Benzopyrone compounds, preparation method and use thereof

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:

##STR00002##

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

##STR00003##

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):

##STR00004##

wherein: A is selected from CH or N;

B is selected from O, S or NR.sub.9; R.sub.9 is selected from H or C.sub.1-C.sub.12alkyl;

R.sub.1 and R.sub.2 are respectively selected from H, C.sub.1-C.sub.12alkyl or C.sub.1-C.sub.12 haloalkyl;

R.sub.3 is selected from H, C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.12 haloalkyl or C.sub.1-C.sub.12 alkoxy;

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

##STR00005##

wherein: R.sub.10 and R.sub.11 are selected from H, C.sub.1-C.sub.12alkyl, aryl or aryl C.sub.1-C.sub.12alkyl; when R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.8 are all H, B is not NR.sub.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.sub.9; R.sub.9 is selected from H or C.sub.1-C.sub.6alkyl;

R.sub.1 and R.sub.2 are respectively selected from H, C.sub.1-C.sub.6alkyl or C.sub.1-C.sub.6 haloalkyl;

R.sub.3 is selected from H, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6 haloalkyl or C.sub.1-C.sub.6alkoxy;

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

##STR00006##

wherein: R.sub.10 and R.sub.11 are respectively selected from H, C.sub.1-C.sub.12alkyl, aryl or arylC.sub.1-C.sub.6alkyl; when R.sub.3, R.sub.4,R.sub.5, R.sub.6, R.sub.7, R.sub.8 are all H, B is not NR.sub.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.sub.1 and R.sub.2 are respectively selected from methyl;

R.sub.3 is selected from H or methyl;

R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.8 may be the same or different, respectively selected from H, halo, CN, NO.sub.2, C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6 alkenyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkoxy, C.sub.1-C.sub.6alkylcarbonyl, C.sub.1-C.sub.6 alkoxyC.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6alkoxycarbonyl, C.sub.1-C.sub.6alkoxycarbonylC.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkoxyC.sub.1-C.sub.3alkyl, or amino C.sub.1-C.sub.3alkyl in which amino is substituted with 0-2 C.sub.1-C.sub.3 alkyl, phenyl, phenoxy, phenylC.sub.1-C.sub.2alkyl, phenylC.sub.1-C.sub.2alkoxy, phenoxyC.sub.1-C.sub.2alkyl, phenylmethyl, phenylmethoxyl, or phenylmethoxyC.sub.1-C.sub.2alkyl substituted with 0-2 halo, NO.sub.2, C.sub.1-C.sub.2alkyl, C.sub.1-C.sub.2haloalkyl, C.sub.1-C.sub.2alkoxy or C.sub.1-C.sub.2alkoxyC.sub.1-C.sub.2alkyl, and the substituted group having general formula is as follows:

##STR00007##

wherein: R.sub.10 and R.sub.11 are respectively selected from H or C.sub.1-C.sub.6alkyl; when R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.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.sub.1 and R.sub.2 are selected from methyl;

R.sub.3 is selected from H or methyl;

R.sub.4, R.sub.5, R.sub.6, R.sub.7, and R.sub.8 may be the same or different, respectively selected from H, Cl, Br, F, CN, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6alkylcarbonyl, Cl -C.sub.6alkoxy, C.sub.1-C.sub.6alkoxyC.sub.1-C.sub.3alkyl, C.sub.1-C.sub.3haloalkoxyC.sub.1-C.sub.3alkyl, amino C.sub.1-C.sub.3alkyl in which amino is substituted with 0-2 C.sub.1-C.sub.3 alkyl, phenyl, phenoxy, phenylmethyl, phenylmethoxyl, substituted with 0-2 halo, NO.sub.2, C.sub.1-C.sub.2alkyl, C.sub.1-C.sub.2haloalkyl, C.sub.1-C.sub.2alkoxy or C.sub.1-C.sub.2alkoxyC.sub.1-C.sub.2alkyl, and the substituted groups having general formula is as follows:

##STR00008##

wherein: R.sub.10 and R.sub.11 are selected from methyl; when R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.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.sub.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.dbd.C and C.dbd.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.

