CN1240422A - Production of pyridazine herbicides - Google Patents
Production of pyridazine herbicides Download PDFInfo
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- CN1240422A CN1240422A CN 97180772 CN97180772A CN1240422A CN 1240422 A CN1240422 A CN 1240422A CN 97180772 CN97180772 CN 97180772 CN 97180772 A CN97180772 A CN 97180772A CN 1240422 A CN1240422 A CN 1240422A
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Abstract
Carboxylic acid ester derivatives of formula (1):wherein R is C1-C6 alkyl, R2 and R3 are independently hydrogen or C1-C3 alkyl, and Q is optionally substituted phenyl, can be easily converted by ring closing into pyridazin-3-one derivatives of formula (7). The carboxylic acids of formula (1) can be produced by reacting hydrazone compounds of formula (5):wherein R3 and Q are as defined above, with malonic acid monoester derivatives of formula (6):wherein R and R2 are as defined above, in the presence of a base.
Description
Technical field
The present invention relates to the production of pyridazine herbicides, more especially relate to the carboxylates derivatives of the intermediate that is used to produce pyridazin-3-ketone derivant, the technology of producing these intermediates, and the technology of producing pyridazin-3-ketone derivants from these intermediates.
Background technology
The pyridazin-3-ketone derivant of general formula (7):
R wherein
2And R
3Be respectively hydrogen or C
1-C
3Alkyl, Q are arbitrarily substituted-phenyl, and it has excellent weeding activity, and the example that comprises is as follows:
For develop have excellent active pyridazine herbicides preferred produce the good method of pyridazin-3-ketone derivant.
Narration of the present invention
Produce the technology of pyridazin-3-ketone derivant in order to seek the method for making good use of, the inventor has carried out intensive research.They find as a result, the carboxylicesters of general formula (1):
R wherein
1Be C
1-C
6Alkyl, R
2, R
3With the definition of Q as mentioned above, it can easily be transformed into the pyridazin-3-ketone derivant of general formula (7), therefore, as their important intermediate, thereby has finished the present invention.
Therefore, the invention provides the compound of general formula (1):
Wherein R is C
1-C
6Alkyl, R
2, R
3With the definition of Q as mentioned above, these compounds are called compound of the present invention below, their production technique, and the technology of producing general formula (7) pyridazin-3-ketone derivant:
R wherein
2, R
3With the definition of Q as mentioned above, this technology comprises the pass ring of general formula (1) compound.
The example that can select the phenyl that replaces arbitrarily with Q representative comprises, for example, the group Q-1 of general formula (2), Q-2, Q-3, Q-4 and Q-5:
Wherein X is a hydrogen or halogen;
Y is halogen, nitro, cyano group or trifluoromethyl;
Z
1And Z
2Be respectively oxygen or sulphur;
N is 0 or 1;
R
4Be hydrogen or C
1-C
3Alkyl;
R
5Be C
1-C
6Alkyl, C
1-C
6Alkylhalide group, (C
3-C
6Cycloalkyl) C
1-C
6Alkyl, C
3-C
6Alkenyl, C
3-C
6Halogen alkenyl, C
3-C
6Alkynyl group, C
3-C
6Halogen alkynyl group, cyano group C
1-C
6Alkyl, C
1-C
4Alkoxy C
1-C
4Alkyl, C
1-C
3Alkoxy C
1-C
3Alkoxy C
1-C
3Alkyl, carboxyl C
1-C
6Alkyl, (C
1-C
6Alkoxyl group) carbonyl C
1-C
6Alkyl, { (C
1-C
4Alkoxyl group) C
1-C
4Alkoxyl group } carbonyl C
1-C
6Alkyl, (C
3-C
8Cycloalkyloxy) carbonyl C
1-C
6Alkyl ,-CH
2CON (R
12) R
13,-CH
2COON (R
12) R
13,-CH (C
1-C
4Alkyl) CON (R
12) R
13-CH (C
1-C
4Alkyl) COON (R
12) R
13, C
1-C
4Alkylthio C
1-C
4Alkyl or hydroxyl C
1-C
6Alkyl;
R
12And R
13Be respectively hydrogen, C
1-C
6Alkyl, C
3-C
8Cycloalkyl, C
1-C
6Alkylhalide group, C
3-C
6Alkenyl, C
3-C
6Alkynyl group, cyano group C
1-C
6Alkyl, C
1-C
4Alkoxy C
1-C
4Alkyl, C
1-C
4Alkylthio C
1-C
4Alkyl, carboxyl C
1-C
6Alkyl, (C
1-C
6Alkoxyl group) carbonyl C
1-C
6Alkyl, (C
3-C
8Cycloalkyloxy) carbonyl C
1-C
6Alkyl, (C
1-C
6Alkyl) ketonic oxygen C
2-C
6Alkyl, (C
1-C
6Alkyl) carbonylamino C
2-C
6Alkyl, hydroxyl C
2-C
6Alkyl, any benzyl of selecting replacement, the phenyl or the { (C of selection replacement arbitrarily
1-C
4Alkoxyl group) C
1-C
4Alkyl } carbonyl C
1-C
6Alkyl, or R
12And R
13Connect together and form trimethylene, tetramethylene, penta-methylene, ethylene oxide,1,2-epoxyethane base ethylene or ethylene sulfenyl ethylene;
R
6Be C
1-C
6Alkyl, C
1-C
6Alkylhalide group, cyano group, carboxyl, hydroxyl C
1-C
6Alkyl, C
1-C
6Alcoxyl C
1-C
6Alkyl, C
1-C
6Alcoxyl C
1-C
6Alcoxyl C
1-C
6Alkyl, (C
1-C
6Alkyl)-ketonic oxygen C
1-C
6Alkyl, (C
1-C
6Alkylhalide group) ketonic oxygen C
1-C
6Alkyl or (C
1-C
6Alcoxyl) carbonyl;
R
7Be hydrogen or C
1-C
6Alkyl;
R
8Be C
1-C
6Alkyl, C
1-C
6Alkylhalide group, hydroxyl C
1-C
6Alkyl, C
1-C
4Alcoxyl C
1-C
4Alkyl, C
1-C
3Alcoxyl C
1-C
3Alcoxyl C
1-C
3Alkyl, (C
1-C
6Alkyl) ketonic oxygen C
1-C
6Alkyl, (C
1-C
6Alkylhalide group) carbonyl C
1-C
6Alkyl, carboxyl, carboxyl C
1-C
6Alkyl, (C
1-C
8Alcoxyl) carbonyl, (C
1-C
6Alkyl halide oxygen) carbonyl, (C
3-C
10Cycloalkanes oxygen) carbonyl, (C
3-C
8Alkene oxygen) carbonyl, (C
3-C
8Alkyne oxygen) carbonyl, (C
1-C
6Alkyl) aminocarboxyl, two (C
1-C
6Alkyl) aminocarboxyl, (C
1-C
6Alkyl) aminocarboxyl oxygen C
1-C
6Alkyl or two (C
1-C
6Alkyl) aminocarboxyl oxygen C
1-C
6Alkyl;
B is hydrogen, halogen, nitro, cyano group, chlorosulfonyl, OR
1, SR
1, SO
2OR
21, COOR
22, CR
23=CR
24COOR
25, or CH
2CHWCOOR
25
W is hydrogen, chlorine or bromine;
R
1For hydrogen, C1-C
6Alkyl, C1-C
6Alkylhalide group, C3-C
8Cycloalkyl, benzyl, C3-C
6Alkenyl, C3-C
6Halogen alkenyl, C3-C
6Alkynyl group, C3-C
6Halogen alkynyl group, cyano group C1-C
6Alkyl, C1-C
4Alkoxy C1-C
4Alkyl, C1-C
4Alkylthio group C1-C
4Alkyl, carboxyl C1-C
6Alkyl, (C1-C
8Alcoxyl) carbonyl C1-C
6Alkyl, (C1-C
6Alkyl halide oxygen) carbonyl C1-C
6Alkyl, { (C1-C
4Alcoxyl) C1-C
4Alcoxyl } carbonyl C1-C
6Alkyl, (C3-C
8Cycloalkanes oxygen) carbonyl C1-C
6Alkyl, (C3
-C
8Cycloalkyl) C1-C
6Alkoxy carbonyl group C1-C
6Alkyl ,-CH2COON(R
12)R
13、-CH-(C
1-C
4Alkyl) COON (R12)R
13、
-CH
2CON(R
12)R
13、-CH(C
1-C
4Alkyl) CON (R12)R
13、C
2-C
6Alkenyl oxygen carbonyl C1-C
6Alkyl, C3-C
6Halogen alkenyl oxygen carbonyl C1-C
6Alkyl, C3
-C
6Chain oxy-acetylene carbonyl C1-C
6Alkyl, C3-C
6Halogen alkynyl group oxygen carbonyl C1-C
6Alkyl, (C1-C
6Alkylthio group) carbonyl C1-C
6Alkyl, (C1-C
6Alkyl halide sulphur) carbonyl C1-C
6Alkyl, (C3-C
6Alkenyl sulphur) carbonyl C1-C
6Alkyl, (C3-C
6Halogen alkene sulphur) carbonyl C1-C
6Alkyl, (C3-C
6Alkyne sulphur) carbonyl C1-C
6Alkyl, (C3-C
6Halogen alkyne sulphur) carbonyl C1-C
6Alkyl, (C3-C
8Cycloalkanes sulphur) carbonyl C1-C
6Alkyl, (C3-C
8Ring alkyl halide sulphur) carbonyl C1-C
6Alkyl, ((C3-C
8Cycloalkyl) C1-
C
6Alkane sulphur) carbonyl C1-C
6Alkyl, two (C1-C
6Alkyl) C=NO carbonyl C1-
C
6Alkyl, (selecting arbitrarily the benzyl sulphur that replaces) carbonyl C1-C
6Alkyl, (selecting arbitrarily the benzene sulphur that replaces) carbonyl C1-C
6Alkyl, hydroxyl C2-C
6Alkoxy carbonyl group C1-C
6Alkyl, (C1
-C
6Alkyl) carbonyl oxygen C2-C
6Alkoxy carbonyl group C1-C
6Alkyl, (C1-C
6Alkyl) carbonyl amino C2-C
6Alkoxy carbonyl group C1-C
6Alkyl, { (C1-C
6Alcoxyl) carbonyl C1-C
6Alkyl } oxygen carbonyl C1-C
6Alkyl, hydroxyl C1-C
6Alkyl, C1-C
6Alkoxy carbonyl group, C1
-C
6Alkylhalide group oxygen carbonyl, C3-C
8Cycloalkyloxy group carbonyl, C3-C
6Chain ene keto carbonyl, benzyloxycarbonyl group, C1-C
6Alkyl-carbonyl, any benzyloxycarbonyl group C that replaces that selects1-C
6Alkyl, any carbobenzoxy C that replaces that selects1-C
6Alkyl, any furans oxygen carbonyl C that replaces that selects1
-C
6Alkyl, any furyl C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any thiophene oxygen carbonyl C that replaces that selects1-C
6Alkyl, any thiophene C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any pyrroles's oxygen carbonyl C that replaces that selects1-C
6Alkyl, any pyrrole radicals C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any imidazoles oxygen carbonyl C that replaces that selects1-C
6Alkyl, any imidazole radicals C that replaces that selects1-C
6Alkoxy carbonyl group C1
-C
6Alkyl, any pyrazoles oxygen carbonyl C that replaces that selects1-C
6Alkyl, any pyrazolyl C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any thiazole oxygen carbonyl C that replaces that selects1
