OC 2 H 5
H
H
H

375
N
NH
CH 3
H
CH 2 OC 2 H 5
H
H
H

376
N
NH
CH 3
H
CH 2 OC 2 H 5
H
H
CH 3

377
N
NH
CH 3
H
CF 3
H
H
CH 3

378
N
NH
CH 3
CH 3
CF 3
H
H
H

379
N
NH
CH 3
CH 3
Cl
H
H
CH 3

380
N
NH
CH 3
H
Cl
H
H
H

381
N
NH
CH 3
H
CH 3
H
H
Cl

382
N
NH
CH 3
H
C 6 H 5
H
H
Cl

383
N
NH
CH 3
CH 3
CH 3
H
H
F

384
N
NH
CH 3
CH 3
CH 3
H
H
H

385
N
NH
CH 3
H
CF 3
H
H
Cl

386
N
NH
CH 3
CH 3
4-F—C 6 H 4
H
H
CH 3

387
N
NH
CH 3
H
2-F—C 6 H 4
H
P
CO 2 CH 3

388
N
NH
CH 3
H
2-Cl—C 6 H 4
H
COCH 3
CO 2 CH 3

389
N
NH
CH 3
H
3-Cl—C 6 H 4
H
H
CO 2 CH 3

390
N
NH
CH 3
H
4-Cl—C 6 H 4
H
H
CO 2 CH 3

391
N
NH
CH 3
H
CH 2 Cl
H
CH 3
H

392
N
NH
CH 3
H
CH 2 Cl
H
CO 2 C 2 H 5
CF 3

393
N
NH
CH 3
H
CH 2 Cl
H
H
CF 3

394
N
NH
CH 3
CH 3
M
H
CO 2 C 2 H 5
CF 3

395
N
NH
CH 3
CH 3
CH 2 Cl
H
H
CF 3

396
N
NH
CH 3
H
CH 2 Cl
H
H
H

397
N
NH
CH 3
H
CH 2 Cl
H
H
P

398
N
NH
CH 3
H
CH 2 Cl
H
P
H

399
N
NH
CH 3
H
CH 2 Cl
H
COCH 3
H

400
N
NH
CH 3
CH 3
3,5-diCl—C 6 H 3
H
CO 2 CH 3
H

401
CH
O
H
C 3 H 7 i
CH 3
H
H
H
oil

402
CH
O
H
n-C 4 H 9
CH 3
H
H
H
117–118

403
CH
O
H
n-C 5 H 11
CH 3
H
H
H

404
CH
O
H
C 2 H 4 Pri
CH 3
H
H
H
oil

405
CH
O
H
n-C 6 H 13
CH 3
H
H
H
113–115

406
CH
O
H
H
n-C 4 H 9
H
H
H

407
CH
O
H
H
n-C 5 H 11
H
H
H

408
CH
O
H
H
CH(CH 3 ) 2
H
H
CH 3
110–112

409
CH
O
H
n-C 3 H 7
n-C 3 H 7
H
H
H
112–114

410
N
O
H
Cl
n-C 3 H 7
H
H
H
136–138

411
N
O
H
Cl
C 6 H 5
H
H
H
166–168

412
N
O
H
n-C 3 H 7
CH 3
H
H
H
121–122

413
N
O
H
n-C 4 H 9
CH 3
H
H
H
100–102

414
N
O
H
n-C 6 H 13
CH 3
H
H
H
75–78

415
CH
O
H
CH 3
n-C 4 H 9
H
H
H

416
CH
O
H
C 2 H 5
n-C 4 H 9
H
H
H

417
CH
O
H
C 3 H 7
n-C 4 H 9
H
H
H

418
CH
O
H
i-C 3 H 7
n-C 4 H 9
H
H
H

419
CH
O
H
n-C 4 H 9
n-C 4 H 9
H
H
H

420
CH
O
H
CH 3
n-C 5 H 11
H
H
H

421
CH
O
H
C 2 H 5
n-C 5 H 11
H
H
H

422
CH
O
H
C 3 H 7
n-C 5 H 11
H
H
H

423
CH
O
H
i-C 3 H 7
n-C 5 H 11
H
H
H

424
CH
O
H
n-C 4 H 9
n-C 5 H 11
H
H
H

425
CH
O
H
H
n-C 6 H 13
H
H
H

426
CH
O
H
CH 3
n-C 6 H 13
H
H
H

427
CH
O
H
C 2 H 5
n-C 6 H 13
H
H
H

428
CH
O
H
C 3 H 7
n-C 6 H 13
H
H
H

429
CH
O
H
i-C 3 H 7
n-C 6 H 13
H
H
H

430
CH
O
H
n-C 4 H 9
n-C 6 H 13
H
H
H

431
N
O
H
CH 3
n-C 4 H 9
H
H
H

432
N
O
H
C 2 H 5
n-C 4 H 9
H
H
H

433
N
O
H
C 3 H 7
n-C 4 H 9
H
H
H

434
N
O
H
i-C 3 H 7
n-C 4 H 9
H
H
H

435
N
O
H
n-C 4 H 9
n-C 4 H 9
H
H
H

436
N
O
H
CH 3
n-C 5 H 11
H
H
H

437
N
O
H
C 2 H 5
n-C 5 H 11
H
H
H

438
N
O
H
C 3 H 7
n-C 5 H 11
H
H
H

439
N
O
H
i-C 3 H 7
n-C 5 H 11
H
H
H

440
N
O
H
n-C 4 H 9
n-C 5 H 11
H
H
H

441
N
O
H
H
n-C 6 H 13
H
H
H

442
N
O
H
CH 3
n-C 6 H 13
H
H
H

443
N
O
H
C 2 H 5
n-C 6 H 13
H
H
H

444
N
O
H
C 3 H 7
n-C 6 H 13
H
H
H

445
N
O
H
i-C 3 H 7
n-C 6 H 13
H
H
H

446
N
O
H
n-C 4 H 9
n-C 6 H 13
H
H
H

447
N
NH
H
CH 3
n-C 4 H 9
H
H
H

448
N
NH
H
C 2 H 5
n-C 4 H 9
H
H
H

449
N
NH
H
C 3 H 7
n-C 4 H 9
H
H
H

450
N
NH
H
i-C 3 H 7
n-C 4 H 9
H
H
H

451
N
NH
H
n-C 4 H 9
n-C 4 H 9
H
H
H

452
N
NH
H
CH 3
n-C 5 H 11
H
H
H

453
N
NH
H
C 2 H 5
n-C 5 H 11
H
H
H

454
N
NH
H
C 3 H 7
n-C 5 H 11
H
H
H

455
N
NH
H
i-C 3 H 7
n-C 5 H 11
H
H
H

456
N
NH
H
n-C 4 H 9
n-C 5 H 11
H
H
H

457
N
NH
H
H
n-C 6 H 13
H
H
H

458
N
NH
H
CH 3
n-C 6 H 13
H
H
H

459
N
NH
H
C 2 H 5
n-C 6 H 13
H
H
H

460
N
NH
H
C 3 H 7
n-C 6 H 13
H
H
H

461
N
NH
H
i-C 3 H 7
n-C 6 H 13
H
H
H

462
N
NH
H
n-C 4 H 9
n-C 6 H 13
H
H
H

463
CH
O
H
H
CH 2 -Ph-4-Cl
H
H
H

464
CH
O
H
CH 3
CH 2 -Ph-4-Cl
H
H
H

465
CH
O
H
C 2 H 5
CH 2 -Ph-4-Cl
H
H
H

466
CH
O
H
CH 2 -Ph-4-Cl
CH 3
H
H
H

467
CH
O
H
CH 2 -Ph-4-Cl
C 2 H 5
H
H
H

468
CH
O
H
CH 2 -Ph-4-Cl
C 3 H 7
H
H
H

469
CH
O
H
CH 3
CF 3
H
H
H

470