##STR00009##

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

TABLE-US-00001 TABLE 1 Physical- No. A B R.sub.3 R.sub.4 R.sub.5 R.sub.6 R.sub.7 R.sub.8 property* 1 CH O H H H H H H oil 2 CH O H H CH.sub.3 H H H 140~143 3 CH O H H CH.sub.3 H H CH.sub.3 188 190 4 CH O H H C.sub.6H.sub.5 H H CH.sub.3 146 148 5 CH O H CH.sub.3 CH.sub.3 H H H 120~122 6 CH O H CH.sub.3 CH.sub.3 H H CH.sub.3 174~176 7 CH O H H CF.sub.3 H H H 164~166 8 CH O H H CH.sub.3 H H P oil 9 CH O H H CH.sub.3 H P H 183~185 10 CH O H H CH.sub.3 H COCH.sub.3 H 169~172 11 CH O H H CH.sub.3 H H COCH.sub.3 165~167 12 CH O H Cl CH.sub.3 H H H 162 164 13 CH O H H CH.sub.2Cl H H H 14 CH O H Cl CH.sub.2Cl H H H 15 CH O H Cl CH.sub.2OCH.sub.3 H H H 16 CH O H Cl CH.sub.2CH.sub.3 H H H 17 CH O H H CH.sub.2CH.sub.3 H H CH.sub.3 154 156 18 CH O H C.sub.2H.sub.5 CH.sub.3 H H H 132 135 19 CH O H H CH.sub.2OCH.sub.3 H H H 140 142 20 CH O H H CH.sub.2OC.sub.2H.sub.5 H H H 21 CH O H Cl CH.sub.2OC.sub.2H.sub.5 H H H 22 CH O H OCH.sub.3 CH.sub.2OCH.sub.3 H H H 23 CH O H N(CH.sub.3).sub.2 CH.sub.3 H H H 24 CH O H CN H H H H 166 168 25 CH O H Cl CH.sub.3 H H CH.sub.3 202 204 26 CH O H H CH(CH.sub.3).sub.2 H H H 128 130 27 CH O H C.sub.3H.sub.7 CH.sub.3 H H H 142 144 28 CH O H H tC.sub.4H.sub.9 H H H 29 CH O H H 4-Cl--C.sub.6H.sub.4 H H H 149 152 30 CH O H Cl 4-Cl--C.sub.6H.sub.4 H H H 31 CH O H H 4-Cl--C.sub.6H.sub.4 H H CH.sub.3 32 CH O H Cl C.sub.6H.sub.5 H H H 142 144 33 CH O H H CH.sub.2CH.sub.3 H H H 134 136 34 CH O H H CH.sub.2C.sub.2H.sub.5 H H H 118 120 35 CH O H H CH.sub.2C.sub.2H.sub.5 H H CH.sub.3 146 148 36 CH O H Cl CH.sub.2C.sub.2H.sub.5 H H H 118 120 37 CH O H CH.sub.3 CH.sub.2C.sub.2H.sub.5 H H H 112 115 38 CH O H H 4-F--C.sub.6H.sub.4 H H H 132 134 39 CH O H Cl 4-F--C.sub.6H.sub.4 H H H 40 CH O H H 4-F--C.sub.6H.sub.4 H H CH.sub.3 41 CH O H H 4-CF.sub.3--C.sub.6H.sub.4 H H H 161 162 42 CH O H Cl 4-CF.sub.3--C.sub.6H.sub.4 H H H 43 CH O H Cl CH.sub.2N(CH.sub.3).sub.2 H H H 44 CH O H OCH.sub.3 C.sub.2H.sub.5 H H H 45 CH O H OCH.sub.3 CH.sub.3 H H H 46 CH O H OC.sub.2H.sub.5 CH.sub.3 H H H 47 CH O H H CH.sub.2OCH.sub.2CF.sub.3 H H H 48 CH O H Cl CH.sub.2OCH.sub.2CF.sub.3 H H H 49 CH O H F CF.sub.3 H H H 50 CH O H F CH.sub.3 H H H 163 164 51 CH O H H CH.sub.2N(CH.sub.3).sub.2 H H H 52 CH O H H C.sub.6H.sub.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.sub.2OCH.sub.2C.sub.6H.sub.5 H P H 56 CH O H OCH.sub.3 4-Cl--C.sub.6H.sub.5 H H H 57 CH O H F 4-Cl--C.sub.6H.sub.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.sub.3 61 CH O H CH.sub.3S CH.sub.3 H H H 62 CH O H CH.sub.3SO.sub.2 CH.sub.3 H H H 63 CH O H F F H H H 64 CH O H CH.sub.3SO.sub.2 Cl H H H 65 CH O H H 4-NO.sub.2--C.sub.6H.sub.5 H H H 66 CH O H Cl 4-NO.sub.2--C.sub.6H.sub.5 H H H 67 CH O H H 4-NO.sub.2--C.sub.6H.sub.5 H H CH.sub.3 68 CH O H PhCH.sub.2 CH.sub.3 H H H 159 162 69 CH O H PhCH.sub.2 CH.sub.3 H H CH.sub.3 70 CH O H CF.sub.3CH.sub.2O C.sub.3H.sub.7 H H H 71 CH NH H CH.sub.3 CH.sub.3 H H H 72 CH NH H CH.sub.3 CH.sub.3 H H CH.sub.3 73 CH NH H OCH.sub.3 CF.sub.3 CH.sub.3 H H 74 CH NH H OCH.sub.3 CH.sub.3 F H P 75 CH NH H H CF.sub.3 H H CH.sub.3 76 CH NH H CH.sub.3 CH.sub.2Cl H H H 77 CH NH H CH.sub.3 CH.sub.2Cl H H CH.sub.3 78 CH NH H Cl CH.sub.2Cl 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.sub.3 H 82 CH NH H H M H H COCH.sub.3 83 CH NH H Cl CH.sub.2OCH.sub.3 H H H 84 CH NH H H 4-C.sub.6H.sub.5Cl H H H 85 CH NH H H 4-C.sub.6H.sub.5Cl H H CH.sub.3 86 CH NH H H CH.sub.2OCH.sub.3 H H CH.sub.3 87 CH NH H CH.sub.3 