-C
6Alkyl, any thiazolyl C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any replacement De oxazole oxygen carbonyl C that selects1-C
6Alkyl, any replacement De oxazolyl C that selects1-
C
6Alkoxy carbonyl group C1-C
6Alkyl, any isothiazole oxygen carbonyl C that replaces that selects1-C
6Alkyl, any isothiazolyl C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any replacement De isoxazole oxygen carbonyl C that selects1-C
6Alkyl, any replacement De isoxazolyl C that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any pyridine oxygen carbonyl C that replaces that selects1-C
6Alkyl, any pyridine radicals C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any pyrazine oxygen carbonyl C that replaces that selects1-C
6Alkyl, any pyrazinyl C that replaces that selects1-C
6Alkoxy carbonyl group C1-
C
6Alkyl, any pyrimidine oxygen carbonyl C that replaces that selects1-C
6Alkyl, any pyrimidine radicals C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any pyridazine oxygen carbonyl C that replaces that selects1-
C
6Alkyl, any pyridazinyl C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any indoline oxygen carbonyl C that replaces that selects1-C
6Alkyl, any indolinyl C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any indoles oxygen carbonyl C that replaces that selects1-C
6Alkyl, any indyl C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any indazole oxygen carbonyl C that replaces that selects1-C
6Alkyl, any indazolyl C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any quinoline oxygen carbonyl C that replaces that selects1-C
6Alkyl, any quinolyl C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any isoquinolin oxygen carbonyl C that replaces that selects1-C
6Alkyl, any isoquinolyl C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, or the group of general formula (3):
R wherein14For C1-C
5Alkyl, R15For hydrogen, hydroxyl or-O-COR16Group; And R16For C1-C
6Alkyl, C1-C
6Alkylhalide group, C3-C
6Alkenyl, C3-C
8Cycloalkyl, the benzyl or the C that select the phenyl that replaces, any selection to replace arbitrarily1-C
6Alkoxyl, or
The group of general formula (4):
R wherein
17Be hydrogen, halogen or C
1-C
6Alkyl; R
18Be C
3-C
8Cycloalkyl, benzyl, with the C of an epoxy group(ing)
2-C
10Alkyl, C
3-C
8Cycloalkyl C
1-C
6Alkyl, C
3-C
8Cycloalkyl C
2-C
6Alkenyl, on same carbon atom, be with OR
19And OR
20Substituent C
1-C
6Alkyl, on same carbon atom, be with OR
19And OR
20Substituent C
2-C
6Alkenyl, on same carbon atom, be with SR
19And SR
20Substituent C
1-C
6Alkyl, on same carbon atom, be with SR
19And SR
20Substituent C
2-C
6Alkenyl, carboxyl C
2-C
6Alkenyl, (C
1-C
8Alcoxyl) carbonyl C
2-C
6Alkenyl, (C
1-C
8Alkyl halide oxygen) carbonyl C
2-C
6Alkenyl, { (C
1-C
4Alcoxyl) C
1-C
4Alcoxyl } carbonyl C
2-C
6Alkenyl or (C
3-C
8Cycloalkanes oxygen) carbonyl C
2-C
6Alkenyl; R
19And R
20Be respectively C
1-C
6Alkyl or C
1-C
6Alkylhalide group, or R
19And R
20Connect together the trimethylene that forms the ethylene selecting arbitrarily to replace with halogen, select arbitrarily to replace with halogen, the tetramethylene of selecting arbitrarily to replace with halogen, select the penta-methylene that replaces arbitrarily with halogen, or select the vinyloxy group ethylene that replaces arbitrarily with halogen;
R
21Be C
1-C
6Alkyl, C
1-C
6Alkylhalide group, C
3-C
8Cycloalkyl, C
3-C
6Alkenyl, C
3-C
6Halogen alkenyl, C
3-C
6Alkynyl group, C
3-C
6Halogen alkynyl group or benzyl;
R
22Be hydrogen, C
1-C
6Alkyl, C
1-C
6Alkylhalide group, C
3-C
8Cycloalkyl, benzyl, C
3-C
6Alkenyl, C
3-C
6Halogen alkenyl, C
3-C
6Alkynyl group, C
3-C
6Halogen alkynyl group, cyano group C
1-C
6Alkyl, C
1-C
4Alcoxyl C
1-C
4Alkyl, C
1-C
4Alkane sulphur C
1-C
4Alkyl, carboxyl C
1-C
6Alkyl, (C
1-C
8Alcoxyl) carbonyl C
1-C
6Alkyl, (C
1-C
6The halogen alkoxyl group) carbonyl C
1-C
6Alkyl, { (C
1-C
4Alcoxyl) C
1-C
4Alcoxyl } carbonyl C
1-C
6Alkyl, (C
3-C
8Cycloalkanes oxygen) carbonyl C
1-C
6Alkyl, (C
1-C
6Alkyl) carbonyl C
1-C
6Alkyl, (C
1-C
6Alkylhalide group) carbonyl C
1-C
6Alkyl, { (C
1-C
4Alcoxyl) C
1-C
4Alkyl } carbonyl C
1-C
6Alkyl, (C
3-C
8Cycloalkyl) carbonyl C
1-C
6Alkyl ,-CH
2COON (R
26) R
27,-CH (C
1-C
4Alkyl) COON (R
26) R
27,-CH
2CON (R
26) R
27,-CH-(C
1-C
4Alkyl) CON (R
26) R
27, { (C
1-C
6Alcoxyl) carbonyl C
1-C
6Alkyl } oxygen carbonyl C
1-C
6Alkyl or hydroxyl C
1-C
6Alkyl;
R
26And R
27Be respectively hydrogen, C
1-C
6Alkyl, C
1-C
6Alkylhalide group, C
3-C
6Alkenyl, C
3-C
6Alkynyl group, cyano group C
1-C
6Alkyl, C
1-C
4Alcoxyl C
1-C
4Alkyl, C
1-C
4Alkylthio C
1-C
4Alkyl, carboxyl C
1-C
6Alkyl, (C
1-C
6Alcoxyl) carbonyl C
1-C
6Alkyl, (C
3-C
8Cycloalkanes oxygen) carbonyl C
1-C
6Alkyl or { (C
1-C
4Alcoxyl) C
1-C
4Alkyl } carbonyl C
1-C
6Alkyl, or R
26And R
27Connect together and form tetramethylene, penta-methylene or vinyloxy group ethylene;
R
25And R
24Be respectively hydrogen, halogen or C
1-C
6Alkyl; With
R
25Be hydrogen, C
1-C
6Alkyl, C
1-C
6Alkylhalide group, C
3-C
8Cycloalkyl or C
3-C
6Alkenyl.
In the definition of the invention described above, various substituting groups are exemplified below:
Example with the halogen of X and Y representative comprises fluorine, chlorine, bromine and iodine.
C with the R representative
1-C
6The example of alkyl comprises methyl, ethyl, propyl group, sec.-propyl and butyl.
R
2And R
3The C of representative
1-C
3The example of alkyl comprises methyl and ethyl.
Use R
1The C of representative
1-C
6The example of alkyl comprises methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, tertiary butyl, amyl group, isopentyl and tertiary amyl, and wherein Te meaning is " uncle's base ", and implication is identical when following employing.
Use R
1The C of representative
1-C
6The example of alkylhalide group can comprise 2-chloroethyl, 2-bromotrifluoromethane and 2,2,2-trifluoroethyl.
Use R
1The C of representative
3-C
8The example of cycloalkyl can comprise cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
Use R
1The C of representative
3-C
6Non-limiting examples of alkenyls can comprise allyl group, 1-methyl-2-propenyl, 3-butenyl, crotyl, 3-methyl-2-butene base and 2-methyl-3-butenyl.
Use R
1The C of representative
3-C
6The halogen non-limiting examples of alkenyls can comprise 2-chloro-2-propenyl and 3,3-two chloro-2-propenyl.
Use R
1The C of representative
3-C
6The example of alkynyl group can comprise propargyl, 1-methyl-2-propynyl, 2-butyne base and 1,1-dimethyl-2-propynyl.
Use R
1The C of representative
3-C
6The example of halogen alkynyl group can comprise 3-bromine propargyl.
Use R
1The cyano group C of representative
1-C
6The example of alkyl can comprise the cyanogen methyl.
Use R
1The C of representative
1-C
4Alcoxyl C
1-C
4The example of alkyl can comprise methoxyl methyl, methoxyethyl, ethoxymethyl and ethoxyethyl.
Use R
1The C of representative
1-C
4Alkane sulphur C
1-C
4The example of alkyl can comprise first thiomethyl and methylthio ethyl.
Use R
1The carboxyl C of representative
1-C
6The example of alkyl can comprise carboxymethyl, 1-carboxy ethyl and 2-carboxy ethyl.
Use R
1(the C of representative
1-C
8Alcoxyl) carbonyl C
1-C
6The example of alkyl can comprise the methoxycarbonyl methyl, ethoxycarbonylmethyl group, the third oxygen carbonyl methyl, the different third oxygen carbonyl methyl, the butoxy carbonyl methyl, the isobutyl boc methyl, special butoxy carbonyl methyl, penta oxygen carbonyl methyl, isoamyl oxygen carbonyl methyl, special penta oxygen carbonyl methyl, 1-methoxycarbonyl ethyl, the 1-ethoxycarbonyl-ethyl, the 1-third oxygen carbonyl ethyl, the different third oxygen carbonyl ethyl of 1-, 1-butoxy carbonyl ethyl, 1-isobutyl boc ethyl, the special butoxy carbonyl ethyl of 1-, 1-penta oxygen carbonyl ethyl, the special penta oxygen carbonyl ethyl of 1-isoamyl oxygen carbonyl ethyl and 1-.
Use R
1{ (the C of representative
1-C
4Alcoxyl) C
1-C
4Alcoxyl } carbonyl C
1-C
6The example of alkyl can comprise methoxy methoxy carbonyl methyl, methoxy (ethoxy) carbonyl methyl and 1-methoxy (ethoxy) carbonyl ethyl.
Use R
1(the C of representative
3-C
8Cycloalkyloxy group) carbonyl C
1-C
6The example of alkyl can comprise cyclobutyl oxygen carbonyl methyl, cyclopentyl oxygen carbonyl methyl, cyclohexyl oxygen carbonyl methyl, 1-cyclobutyl oxygen carbonyl ethyl, 1-cyclopentyl oxygen carbonyl ethyl and 1-cyclohexyl oxygen carbonyl ethyl.