CH
O
H
Cl
CF 3
H
H
H

471
CH
O
H
C 2 H 5
CF 3
H
H
H

472
CH
O
H
n-C 3 H 7
CF 3
H
H
H

473
CH
O
H
n-C 4 H 9
CF 3
H
H
H

474
CH
O
H
H
CH 2 CH 2 -Ph-
H
H
H






4-Cl

475
CH
O
H
CH 3

H
H
H

476
CH
O
H
H
CH 2 Bu-t
H
H
H

477
CH
O
H
CH 3
CH 2 Bu-t
H
H
H

478
CH
O
H
n-C 3 H 7
CH 2 Bu-t
H
H
H

479
CH
O
H
CH 2 Bu-t
CH 3
H
H
H

480
CH
O
H
CH 2 CH 2 -Ph-
CH 3
H
H
H





4-Cl

481
CH
O
H

C 2 H 5
H
H
H

482
CH
O
H

C 3 H 7
H
H
H

483
CH
O
H
CO 2 CH 3
CH 3
H
H
H

484
CH
O
H
CO 2 CH 3
CF 3
H
H
H

485
CH
O
H
CO 2 C 2 H 5
C 2 H 5
H
H
H

486
CH
O
H
CO 2 C 2 H 5
n-C 3 H 7
H
H
H

487
CH
O
H
CONHCH 3
CH 3
H
H
H

488
CH
O
H
CONHC 2 H 5
CH 3
H
H
H

489
CH
O
H
CON(CH 3 ) 2
CH 3
H
H
H

490
CH
O
H
CH 3
CO 2 CH 3
H
H
H



*stands for melting point. ° C. is the unit.
































































































































































































































































































































































































































































































































The present invention also includes preparation of benzopyrone compounds and their isomers having general formula (I).
The compounds of formula I can be easily prepared by reaction of the benzylhalide having general formula (II) with benzopyrone compounds containing hydroxy group having general formula (III) under base condition according to the scheme I.









wherein: Z is leaving group, such as halogen (Cl, Br, or I).
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , A, B, is as defined above.
Preparation condition of compounds having general formula (I): In proper solvent, hydroxylbenzopyrone compounds having general formula (III) are treated with proper base to become salts, then the compound having general formula (II) is added into the mixture, the reaction is carried out at proper temperature. After reaction is completed, the target compound I is obtained by normal way.
The proper solvent mentioned may be selected from the following ones, such as tetrahydrofuran, acetonitrile, toluene, xylene, benzene, DMF, DMSO, acetone or butanone and so on.
The proper base mentioned may be selected from the following ones, such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, triethylamine, pyridine, pyridine or sodium hydride and so on.
The proper temperature mentioned is from room temperature to boiling point of solvent. Normal temperature is from 20 to 100° C.
The reaction may be finished in the course of 30 minutes-20 hours, generally 1-10 hours.
The reaction can be controlled by Thin-Layer Chromatography.
The intermediates of general formula (II) can be prepared according to the known methods, refer to U.S. Pat. No. 4,723,034 and U.S. Pat. No. 5,554,578.
Some of the hydroxylbenzopyrone compounds having general formula (III) are available from the chemical company, and are also prepared according to the methods reported in Journal of Medicinal Chemistry, 2001, 44 (5), 664-671, by the reaction R 5 COCHR 4 CO 2 CH 3 (C 2 H 5 ) with substituted resorcinol. Moreover, the compound may be straightly used to prepare the target compounds without further purification. Some of the hydroxylbnezopyrone compounds having general formula (III) synthesized are showed in table 2.