CH.sub.2OCH.sub.3 H H H 88 CH NH H CH.sub.3 CH.sub.2OCH.sub.3 H H CH.sub.3 89 CH NH H H CH.sub.2OCH.sub.3 H H H 90 CH NH H H CH.sub.2OCH.sub.3 H H P 91 CH NH H H CH.sub.2OCH.sub.2CF.sub.3 H P H 92 CH NH H H CH.sub.2N(CH.sub.3).sub.2 H H H 93 CH NH H H CH.sub.2OCH.sub.2CF.sub.3 H H COCH.sub.3 94 CH NH H Cl CH.sub.2OC.sub.2H.sub.5 H H H 95 CH NH H H CH.sub.2OC.sub.2H.sub.5 H H H 96 CH NH H H CH.sub.2OC.sub.2H.sub.5 H H CH.sub.3 97 CH NH H H CF.sub.3 H H CH.sub.3 98 CH NH H CH.sub.3 CF.sub.3 H H H 99 CH NH H CH.sub.3 Cl H H CH.sub.3 100 N O H Cl CH.sub.3 H H H 172 174 101 N O H H CH.sub.3 H H H 150~152 102 N O H H CH.sub.3 H H CH.sub.3 178 180 103 N O H CH.sub.3 CH.sub.3 H H H 112~118 104 N O H F CH.sub.3 H H H 105 N O H H CF.sub.3 H H Cl 106 N O H CH.sub.3 CH.sub.3 H H CH.sub.3 184~186 107 N O H H CH.sub.3 H P CO.sub.2CH.sub.3 108 N O H H CH.sub.3 H COCH.sub.3 CO.sub.2CH.sub.3 109 N O H Cl CH.sub.3 H H CH.sub.3 198 200 110 N O H H CH.sub.2Cl H H CO.sub.2CH.sub.3 111 N O H H H H H H 106~110 112 N O H H CH.sub.2Cl H H CF.sub.3 113 N O H H 3-CF.sub.3--C.sub.6H.sub.4 H H CF.sub.3 114 N O H CH.sub.3 3-CH.sub.3--C.sub.6H.sub.4 H H CF.sub.3 115 N O H CH.sub.3 4-CH.sub.3--C.sub.6H.sub.4 H H CF.sub.3 116 N O H H CH.sub.2Cl H H H 117 N O H Cl CH.sub.2Cl H H H 118 N O H Cl CH.sub.2F H H H 119 N O H H CH.sub.2F H H H 120 N O H H CH.sub.2Br H H H 121 N O H H CH.sub.2OCH.sub.3 H H CH.sub.2N(CH.sub.3).sub.2 122 N O H Cl CH.sub.2OCH.sub.3 H H CH.sub.2N(CH.sub.3).sub.2 123 N O H CH.sub.3 CH.sub.2OCH.sub.3 H H CH.sub.2N(CH.sub.3).sub.2 124 N O H H CH.sub.2OCH.sub.3 H H F 125 N O H CH.sub.3 CH.sub.2OCH.sub.3 H H F 126 N O H CH.sub.3 CH.sub.2OCH.sub.3 H CO.sub.2CH.sub.3 CH.sub.2N(CH.sub.3- ).sub.2 127 N O H H CH.sub.2OCH.sub.3 H H H 128 N O H H CH.sub.2OCH.sub.3 H H P 129 N O H H 3-CF.sub.3--C.sub.6H.sub.4 H P H 130 N O H H 3-CH.sub.3--C.sub.6H.sub.4 H COCH.sub.3 H 131 N O H H 4-CH.sub.3--C.sub.6H.sub.4 H H COCH.sub.3 132 N O H Cl CH.sub.2OC.sub.2H.sub.5 H H H 133 N O H H CH.sub.2OC.sub.2H.sub.5 H H H 134 N O H H CH.sub.2OC.sub.2H.sub.5 H H CH.sub.3 135 N O H H 3-OCH.sub.3--C.sub.6H.sub.4 H H CH.sub.3 136 N O H CH.sub.3 4-OCH.sub.3--C.sub.6H.sub.4 H H H 137 N O H CH.sub.3 2-OCH.sub.3--C.sub.6H.sub.4 H H CH.sub.3 138 N O H H CH.sub.2OC.sub.2H.sub.5 H H Cl 139 N O H H CH.sub.2OC.sub.2H.sub.5 H H P 140 N O H H M H P H 141 N O H H 3-CF.sub.3--C.sub.6H.sub.4 H COCH.sub.3 H 142 N O H H 3-CH.sub.3--C.sub.6H.sub.4 H H COCH.sub.3 143 N O H H 4-CH.sub.3--C.sub.6H.sub.4 H H H 144 N O H H 2-Cl--C.sub.6H.sub.4 H H H 145 N O H H 3-Cl--C.sub.6H.sub.4 H H CH.sub.3 146 N O H H CH.sub.2OCH.sub.2CF.sub.3 H H CH.sub.3 147 N O H CH.sub.3 CH.sub.2OCH.sub.2CF.sub.3 H H H 148 N O H CH.sub.3 --CH.sub.2OC.sub.6H.sub.5 H H CH.sub.3 149 N O H H --CH.sub.2OC.sub.6H.sub.5 H H H 150 N O H H CH.sub.2OCH.sub.2C.sub.6H.sub.5 H H P 151 N O H H CH.sub.2OCH.sub.2C.sub.6H.sub.5 H P H 152 N O H H 4-Cl--C.sub.6H.sub.4 H COCH.sub.3 H 153 N NH H H CH.sub.3 H H H 210 214 154 N NH H CH.sub.3 CH.sub.3 H H CH.sub.3 178~180 155 N NH H H 2-Cl--C.sub.6H.sub.4 H H CH.sub.3 156 N NH H CH.sub.3 3-Cl--C.sub.6H.sub.4 H H H 157 N NH H CH.sub.3 4-Cl--C.sub.6H.sub.4 H H CH.sub.3 158 N NH H Cl CH.sub.2Cl H H H 159 N NH H Cl CH.sub.3 H H H 160 N NH H H 3-CF.sub.3--C.sub.6H.sub.4 H P H 161 N NH H H 3-CH.sub.3--C.sub.6H.sub.4 H COCH.sub.3 H 162 N NH H H 4-CH.sub.3--C.sub.6H.sub.4 H H COCH.sub.3 163 N NH H H CH.sub.2OCH.sub.3 H H H 164 N NH H H 4-F--C.sub.6H.sub.4 H H H 165 N NH H H 2-F--C.sub.6H.sub.4 H H CH.sub.3 166 N NH H H