Use R
1The C of representative
1-C
6The example of carbalkoxy can comprise methoxycarbonyl, ethoxycarbonyl, the third oxygen carbonyl, butoxy carbonyl, the different third oxygen carbonyl, isobutyl boc and special butoxy carbonyl.
Use R
1The C of representative
1-C
6The example of alkyl halide oxygen carbonyl can comprise 2,2,2-three chloroethyl carbonyls.
Use R
1The C of representative
3-C
8The example of cycloalkoxycarbonyl can comprise cyclopropyl oxygen carbonyl and cyclobutyl oxygen carbonyl.
Use R
1The C of representative
3-C
6The example of chain ene keto carbonyl can comprise allyloxycarbonyl.
Use R
1{ (the C of representative
1-C
6Alcoxyl) carbonyl C
1-C
6Alkyl } oxygen carbonyl C
1-C
6The example of alkyl can comprise (methoxycarbonyl) methoxycarbonyl methyl and (ethoxycarbonyl) methoxycarbonyl methyl.
Use R
12And R
13The C of representative
1-C
6The example of alkyl can comprise methyl, ethyl, propyl group and sec.-propyl.
Use R
4The C of representative
1-C
3The example of alkyl can comprise methyl.
Use R
5The C of representative
1-C
6The example of alkyl comprises methyl, ethyl, propyl group, sec.-propyl, isobutyl-, butyl and isopentyl.
Use R
5The C of representative
1-C
6The example of alkylhalide group can comprise 2-chloroethyl, 2-bromotrifluoromethane, 3-chlorobutyl, 3-brombutyl and difluoromethyl.
Use R
5(the C of representative
3-C
8Cycloalkyl) C
1-C
6The example of alkyl can comprise cyclopentyl-methyl.
Use R
5The C of representative
3-C
6Non-limiting examples of alkenyls can comprise allyl group, 1-methyl-2-propenyl, 3-butenyl, crotyl, 3-methyl-2-butene base and 2-methyl-3-butenyl.
Use R
5The C of representative
3-C
6The halogen non-limiting examples of alkenyls can comprise 2-chloro-2-propenyl and 3,3-two chloro-2-propenyl.
Use R
5The C of representative
3-C
6The example of alkynyl group can comprise propargyl, 1-methyl-2-propynyl, 2-butyne base, 3-butynyl and 1,1-dimethyl-2-propynyl.
Use R
5The C of representative
3-C
6The example of halogen alkynyl group can comprise 3-iodo-2-propynyl and 3-bromo-2-propynyl.
Use R
5The cyano group C of representative
1-C
6The example of alkyl can comprise the cyanogen methyl.
Use R
5The C of representative
1-C
4Alkoxy C
1-C
4The example of alkyl can comprise methoxyl methyl, 1-methoxy ethyl and ethoxyl methyl.
Use R
5The carboxyl C of representative
1-C
6The example of alkyl can comprise carboxymethyl, 1-carboxy ethyl and 2-carboxy ethyl.
Use R
5(the C of representative
1-C
6Alkoxyl group) carbonyl C
1-C
6The example of alkyl can comprise the methoxycarbonyl methyl, ethoxycarbonylmethyl group, the third oxygen carbonyl methyl, the different third oxygen carbonyl methyl, the butoxy carbonyl methyl, the isobutyl boc methyl, special butoxy carbonyl methyl, penta oxygen carbonyl methyl, isoamyl oxygen carbonyl methyl, special penta oxygen carbonyl methyl, 1-methoxycarbonyl ethyl, the 1-ethoxycarbonyl-ethyl, the 1-third oxygen carbonyl ethyl, the different third oxygen carbonyl ethyl of 1-, 1-butoxy carbonyl ethyl, 1-isobutyl boc ethyl, the special butoxy carbonyl ethyl of 1-, 1-penta oxygen carbonyl ethyl, the special penta oxygen carbonyl ethyl of 1-isoamyl oxygen carbonyl ethyl and 1-.
Use R
5{ (the C of representative
1-C
4Alcoxyl) C
1-C
4Alcoxyl } carbonyl C
1-C
6The example of alkyl can comprise methoxy (ethoxy) carbonyl methyl and 1-methoxy methoxy carbonyl ethyl.
Use R
5(the C of representative
3-C
8Cycloalkanes oxygen) carbonyl C
1-C
6The example of alkyl can comprise cyclobutyl oxygen carbonyl methyl, cyclopentyl oxygen carbonyl methyl, cyclohexyl oxygen carbonyl methyl, 1-cyclobutyl oxygen carbonyl ethyl, 1-cyclopentyl oxygen carbonyl ethyl and 1-cyclohexyl oxygen carbonyl ethyl.
Use R
5The hydroxyl C of representative
1-C
6The example of alkyl can comprise methylol, hydroxyethyl and hydroxypropyl.
Use R
6The C of representative
1-C
6The example of alkyl comprises methyl and ethyl.
Use R
6The C of representative
1-C
6The example of alkylhalide group can comprise brooethyl, two brooethyls, trisbromomethyl, 1-bromotrifluoromethane, chloromethyl, dichloromethyl and trichloromethyl.
Use R
6The hydroxyl C of representative
1-C
6The example of alkyl can comprise methylol.
Use R
6(the C of representative
1-C
6Alcoxyl) C
1-C
6The example of alkyl can comprise methoxyl methyl, ethoxymethyl, the third oxygen methyl and the different third oxygen methyl.
Use R
6{ (the C of representative
1-C
6Alcoxyl) C
1-C
6Alcoxyl } C
1-C
6The example of alkyl can comprise methoxy methoxy methyl, methoxy (ethoxy) methyl and ethoxy methoxyl methyl.
Use R
6(the C of representative
1-C
6Alkyl) ketonic oxygen C
1-C
6The example of alkyl can comprise acetyl yloxymethyl, ethyl ketonic oxygen methyl and sec.-propyl ketonic oxygen methyl.
Use R
6(the C of representative
1-C
6Alkylhalide group) ketonic oxygen C
1-C
6The example of alkyl can comprise trifluoroacetyl yloxymethyl, chloracetyl yloxymethyl and tribromo-acetyl yloxymethyl.
Use R
6(the C of representative
1-C
6Alcoxyl) example of carbonyl can comprise methoxycarbonyl, ethoxycarbonyl, the third oxygen carbonyl, butoxy carbonyl, penta oxygen carbonyl, the different third oxygen carbonyl, isobutyl boc and isoamyl oxygen carbonyl.
Use R
7The C of representative
1-C
6The example of alkyl can comprise methyl.
Use R
8The C of representative
1-C
6The example of alkyl can comprise methyl and ethyl.
Use R
8The C of representative
1-C
6The example of alkylhalide group can comprise chloromethyl and brooethyl.
Use R
8The C of representative
1-C
6The example of hydroxyalkyl can comprise methylol.
Use R
8The C of representative
1-C
4Alcoxyl C
1-C
4The example of alkyl can comprise methoxyl methyl, ethoxymethyl, the different third oxygen methyl, fourth oxygen methyl and isobutyl oxygen methyl.
Use R
8The C of representative
1-C
3Alcoxyl C
1-C
3Alcoxyl C
1-C
3The example of alkyl can comprise methoxy methoxy methyl, methoxy (ethoxy) methyl and ethoxy methoxyl methyl.
Use R
8(the C of representative
1-C
6Alkyl) ketonic oxygen C
1-C
6The example of alkyl can comprise acetyl-o-methyl, ethyl ketonic oxygen methyl and sec.-propyl ketonic oxygen methyl.
Use R
8(the C of representative
1-C
6Alkylhalide group) carbonyl C
1-C
6The example of alkyl can comprise 2-chloroethyl ketonic oxygen methyl.
Use R
8The carboxyl C of representative
1-C
6The example of alkyl can comprise carboxymethyl.
Use R
8(the C of representative
1-C
8Alcoxyl) example of carbonyl can comprise methoxycarbonyl, ethoxycarbonyl, the third oxygen carbonyl, butoxy carbonyl, penta oxygen carbonyl, the different third oxygen carbonyl, isobutyl boc and isoamyl oxygen carbonyl.
Use R
8(the C of representative
1-C
6The halogen alkoxyl group) example of carbonyl can comprise 2-chloroethene oxygen carbonyl, 2-bromine ethoxycarbonyl, 3-neoprene oxygen carbonyl, the 1-chloro-2-third oxygen carbonyl, 1, the 3-two chloro-2-third oxygen carbonyl, 2,2-dichloro ethoxycarbonyl, 2,2,2-trifluoro ethoxycarbonyl, 2,2,2-trichloro-ethoxycarbonyl and 2,2,2-tribromo ethoxycarbonyl.
Use R
8(the C of representative
3-C
10Cycloalkyloxy group) example of carbonyl can comprise cyclobutyl oxygen carbonyl, cyclopentyl oxygen carbonyl and cyclohexyl oxygen carbonyl.
Use R
8(the C of representative
3-C
8Alkene oxygen) example of carbonyl can comprise allyloxycarbonyl, 3-butylene oxygen carbonyl and 1-methyl-2-propenyl oxygen carbonyl.
Use R
8(the C of representative
3-C
8Alkyne oxygen) example of carbonyl can comprise the alkynes third oxygen carbonyl, 3-butine oxygen carbonyl and 1-methyl-2-propine oxygen carbonyl.
Use R
8(the C of representative
1-C
6Alkyl) aminocarboxy example can comprise methylamino carbonyl, ethylamino carbonyl and propyl group aminocarboxyl.
Use R
8Two (C of representative
1-C
6Alkyl) aminocarboxy example can comprise dimethylamino carbonyl, diethylamino carbonyl and diisopropylaminoethyl carbonyl.
Use R
8(the C of representative
1-C
6Alkyl) aminocarboxyl oxygen C
1-C
6The example of alkyl can comprise methylamino ketonic oxygen methyl, ethylamino ketonic oxygen methyl and propyl group aminocarboxyl oxygen methyl.
Use R
8Two (C of representative
1-C
6Alkyl) aminocarboxyl oxygen C
1-C
6The example of alkyl can comprise dimethylamino ketonic oxygen methyl and diethylamino ketonic oxygen methyl.
Use R
22The C of representative
1-C
6The example of alkyl comprises methyl, ethyl, propyl group, sec.-propyl, isobutyl-, butyl, tertiary butyl, amyl group, isopentyl and tertiary amyl.
Use R
22The C of representative
1-C
6The example of alkylhalide group can comprise 2-chloroethyl, 2-bromotrifluoromethane and 2,2,2-trifluoroethyl.
Use R
22The C of representative
3-C
8The example of cycloalkyl can comprise cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
Use R
22The C of representative
3-C
6Non-limiting examples of alkenyls can comprise allyl group, 1-methyl-2-propenyl, 3-butenyl, crotyl, 3-methyl-2-butene base and 2-methyl-3-butenyl.