TABLE 2



III
R 4
R 5
R 6
R 7
R 8
Physical property*



III-1
H
CH 3
H
H
COCH 3
158–160

III-2
H
CH 3
H
H
C(═NOMe)CH 3
129–140

III-3
H
H 3
H
H
CO 2 CH 3
219–222

III-4
H
CH 3
H
H
CH 3
256–258

III-5
Cl
CH 3
H
H
H
230–234

III-6
H
CF 3
H
H
H
180–183

III-7
C 6 H 5 CH 2
CH 3
H
H
H
208–212

III-8
H
4-F—C 6 H 4
H
H
H
256–262

III-9
H
3,4-(MeO) 2 C 6 H 4
H
H
H
184–188

III-10
F
CH 3
H
H
H
203–206

III-11
H
C 6 H 5
H
H
H
240–242

III-12
H
C 6 H 5
H
H
CH 3
260–262

III-13
Cl
C 6 H 5
H
H
H
188–190

III-14
CH 3
CH 3
H
H
H
118–120

III-15
CH 3
CH 3
H
H
CH 3
218–222

III-16
H
n-C 3 H 7
H
H
CH 3
176–178

III-17
Cl
n-C 3 H 7
H
H
H
148–150

III-18
H
i-C 3 H 7
H
H
H
160–162

III-19
n-C 6 H 13
CH 3
H
H
H
170–172

III-20
i-C 3 H 7 CH 2 CH 2
CH 3
H
H
H
101–102

III-21
n-C 4 H 9
CH 3
H
H
H
134–136

III-22
n-C 3 H 7
CH 3
H
H
H
142–144

III-23
H
CH 2 OCH 3
H
H
H
186–190



*stands for melting point. ° C. is the unit.






































The compounds of general formula (V) and (VII) can be easily prepared by reaction of the general formula (IV) and (VI), respectively, with methylamine aqueous solution.









The present invention also provides a composition of insecticides and fungicides. The active ingredients of the composition are the compounds having general formula (I), wherein the active ones being present in a total amount of 0.1 to 99% by weight, the rest being the acceptable carrier by agriculture.
The present invention, further more, provides preparation method of the said composition thereon. The compounds of general formula (I) and the carrier are mixed. The said composition may be a single component compound or mixture of compounds with several components.
The carrier in the invention accords to the requirements: it is easy to apply to the sites being to be treated for the carrier after it is confected with active component. For example, the sites could be plant, seed or soil convenient for store, transport or operation. The carrier could be solid or liquid, including the liquid which usually turns from gas condition under pressure. And the carriers which are used to confect insecticidal, bactericidal composition are applied.
Suitable solid carriers include natural and synthetic clays and silicates, for example diatomaceous earths, talcs, magnesium aluminium silicates, aluminium silicates(kaolin), montmorillonites and micas; calcium carbonate; calcium sulphate; ammonium sulphate; synthetic silicon oxides and synthetic calcium silicates or aluminium silicates; elements, for example carbon and sulphur; natural and synthetic resins, for example coumarone resins, polyvinyl chloride, and styrene polymers or copolymers; solid polychlorophenols; bitumen; waxes, beeswax or paraffin wax for instance.
Suitable liquid carriers include water, alcohols such as isopropanol or alcohol; ketones such as acetone, methyl ethyl ketone, methyl isopropy ketone or cyclohexanone; ethers; aromatics such as benzene, xylene, toluene; petroleum fractions such as kerosene or mineral oils, chlorinated aliphatic hydrocarbons such as carbon tetrachloride, tetrachloride ethylene or trichloride ethylene. Mixtures of these different liquids generally are often suitable.
The compositions of insecticides and fungicides are often formulated and transported in a concentrated form which is subsequently diluted by the user before application. The presence of small amounts of surfactant facilitates this process of dilution. Thus preferably at least one carrier in a composition according to the invention is a surfactant. For example the composition may contain at least two carriers, at least one of which is, a surfactant.
A surfactant may be an emulsifier, a dispersant or a wetting agent; it may be nonionic or ionic. Examples of suitable surfactant include the sodium or calcium salts of polyacrylic acids and lignin sulphonic acids; the condensation products of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide; fatty acid esters of glycol, sorbic alcohol, sucrose or pentaerythritol and condensations of these with ethylene oxide and/or propylene oxide; condensation products of fatty alcohol or alkyl phenols such as p-octylphenol or p-octylcresol, with ethylene-oxide and/or propylene oxide; sulphates or sulphonates of these condensation products; alkaline metal salts or alkaline earth metal salts, preferably sodium salts, of sulphuric or sulphonic acid esters containing at least 10 carbon atoms in the molecule, for example sodium lauryl sulphate, sodium secondary alkyl sulphates, sodium salts of sulphonated castor oil, and sodium alkylaryl sulphonates such as sodium dodecylbenzene sulphonate.
Examples of compositions and formulations according to the invention are wettable powder, Dustable powder, granule and aqueous solution; emulsifiable concentrate, emulsion, suspension concentrate, aerosol composition and fumigant. Wettable powder usually contains 25, 50 or 75% weight(ab.w) of active ingredient and usually contain in addition to solid inert carrier, 3-10% w of a dispersant and, where necessary, 0-10% w of stabiliser(s) and/or other additives such as penetrants or stickers. Dustable powder are usually formulated as a dust concentrate having a similar composition to that of a wettable powder but a dispersant, and are diluted with further solid carrier to give a composition usually containing 0.5-10% weight of active ingredient. Granules are usually prepared to have a size between 10 and 100 BS mesh (1.676-0.152 mm), and may be manufactured by agglomeration or impregnation techniques. Generally, granules contain 0.5-75% w active ingredient and 0-10% weight of additives such as stabilisers, surfactants, slow release modifiers. The so-called “dry flowable powders” consist of relatively small granules having a relatively high concentration of active ingredient. Emulsifiable concentrates usually contain, in addition to a solvent and, when necessary, co-solvent, 1-50% weight /volume(ab. w/v) active ingredient, 2-20% w/v emulsifiers and 0-20% w/v of other additives such as stabilisers, penetrants and corrosion inhibitors. Suspension concentrates are usually contain 10-75% w active ingredient, 0.5-15% w of dispersing agents, 0.1-10% w of other additives such as defoamers, corrosion inhibitors, stabilisers, penetrants and stickers.
Aqueous dispersant and emulsions, for example compositions obtained by diluting a wettable powder or a concentrate according to the invention with water, also lie within the scope of the invention. The said emulsions may be of the water-in-oil or of the oil-in-water type.
The composition to which one or more other fungicides are added has wider spectrum activity than single compound having general formula (I). In addition, other fungicides may have synergistic effect on the fungicidal activity of the compound having general formula (I). The compound having general formula (I) can also be used with other insecticides, or with another fungicide and other insecticides simultaneously.
This invention has the following advantages:
The compounds of present invention have very good insecticide activity, and may be used to control insects such as armyworm, diamond backmoth, aphids, carmine spider mite, two-spotted spider mite, lady beetles, mites and culex mosquitoes, especially for lady beetles and culex mosquitoes. All these attributes are suitable for integrated insect management.
The compounds of present invention have wide spectrum fungicidal activity, and may be used to control diseases in all sorts of plants caused by by oomycete, basidiomycete, ascomycete pathogens, and it may also provide good control efficacy at very low rate because of the high activity. These compounds have penetration activity and can be used as soil and foliar fungicides. They can provide satisfied control of grape downy mildew, rice sheath blight, rice blast, tomato early blight, tomato late blight, wheat leaf rust, wheat leaf blotch, wheat powdery mildew, cucumber powdery mildew, cucumber downy mildew and cucumber grey mold