C.sub.6H.sub.3-3,5(Cl).sub.2 H H CH.sub.3 167 N NH H CH.sub.3 2-OCH.sub.3--C.sub.6H.sub.4 H H H 168 N NH H CH.sub.3 2-OCH.sub.3--C.sub.6H.sub.4 H H CH.sub.3 169 N NH H Cl CH.sub.2OCH.sub.3 H H H 170 N NH H H CH.sub.2OCH.sub.3 H H P 171 N NH H H 3,5(Cl).sub.2--C.sub.6H.sub.3 H P H 172 N NH H H 2,4(Cl).sub.2--C.sub.6H.sub.3 H H H 173 N NH H H 3,4(Cl).sub.2--C.sub.6H.sub.3 H H H 174 N NH H Cl CH.sub.2OC.sub.2H.sub.5 H H H 175 N NH H H CH.sub.2OC.sub.2H.sub.5 H H H 176 N NH H H CH.sub.2OC.sub.2H.sub.5 H H CH.sub.3 177 N NH H H CF.sub.3 H H CH.sub.3 178 N NH H CH.sub.3 CF.sub.3 H H H 179 N NH H CH.sub.3 Cl H H CH.sub.3 180 N NH H H Cl H H H 181 N NH H H CH.sub.3 H H Cl 182 N NH H H C.sub.6H.sub.5 H H Cl 183 N NH H CH.sub.3 CH.sub.3 H H F 184 N NH H CH.sub.3 CH.sub.3 H H H 185 N NH H H CF.sub.3 H H Cl 186 N NH H CH.sub.3 4-F--C.sub.6H.sub.4 H H CH.sub.3 187 N NH H H 2-F--C.sub.6H.sub.4 H P CO.sub.2CH.sub.3 188 N NH H H 2-Cl--C.sub.6H.sub.4 H COCH.sub.3 CO.sub.2CH.sub.3 189 N NH H H 3-Cl--C.sub.6H.sub.4 H H CO.sub.2CH.sub.3 190 N NH H H 4-Cl--C.sub.6H.sub.4 H H CO.sub.2CH.sub.3 191 N NH H H CH.sub.2Cl H CH.sub.3 H 192 N NH H H CH.sub.2Cl H CO.sub.2C.sub.2H.sub.5 CF.sub.3 193 N NH H H CH.sub.2Cl H H CF.sub.3 194 N NH H CH.sub.3 M H CO.sub.2C.sub.2H.sub.5 CF.sub.3 195 N NH H CH.sub.3 CH.sub.2Cl H H CF.sub.3 196 N NH H H CH.sub.2Cl H H H 197 N NH H H CH.sub.2Cl H H P 198 N NH H H CH.sub.2Cl H P H 199 N NH H H CH.sub.2Cl H COCH.sub.3 H 200 N NH H CH.sub.3 3,5-diCl--C.sub.6H.sub.3 H CO.sub.2CH.sub.3 H 201 CH O CH.sub.3 H H H H H 202 CH O CH.sub.3 H CH.sub.3 H H H 203 CH O CH.sub.3 H CH.sub.3 H H CH.sub.3 204 CH O CH.sub.3 H C.sub.6H.sub.5 H H CH.sub.3 205 CH O CH.sub.3 CH.sub.3 CH.sub.3 H H H 206 CH O CH.sub.3 CH.sub.3 CH.sub.3 H H CH.sub.3 207 CH O CH.sub.3 H CF.sub.3 H H H 208 CH O CH.sub.3 H CH.sub.3 H H P 209 CH O CH.sub.3 H CH.sub.3 H P H 210 CH O CH.sub.3 H CH.sub.3 H COCH.sub.3 H 211 CH O CH.sub.3 H CH.sub.3 H H COCH.sub.3 212 CH O CH.sub.3 H CH.sub.2Cl H H H 213 CH O CH.sub.3 Cl CH.sub.2Cl H H H 214 CH O CH.sub.3 H CH.sub.2Cl H H CF.sub.3 215 CH O CH.sub.3 H CH.sub.2Cl H H CH.sub.3 216 CH O CH.sub.3 CH.sub.3 CH.sub.2OCH.sub.3 H H H 217 CH O CH.sub.3 CH.sub.3 CH.sub.2OCH.sub.3 H H CH.sub.3 218 CH O CH.sub.3 OCH.sub.3 CH.sub.2Cl H H H 219 CH O CH.sub.3 H CH.sub.2Cl H H P 220 CH O CH.sub.3 H CH.sub.2Cl H P H 221 CH O CH.sub.3 H CH.sub.2Cl H COCH.sub.3 H 222 CH O CH.sub.3 H CH.sub.2Cl H H COCH3 223 CH O CH.sub.3 H CH.sub.2OCH.sub.2CF.sub.3 H H H 224 CH O CH.sub.3 Cl CH.sub.2OC.sub.2H.sub.5 H H H 225 CH O CH.sub.3 Cl CH.sub.2OCH.sub.3 H H CH.sub.3 226 CH O CH.sub.3 H CH.sub.2OCH.sub.3 H H CH.sub.3 227 CH O CH.sub.3 CH.sub.3 3-CF.sub.3--C.sub.6H.sub.4 H H H 228 CH O CH.sub.3 CH.sub.3 3-CH.sub.3--C.sub.6H.sub.4 H H CH.sub.3 229 CH O CH.sub.3 H 4-CH.sub.3--C.sub.6H.sub.4 H H H 230 CH O CH.sub.3 H 2-Cl --C.sub.6H.sub.4 H H P 231 CH O CH.sub.3 H 3-Cl --C.sub.6H.sub.4 H P H 232 CH O CH.sub.3 H CF.sub.3 H COCH.sub.3 H 233 CH O CH.sub.3 Cl CH.sub.2OCH.sub.3 H H COCH.sub.3 234 CH O CH.sub.3 OCH.sub.3 CH.sub.2OC.sub.2H.sub.5 H H H 235 CH O CH.sub.3 C.sub.2H.sub.5 CH.sub.2OC.sub.2H.sub.5 H CH.sub.3 H 236 CH O CH.sub.3 H CH.sub.2OC.sub.2H.sub.5 H H CH.sub.3 237 CH O CH.sub.3 Cl CH.sub.2OC.sub.2H.sub.5 H CO.sub.2C.sub.2H.sub.5 CH.s- ub.3 238 CH O CH.sub.3 CH.sub.3 2-F--C.sub.6H.sub.4 H H H 239 CH O CH.sub.3 CH.sub.3 3-F--C.sub.6H.sub.4 H H CH.sub.3 240 CH O CH.sub.3 H 4-F--C.sub.6H.sub.4 H H H 241 CH O CH.sub.3 H CH.sub.2OC.sub.2H.sub.5 H H P 242 CH O CH.sub.3 H CH.sub.2OC.sub.2H.sub.5 H P H