Use R
22The C of representative
3-C
6The halogen non-limiting examples of alkenyls can comprise 2-chloro-2-propenyl and 3,3-two chloro-2-propenyl.
Use R
22The C of representative
3-C
6The example of alkynyl group can comprise propargyl, 1-methyl-2-propynyl and 2-butyne base.
Use R
22The C of representative
3-C
6The example of halogen alkynyl group can comprise 3-bromine propargyl.
Use R
22The cyano group C of representative
1-C
6The example of alkyl can comprise cyanoethyl.
Use R
22The C of representative
1-C
4Alcoxyl C
1-C
4The example of alkyl can comprise methoxyl methyl, methoxyethyl, ethoxymethyl and ethoxyethyl.
Use R
22The C of representative
1-C
4Alkane sulphur C
1-C
4The example of alkyl can comprise methylthio ethyl.
Use R
22The carboxyl C of representative
1-C
6The example of alkyl can comprise carboxymethyl, 1-carboxy ethyl and 2-carboxy ethyl.
Use R
22(the C of representative
1-C
8Alcoxyl) carbonyl C
1-C
6The example of alkyl can comprise the methoxycarbonyl methyl, ethoxycarbonylmethyl group, the third oxygen carbonyl methyl, the different third oxygen carbonyl methyl, the butoxy carbonyl methyl, the isobutyl boc methyl, special butoxy carbonyl methyl, penta oxygen carbonyl methyl, isoamyl oxygen carbonyl methyl, special penta oxygen carbonyl methyl, 1-methoxycarbonyl ethyl, the 1-ethoxycarbonyl-ethyl, the 1-third oxygen carbonyl ethyl, the different third oxygen carbonyl ethyl of 1-, 1-butoxy carbonyl ethyl, 1-isobutyl boc ethyl, the special butoxy carbonyl ethyl of 1-, 1-penta oxygen carbonyl ethyl, the special penta oxygen carbonyl ethyl of 1-isoamyl oxygen carbonyl ethyl and 1-.
Use R
22{ (the C of representative
1-C
4Alcoxyl) C
1-C
4Alcoxyl } carbonyl C
1-C
6The example of alkyl can comprise methoxy methoxy carbonyl methyl, methoxy (ethoxy) carbonyl methyl and 1-methoxy (ethoxy) carbonyl ethyl.
Use R
22(the C of representative
3-C
8Cycloalkyloxy group) carbonyl C
1-C
6The example of alkyl can comprise cyclobutyl oxygen carbonyl methyl, cyclopentyl oxygen carbonyl methyl, cyclohexyl oxygen carbonyl methyl, 1-cyclobutyl oxygen carbonyl ethyl, 1-cyclopentyl oxygen carbonyl ethyl and 1-cyclohexyl oxygen carbonyl ethyl.
Use R
23And R
24The C of representative
1-C
6The example of alkyl can comprise methyl.
Use R
23And R
24The example of the halogen of representative can comprise chlorine and bromine.
Use R
25The C of representative
1-C
6The example of alkyl can comprise methyl, ethyl, propyl group, sec.-propyl, isobutyl-, butyl, tertiary butyl, amyl group, isopentyl and tertiary amyl.
Use R
25The C of representative
1-C
6The example of alkylhalide group can comprise 2-chloroethyl, 2-bromotrifluoromethane and 2,2,2-trifluoroethyl.
Use R
25The C of representative
3-C
8The example of cycloalkyl can comprise cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
Use R
25The C of representative
3-C
6Non-limiting examples of alkenyls can comprise allyl group, 1-methyl-2-propenyl, 3-butenyl, crotyl, 3-methyl-2-butene base and 2-methyl-3-butenyl.
Use R
26And R
27The C of representative
1-C
6The example of alkyl can comprise methyl, ethyl, propyl group and sec.-propyl.
Compound of the present invention has the geometrical isomer based on two keys, and based on the optical isomer and the diastereomer of at least one unsymmetrical carbon that exists, these isomer and composition thereof are also included within the scope of the present invention certainly.
The following describes the technology of producing The compounds of this invention.
The compounds of this invention can be in the presence of alkali, by the hydrazone compound of general formula (5):
R wherein
3With the definition of Q as mentioned above, and the malonic acid monoester derivatives reaction of general formula (6):
Wherein R and R
2Definition as mentioned above, this technology is called technology 1 below.
Technology 1 can be carried out under following technology 1-1 or the described reaction conditions of 1-2.
I) technology 1-1, the hydrazone compound of its formula of (5) with pyridine and/or quinoline bonded secondary amine in the presence of with the malonic acid monoester derivatives reaction of general formula (6).
This reaction is finished in pyridine and/or quinoline usually.Temperature of reaction usually in 40 °～140 ℃ scope, preferred 60 °～100 ℃.Reaction times usually in the scope of moment to 24 hour, preferred 1～5 hour.
The amount of each used reagent in this reaction, for the hydrazone compound of the general formula (5) of each mole, normally the malonic acid monoester derivative of 1～10 mole general formula (6) and 0.1～5 mole, preferred 0.8～2 mole, more preferably 1～2 mole secondary amine.
The example of used secondary amine can comprise cyclammonium in this reaction, for example piperidines, morpholine and tetramethyleneimine; And dialkylamine, for example diethylamine and Diisopropylamine.
Also can adopt cosolvent in this reaction, the example can comprise aliphatic hydrocarbon for example hexane, heptane, V.M.. naphtha and sherwood oil; Aromatic hydrocarbons is benzene, toluene and dimethylbenzene for example; Halohydrocarbon is methylene dichloride, chloroform, tetracol phenixin, 1 for example, 2-ethylene dichloride, 1, chlorobenzene, dichlorobenzene and phenylfluoroform; Ethers is ether, diisopropyl ether, 1 for example, 4-dioxane, tetrahydrofuran (THF), glycol dimethyl ether and methyl-tertiary butyl ether; Nitrile is acetonitrile and isopropyl cyanide for example; The ester class is ethyl acetate and butylacetate for example; Alcohols is methyl alcohol, ethanol, propyl alcohol, butanols and Virahol for example; The acid amides is N for example, dinethylformamide; Sulfocompound is dimethyl sulfoxide (DMSO) and sulforane for example; And their mixture.
II) technology 1-2, the hydrazone compound of its formula of (5) in the presence of alkali with the malonic acid monoester derivatives reaction of general formula (6).
This reaction is not having solvent or is finishing in solvent usually.The temperature of this reaction is usually at 20 °～200 ℃, in preferred 40 °～150 ℃ scope.Reaction times is usually in the scope of moment to 72 hour.
The amount of each used reagent in this reaction, for normally 1～10 mole of the hydrazone compound of per 1 mole general formula (5), the malonic acid monoester derivative of preferred 1～2 mole general formula (6), for the malonic acid monoester derivative of per 1 mole general formula (6) normally 1 mole to more excessive, preferred 1～10 mole alkali.
The example of used alkali can comprise organic bases in this reaction, and preferred tertiary amine is the dialkyl benzene sulfonamide derivatives for example, as N, and accelerine and N, N-Diethyl Aniline; Triethylamine, diisopropylethylamine, Tri-n-Propylamine, tri-n-butylamine, benzyldimethylamine, styroyl dimethyl amine, N-methylmorpholine, 1,8-diazabicyclo (5.4.0) 11 carbon-7-alkene, 1,5-diazabicyclo (4.3.0) ninth of the ten Heavenly Stems-5-alkene and 1,4-diazabicyclo (2.2.2) octane.Preferred trialkylamine is triethylamine, diisopropyl ethyl amine, Tri-n-Propylamine and tri-n-butylamine for example.
The example of solvent for use can comprise aliphatic hydrocarbon for example hexane, heptane, V.M.. naphtha and sherwood oil in this reaction; Aromatic hydrocarbons is benzene, toluene and dimethylbenzene for example; Halohydrocarbon is methylene dichloride, chloroform, tetracol phenixin, 1 for example, 2-ethylene dichloride, 1, chlorobenzene, dichlorobenzene and phenylfluoroform; Ethers is ether, diisopropyl ether, 1 for example, 4-dioxane, tetrahydrofuran (THF), glycol dimethyl ether and methyl tert butyl ether; Nitrogenous aromatic compound is pyridine and quinoline for example; The acid acid amides, N for example, dinethylformamide; The ester class is ethyl acetate and butylacetate for example; Ketone is acetone, methylethylketone, methyl iso-butyl ketone (MIBK) and pimelinketone for example; Nitrile is acetonitrile and isopropyl cyanide for example; Alcohols is methyl alcohol, ethanol, propyl alcohol, butanols and Virahol for example; Water; And their mixture.
After reaction is finished, direct concentrated reaction mixture, or carry out aftertreatment.Pour reaction mixture into ore deposit acid for example in the aqueous solution of hydrochloric acid or dilute sulphuric acid, use organic solvent extraction then, organic layer is dried, concentrates.If desired, then purify by recrystallization or column chromatography technology.Thus, can obtain The compounds of this invention.
Usually the The compounds of this invention that obtains is the mixture of diastereomer.These diastereomers are not separating especially, or after the chromatogram fine separation, are used as initial substance in the reaction afterwards.
The malonic acid monoester derivative of the general formula that adopts in above-mentioned production technique (6) can prepare by the corresponding diester malonate of hydrolysis in the presence of alkali.
This reaction is finished in solvent usually.Temperature of reaction is usually in 0 °～110 ℃ scopes.Reaction times is usually in the scope of moment to 72 hour.
The normally per 1 mole initial substance diester malonate of the amount of used alkali in this reaction, with 1 mole, this is stoichiometrical ratio, and preferably uses 1 mol alkali.
The example of used alkali can comprise mineral alkali for example sodium hydroxide and potassium hydroxide in this reaction.
The example of used solvent can comprise aliphatic hydrocarbon for example hexane, heptane, V.M.. naphtha and sherwood oil in this reaction; Aromatic hydrocarbons is benzene, toluene and dimethylbenzene for example; Ethers is ether, diisopropyl ether, 1 for example, 4-dioxane, tetrahydrofuran (THF), glycol dimethyl ether and methyl tert butyl ether; Alcohols is methyl alcohol, ethanol, ethylene glycol and Virahol for example; Water; And their mixture.
After reaction is finished, reaction mixture is carried out aftertreatment.Pour reaction mixture into ore deposit acid for example in the aqueous solution of hydrochloric acid or dilute sulphuric acid, use organic solvent extraction again, organic layer carries out drying and concentrates.If desired, then can purify by for example recrystallization or column chromatography technology.Thus, can obtain the malonic acid monoester derivative of general formula (6).
The hydrazone compound of general formula (5) can pass through the compound of general formula (8):
CF
3C (=O) CV
2R
3R wherein
3Definition as mentioned above, V is iodine, bromine or chlorine, reacts the carbonyl compound that obtains general formula (9) with water in the presence of alkali:
CF
3C (=O) C (=O) R
3R wherein
3Definition as mentioned above, or its hydrate or its acetal derivatives, this is reflected at hereinafter referred to as reaction 1; The carbonyl compound of general formula (9), or its hydrate then or its acetal derivatives, and the hydrazine derivative of general formula (10) reaction:
Q-NHNH
2Wherein the definition of Q as mentioned above, this be reflected at hereinafter referred to as the reaction 2.