DESCRIPTION OF THE INVENTION IN DETAIL
The following examples are illustrative of the present invention.
PREPARATION EXAMPLE
Example 1
The Preparation of Compound 1
A reaction flask was charged a suspension of 60% sodium hydride 0.84 g (washed with petroleum ether), and then 30 ml of dry N,N-dimethylformamide (DMF) was added, the mixture was stirred at room temperature for 30 minutes. To this agitated suspension, 1.7 g of 7-hydroxycoumarin was added, the mixture was agitated continuously till to no gas emerging. 3.0 g of methyl (E)-α-[2-(bromomethyl)phenyl]-β-methoxyacrylate was added to the reaction mixture and they were agitated continuously for 3 hours at room temperature. The reaction mixture was poured into ice water, extracted with ethyl acetate 3 times. The combined extracts were washed with brine 3 times, dried, filtered and concentrated under vacuum, to obtain the crude oil product 5 g. This was subjected to column chromatography to obtain 2.8 g of compound 1 as a faint red-yellow oily substance in 76.5% yield.
1 HNMR(300 MHz, internal standard=TMS, CDCl 3 ): δppm 3.69 (3H, s), 3.88 (3H, s), 5.04 (2H, s), 6.19-6.23 (1H, d), 6.77 (1H, s), 6.83-6.87 (1H, d), 7.18-7.20 (1H, m), 7.26-7.34 (4H, m), 7.48-7.64 (2H, m).
Example 2
The Preparation of Compound 2
A reaction flask was charged a suspension of 60% sodium hydride 0.45 g (washed with petroleum ether), and then 20 ml of dry N,N-dimethylformamide (DMF) was added, the mixture was stirred at room temperature for 30 minutes. To this agitated suspension, 1.0 g of 7-hydroxy-4-methylcoumarin was added, the mixture was agitated continuously till to no gas emerging. 1.66 g of methyl (E)-α-[2-(chloromethyl)phenyl]-β-methoxyacrylate was added to the reaction mixture and they were agitated continuously for 3 hours at room temperature. The reaction mixture was poured into ice water, extracted with ethyl acetate 3 times. The combined extracts were washed with brine 3 times. Dried, filtered and concentrated, to obtain the crude product, as a yellow solid substance. This was subjected to column chromatography, using a 1:2 mixture of ethyl acetate and petroleum ether as the eluting solution to obtain 1.73 g of compound 2, with melting point of 140-143° C. in 80% yield.
1 HNMR(300 MHz, internal standard=TMS, CDCl 3 ): δppm 2.38 (3H, s), 3.74 (3H, s), 3.89 (3H, s), 5.04 (2H, s), 6.11 (1H, s), 6.77 (1H, s), 6.85-6.89 (1H, d), 7.17-7.20 (1H, m), 7.32-7.35 (2H, m), 7.49-7.52 (2H, m), 7.64 (1H, s).
Example 3
The Preparation of Compound 101
A reaction flask was added 1.2 g of K 2 CO 3 , 1.0 g of 7-hydroxy-4-methylcoumarin, 1.70 g of methyl (E)-2-(bromomethyl)-α-(methoxyimino)benzeneacetate and 20 ml Butanone, the reaction mixture was refluxed and agitated continuously for 5 hours. The reaction mixture was poured into ice water, extracted with ethyl acetate 3 times. The combined extracts were washed with brine 3 times, dried, filtered and concentrated under vacuum, to obtain the crude product, as a yellow solid substance. This was subjected to column chromatography, using a 1:2 mixture of ethyl acetate and petroleum ether as the eluting solution to obtain 1.77 g of compound 101, with melting point of 150-152° C. in 83% yield.