243 CH O CH.sub.3 H CH.sub.2OC.sub.2H.sub.5 H COCH.sub.3 H 244 CH O CH.sub.3 H CH.sub.2OC.sub.2H.sub.5 H H COCH.sub.3 245 CH O CH.sub.3 H CH.sub.2OCH.sub.2CF.sub.3 H H H 246 CH O CH.sub.3 Cl CH.sub.2OCH.sub.2CF.sub.3 H H H 247 CH O CH.sub.3 H CF.sub.3 H H CH.sub.3 248 CH O CH.sub.3 H CH.sub.2OCH.sub.2CF.sub.3 H H CH.sub.3 249 CH O CH.sub.3 CH.sub.3 CH.sub.2OCH.sub.2CF.sub.3 H H H 250 CH O CH.sub.3 CH.sub.3 --CH.sub.2OPh H H CH.sub.3 251 CH O CH.sub.3 H --CH.sub.2OPh H H H 252 CH O CH.sub.3 H CH.sub.2OCH.sub.2Ph H H P 253 CH O CH.sub.3 H CH.sub.2OCH.sub.2Ph H P H 254 CH O CH.sub.3 H 4-Cl--C.sub.6H.sub.5 H COCH.sub.3 H 255 CH O CH.sub.3 H 4-Cl--C.sub.6H.sub.5 H H COCH.sub.3 256 CH O CH.sub.3 H M H CO.sub.2C.sub.2H.sub.5 H 257 CH O CH.sub.3 H M H H H 258 CH O CH.sub.3 Cl M H H CH.sub.3 259 CH O CH.sub.3 H M H H CH.sub.3 260 CH O CH.sub.3 CH.sub.3 M H H H 261 CH NH CH.sub.3 Cl H H H H 262 CH NH CH.sub.3 Cl CH.sub.3 H H H 263 CH NH CH.sub.3 H CH.sub.3 H H CH.sub.3 264 CH NH CH.sub.3 H C.sub.6H.sub.5 H H CH.sub.3 265 CH NH CH.sub.3 CH.sub.3 CH.sub.3 H H H 266 CH NH CH.sub.3 CH.sub.3 CH.sub.3 H H CH.sub.3 267 CH NH CH.sub.3 OCH.sub.3 CF.sub.3 H H H 268 CH NH CH.sub.3 OCH.sub.3 CH.sub.3 H H P 269 CH NH CH.sub.3 H CH.sub.3 H P H 270 CH NH CH.sub.3 H CH.sub.3 H COCH.sub.3 H 271 CH NH CH.sub.3 H CH.sub.3 H H COCH.sub.3 272 CH NH CH.sub.3 H CH.sub.2Cl H H H 273 CH NH CH.sub.3 H M H H H 274 CH NH CH.sub.3 H CH.sub.2Cl H H CH.sub.3 275 CH NH CH.sub.3 H CF.sub.3 H H CH.sub.3 276 CH NH CH.sub.3 CH.sub.3 CH.sub.2Cl H H H 277 CH NH CH.sub.3 CH.sub.3 CH.sub.2Cl H H CH.sub.3 278 CH NH CH.sub.3 Cl CH.sub.2Cl H H H 279 CH NH CH.sub.3 H M H H P 280 CH NH CH.sub.3 H M H P H 281 CH NH CH.sub.3 H M H COCH.sub.3 H 282 CH NH CH.sub.3 H M H H COCH.sub.3 283 CH NH CH.sub.3 Cl CH.sub.2OCH.sub.3 H H H 284 CH NH CH.sub.3 H 4-C.sub.6H.sub.5Cl H H H 285 CH NH CH.sub.3 H 4-C.sub.6H.sub.5Cl H H CH.sub.3 286 CH NH CH.sub.3 H CH.sub.2OCH.sub.3 H H CH.sub.3 287 CH NH CH.sub.3 CH.sub.3 CH.sub.2OCH.sub.3 H H H 288 CH NH CH.sub.3 CH.sub.3 CH.sub.2OCH.sub.3 H H CH.sub.3 289 CH NH CH.sub.3 H CH.sub.2OCH.sub.3 H H H 290 CH NH CH.sub.3 H CH.sub.2OCH.sub.3 H H P 291 CH NH CH.sub.3 H CH.sub.2OCH.sub.2CF.sub.3 H P H 292 CH NH CH.sub.3 H CH.sub.2OCH.sub.2CF.sub.3 H COCH.sub.3 H 293 CH NH CH.sub.3 H CH.sub.2OCH.sub.2CF.sub.3 H H COCH.sub.3 294 CH NH CH.sub.3 Cl CH.sub.2OC.sub.2H.sub.5 H H H 295 CH NH CH.sub.3 H CH.sub.2OC.sub.2H.sub.5 H H H 296 CH NH CH.sub.3 H CH.sub.2OC.sub.2H.sub.5 H H CH.sub.3 297 CH NH CH.sub.3 H CF.sub.3 H H CH.sub.3 298 CH NH CH.sub.3 CH.sub.3 CF.sub.3 H H H 299 CH NH CH.sub.3 CH.sub.3 Cl H H CH.sub.3 300 CH NH CH.sub.3 H Cl H H H 301 N O CH.sub.3 H CH.sub.3 H H H 302 N O CH.sub.3 H C.sub.6H.sub.5 H H Cl 303 N O CH.sub.3 CH.sub.3 CH.sub.3 H H H 304 N O CH.sub.3 CH.sub.3 CH.sub.3 H H H 305 N O CH.sub.3 H CF.sub.3 H H Cl 306 N O CH.sub.3 CH.sub.3 CH.sub.3 H H CH.sub.3 307 N O CH.sub.3 H CH.sub.3 H P CO.sub.2CH.sub.3 308 N O CH.sub.3 H CH.sub.3 H COCH.sub.3 CO.sub.2CH.sub.3 309 N O CH.sub.3 H CH.sub.3 H H CO.sub.2CH.sub.3 310 N O CH.sub.3 H CH.sub.2Cl H H CO.sub.2CH.sub.3 311 N O CH.sub.3 H H H H H 312 N O CH.sub.3 H CH.sub.2Cl H H CF.sub.3 313 N O CH.sub.3 H 3-CF.sub.3--C.sub.6H.sub.4 H H CF.sub.3 314 N O CH.sub.3 CH.sub.3 3-CH.sub.3--C.sub.6H.sub.4 H H CF.sub.3 315 N O CH.sub.3 CH.sub.3 4-CH.sub.3--C.sub.6H.sub.4 H H CF.sub.3 316 N O CH.sub.3 H CH.sub.2Cl H H H 317 N O CH.sub.3 H CH.sub.2Cl H H P 318 N O CH.sub.3 H CH.sub.2Cl H P H 319 N O CH.sub.3 H CH.sub.2Cl H COCH.sub.3 H 320 N O CH.sub.3 H CH.sub.2Cl H H COCH3 321 N O CH.sub.3 H CH.sub.2OCH.sub.3 H H CH.sub.2N(CH.sub.3).sub.2 322 N O CH.sub.3 Cl CH.sub.2OCH.sub.3 H H CH.sub.2N(CH.sub.3).sub.2 323 N O CH.sub.3 CH.sub.3 CH.sub.2OCH.sub.3 H H CH.sub.2N(CH.sub.3).sub.2 324 N O CH.sub.3 H CH.sub.2OCH.sub.3 H H F 325 N O CH.sub.3 CH.sub.3 CH.sub.2OCH.sub.3 H H F 326 N O CH.sub.3 CH.sub.3 CH.sub.2OCH.sub.3 H CO.sub.2CH.sub.3 CH.sub.2N(C- H.sub.3).sub.2 327 N O CH.sub.3 H