Reaction 1 is finished in solvent usually.Temperature of reaction is normally in 0 °-100 ℃ scope.Reaction times is usually in the scope of moment to 72 hour.
The amount of each used reagent is normally for per 1 mole of general formula (8) compound in reaction, and with the alkali of 2 moles water and 2 moles, this is stoichiometrical ratio.If desired, these reagents also can excessively use.
As alkali, organic bases or mineral alkali can be used, and the example can comprise sodium acetate and potassium acetate.
The carbonyl compound of general formula (9) also can be in the presence of water or alcohol, with the form reaction of hydrate or acetal derivatives.
Reaction 2 is finished in solvent usually.Temperature of reaction is normally in 0 °～100 ℃ scopes.Reaction times is normally in the scope of moment to 72 hour.
Normally for general formula (8) compound used in per 1 mole of technology 1, with the hydrazine derivative of 1 mole of general formula (10), this is stoichiometrical ratio to the amount of used reagent in reaction.If desired, the compound of general formula (8) can be with excessive.The hydrazine derivative of general formula (10) also can hydrochloride or the form of vitriol be used.
Can comprise for example for example benzene, toluene and dimethylbenzene of hexane, heptane, V.M.. naphtha and sherwood oil, aromatic hydrocarbons of aliphatic hydrocarbon at the example of reaction used solvent in 1 and 2; Halohydrocarbon is chlorobenzene, dichlorobenzene and phenylfluoroform for example; Ethers is ether, diisopropyl ether, 1 for example, 4-dioxane, tetrahydrofuran (THF), glycol dimethyl ether and methyl tert butyl ether; The ester class is ethyl acetate and butylacetate for example; Nitrile is acetonitrile and isopropyl cyanide for example; Alcohols is methyl alcohol, ethanol, ethylene glycol and Virahol for example; Water; And their mixture.
After reaction is finished, if desired, toward reaction mixture in, add water, by filter collecting the crystallization of gained, or reaction mixture is carried out conventional aftertreatment, for example with organic solvent extraction and concentrated.If desired, then can purify by for example chromatogram or recrystallization technology.Thus, separablely go out desired product.
The hydrazine derivative of general formula (10) can be used the anils of nitrous acid, Sodium Nitrite or other reagent diazotization general formula (11) by under acidic conditions:
Q-NH
2Wherein the definition of Q makes (seeing, as organic synthetic compilation volume 1 p.442) with tin protochloride or other reagent reduction diazonium salt as mentioned above then.
The anils of general formula (11) is known, for example at the open No.61741-A of European patent, U.S.P.4,670,046,4,770,695,4,709,049,4,640,707,4,720,297 and 5,169,431, with the open No.63-156787 of Japanese Patent, perhaps can prepare according to method described here.
The hydrazone compound of general formula (5) also can be produced from the anils of general formula (11) according to following formula:
Wherein the definition of Q as mentioned above and R
28Be C
1-C
6Alkyl.
This reaction substep is finished for example as follows:
(1) from the step of compound (1) production compound (II)
Compound (II) can by compound (I) under acidic conditions with nitrite for example Sodium Nitrite or potassium nitrite in water, react and obtain corresponding diazonium salt, the compound of this diazonium salt and general formula (12) then:
CF
3C (=O) CH
2C (=O) OR
28Wherein Q and R
28Definition as mentioned above, for example react and to make (seeing tetrahedron, volume 35, p.2013, (1979)) in the presence of sodium acetate or the pyridine at alkali.
(2) from the step of compound (II) production compound (III)
Compound (III) usually can be in the presence of alkali, and in solvent, (II) produces by the hydrolysis compound.
Temperature of reaction is usually in 0 ° of-100 ℃ of scope.Reaction times is usually in the scope of moment to 24 hour.
The amount of used reagent is normally for per 1 mole compound (II) in reaction, and with 1 mole alkali, this is stoichiometrical ratio; If desired, also can change.
The example of used alkali can comprise mineral alkali for example sodium hydroxide, lithium hydroxide, single hydronium(ion) oxidation lithium, hydrated barta and potassium hydroxide in this reaction.
The example of used solvent can comprise for example for example benzene, toluene and dimethylbenzene of hexane, heptane, V.M.. naphtha and sherwood oil, aromatic hydrocarbons of aliphatic hydrocarbon in this reaction; Halohydrocarbon is chlorobenzene, dichlorobenzene and phenylfluoroform for example; Ethers is ether, diisopropyl ether, 1 for example, 4-dioxane, tetrahydrofuran (THF), glycol dimethyl ether and methyl tert butyl ether; Alcohols is methyl alcohol, ethanol, ethylene glycol and Virahol for example; Water; And their mixture.
(3) from the step of compound (III) production compound (IV)
Compound (IV) can make it decarboxylation by heating compound (III) and produce in solvent.
Temperature of reaction is usually in 50 °～200 ℃ scopes.Reaction times is usually in moment to 72 hour scope.
The example of solvent for use comprises for example for example benzene, toluene and dimethylbenzene of hexane, heptane, V.M.. naphtha and sherwood oil, aromatic hydrocarbons of aliphatic hydrocarbon in reaction; Halohydrocarbon is chloroform, tetracol phenixin, 1 for example, 2-ethylene dichloride, chlorobenzene, dichlorobenzene and phenylfluoroform; Ethers is ether, diisopropyl ether, 1 for example, 4-dioxane, tetrahydrofuran (THF), glycol dimethyl ether and methyl tert butyl ether; Ketone is acetone, methylethylketone, methyl iso-butyl ketone (MIBK) and pimelinketone for example; The acid acid amides is N for example, dinethylformamide; Tertiary amine is triethylamine, diisopropyl ethyl amine, N for example, accelerine, N, N-Diethyl Aniline and N-methylmorpholine; Nitrogenous aromatic compound is pyridine and picoline for example; Sulfocompound is dimethyl sulfoxide (DMSO) and sulforane for example; Lipid acid is formic acid, acetate and propionic acid for example; Alcohols is methyl alcohol, ethanol, ethylene glycol and Virahol for example; Water; And their mixture.
If desired, this reaction also can be finished under the condition of using metal catalyst such as copper.
After reaction was finished, filter reaction mixture to be collecting the crystallization of gained, or carried out conventional aftertreatment, for example with organic solvent extraction with concentrate.If desired, then purify by for example chromatogram or recrystallization technology.Thus, separablely go out desired product.
Wherein Q is Q-1, and B is OR
1Or SR
1And R
1Be carboxyl C
1-C
6The hydrazone compound of the general formula of alkyl (IV) can be Q-1 by Q wherein also, and B is OR
1Or SR
1, and R
1Be (C
1-C
8Alcoxyl) carbonyl C
1-C
6The hydrolysis and the decarboxylation of the general formula of alkyl (II) compound are produced.
The The compounds of this invention that obtains by above-mentioned production technique has been listed in table 1～21, and table 22 and 23 has been listed the hydrazone compound of the general formula (5) that adopts and the malonic acid monoester derivative of general formula (6) respectively in technology 1.These compounds only illustrate the present invention, but the present invention is not limited to this.It is different that " c-" represents ring-" i " representative in these tables, and " Et " represents ethyl; " Bu " represents butyl.
General formula (13) compound:
Table 1
| Compound | ????X | ????Y | ????R | ????R 2 | ????R 3 | ????B |
| ????1-1 ????1-2 ????1-3 ????1-4 ????1-5 ????1-6 ????1-7 ????1-8 ????1-9 ????1-10 ????1-11 ????1-12 ????1-13 ????1-14 ????1-15 ????1-16 ????1-17 ????1-18 ????1-19 ????1-20 ????1-21 ????1-22 ????1-23 ????1-24 ????1-25 ????1-26 | ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F | ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl | ??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3 | ??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3 | ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H | ????H ????OH ????OCH 3????OC 2H 5????OCH(CH 3) 2????OCH 2CH＝CH 2????OCH 2C≡CH ????OCH(CH 3)C≡CH ????OCH 2COOH ????OCH 2COOCH 3????OCH 2COOC 2H 5????OCH 2COOC 3H 7????OCH 2COOC 4H 9????OCH 2COOC 5H 11????OCH 2COO-i-C 3H 7????OCH 2COO-i-C 4H 9????OCH 2COO-c-C 5H 9????OCH 2COO-c-C 6H 11????OCH(CH 3)COOH ????OCH(CH 3)COOCH 3????OCH(CH 3)COOC 2H 5????OCH(CH 3)COOC 3H 7????OCH(CH 3)COOC 4H 9????OCH(CH 3)COOC 5H 11????OCH(CH 3)COO-i-C 3H 7????OCH(CH 3)COO-i-C 4H 9 |
Table 2
| Compound | ????X | ????Y | ????R | ????R 2 | ????R 3 | ????B |
