Substituted pyrimidines as pharmaceuticals and insecticides
The invention discloses a homopiperony lamine compound which has a structural general formula I as follows as shown in the specification: wherein definitions of substituents in the formula are as shown in the specification. The compound shown as the general formula I has broad-spectrum bactericidal and insecticidal activity in the field of agriculture. The compound shown as the general formula I has a good prevention effect on various germs such as cucumber downy mildew, wheat powdery mildew, puccinia sorghi , rice blast and cucumber gray mold, and particularly, still has the good prevention and control effect on the cucumber downy mildew, the puccinia sorghi and the wheat powdery mildew at a lower dosage. At the same time, a part of compound has better insecticidal activity, and can be used for preventing and controlling various insect pests such as diamondback moths, myzus persicae , armyworms and tetranychus cinabarinus boisdu.
1. A compound of formula I:
wherein:
R 1 is selected from halo, C 1 -C 8 alkyl, haloC 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 1 -C 8 alkoxy, haloC 1 -C 8 alkoxy, C 3 -C 8 alkenyloxy, haloC 3 -C 8 alkenyloxy, C 3 -C 8 alkynyloxy, haloC 3 -C 8 alkynyloxy, C 1 -C 8 alkylsulfonyloxy, C 1 -C 8 alkylthio, C 1 -C 8 alkylsulfinyl, C 1 -C 8 alkylsulfonyl, C 1 -C 8 alkylamino, di(C 1 -C 8 alkyl)amino, cyanoC 1 -C 8 alkylamino, C 1 -C 8 alkylcarbonylamino, C 1 -C 8 alkoxycarbonylamino, C 1 -C 8 alkoxyC 1 -C 8 alkyl, C 1 -C 8 alkylthioC 1 -C 8 alkyl, C 1 -C 8 alkylsulfinylC 1 -C 8 alkyl, C 1 -C 8 alkylsulfonylC 1 -C 8 alkyl, hydroxyC 1 -C 8 alkyl or C 1 -C 8 alkylcarbonyloxyC 1 -C 8 alkyl;
R 2 is selected from H, halo, CN, NO 2 , C 1 -C 8 alkyl, C 1 -C 8 alkoxy or haloC 1 -C 8 alkoxy;
R 3 is selected from H, halo or C 1 -C 8 alkyl;
R 4 is selected from H, OH, C(═O)H, C 1 -C 8 alkyl, haloC 1 -C 8 alkyl, C 1 -C 8 alkoxy, haloC 1 -C 8 alkoxy, C 3 -C 8 cycloalkyl, C 1 -C 8 alkylthio, C 2 -C 8 alkenylthio, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, haloC 2 -C 8 alkenyl, haloC 2 -C 8 alkynyl, C 1 -C 8 alkoxyC 1 -C 8 alkyl, haloC 1 -C 8 alkoxyC 1 -C 8 alkyl, C 1 -C 8 alkylthioC 1 -C 8 alkyl, haloC 1 -C 8 alkylthioC 1 -C 8 alkyl, C 1 -C 8 alkylsulfinyl, haloC 1 -C 8 alkylsulfinyl, C 1 -C 8 alkylsulfonyl, haloC 1 -C 8 alkylsulfonyl, C 1 -C 8 alkylaminosulfonyl, di(C 1 -C 8 alkyl)aminosulfonyl, C 1 -C 8 alkylsulfonylaminocarbonyl, C 1 -C 8 alkylcarbonylaminosulfonyl, C 3 -C 8 cycloalkyloxycarbonyl, C 1 -C 8 alkylcarbonyl, haloC 1 -C 8 alkylcarbonyl, C 1 -C 8 alkoxycarbonyl, haloC 1 -C 8 alkoxycarbonyl, C 1 -C 8 alkylcarbonylC 1 -C 8 alkyl, C 1 -C 8 alkoxycarbonylC 1 -C 8 alkyl, C 1 -C 8 alkylaminocarbonyl, di(C 1 -C 8 alkyl)aminocarbonyl, C 2 -C 8 alkenoxycarbonyl, C 2 -C 8 alkynoxycarbonyl, C 1 -C 8 alkoxyC 1 -C 8 alkoxycarbonyl, C 1 -C 8 alkylaminothio, di(C 1 -C 8 alkyl)aminothio, optionally substituted arylcarbonylC 1 -C 6 alkyl, arylcarbonyl, aryloxycarbonyl, arylC 1 -C 6 alkoxycarbonyl, arylC 1 -C 6 alkyl or heteroarylC 1 -C 6 alkyl, wherein substituents are independently selected from the group consisting of halo, NO 2 , CN, C 1 -C 6 alkyl, haloC 1 -C 6 alkyl, C 1 -C 4 alkoxy and haloC 1 -C 4 alkoxy; and
R 5 and R 6 are independently selected from H, C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, haloC 2 -C 8 alkenyl, haloC 2 -C 8 alkynyl, C 1 -C 8 alkoxyC 1 -C 8 alkyl, optionally substituted arylC 1 -C 4 alkyl or heteroarylC 1 -C 4 alkyl, wherein substituents are independently selected from the group consisting of halo, C 1 -C 4 alkyl, haloC 1 -C 4 alkyl, C 1 -C 4 alkoxy and haloC 1 -C 4 alkoxy;
or R 5 and R 6 , together with the carbon to which they are attached, form a C 3 -C 8 carbocycle;
or an agricultural or pharmaceutical salt thereof.