CH.sub.2OCH.sub.3 H H H 328 N O CH.sub.3 H CH.sub.2OCH.sub.3 H H P 329 N O CH.sub.3 H 3-CF.sub.3--C.sub.6H.sub.4 H P H 330 N O CH.sub.3 H 3-CH.sub.3--C.sub.6H.sub.4 H COCH.sub.3 H 331 N O CH.sub.3 H 4-CH.sub.3--C.sub.6H.sub.4 H H COCH.sub.3 332 N O CH.sub.3 Cl CH.sub.2OC.sub.2H.sub.5 H H H 333 N O CH.sub.3 H CH.sub.2OC.sub.2H.sub.5 H H H 334 N O CH.sub.3 H CH.sub.2OC.sub.2H.sub.5 H H CH.sub.3 335 N O CH.sub.3 H 3-OCH.sub.3--C.sub.6H.sub.4 H H CH.sub.3 336 N O CH.sub.3 CH.sub.3 4-OCH.sub.3--C.sub.6H.sub.4 H H H 337 N O CH.sub.3 CH.sub.3 2-OCH.sub.3--C.sub.6H.sub.4 H H CH.sub.3 338 N O CH.sub.3 H CH.sub.2OC.sub.2H.sub.5 H H Cl 339 N O CH.sub.3 H CH.sub.2OC.sub.2H.sub.5 H H P 340 N O CH.sub.3 H M H P H 341 N O CH.sub.3 H 3-CF.sub.3--C.sub.6H.sub.4 H COCH.sub.3 H 342 N O CH.sub.3 H 3-CH.sub.3--C.sub.6H.sub.4 H H COCH.sub.3 343 N O CH.sub.3 H 4-CH.sub.3--C.sub.6H.sub.4 H H H 344 N O CH.sub.3 H 2-Cl--C.sub.6H.sub.4 H H H 345 N O CH.sub.3 H 3-Cl--C.sub.6H.sub.4 H H CH.sub.3 346 N O CH.sub.3 H CH.sub.2OCH.sub.2CF.sub.3 H H CH.sub.3 347 N O CH.sub.3 CH.sub.3 CH.sub.2OCH.sub.2CF.sub.3 H H H 348 N O CH.sub.3 CH.sub.3 --CH.sub.2OPh H H CH.sub.3 349 N O CH.sub.3 H --CH.sub.2OPh H H H 350 N O CH.sub.3 H CH.sub.2OCH.sub.2Ph H H P 351 N O CH.sub.3 H CH.sub.2OCH.sub.2Ph H P H 352 N O CH.sub.3 H 4-Cl--C.sub.6H.sub.4 H COCH.sub.3 H 353 N NH CH.sub.3 H CH.sub.3 H H H 354 N NH CH.sub.3 CH.sub.3 CH.sub.3 H H CH.sub.3 355 N NH CH.sub.3 H 2-Cl--C.sub.6H.sub.4 H H CH.sub.3 356 N NH CH.sub.3 CH.sub.3 3-Cl--C.sub.6H.sub.4 H H H 357 N NH CH.sub.3 CH.sub.3 4-Cl--C.sub.6H.sub.4 H H CH.sub.3 358 N NH CH.sub.3 H CH.sub.2Cl H H H 359 N NH CH.sub.3 H M H H P 360 N NH CH.sub.3 H 3-CF.sub.3--C.sub.6H.sub.4 H P H 361 N NH CH.sub.3 H 3-CH.sub.3--C.sub.6H.sub.4 H COCH.sub.3 H 362 N NH CH.sub.3 H 4-CH.sub.3--C.sub.6H.sub.4 H H COCH.sub.3 363 N NH CH.sub.3 H CH.sub.2OCH.sub.3 H H H 364 N NH CH.sub.3 H 4-F--C.sub.6H.sub.4 H H H 365 N NH CH.sub.3 H 2-F--C.sub.6H.sub.4 H H CH.sub.3 366 N NH CH.sub.3 H C.sub.6H.sub.3-3,5(Cl).sub.2 H H CH.sub.3 367 N NH CH.sub.3 CH.sub.3 2-OCH.sub.3--C.sub.6H.sub.4 H H H 368 N NH CH.sub.3 CH.sub.3 2-OCH.sub.3--C.sub.6H.sub.4 H H CH.sub.3 369 N NH CH.sub.3 Cl CH.sub.2OCH.sub.3 H H H 370 N NH CH.sub.3 H CH.sub.2OCH.sub.3 H H P 371 N NH CH.sub.3 H C.sub.6H.sub.3-3,5(Cl).sub.2 H P H 372 N NH CH.sub.3 H CH.sub.2OCH.sub.2CF.sub.3 H COCH.sub.3 H 373 N NH CH.sub.3 H CH.sub.2OCH.sub.2CF.sub.3 H H COCH.sub.3 374 N NH CH.sub.3 Cl CH.sub.2OC.sub.2H.sub.5 H H H 375 N NH CH.sub.3 H CH.sub.2OC.sub.2H.sub.5 H H H 376 N NH CH.sub.3 H CH.sub.2OC.sub.2H.sub.5 H H CH.sub.3 377 N NH CH.sub.3 H CF.sub.3 H H CH.sub.3 378 N NH CH.sub.3 CH.sub.3 CF.sub.3 H H H 379 N NH CH.sub.3 CH.sub.3 Cl H H CH.sub.3 380 N NH CH.sub.3 H Cl H H H 381 N NH CH.sub.3 H CH.sub.3 H H Cl 382 N NH CH.sub.3 H C.sub.6H.sub.5 H H Cl 383 N NH CH.sub.3 CH.sub.3 CH.sub.3 H H F 384 N NH CH.sub.3 CH.sub.3 CH.sub.3 H H H 385 N NH CH.sub.3 H CF.sub.3 H H Cl 386 N NH CH.sub.3 CH.sub.3 4-F--C.sub.6H.sub.4 H H CH.sub.3 387 N NH CH.sub.3 H 2-F--C.sub.6H.sub.4 H P CO.sub.2CH.sub.3 388 N NH CH.sub.3 H 2-Cl--C.sub.6H.sub.4 H COCH.sub.3 CO.sub.2CH.sub.3 389 N NH CH.sub.3 H 3-Cl--C.sub.6H.sub.4 H H CO.sub.2CH.sub.3 390 N NH CH.sub.3 H 4-Cl--C.sub.6H.sub.4 H H CO.sub.2CH.sub.3 391 N NH CH.sub.3 H CH.sub.2Cl H CH.sub.3 H 392 N NH CH.sub.3 H CH.sub.2Cl H CO.sub.2C.sub.2H.sub.5 CF.sub.3 393 N NH CH.sub.3 H CH.sub.2Cl H H CF.sub.3 394 N NH CH.sub.3 CH.sub.3 M H CO.sub.2C.sub.2H.sub.5 CF.sub.3 395 N NH CH.sub.3 CH.sub.3 CH.sub.2Cl H H CF.sub.3 396 N NH CH.sub.3 H CH.sub.2Cl H H H 397 N NH CH.sub.3 H CH.sub.2Cl H H P 398 N NH CH.sub.3 H CH.sub.2Cl H P H 399 N NH CH.sub.3 H CH.sub.2Cl H COCH.sub.3 H 400 N NH CH.sub.3 CH.sub.3 3,5-diCl--C.sub.6H.sub.3 H CO.sub.2CH.sub.3 H 401 CH O H C.sub.3H.sub.7i CH.sub.3 H H H oil 402 CH O H n-C.sub.4H.sub.9 CH.sub.3 H H H 117 118 403 CH O H n-C.sub.5H.sub.11 CH.sub.3 H H H 404 CH O H C.sub.2H.sub.4Pri CH.sub.3 H H H oil 405 CH O H n-C.sub.6H.sub.13 