| ????1-27 ????1-28 ????1-29 ????1-30 ????1-31 ????1-32 ????1-33 ????1-34 ????1-35 ????1-36 ????1-37 ????1-38 ????1-39 ????1-40 ????1-41 ????1-42 ????1-43 ????1-44 ????1-45 ????1-46 ????1-47 ????1-48 ????1-49 ????1-50 ????1-51 ????1-52 | ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F | ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl | ??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3 | ??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3 | ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H | ????OCH(CH 3)COO-c-C 5H 9????OCH(CH 3)COO-c-C 6H 11????O-c-C 5H 9????O-c-C 6H 11????SCH 2C≡CH ????SCH(CH 3)C≡CH ????SCH 2COOH ????SCH 2COOCH 3????SCH 2COOC 2H 5????SCH 2COOC 3H 7????SCH 2COOC 4H 9????SCH 2COOC 5H 11????SCH 2COO-i-C 3H 7????SCH 2COO-i-C 4H 9????SCH 2COO-c-C 5H 9????SCH 2COO-c-C 6H 11????SCH(CH 3)COOH ????SCH(CH 3)COOCH 3????SCH(CH 3)COOC 2H 5????SCH(CH 3)COOC 3H 7????SCH(CH 3)COOC 4H 9????SCH(CH 3)COOC 5H 11????SCH(CH 3)COO-i-C 3H 7????SCH(CH 3)COO-i-C 4H 9????SCH(CH 3)COO-c-C 5H 9????SCH(CH 3)COO-c-C 6H 11 |
Table 3
| Compound | ????X | ????Y | ????R | ????R 2 | ????R 3 | ????B |
| ????1-53 ????1-54 ????1-55 ????1-56 ????1-57 ????1-58 ????1-59 ????1-60 ????1-61 ????1-62 ????1-63 ????1-64 ????1-65 ????1-66 ????1-67 ????1-68 ????1-69 ????1-70 ????1-71 ????1-72 ????1-73 ????1-74 ????1-75 ????1-76 ????1-77 ????1-78 | ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F | ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl | ??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3 | ????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H | ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H | ????COOH ????COOCH 3????COOC 2H 5????COOC 3H 7????COOC 4H 9????COOCH(CH 3) 2????CH 2CH 2COOC 2H 5????CH 2CHClCOOC 2H 5????H ????OH ????OCH 3????OC 2H 5????OCH(CH 3) 2????OCH 2CH＝CH 2????OCH 2C≡CH ????OCH(CH 3)C≡CH ????OCH 2COOH ????OCH 2COOCH 3????OCH 2COOC 2H 5????OCH 2COOC 3H 7????OCH 2COOC 4H 9????OCH 2COOC 5H 11????OCH 2COO-i-C 3H 7????OCH 2COO-i-C 4H 9????OCH 2COO-c-C 5H 9????OCH 2COO-c-C 6H 11 |
Table 4
| Compound | ????X | ????Y | ????R | ????R 2 | ????R 3 | ????B |
| ????1-79 ????1-80 ????1-81 ????1-82 ????1-83 ????1-84 ????1-85 ????1-86 ????1-87 ????1-88 ????1-89 ????1-90 ????1-91 ????1-92 ????1-93 ????1-94 ????1-95 ????1-96 ????1-97 ????1-98 ????1-99 ????1-100 ????1-101 ????1-102 ????1-103 ????1-104 | ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F | ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl | ??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3 | ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H | ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H | ????OCH(CH 3)COOH ????OCH(CH 3)COOCH 3????OCH(CH 3)COOC 2H 5????OCH(CH 3)COOC 3H 7????OCH(CH 3)COOC 4H 9????OCH(CH 3)COOC 5H 11????OCH(CH 3)COO-i-C 3H 7????OCH(CH 3)COO-i-C 4H 9????OCH(CH 3)COO-c-C 5H 9????OCH(CH 3)COO-c-C 6H 11????O-c-C 5H 9????O-c-C 6H 11????SCH 2C≡CH ????SCH(CH 3)C≡CH ????SCH 2COOH ????SCH 2COOCH 3????SCH 2COOC 2H 5????SCH 2COOC 3H 7????SCH 2COOC 4H 9????SCH 2COOC 5H 11????SCH 2COO-i-C 3H 7????SCH 2COO-i-C 4H 9????SCH 2COO-c-C 5H 9????SCH 2COO-c-C 6H 11????SCH(CH 3)COOH ????SCH(CH 3)COOCH 3 |
Table 5
| Compound | ????X | ????Y | ????R | ????R 2 | ????R 3 | ????B |
| ????1-105 ????1-106 ????1-107 ????1-108 ????1-109 ????1-110 ????1-111 ????1-112 ????1-113 ????1-114 ????1-115 ????1-116 ????1-117 ????1-118 ????1-119 ????1-120 ????1-121 ????1-122 ????1-123 ????1-124 ????1-125 ????1-126 ????1-127 ????1-128 ????1-129 ????1-130 | ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H | ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl | ??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3 | ???H ???H ???H ???H ???H ???H ???H ???H ???H ???H ???H ???H ???H ???H ???H ???H ???CH 3???CH 3???CH 3???CH 3???CH 3???CH 3???CH 3???H ???H ???H | ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H | ????SCH(CH 3)COOC 2H 5????SCH(CH 3)COOC 3H 7????SCH(CH 3)COOC 4H 9????SCH(CH 3)COOC 5H 11????SCH(CH 3)COO-i-C 3H 7????SCH(CH 3)COO-i-C 4H 9????SCH(CH 3)COO-c-C 5H 9????SCH(CH 3)COO-c-C 6H 11????COOH ????COOCH 3????COOC 2H 5????COOC 3H 7????COOC 4H 9????COOCH(CH 3) 2????CH 2CH 2COOC 2H 5????CH 2CHClCOOC 2H 5????H ????OH ????OCH 3????OC 2H 5????OCH(CH 3) 2????OCH 2C≡CH ????OCH(CH 3)C≡CH ????H ????OH ????OCH 3 |
Table 6
| Compound | ????X | ????Y | ????R | ????R 2 | ????R 3 | ????B |
| ????1-131 ????1-132 ????1-133 ????1-134 ????1-135 ????1-136 ????1-137 ????1-138 ????1-139 ????1-140 ????1-141 ????1-142 ????1-143 ????1-144 ????1-145 ????1-146 ????1-147 ????1-148 ????1-149 ????1-150 ????1-151 ????1-152 ????1-153 ????1-154 ????1-155 ????1-156 | ????H ????H ????H ????H ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????F ????F ????F ????F ????F ????F ????F ????F | ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl | ??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3 | ??H ??H ??H ??H ??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??H ??H ??H ??H ??H ??H ??H ??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5 | ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H | ????OC 2H 5????OCH(CH 3) 2????OCH 2C≡CH ????OCH(CH 3)C≡CH ????H ????OH ????OCH 3????OC 2H 5????OCH(CH 3) 2????OCH 2C≡CH ????OCH(CH 3)C≡CH ????H ????OH ????OCH 3????OC 2H 5????OCH(CH 3) 2????OCH 2C≡CH ????OCH(CH 3)C≡CH ????H ????OH ????OCH 3????OC 2H 5????OCH(CH 3) 2????OCH 2C≡CH ????OCH(CH 3)C≡CH ????OCH 2COOH |
Table 7
| Compound | ????X | ????Y | ????R | ????R 2 | ????R 3 | ????B |
| ????1-157 ????1-158 ????1-159 ????1-160 ????1-161 ????1-162 ????1-163 ????1-164 ????1-165 ????1-166 ????1-167 ????1-168 ????1-169 ????1-170 ????1-171 ????1-172 ????1-173 ????1-174 ????1-175 ????1-176 ????1-177 ????1-178 ????1-179 ????1-180 ????1-181 ????1-182 | ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F | ??Cl ??Cl ??Cl ??Cl ??Cl ??Cl ??Cl ??Cl ??Cl ??Cl ??Cl ??Cl ??Cl ??Cl ??Cl ??Cl ??Cl ??Cl ??Cl ??Cl ??Cl ??Cl ??Cl ??Cl ??Cl ??Cl | ??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3 | ??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??H ??H ??H ??H ??H ??H ??H ??H ??H | ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3 | ????OCH 2COOCH 3????OCH 2COOC 2H 5????OCH 2COOC 3H 7????OCH 2COOC 4H 9????OCH 2COOC 5H 11????OCH(CH 3)COOH ????OCH(CH 3)COOCH 3????OCH(CH 3)COOC 2H 5????OCH(CH 3)COOC 3H 7????OCH(CH 3)COOC 4H 9????OCH(CH 3)COOC 5H 11????COOH ????COOCH 3????COOC 2H 5????COOC 3H 7????COOC 4H 9????COOCH(CH 3) 2????H ????OH ????OCH 3????OC 2H 5????OCH(CH 3) 2????OCH 2C≡CH ????OCH(CH 3)C≡CH ????OCH 2COOH ????OCH 2COOCH 3 |
Table 8
| Compound | ????X | ????Y | ????R | ????R 2 | ????R 3 | ????B |
| ????1-183 ????1-184 ????1-185 ????1-186 ????1-187 ????1-188 ????1-189 ????1-190 ????1-191 ????1-192 ????1-193 ????1-194 ????1-195 ????1-196 ????1-197 ????1-198 ????1-199 ????1-200 ????1-201 ????1-202 ????1-203 ????1-204 ????1-205 ????1-206 ????1-207 ????1-208 | ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F | ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl | ??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3 | ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H | ??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3 | ????OCH 2COOC 2H 5????OCH 2COOC 3H 7????OCH 2COOC 4H 9????OCH 2COOC 5H 11????OCH(CH 3)COOH ????OCH(CH 3)COOCH 3????OCH(CH 3)COOC 2H 5????OCH(CH 3)COOC 3H 7????OCH(CH 3)COOC 4H 9????OCH(CH 3)COOC 5H 11????SCH 2COOH ????SCH 2COOCH 3????SCH 2COOC 2H 5????SCH 2COOC 3H 7????SCH 2COOC 4H 9????SCH 2COOC 5H 11????SCH 2COO-c-C 5H 9????SCH 2COO-c-C 6H 11????SCH(CH 3)COOH ????SCH(CH 3)COOCH 3????SCH(CH 3)COOC 2H 5????SCH(CH 3)COOC 3H 7????SCH(CH 3)COOC 4H 9????SCH(CH 3)COOC 5H 11????COOH ????COOCH 3 |
Table 9
| Compound | ????X | ????Y | ????R | ????R 2 | ????R 3 | ????B |
| ????1-209 ????1-210 ????1-211 ????1-212 ????1-213 ????1-214 ????1-215 ????1-216 ????1-217 ????1-218 ????1-219 ????1-220 ????1-221 ????1-222 ????1-223 ????1-224 ????1-225 ????1-226 ????1-227 ????1-228 ????1-229 ????1-230 ????1-231 ????1-232 ????1-233 ????1-234 | ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F | ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl | ??CH 3??CH 3??CH 3??CH 3??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5 | ??H ??H ??H ??H ??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3 | ????CH 3????CH 3????CH 3????CH 3????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H | ????COOC 2H 5????COOC 3H 7????COOC 4H 9????COOCH(CH 3) 2????H ????OH ????OCH 3????OC 2H 5????OCH(CH 3) 2????OCH 2CH≡CH 2????OCH 2C≡CH ????OCH(CH 3)C≡CH ????OCH 2COOH ????OCH 2COOCH 3????OCH 2COOC 2H 5????OCH 2COOC 3H 7????OCH 2COOC 4H 9????OCH 2COOC 5H 11????OCH 2COO-i-C 3H 7????OCH 2COO-i-C 4H 9????OCH 2COO-c-C 5H 9????OCH 2COO-c-C 6H 11????OCH(CH 3)COOH ????OCH(CH 3)COOCH 3????OCH(CH 3)COOC 2H 5????OCH(CH 3)COOC 3H 7 |
Table 10
| Compound | ????X | ????Y | ????R | ????R 2 | ????R 3 | ????B |