1 HNMR(300 MHz, internal standard=TMS, CDCl 3 ): δppm 2.39 (3H, s), 3.87 (3H, s), 4.05 (3H, s), 5.02 (2H, s), 6.13 (1H, s), 6.80-6.86 (2H, m), 7.23-7.26 (1H, m), 7.43-7.49 (4H, m).
Example 4
The Preparation of Compound 153
A reaction flask was added 0.27 g of compound 101, more than two fold(mol)methylamine and 30 ml methanol, the reaction mixture was continuously agitated overnight, then concentrated and extracted with ethyl acetate 2 times. The combined extracts were washed with water 3 times and then washed with brine 2 times, dried, filtered and concentrated, to obtain 0.24 g of compound 153, with melting point of 210-214° C. in 89% yield.
1 HNMR(300 MHz, internal standard=TMS, CDCl 3 ): δppm 2.38 (3H, s), 2.91-2.93 (3H, d), 3.97 (3H, s), 5.02 (2H, s), 6.13 (1H, s), 6.82-6.87 (3H, m), 7.23 (1H, d), 7.39-7.50 (4H, m).
The preparation of other compounds, please refers to the way as above. 1 HNMR of other compounds are provided as follows (300 MHz, internal standard=TMS, CDCl 3 ):
Compound 3: δppm 2.36 (3H, s), 2.37 (3H, s), 3.72 (3H, s), 3.84 (3H, s), 5.09 (2H, s), 6.13 (1H, s), 6.75-6.78 (1H, d), 7.18-7.21 (1H, m), 7.34-7.36 (3H, m), 7.50-7.52 (1H, m)7.61 (1H, s).
Compound 4: δppm 2.41 (3H, s), 3.69 (3H, s), 3.81 (3H, s), 5.08 (2H, s), 6.20 (1H, s), 6.68-6.71 (1H, d), 7.18-7.21 (4H, m), 7.32-7.50 (5H, m), 7.59 (1H, s), 7.92 (1H, m).
Compound 5: δppm 2.17 (3H, s), 2.35 (3H, s), 3.73 (3H, s), 3.88 (3H, s), 5.02 (2H, s), 6.78 (1H, s), 6.83-6.85 (1H, d), 7.31-7.34 (3H, m), 7.45-7.47 (2H, d), 7.62 (1H, s).
Compound 6: δppm 2.32 (3H, s), 2.31-2.36 (6H, d), 3.69 (3H, s), 3.84 (3H, s), 5.07 (2H, s), 6.74-6.77 (1H, d), 7.17-7.20 (1H, m), 7.31-7.36 (3H, m), 7.51-7.54 (1H, m), 7.61 (1H, s).
Compound 12: δppm 2.53 (3H, s), 3.74 (3H, s), 3.89 (3H, s), 5.04 (2H, s), 6.78 (1H, s), 6.83-6.85 (1H, d), 7.18-7.21 (1H, m), 7.32-7.35 (2H, m), 7.47-7.50 (2H, d), 7.64 (1H, s).
Compound 17: δppm 1.25-1.32 (3H, m), 2.36 (3H, s), 2.74-2.76 (2H, m), 3.71 (3H, s), 3.84 (3H, s), 5.08 (2H, s), 6.15 (1H, s), 6.75-6.78 (1H, d), 7.18-7.21 (1H, m), 7.33-7.38 (3H, m), 7.50-7.54 (1H, m), 7.61 (1H, s).
Compound 18: δppm 1.10-1.15 (3H, t), 2.37 (3H, s), 2.60-2.68 (2H, q), 3.74 (3H, s), 3.89 (3H, s), 5.03 (2H, s), 6.76 (1H, d), 6.84-6.88 (1H, dd), 7.18-7.21 (1H, m), 7.32-7.35 (2H, m), 7.45-7.53 (2H, m), 7.63 (1H, s).
Compound 19: δppm 3.48 (3H, s), 3.74 (3H, s), 3.89 (3H, s), 4.56 (2H, s), 5.04 (2H, s), 6.34 (1H, s), 6.79 (1H, d), 6.84-6.88 (1H, dd), 7.18-7.21 (1H, m), 7.30-7.36 (2H, m), 7.41-7.44 (1H, d), 7.48-7.51 (1H, m), 7.64 (1H, s).
Compound 24: δppm 3.72 (3H, s), 3.92 (3H, s), 5.10 (2H, s), 6.78 (1H, s), 6.94-7.21 (1H, d), 7.22 (1H, m), 7.33-7.35 (2H, m), 7.36-7.45 (2H, m), 7.66 (1H, s), 8.13 (1H, s).
Compound 25: δppm 2.36 (3H, d), 2.62 (3H, d), 3.71 (3H, s), 3.84 (3H, s), 5.09 (2H, s), 6.82 (1H, d), 7.19-7.21 (1H, m), 7.33-7.35 (3H, m), 7.36-7.37 (1H, m), 7.61 (1H, s).
Compound 26: δppm 1.25-1.30 (6H, m), 3.20-3.23 (1H, m), 3.74 (3H, s), 3.91 (3H, s), 5.04 (2H, s), 6.15 (1H, s), 6.790-6.799 (1H, d), 6.80-6.90 (1H, m), 7.18-7.23 (1H, m), 7.32-7.37 (2H, m), 7.48-7.57 (2H, m), 7.64 (1H, s).