CH.sub.3 H H H 113 115 406 CH O H H n-C.sub.4H.sub.9 H H H 407 CH O H H n-C.sub.5H.sub.11 H H H 408 CH O H H CH(CH.sub.3).sub.2 H H CH.sub.3 110 112 409 CH O H n-C.sub.3H.sub.7 n-C.sub.3H.sub.7 H H H 112 114 410 N O H Cl n-C.sub.3H.sub.7 H H H 136 138 411 N O H Cl C.sub.6H.sub.5 H H H 166 168 412 N O H n-C.sub.3H.sub.7 CH.sub.3 H H H 121 122 413 N O H n-C.sub.4H.sub.9 CH.sub.3 H H H 100 102 414 N O H n-C.sub.6H.sub.13 CH.sub.3 H H H 75 78 415 CH O H CH.sub.3 n-C.sub.4H.sub.9 H H H 416 CH O H C.sub.2H.sub.5 n-C.sub.4H.sub.9 H H H 417 CH O H C.sub.3H.sub.7 n-C.sub.4H.sub.9 H H H 418 CH O H i-C.sub.3H.sub.7 n-C.sub.4H.sub.9 H H H 419 CH O H n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 H H H 420 CH O H CH.sub.3 n-C.sub.5H.sub.11 H H H 421 CH O H C.sub.2H.sub.5 n-C.sub.5H.sub.11 H H H 422 CH O H C.sub.3H.sub.7 n-C.sub.5H.sub.11 H H H 423 CH O H i-C.sub.3H.sub.7 n-C.sub.5H.sub.11 H H H 424 CH O H n-C.sub.4H.sub.9 n-C.sub.5H.sub.11 H H H 425 CH O H H n-C.sub.6H.sub.13 H H H 426 CH O H CH.sub.3 n-C.sub.6H.sub.13 H H H 427 CH O H C.sub.2H.sub.5 n-C.sub.6H.sub.13 H H H 428 CH O H C.sub.3H.sub.7 n-C.sub.6H.sub.13 H H H 429 CH O H i-C.sub.3H.sub.7 n-C.sub.6H.sub.13 H H H 430 CH O H n-C.sub.4H.sub.9 n-C.sub.6H.sub.13 H H H 431 N O H CH.sub.3 n-C.sub.4H.sub.9 H H H 432 N O H C.sub.2H.sub.5 n-C.sub.4H.sub.9 H H H 433 N O H C.sub.3H.sub.7 n-C.sub.4H.sub.9 H H H 434 N O H i-C.sub.3H.sub.7 n-C.sub.4H.sub.9 H H H 435 N O H n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 H H H 436 N O H CH.sub.3 n-C.sub.5H.sub.11 H H H 437 N O H C.sub.2H.sub.5 n-C.sub.5H.sub.11 H H H 438 N O H C.sub.3H.sub.7 n-C.sub.5H.sub.11 H H H 439 N O H i-C.sub.3H.sub.7 n-C.sub.5H.sub.11 H H H 440 N O H n-C.sub.4H.sub.9 n-C.sub.5H.sub.11 H H H 441 N O H H n-C.sub.6H.sub.13 H H H 442 N O H CH.sub.3 n-C.sub.6H.sub.13 H H H 443 N O H C.sub.2H.sub.5 n-C.sub.6H.sub.13 H H H 444 N O H C.sub.3H.sub.7 n-C.sub.6H.sub.13 H H H 445 N O H i-C.sub.3H.sub.7 n-C.sub.6H.sub.13 H H H 446 N O H n-C.sub.4H.sub.9 n-C.sub.6H.sub.13 H H H 447 N NH H CH.sub.3 n-C.sub.4H.sub.9 H H H 448 N NH H C.sub.2H.sub.5 n-C.sub.4H.sub.9 H H H 449 N NH H C.sub.3H.sub.7 n-C.sub.4H.sub.9 H H H 450 N NH H i-C.sub.3H.sub.7 n-C.sub.4H.sub.9 H H H 451 N NH H n-C.sub.4H.sub.9 n-C.sub.4H.sub.9 H H H 452 N NH H CH.sub.3 n-C.sub.5H.sub.11 H H H 453 N NH H C.sub.2H.sub.5 n-C.sub.5H.sub.11 H H H 454 N NH H C.sub.3H.sub.7 n-C.sub.5H.sub.11 H H H 455 N NH H i-C.sub.3H.sub.7 n-C.sub.5H.sub.11 H H H 456 N NH H n-C.sub.4H.sub.9 n-C.sub.5H.sub.11 H H H 457 N NH H H n-C.sub.6H.sub.13 H H H 458 N NH H CH.sub.3 n-C.sub.6H.sub.13 H H H 459 N NH H C.sub.2H.sub.5 n-C.sub.6H.sub.13 H H H 460 N NH H C.sub.3H.sub.7 n-C.sub.6H.sub.13 H H H 461 N NH H i-C.sub.3H.sub.7 n-C.sub.6H.sub.13 H H H 462 N NH H n-C.sub.4H.sub.9 n-C.sub.6H.sub.13 H H H 463 CH O H H CH.sub.2-Ph-4-Cl H H H 464 CH O H CH.sub.3 CH.sub.2-Ph-4-Cl H H H 465 CH O H C.sub.2H.sub.5 CH.sub.2-Ph-4-Cl H H H 466 CH O H CH.sub.2-Ph-4-Cl CH.sub.3 H H H 467 CH O H CH.sub.2-Ph-4-Cl C.sub.2H.sub.5 H H H 468 CH O H CH.sub.2-Ph-4-Cl C.sub.3H.sub.7 H H H 469 CH O H CH.sub.3 CF.sub.3 H H H 470 CH O H Cl CF.sub.3 H H H 471 CH O H C.sub.2H.sub.5 CF.sub.3 H H H 472 CH O H n-C.sub.3H.sub.7 CF.sub.3 H H H 473 CH O H n-C.sub.4H.sub.9 CF.sub.3 H H H 474 CH O H H CH.sub.2CH.sub.2-Ph- H H H 4-Cl 475 CH O H CH.sub.3 H H H 476 CH O H H CH.sub.2Bu-t H H H 477 CH O H CH.sub.3 CH.sub.2Bu-t H H H 478 CH O H n-C.sub.3H.sub.7 CH.sub.2Bu-t H H H 479 CH O H CH.sub.2Bu-t CH.sub.3 H H H 480 CH O H CH.sub.2CH.sub.2-Ph- CH.sub.3 H H H 4-Cl 481 CH O H C.sub.2H.sub.5 H H H 482 CH O H C.sub.3H.sub.7 H H H 483 CH O H CO.sub.2CH.sub.3 CH.sub.3 H H H 484 CH O H CO.sub.2CH.sub.3 CF.sub.3 H H H 485 CH O H CO.sub.2C.sub.2H.sub.5 C.sub.2H.sub.5 H H H 486 CH O H CO.sub.2C.sub.2H.sub.5 n-C.sub.3H.sub.7 H H H 487 CH O H CONHCH.sub.3 CH.sub.3 H H H 488 CH O H CONHC.sub.2H.sub.5 CH.sub.3 H H H 489 CH O H CON(CH.sub.3).sub.2 CH.sub.3 H H H 490 CH O H CH.sub.3 CO.sub.2CH.sub.3 H H H