| ????1-235 ????1-236 ????1-237 ????1-238 ????1-239 ????1-240 ????1-241 ????1-242 ????1-243 ????1-244 ????1-245 ????1-246 ????1-247 ????1-248 ????1-249 ????1-250 ????1-251 ????1-252 ????1-253 ????1-254 ????1-255 ????1-256 ????1-257 ????1-258 ????1-259 ????1-260 | ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F | ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl | ??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5 | ??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3 | ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H | ????OCH(CH 3)COOC 4H 9????OCH(CH 3)COOC 5H 11????OCH(CH 3)COO-i-C 3H 7????OCH(CH 3)COO-i-C 4H 9????OCH(CH 3)COO-c-C 5H 9????OCH(CH 3)COO-c-C 6H 11????O-c-C 5H 9????O-c-C 6H 11????SCH 2C≡CH ????SCH(CH 3)C≡CH ????SCH 2COOH ????SCH 2COOCH 3????SCH 2COOC 2H 5????SCH 2COOC 3H 7????SCH 2COOC 4H 9????SCH 2COOC 5H 11????SCH 2COO-i-C 3H 7????SCH 2COO-i-C 4H 9????SCH 2COO-c-C 5H 9????SCH 2COO-c-C 6H 11????SCH(CH 3)COOH ????SCH(CH 3)COOCH 3????SCH(CH 3)COOC 2H 5????SCH(CH 3)COOC 3H 7????SCH(CH 3)COOC 4H 9????SCH(CH 3)COOC 5H 11 |
Table 11
| Compound | ????X | ????Y | ????R | ????R 2 | ????R 3 | ????B |
| ????1-261 ????1-262 ????1-263 ????1-264 ????1-265 ????1-266 ????1-267 ????1-268 ????1-269 ????1-270 ????1-271 ????1-272 ????1-273 ????1-274 ????1-275 ????1-276 ????1-277 ????1-278 ????1-279 ????1-280 ????1-281 ????1-282 ????1-283 ????1-284 ????1-285 ????1-286 | ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F | ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl | ??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5 | ??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H | ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H | ????SCH(CH 3)COO-i-C 3H 7????SCH(CH 3)COO-i-C 4H 9????SCH(CH 3)COO-c-C 5H 9????SCH(CH 3)COO-c-C 6H 11????COOH ????COOCH 3????COOC 2H 5????COOC 3H 7????COOC 4H 9????COOCH(CH 3) 2????CH 2CH 2COOC 2H 5????CH 2CHClCOOC 2H 5????H ????OH ????OCH 3????OC 2H 5????OCH(CH 3) 2????OCH 2CH≡CH 2????OCH 2C≡CH ????OCH(CH 3)C≡CH ????OCH 2COOH ????OCH 2COOCH 3????OCH 2COOC 2H 5????OCH 2COOC 3H 7????OCH 2COOC 4H 9????OCH 2COOC 5H 11 |
Table 12
| Compound | ????X | ????Y | ????R | ????R 2 | ????R 3 | ????B |
| ????1-287 ????1-288 ????1-289 ????1-290 ????1-291 ????1-292 ????1-293 ????1-294 ????1-295 ????1-296 ????1-297 ????1-298 ????1-299 ????1-300 ????1-301 ????1-302 ????1-303 ????1-304 ????1-305 ????1-306 ????1-307 ????1-308 ????1-309 ????1-310 ????1-311 ????1-312 | ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F | ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl | ??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5 | ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H | ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H | ????OCH 2COO-i-C 3H 7????OCH 2COO-i-C 4H 9????OCH 2COO-c-C 5H 9????OCH 2COO-c-C 6H 11????OCH(CH 3)COOH ????OCH(CH 3)COOCH 3????OCH(CH 3)COOC 2H 5????OCH(CH 3)COOC 3H 7????OCH(CH 3)COOC 4H 9????OCH(CH 3)COOC 5H 11????OCH(CH 3)COO-i-C 3H 7????OCH(CH 3)COO-i-C 4H 9????OCH(CH 3)COO-c-C 5H 9????OCH(CH 3)COO-c-C 6H 11????O-c-C 5H 9????O-c-C 6H 11????SCH 2C≡CH ????SCH(CH 3)C≡CH ????SCH 2COOH ????SCH 2COOCH 3????SCH 2COOC 2H 5????SCH 2COOC 3H 7????SCH 2COOC 4H 9????SCH 2COOC 5H 11????SCH 2COO-i-C 3H 7????SCH 2COO-i-C 4H 9 |
Table 13
| Compound | ????X | ????Y | ????R | ????R 2 | ????R 3 | ????B |
| ????1-313 ????1-314 ????1-315 ????1-316 ????1-317 ????1-318 ????1-319 ????1-320 ????1-321 ????1-322 ????1-323 ????1-324 ????1-325 ????1-326 ????1-327 ????1-328 ????1-329 ????1-330 ????1-331 ????1-332 ????1-333 ????1-334 ????1-335 ????1-336 ????1-337 ????1-338 | ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????H ????H ????H ????H ????H ????H | ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl | ??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5 | ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??H ??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3 | ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H | ????SCH 2COO-c-C 5H 9????SCH 2COO-c-C 6H 11????SCH(CH 3)COOH ????SCH(CH 3)COOCH 3????SCH(CH 3)COOC 2H 5????SCH(CH 3)COOC 3H 7????SCH(CH 3)COOC 4H 9????SCH(CH 3)COOC 5H 11????SCH(CH 3)COO-i-C 3H 7????SCH(CH 3)COO-i-C 4H 9????SCH(CH 3)COO-c-C 5H 9????SCH(CH 3)COO-c-C 6H 11????COOH ????COOCH 3????COOC 2H 5????COOC 3H 7????COOC 4H 9????COOCH(CH 3) 2????CH 2CH 2COOC 2H 5????CH 2CHClCOOC 2H 5????H ????OH ????OCH 3????OC 2H 5????OCH(CH 3) 2????OCH 2C≡CH |
Table 14
| Compound | ????X | ????Y | ????R | ????R 2 | ????R 3 | ????B |
| ????1-339 ????1-340 ????1-341 ????1-342 ????1-343 ????1-344 ????1-345 ????1-346 ????1-347 ????1-348 ????1-349 ????1-350 ????1-351 ????1-352 ????1-353 ????1-354 ????1-355 ????1-356 ????1-357 ????1-358 ????1-359 ????1-360 ????1-361 ????1-362 ????1-363 ????1-364 | ????H ????H ????H ????H ????H ????H ????H ????H ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????F ????F ????F ????F | ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl | ??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5 | ????CH 3????H ????H ????H ????H ????H ????H ????H ????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????H ????H ????H ????H ????H ????H ????H ????C 2H 5????C 2H 5????C 2H 5????C 2H 5 | ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H | ????OCH(CH 3)C≡CH ????H ????OH ????OCH 3????OC 2H 5????OCH(CH 3) 2????OCH 2C≡CH ????OCH(CH 3)C≡CH ????H ????OH ????OCH 3????OC 2H 5????OCH(CH 3) 2????OCH 2C≡CH ????OCH(CH 3)C≡CH ????H ????OH ????OCH 3????OC 2H 5????OCH(CH 3) 2????OCH 2C≡CH ????OCH(CH 3)C≡CH ????H ????OH ????OCH 3????OC 2H 5 |
Table 15
| Compound | ????X | ????Y | ????R | ????R 2 | ????R 3 | ????B |
| ????1-365 ????1-366 ????1-367 ????1-368 ????1-369 ????1-370 ????1-371 ????1-372 ????1-373 ????1-374 ????1-375 ????1-376 ????1-377 ????1-378 ????1-379 ????1-380 ????1-381 ????1-382 ????1-383 ????1-384 ????1-385 ????1-386 ????1-387 ????1-388 ????1-389 ????1-390 | ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F | ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl | ??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5 | ??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??H ??H ??H ??H ??H | ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????CH 3????CH 3????CH 3????CH 3????CH 3 | ????OCH(CH 3) 2????OCH 2C≡CH ????OCH(CH 3)C≡CH ????OCH 2COOH ????OCH 2COOCH 3????OCH 2COOC 2H 5????OCH 2COOC 3H 7????OCH 2COOC 4H 9????OCH 2COOC 5H 11????OCH(CH 3)COOH ????OCH(CH 3)COOCH 3????OCH(CH 3)COOC 2H 5????OCH(CH 3)COOC 3H 7????OCH(CH 3)COOC 4H 9????OCH(CH 3)COOC 5H 11????COOH ????COOCH 3????COOC 2H 5????COOC 3H 7????COOC 4H 9????COOCH(CH 3) 2????H ????OH ????OCH 3????OC 2H 5????OCH(CH 3) 2 |
Table 16
| Compound | ????X | ????Y | ????R | ????R 2 | ????R 3 | ????B |
| ????1-391 ????1-392 ????1-393 ????1-394 ????1-395 ????1-396 ????1-397 ????1-398 ????1-399 ????1-400 ????1-401 ????1-402 ????1-403 ????1-404 ????1-405 ????1-406 ????1-407 ????1-408 ????1-409 ????1-410 ????1-411 ????1-412 ????1-413 ????1-414 ????1-415 ????1-416 | ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F | ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl | ??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5 | ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H | ??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3 | ????OCH 2C≡CH ????OCH(CH 3)C≡CH ????OCH 2COOH ????OCH 2COOCH 3????OCH 2COOC 2H 5????OCH 2COOC 3H 7????OCH 2COOC 4H 9????OCH 2COOC 5H 11????OCH(CH 3)COOH ????OCH(CH 3)COOCH 3????OCH(CH 3)COOC 2H 5????OCH(CH 3)COOC 3H 7????OCH(CH 3)COOC 4H 9????OCH(CH 3)COOC 5H 11????SCH 2COOH ????SCH 2COOCH 3????SCH 2COOC 2H 5????SCH 2COOC 3H 7????SCH 2COOC 4H 9????SCH 2COOC 5H 11????SCH 2COO-c-C 5H 9????SCH 2COO-c-C 6H 11????SCH(CH 3)COOH ????SCH(CH 3)COOCH 3????SCH(CH 3)COOC 2H 5????SCH(CH 3)COOC 3H 7 |
Table 17
| Compound | ????X | ????Y | ????R | ????R 2 | ????R 3 | ????B |
| ????1-417 ????1-418 ????1-419 ????1-420 ????1-421 ????1-422 ????1-423 ????1-424 ????1-425 | ????F ????F ????F ????F ????F ????F ????F ????F ????F | ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl | ??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 3H 7 | ????H ????H ????H ????H ????H ????H ????H ????H ????H | ??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3 | ????SCH(CH 3)COOC 4H 9????SCH(CH 3)COOC 5H 11????COOH ????COOCH 3????COOC 2H 5????COOC 3H 7????COOC 4H 9????COOCH(CH 3) 2????OCH(CH 3) 2 |
General formula (14) compound:
Table 18
| Compound | ????X | ????Z 1 | ????R | ????n | ????R 2 | ????R 5 |
| ????2-1 ????2-2 ????2-3 ????2-4 ????2-5 ????2-6 ????2-7 ????2-8 ????2-9 ????2-10 ????2-11 ????2-12 ????2-13 ????2-14 ????2-15 ????2-16 ????2-17 ????2-18 ????2-19 ????2-20 ????2-21 ????2-22 ????2-23 ????2-24 ????2-25 ????2-26 | ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H | ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O | ??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3 | ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 | ??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??H ??H ??H ??H ??H ??H ??H ??H ??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??H ??H | ????CH 2C≡CH ????CH(CH 3)C≡CH ????CH 2COOCH 3????CH 2COOC 2H 5????CH(CH 3)COOC 2H 5????CH 2CN ????CH(CH 3) 2????CH(CH 3)C 2H 5????CH 2C≡CH ????CH(CH 3)C≡CH ????CH 2COOCH 3????CH 2COOC 2H 5????CH(CH 3)COOC 2H 5????CH 2CN ????CH(CH 3) 2????CH(CH 3)C 2H 5????CH 2C≡CH ????CH(CH 3)C≡CH ????CH 2COOCH 3????CH 2COOC 2H 5????CH(CH 3)COOC 2H 5????CH 2CN ????CH(CH 3) 2????CH(CH 3)C 2H 5????CH 2C≡CH ????CH(CH 3)C≡CH |