2. The compound according to claim 1 , wherein:
R 1 is selected from halo, C 1 -C 4 alkyl, haloC 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, C 1 -C 4 alkoxy, haloC 1 -C 4 alkoxy, C 3 -C 6 alkenyloxy, haloC 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, haloC 3 -C 6 alkynyloxy, C 1 -C 4 alkylsulfonyloxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 alkylamino, di(C 1 -C 4 alkyl)amino, cyanoC 1 -C 4 alkylamino, C 1 -C 4 alkylcarbonylamino, C 1 -C 4 alkoxycarbonylamino, C 1 -C 4 alkoxyC 1 -C 4 alkyl, C 1 -C 4 alkylthioC 1 -C 4 alkyl, C 1 -C 4 alkylsulfinylC 1 -C 4 alkyl, C 1 -C 4 alkylsulfonylC 1 -C 4 alkyl, hydroxyC 1 -C 4 alkyl or C 1 -C 4 alkylcarbonyloxyC 1 -C 4 alkyl;
R 2 is selected from H, halo, CN, NO 2 , C 1 -C 4 alkyl, C 1 -C 4 alkoxy or haloC 1 -C 4 alkoxy;
R 3 is H;
R 4 is selected from H, OH, C(═O)H, C 1 -C 4 alkyl, haloC 1 -C 4 alkyl, C 1 -C 4 alkoxy, haloC 1 -C 4 alkoxy, C 3 -C 6 cycloalkyl, C 1 -C 4 alkylthio, C 2 -C 4 alkenylthio, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, haloC 2 -C 4 alkenyl, haloC 2 -C 4 alkynyl, C 1 -C 4 alkoxyC 1 -C 4 alkyl, haloC 1 -C 4 alkoxyC 1 -C 4 alkyl, C 1 -C 4 alkylthioC 1 -C 4 alkyl, haloC 1 -C 4 alkylthioC 1 -C 4 alkyl, C 1 -C 4 alkylsulfinyl, haloC 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, haloC 1 -C 4 alkylsulfonyl, C 1 -C 4 alkylaminosulfonyl, di(C 1 -C 4 alkyl)aminosulfonyl, C 1 -C 4 alkylsulfonylaminocarbonyl, C 1 -C 4 alkylcarbonylaminosulfonyl, C 3 -C 6 cycloalkyloxycarbonyl, C 1 -C 4 alkylcarbonyl, haloC 1 -C 4 alkylcarbonyl, C 1 -C 4 alkoxycarbonyl, haloC 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkylcarbonylC 1 -C 4 alkyl, C 1 -C 8 alkoxycarbonylC 1 -C 4 alkyl, C 1 -C 4 alkylaminocarbonyl, di(C 1 -C 4 alkyl)aminocarbonyl, C 2 -C 4 alkenoxycarbonyl, C 2 -C 4 alkynoxycarbonyl, C 1 -C 4 alkoxyC 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkylaminothio, di(C 1 -C 4 alkyl)aminothio, optionally substituted arylcarbonylC 1 -C 4 alkyl, arylcarbonyl, aryloxycarbonyl, arylC 1 -C 4 alkoxycarbonyl, arylC 1 -C 4 alkyl or heteroarylC 1 -C 4 alkyl, wherein substituents are independently selected from the group consisting of halo, NO 2 , CN, C 1 -C 4 alkyl, haloC 1 -C 4 alkyl, C 1 -C 4 alkoxy and haloC 1 -C 4 alkoxy; and
R 5 and R 6 are independently selected from H, C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, haloC 2 -C 4 alkenyl, haloC 2 -C 4 alkynyl, C 1 -C 4 alkoxyC 1 -C 4 alkyl, optionally substituted arylC 1 -C 4 alkyl or heteroarylC 1 -C 4 alkyl, wherein substituents are independently selected from the group consisting of halo, C 1 -C 4 alkyl, haloC 1 -C 4 alkyl, C 1 -C 4 alkoxy and haloC 1 -C 4 alkoxy;
or R 5 and R 6 , together with the carbon to which they are attached, form a C 3 -C 8 carbocycle;
or an agricultural or pharmaceutical salt thereof selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methylsulfonic acid, p-toluenesulfonic acid, benzoic acid, alizaric acid, maleic acid, sorbic acid, malic acid and citric acid.