Compound 27: 8ppm 0.95-1.00 (3H, t), 1.58 (2H, m), 2.36 (3H, s), 2.58 (2H, t), 3.73 (3H, s), 3.89 (3H, s), 5.02 (2H, s), 6.75 (1H, d), 6.84-6.88 (1H, dd), -7.18 (1H, m), 7.31-7.34 (1H, m), 7.47-7.51 (2H, m), 7.63 (1H, s).
Compound 29: δppm 3.74 (3H, s), 3.90 (3H, s), 5.06 (2H, s, ), 6.17 (1H, s), 6.80-6.85 (2H, m), 7.24-7.26 (1H, m), 7.28-7.35 (5H, m), 7.38-7.51 (3H, m), 7.66 (1H, s).
Compound 32: δppm 3.73 (3H, s), 3.90 (3H, s), 5.05 (2H, s), 6.75-6.78 (1H, dd), 6.84-6.85 (1H, d), 6.94-6.98 (1H, d), 7.19-7.21 (1H, m), 7.30-7.35 (4H, m), 7.53-7.55 (4H, m), 7.65 (1H, s).
Compound 33: δppm 1.27-1.32 (3H, m), 2.74-2.77 (2H, m), 3.74 (3H, s), 3.89 (3H, s), 5.04 (2H, s), 6.13 (1H, s), 6.78-6.79 (1H, d), 6.85-6.89 (1H, m), 7.18-7.21 (1H, m), 7.32-7.35 (2H, m), 7.48-7.52 (2H, m), 7.64 (1H, s).
Compound 34: δppm 0.90-1.03 (3H, m), 1.67-1.72 (2H, m), 2.65-2.70 (2H, m), 3.73 (3H, s), 3.89 (3H, s), 5.04 (2H, s), 6.10 (1H, s), 6.78-6.79 (1H, d), 6.85-6.89 (1H, m), 7.19-7.21 (1H, m), 7.33-7.35 (2H, m), 7.47-7.51 (2H, m), 7.64 (1H, s).
Compound 35: δppm 1.00-1.25 (3H, m), 1.69-1.72 (2H, m), 2.36 (3H, s), 2.65-2.70 (2H, m), 3.71 (3H, s), 3.84 (3H, s), 5.08 (2H, s), 6.12 (1H, s), 6.75-6.78 (1H, d), 7.21-7.26 (1H, m), 7.33-7.38 (3H, m), 7.50-7.53 (1H, m), 7.61 (1H, s).
Compound 36: δppm 0.97 (3H, t), 1.66 (2H, m), 2.67 (3H, s), 3.74 (3H, s), 3.89 (3H, s), 5.04 (2H, s), 6.78 (1H, d), 6.85-6.88 (1H, dd), 7.22 (1H, m), 7.33-7.35 (2H, m), 7.46-7.49 (2H, m), 7.64 (1H, s).
Compound 37: δppm 1.05 (3H, m), 1.57-1.64 (2H, m), 2.16 (3H, s), 2.71-2.76 (2H, t), 3.70 (3H, s), 3.83 (3H, s), 5.02 (2H, s), 6.78 (1H, d), 6.87 (1H, m), 7.20 (1H, m), 7.32 (2H, m), 7.45 (2H, m), 7.64 (1H, s).
Compound 38: δppm(DMSO-d 6 ) 3.65 (3H, s), 3.88 (3H, s), 5.03 (2H, s), -6.15 (1H, s), 6.83-6.87 (1H, dd), 6.91 (1H, d), 7.09-7.17 (2H, m), 7.23-7.35 (4H, m), 7.43-7.46 (1H, m), 7.51-7.55 (2H, m), 7.66 (1H, s).
Compound 41: δppm 3.74 (3H, s), 3.91 (3H, s), 5.06 (2H, s), 6.20 (1H, s), 6.86 (2H, m), 7.22 (2H, m), 7.33-7.36 (2H, m), 7.56 (3H, m), 7.66 (1H, s), 7.77 (2H, d). Compound 50: δppm 2.34 (3H, s), 3.74 (3H, s), 3.89 (3H, s), 5.04 (2H, s), 6.78-6.79 (1H, d), 6.92-6.96 (1H, dd), 7.18-7.21 (1H, m), 7.32-7.35 (2H, m), 7.41-7.44 (1H, d), 7.48-7.51 (1H, m), 7.65 (1H, s).
Compound 52: δppm 3.74 (3H, s), 3.90 (3H, s), 5.06 (2H, s), 6.20 (1H, s), 6.80-6.86 (1H, m), 7.18-7.22 (1H, m), 7.32-7.37 (4H, m), 7.41-7.44 (2H, m), 7.50-7.52 (4H, m), 7.65 (1H, s).
Compound 58: δppm 3.74 (3H, s), 3.91 (6H, d), 3.96 (3H, s), 5.06 (2H, s), 6.19 (1H, s), 6.81-6.82 (1H, m), .6.85 (1H, s), 6.93-7.04 (3H, m), 7.19-7.22 (1H, m), 7.33-7.36 (2H, m), 7.44-7.52 (2H, m), 7.66 (11H, s).
Compound 68: δppm(DMSO-d 6 ) 2.49 (3H, s), 3.66 (3H, s), 3.89 (3H, s), 3.92 (2H, s), 5.00 (2H, s), 6.78-6.79 (1H, d), 6.85-6.89 (1H, dd), 7.10-7.22 (6H, m), 7.26-7.29 (2H, m), 7.42 (1H, m), 7.61-7.66 (2H, m).
Compound 100: 8ppm 2.54 (3H, s), 3.87 (3H, s), 4.04 (3H, s), 5.02 (2H, s), 6.81-6.85 (1H, s), 7.26 (1H, d), 7.43-7.52 (5H, m).