*stands for melting point. .degree. 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.

##STR00010##

wherein: Z is leaving group, such as halogen (Cl, Br, or I).

R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.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.degree. 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.sub.5COCHR.sub.4CO.sub.2CH.sub.3(C.sub.2H.sub.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-US-00002 TABLE 2 III R.sub.4 R.sub.5 R.sub.6 R.sub.7 R.sub.8 Physical property* III-1 H CH.sub.3 H H COCH.sub.3 158 160 III-2 H CH.sub.3 H H C(.dbd.NOMe)CH.sub.3 129 140 III-3 H H.sub.3 H H CO.sub.2CH.sub.3 219 222 III-4 H CH.sub.3 H H CH.sub.3 256 258 III-5 Cl CH.sub.3 H H H 230 234 III-6 H CF.sub.3 H H H 180 183 III-7 C.sub.6H.sub.5CH.sub.2 CH.sub.3 H H H 208 212 III-8 H 4-F--C.sub.6H.sub.4 H H H 256 262 III-9 H 3,4-(MeO).sub.2C.sub.6H.sub.4 H H H 184 188 III-10 F CH.sub.3 H H H 203 206 III-11 H C.sub.6H.sub.5 H H H 240 242 III-12 H C.sub.6H.sub.5 H H CH.sub.3 260 262 III-13 Cl C.sub.6H.sub.5 H H H 188 190 III-14 CH.sub.3 CH.sub.3 H H H 118 120 III-15 CH.sub.3 CH.sub.3 H H CH.sub.3 218 222 III-16 H n-C.sub.3H.sub.7 H H CH.sub.3 176 178 III-17 Cl n-C.sub.3H.sub.7 H H H 148 150 III-18 H i-C.sub.3H.sub.7 H H H 160 162 III-19 n-C.sub.6H.sub.13 CH.sub.3 H H H 170 172 III-20 i-C.sub.3H.sub.7CH.sub.2CH.sub.2 CH.sub.3 H H H 101 102 III-21 n-C.sub.4H.sub.9 CH.sub.3 H H H 134 136 III-22 n-C.sub.3H.sub.7 CH.sub.3 H H H 142 144 III-23 H CH.sub.2OCH.sub.3 H H H 186 190 *stands for melting point. .degree. 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.

##STR00011##

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)-.alpha.-[2-(bromomethyl)phenyl]-.beta.-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.

.sup.1HNMR(300 MHz, internal standard=TMS, CDCl.sub.3): .delta.ppm 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)-.alpha.-[2-(chloromethyl)phenyl]-.beta.-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.degree. C. in 80% yield.

.sup.1HNMR(300 MHz, internal standard=TMS, CDCl.sub.3): .delta.ppm 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.sub.2CO.sub.3, 1.0 g of 7-hydroxy-4-methylcoumarin, 1.70 g of methyl (E)-2-(bromomethyl)-.alpha.-(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.degree. C. in 83% yield.

.sup.1HNMR(300 MHz, internal standard=TMS, CDCl.sub.3): .delta.ppm 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.degree. C. in 89% yield.

.sup.1HNMR(300 MHz, internal standard=TMS, CDCl.sub.3): .delta.ppm 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. .sup.1HNMR of other compounds are provided as follows (300 MHz, internal standard=TMS, CDCl.sub.3):

Compound 3: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm(DMSO-d.sub.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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm(DMSO-d.sub.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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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: .delta.ppm 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

TABLE-US-00003 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

TABLE-US-00004 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

TABLE-US-00005 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

TABLE-US-00006 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.degree. 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-US-00007 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.sup.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.