3. The compound according to claim 2 , wherein:
R 1 is selected from halo, C 1 -C 4 alkyl, CF 3 , CHF 2 , CCl 3 , CHCl 2 , C 3 -C 6 cycloalkyl, C 1 -C 4 alkoxy, haloC 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 alkoxyC 1 -C 4 alkyl or C 1 -C 4 alkylthioC 1 -C 4 alkyl;
R 2 is selected from H, halo, CN, NO 2 , C 1 -C 4 alkyl, C 1 -C 4 alkoxy or haloC 1 -C 4 alkoxy;
R 3 is H;
R 4 is selected from H, OH, C(═O)H, C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, optionally substituted arylcarbonylC 1 -C 4 alkyl, arylcarbonyl, aryloxycarbonyl, arylC 1 -C 4 alkoxycarbonyl, arylC 1 -C 4 alkyl or heteroarylC 1 -C 4 alkyl, wherein substituents are independently selected from the group consisting of halo, NO 2 , CN, C 1 -C 4 alkyl, haloC 1 -C 4 alkyl, C 1 -C 4 alkoxy and haloC 1 -C 4 alkoxy; and
R 5 and R 6 are independently selected from H or C 1 -C 4 alkyl;
or an agricultural or pharmaceutical salt thereof selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methylsulfonic acid, p-toluenesulfonic acid, benzoic acid, alizaric acid, maleic acid, sorbic acid, malic acid and citric acid.
4. The compound according to claim 3 , wherein:
R 1 is selected from halo, C 1 -C 4 alkyl, CF 3 , CHF 2 or C 3 -C 6 cycloalkyl;
R 2 is selected from H, halo, CN, NO 2 or C 1 -C 4 alkyl;
R 3 is H;
R 4 is H; and
R 5 and R 6 are independently selected from H, CH 3 or CH 2 CH 3 ;
or an agricultural or pharmaceutical salt thereof selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methylsulfonic acid, p-toluenesulfonic acid, benzoic acid, alizaric acid, maleic acid, sorbic acid, malic acid and citric acid.
5. The compound according to claim 4 , wherein:
R 1 is selected from F, Cl, Br, CH 3 , CH 2 CH 3 , (CH 2 ) 2 CH 3 , CH(CH 3 ) 2 , (CH 2 ) 3 CH 3 , CH 2 CH(CH 3 ) 2 , C(CH 3 ) 3 , CF 3 , CHF 2 or cyclopropyl;
R 2 is Cl;
R 3 is H;
R 4 is H; and
R 5 and R 6 are independently selected from H, CH 3 or CH 2 CH 3 ;
or an agricultural or pharmaceutical salt thereof selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, methylsulfonic acid, p-toluenesulfonic acid, benzoic acid, alizaric acid, maleic acid, sorbic acid, malic acid and citric acid.
6. The compound according to claim 5 , wherein:
R 1 is selected from Cl, CH 3 , CH 2 CH 3 , CF 3 or CHF 2 ;
R 2 is Cl;
R 3 is H;
R 4 is H;
R 5 is H; and
R 6 is H;
or an agricultural or pharmaceutical salt thereof selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, trifluoroacetic acid, methylsulfonic acid and p-toluenesulfonic acid.
7. A composition comprising a compound according to claim 1 as an active ingredient and an agriculturally acceptable carrier.
8. A method of treating a fungal condition in a subject, comprising administering to said subject an effective amount of a compound according to claim 1 .
9. A method of treating crops, comprising contacting said crops with an effective amount of a compound according to claim 1 .
10. A method for treating tumors in a subject, comprising administering to said subject an effective amount of a compound according to claim 1 .
11. A method for the preparation of a compound of formula I according to claim 1 , comprising:
reacting a compound of formula II:
wherein R 1 , R 2 and R 3 are as defined in claim 1 ;
with a compound of formula III:
wherein R 4 , R 5 and R 6 are as defined in claim 1 ;
to provide a compound of formula I:
wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are as defined in claim 1 .