Compound 102: δppm 2.32 (3H, s), 2.37 (3H, s), 3.84 (3H, s), 4.03 (3H, s), 5.05 (2H, s), 6.13 (1H, s), 6.76-6.79 (1H, d), 7.26 (1H, d), 7.34-7.43 (3H, m), 7.45-7.46 (1H, d).
Compound 103: δppm 2.18 (3H, s), 2.37 (3H, s), 3.91 (3H, s), 3.98 (3H, s), 5.35 (2H, s), 6.85 (1H, s), 6. 86-6.88 (1H, d), 7.26-7.40 (3H, m), 7.49-7.52 (1H, d), 7.62-7.65 (1H, d).
Compound 104: δppm 2.17 (3H, s), 2.35 (3H, s), 3.86 (3H, s), 4.04 (3H, s), 5.00 (2H, s), 6.78-6.85 (2H, m), 7.20-7.25 (1H, d), 7.40-7.61 (4H, m).
Compound 109: δppm 2.91-2.93 (3H, d), 3.97 (3H, s), 5.02 (2H, s), 6.23-6.26 (1H, d), 6.82-6.86 (3H, m), 7.20-7.23 (1H, m), 7.34-7.37 (1H, d), 7.39-7.45 (2H, m), 7.50-7.53 (1H, m), 7.61-7.64 (1H, d).
Compound 111: 8ppm 3.87 (3H, s), 4.05 (3H, s), 5.02 (2H, s), 6.23-6.26 (1H, d), 6.79-6.85 (2H, m), 7.21 (1H, d), 7.34-7.37 (1H, d), 7.41-7.45 (2H, m), 7.47-7.53 (1H, m), 7.61-7.64 (1H, d).
Compound 401: δppm 1.32-1.36 (6H, m), 2.39 (3H, s), 3.27 (1H, m), 3.74 (3H, s), 3.89 (3H, s), 5.03 (2H, s), 6.72-6.73 (1H, d), 6.83-6.87 (1H, dd), 7.17-7.20 (1H, m), 7.31-7.34 (2H, m), 7.46-7.52 (2H, m), 7.63 (1H, s).
Compound 402: δppm 0.93 (3H, m), 1.45 (4H, m), 2.35 (3H, s), 2.60 (2H, t), 3.74 (3H, s), 3.89 (3H, s), 5.04 (2H, s), 6.78 (1H, d), 6.84-6.85 (1H, m), 7.18-7.20 (1H, m), 7.30-7.35 (2H, m), 7.45-7.50 (2H, d), 7.64 (1H, s).
Compound 404: δppm 1.25 (6H, m), 1.39 (2H, m), 1.63 (1H, m), 2.39 (3H, s), 2.62 (2H, t), 3.72 (3H, s), 3.86 (3H, s), 5.01 (2H, s), 6.78 (1H, d), 6.84 (1H, m), 7.20 (1H, m), 7.32 (2H, m), 7.45 (2H, d), 7.64 (1H, s).
Compound 405: δppm 0.88 (3H, t), 1.42-1.52 (8H, m), 2.38 (3H, s), 2.64 (2H, t), 3.72 (3H, s), 3.86 (3H, s), 5.01 (2H, s), 6.78 (1H, d), 6.84 (1H, m), 7.20 (1H, m), 7.32 (2H, m), 7.45 (2H, d), 7.64 (1H, s).
Compound 408: 8ppm 2.37 (3H, s), 3.2-3.6 (1H, m), 3.72 (3H, s), 3.85 (3H, s), 5.09 (2H, s), 6.18 (1H, s), 6.76-6.79 (1H, d), 7.18-7.21 (1H, m), 7.34-7.43 (3H, m), 7.51-7.54 (1H, m), 7.68 (1H, 5).
Compound 409: δppm 0.96-1.03 (6H, m), 1.58-1.63 (4H, m), 2.71-2.79 (4H, m), 3.72 (3H, s), 3.85 (3H, s), 5.00 (2H, s), 6.79 (1H, d), 6.87 (1H, m), 7.19 (1H, m), 7.32 (2H, m), 7.45 (2H, m), 7.64 (1H, s).
Compound 410: 8ppm 0.86-0.88 (3H, m), 1.68-1.75 (2H, m), 2.66-2.71 (2H, m), 3.87 (3H, s), 4.05 (3H, s), 5.02 (2H, s), 6.80-6.92 (3H, m), 7.21-7.26 (1H, d), 7.39-7.69 (3H, m).
Compound 411: δppm 3.87 (3H, s), 4.05 (3H, s), 5.02 (2H, s), 6.73-6.77 (1H, m), 6.87-6.88 (1H, d), 6.97-7.00 (1H, d), 7.21-7.24 (1H, m), 7.28-7.32 (2H, m), 7.42-7.57 (6H, m).
Compound 412: δppm 0.94 (3H, t), 1.46 (2H, m), 2.35 (3H, s), 2.60 (2H, t), 3.74 (3H, s), 3.89 (3H, s), 5.04 (2H, s), 6.78 (1H, d), 6.84 (1H, m), 7.20 (1H, m), 7.32 (2H, m), 7.42-7.45 (2H, d), 7.64 (1H, s).
Compound 413: δppm 0.94 (3H, m), 1.45 (4H, m), 2.36 (3H, s), 2.60 (2H, t), 3.86 (3H, s), 4.05 (3H, s), 5.00 (2H, s), 6.78 (1H, d), 6.84 (1H, m), 7.20 (1H, m), 7.38-7.45 (4H, m).
Compound 414: δppm 0.88 (3H, m), 1.48-1.65 (8H, m), 2.36 (3H, s), 2.62 (2H, t), 3.86 (3H, s), 4.05 (3H, s), 5.00 (2H,.s), 6.85 (1H, m), 6.84 (1H, m), 7.20 (1H, m), 7.39-7.45 (4H, m).
Formulation Example (Weight/Weight %)
Example 5
60% Wettable Powder











Compound 6
60%


Sodium dodecylnaphthalenesulfate
2%


Sodium lignosulphonate
9%


Kaolin
complement to 100%


















All the solid components are well mixed and shattered until the particle size of the active ingredient reaches the standard in order to obtain 60% wettable powder.
Example 6
35% Emulsion Concentrate











Compound 1
35%


Phosphorous acid
10%


Ethylenoxy aliphatic acid glycerin ester
15%


Cyclohexanone
complement to 100%


















Phosphorous acid is dissolved in cyclohexanone, then the compound 1 and ethylenoxy aliphatic acid glycerin ester are added, a emulsifiable concentrate in transparent solution is obtained finally.
Example 7
30% Aqueous Suspension Concentrate











Compound 25
30%


Sodium dodecylnaphthalenesulfate
4%


Hemicellulose
2%


Epoxypropane
8%


Water
complement to 100%



















The mixture of compound 25, 80% of the amount of water should being added and sodium dodecylnaphthalenesulfate are shattered in a mill (1 mm ball). Other components are dissolved in the rest water, and are added under stirring.
Example 8
25% Suspension Emulsifier








Compound 12
25%

Alkylsulphonates (emulsifier 1)
4%

Ethylenoxy aliphatic acid glycerin ester
2%

(emulsifier 2)

Calcium dodecylbenzenesulfate (emulsifier 3)
1.5%

Polyethylenoxyalkyl propyl ether (dispersant)
2.5%

Cyclohexanone (solvent 1)
30%

Petroleum fractions (boiling point >200° C.)
complement to 100%

(solvent 2)






















Compound 12 is dissolved in 80% of the amount of solvent should being added, and then emulsifiers and dispersant are added, the mixture is stirred completely and shattered in a mill(1 mm ball). Other solvents are added.
Test of Biological Activity
Example 9
Fungicidal Activity Determination
Determination of fungicidal activities against plant diseases of selected compounds were carried out by following procedure:
Plants were prepared in pot. Technical samples were dissolved in DMF and diluted to required concentration by water. Test solution was sprayed onto potted plant. Pathogen inoculation was carried out after 24 hours then plants were hold in growth chambers containing constant temperature and moisture for effect. When untreated plant was under desirable disease severity (after 1 week approximately), assessment was carried out by visual observation.
Part of test results:
At 200 ppm, compound 1, 2, 4, 5, 6, 12, 18, 19, 25, 26, 33, 34, 35, 37, 50, 52, 58, 69, 109, 402, 405, 409, 410, 413, 414 showed 100% control against cucumber downy mildew, while compound 3, 24, 36, 38, 153, 411 showed >95% control.
At 200 ppm, compound 2, 6, 18, 50, 58, 100, 402 showed 100% control against cucumber grey mold, while 6, 101, 102, 103, 106, 412 showed >75% control.
At 200 ppm, compound 6, 7, 10 showed 100% against grape downy mildew, while 8, 106, 154 showed >85% control.
At 200 ppm, compound 3, 101 showed >85% control against rice sheath blight.
At 200 ppm, compound 6, 8, 10 showed >85% control against rice blast.
At 200 ppm, compound 402, 412, 413 showed 100% control against wheat powdery mildew, while 9, 101, 111, 410 showed >70% control.
At 200 ppm, compound 6 showed 100% control against wheat leaf rust, while 7, 10 showed >95% control and 8, 154 showed >75% control.
At 200 ppm, compound 6>90% and compound 7, 8, 9, 10, 11, 154 showed >80% control against wheat leaf blotch.
At 200 ppm, compound 6, 7 showed >100% control against tomato early stage blight, while 8, 10 showed >90% control, while 11 showed >75% control.
At 200 ppm, compound 6 showed >95% control against tomato late blight, while 10 showed >75% control.
At 200 ppm, compound 5, 6 showed >95% control against corn leaf blight. Comparing with the compound JP51 in JP04-182461, the part of test results of some compounds activity against cucumber downy mildew refers to table 3.





TABLE 3



Comparision of fungicidal activity against cucumber downy mildew (50 ppm)





Compound

















1
2
5
6
12
26
37
52
402
405
409
141
JP51



















control(%)
100
100
100
100
100
100
100
100
100
100
100
100
20




























Example 10
Determination of Insecticidal/Acaricidal Activity
Numerous insect larvae were put into containers then were fed with treated corn leaves. Potter's spraying tower was used as the sprayer and spraying volume was 1 mL. The spraying pressure was 13.5 lb/in 2 .
Test Result:
At 10 ppm, compound 2, 5, 6 showed 100% control of culex mosquitoes. At 600 ppm, compound 5 and 6 showed >50% control of army worm, diamond backmoth and green peach aphid.
At 300 ppm, compound 7, 9, 10 showed 100% control of Mexican lady beetle, while compound 7 showed >50% control of two-spotted spider mite.