Table 19
| Compound | ????X | ????Z 1 | ????R | ????n | ????R 2 | ????R 5 |
| ????2-27 ????2-28 ????2-29 ????2-30 ????2-31 ????2-32 ????2-33 ????2-34 ????2-35 ????2-36 ????2-37 ????2-38 ????2-39 ????2-40 ????2-41 ????2-42 ????2-43 ????2-44 ????2-45 ????2-46 ????2-47 ????2-48 | ????H ????H ????H ????H ????H ????H ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F | ????O ????O ????O ????O ????O ????O ????S ????S ????S ????S ????S ????S ????S ????S ????S ????S ????S ????S ????S ????S ????S ????S | ??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3 | ????1 ????1 ????1 ????1 ????1 ????1 ????0 ????0 ????0 ????0 ????0 ????0 ????0 ????0 ????O ????O ????0 ????0 ????0 ????0 ????0 ????0 | ????H ????H ????H ????H ????H ????H ????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????H ????H ????H ????H ????H ????H ????H ????H | ????CH 2COOCH 3????CH 2COOC 2H 5????CH(CH 3)COOC 2H 5????CH 2CN ????CH(CH 3) 2????CH(CH 3)C 2H 5????CH 2C≡CH ????CH(CH 3)C≡CH ????CH 2COOCH 3????CH 2COOC 2H 5????CH(CH 3)COOC 2H 5????CH 2CN ????CH(CH 3) 2????CH(CH 3)C 2H 5????CH 2C≡CH ????CH(CH 3)C≡CH ????CH 2COOCH 3????CH 2COOC 2H 5????CH(CH 3)COOC 2H 5????CH 2CN ????CH(CH 3) 2????CH(CH 3)C 2H 5 |
Table 20
| Compound | ????X | ????Z 1 | ????R | ????n | ????R 2 | ????R 5 |
| ????2-49 ????2-50 ????2-51 ????2-52 ????2-53 ????2-54 ????2-55 ????2-56 ????2-57 ????2-58 ????2-59 ????2-60 ????2-61 ????2-62 ????2-63 ????2-64 ????2-65 ????2-66 ????2-67 ????2-68 ????2-69 ????2-70 ????2-71 ????2-72 ????2-73 ????2-74 | ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H | ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O ????O | ??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5 | ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????l ????1 ????1 ????1 ????1 | ??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??H ??H ??H ??H ??H ??H ??H ??H ??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??H ??H | ????CH 2C≡CH ????CH(CH 3)C≡CH ????CH 2COOCH 3????CH 2COOC 2H 5????CH(CH 3)COOC 2H 5????CH 2CN ????CH(CH 3) 2????CH(CH 3)C 2H 5????CH 2C≡CH ????CH(CH 3)C≡CH ????CH 2COOCH 3????CH 2COOC 2H 5????CH(CH 3)COOC 2H 5????CH 2CN ????CH(CH 3) 2????CH(CH 3)C 2H 5????CH 2C≡CH ????CH(CH 3)C≡CH ????CH 2COOCH 3????CH 2COOC 2H 5????CH(CH 3)COOC 2H 5????CH 2CN ????CH(CH 3) 2????CH(CH 3)C 2H 5????CH 2C≡CH ????CH(CH 3)C≡CH |
Table 21
| Compound | ????X | ????Z 1 | ????R | ????n | ????R 2 | ????R 5 |
| ????2-75 ????2-76 ????2-77 ????2-78 ????2-79 ????2-80 ????2-81 ????2-82 ????2-83 ????2-84 ????2-85 ????2-86 ????2-87 ????2-88 ????2-89 ????2-90 ????2-91 ????2-92 ????2-93 ????2-94 ????2-95 ????2-96 | ????H ????H ????H ????H ????H ????H ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F | ????O ????O ????O ????O ????O ????O ????S ????S ????S ????S ????S ????S ????S ????S ????S ????S ????S ????S ????S ????S ????S ????S | ??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5??C 2H 5 | ????1 ????1 ????1 ????1 ????1 ????1 ????0 ????0 ????0 ????0 ????0 ????0 ????0 ????0 ????0 ????0 ????0 ????0 ????0 ????0 ????0 ????0 | ????H ????H ????H ????H ????H ????H ????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????CH 3????H ????H ????H ????H ????H ????H ????H ????H | ????CH 2COOCH 3????CH 2COOC 2H 5????CH(CH 3)COOC 2H 5????CH 2CN ????CH(CH 3) 2????CH(CH 3)C 2H 5????CH 2C≡CH ????CH(CH 3)C≡CH ????CH 2COOCH 3????CH 2COOC 2H 5????CH(CH 3)COOC 2H 5????CH 2CN ????CH(CH 3) 2????CH(CH 3)C 2H 5????CH 2C≡CH ????CH(CH 3)C≡CH ????CH 2COOCH 3????CH 2COOC 2H 5????CH(CH 3)COOC 2H 5????CH 2CN ????CH(CH 3) 2????CH(CH 3)C 2H 5 |
The hydrazone compound of general formula (5):
Table 22
| Compound | ??Q | ??X | ??Y | ????B | ????R 3 |
| ????3-1 ????3-2 ????3-3 ????3-4 ????3-5 ????3-6 ????3-7 ????3-8 ????3-9 ????3-10 ????3-11 ????3-12 ????3-13 | ??Q-1 ??Q-1 ??Q-1 ??Q-1 ??Q-1 ??Q-1 ??Q-1 ??Q-1 ??Q-1 ??Q-1 ??Q-1 ??Q-1 ??Q-1 | ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????H ????H ????Cl | ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl | ????OH ????H ????OCH(CH 3) 2????OCH 2C≡CH ????OCH(CH 3)C≡CH ????OCH 2COOH ????OCH 2COOCH 3????OCH 2COOC 2H 5????COOCH 3????COOC 2H 5????H ????OCH(CH 3) 2????OCH(CH 3) 2 | ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H |
The malonic acid monoester derivative of general formula (6):
Table 23
| Compound | ????R | ????R 2 |
| ????4-1 ????4-2 ????4-3 ????4-4 ????4-5 ????4-6 ????4-7 | ??CH 3??C 2H 5??CH 3??C 2H 5??CH 3??C 2H 5??C 3H 7 | ??H ??H ??CH 3??CH 3??C 2H 5??C 2H 5??CH 3 |
Be called technology 2 below the following explanation technology of producing the pyridazin-3-ketone derivant of general formula (7), this technology from The compounds of this invention.
Carry out under the condition that technology 2 can be described below.
1) technology 2-1
The compounds of this invention can under the existence of 8-diazabicyclo (5.4.0) 11 carbon-7-alkene, close the pyridazin-3-ketone derivant that ring produces general formula (7) at organic bases for example 1.
The amount of used alkali is normally for per 1 mole The compounds of this invention in reaction, with catalytic amount to more excessive, preferred 1 mole to excessive.Temperature of reaction changes with used alkali, usually in 30 °～250 ℃ scopes.Reaction times is usually in the scope of moment to 240 hour.
This reaction is usually solvent-free or finish in solvent.The example of solvent for use can comprise for example for example benzene, toluene and ethylbenzene, dimethylbenzene and 1,3 of hexane, heptane, octane and V.M.. naphtha, aromatic hydrocarbons of aliphatic hydrocarbon, 5-trimethylbenzene in the reaction; Halohydrocarbon is methylene dichloride, chloroform, tetracol phenixin, 1 for example, 2-ethylene dichloride, chlorobenzene, dichlorobenzene, trichlorobenzene and phenylfluoroform; Ethers for example 1,4-dioxane, tetrahydrofuran (THF), glycol dimethyl ether and methyl tert butyl ether; Ketone is methyl iso-butyl ketone (MIBK) and pimelinketone for example; The acid amides of acid is N for example, dinethylformamide; And their mixture.
After reaction was finished, directly concentrated reaction mixture or carry out aftertreatment was poured reaction mixture in the water into, uses organic solvent extraction then, and dry organic layer also concentrates.If desired, then purify by for example recrystallization or column chromatography technology.Thus, can obtain the pyridazin-3-ketone derivant of general formula (7).
2) technology 2-2
The compounds of this invention exists ShiShimonoseki ring to produce the pyridazin-3-ketone derivant of general formula (7) at sulfonic acid.
The example of used sulfonic acid can comprise tosic acid and Phenylsulfonic acid in reaction.The amount of used sulfonic acid is normally for the The compounds of this invention of each mole in reaction, and to more excessive, preferably 1 mole to excessive with catalytic amount.Temperature of reaction is normally in 30 °～250 ℃ scope.Reaction times is usually in the scope of moment to 240 hour.
Reaction is finished in solvent usually.The example of solvent for use can comprise for example for example benzene, toluene, ethylbenzene, dimethylbenzene and 1,3 of hexane, heptane, octane and V.M.. naphtha, aromatic hydrocarbons of aliphatic hydrocarbon, 5-trimethylbenzene in reaction; Halohydrocarbon is methylene dichloride, chloroform, tetracol phenixin, 1 for example, 2-ethylene dichloride, chlorobenzene, dichlorobenzene, trichlorobenzene and phenylfluoroform; Ethers for example 1,4-dioxane, tetrahydrofuran (THF), glycol dimethyl ether and methyl tert butyl ether; Ketone is methyl iso-butyl ketone (MIBK) and pimelinketone for example; And their mixture.
After reaction is finished, direct concentrated reaction mixture, or carry out aftertreatment, and reaction mixture is poured in the water, use organic solvent extraction then, dry organic layer also concentrates.If desired, then purify by for example recrystallization or column chromatography technology.Thus, can obtain the pyridazin-3-ketone derivant of general formula (7).
In technology 2, depend on condition, the formation of pyridazin-3-one ring can be attended by and replace a substituting group on the phenyl ring.
Can be listed in table 24 by the examples for compounds that technology 2 is produced.
The compound of general formula (15)
Table 24
| Compound | ??X | ??Y | ????B | ??R 2 | ??R 3 |
| ????5-1 ????5-2 ????5-3 ????5-4 ????5-5 ????5-6 ????5-7 ????5-8 ????5-9 ????5-10 ????5-11 ????5-12 | ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????F ????H | ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl ????Cl | ????OH ????OCH(CH 3) 2????OCH 2C≡CH ????OCH(CH 3)C≡CH ????OCH 2COOCH 3????OCH 2COOC 2H 5????COOCH 3????COOC 2H 5????OCH(CH 3) 2????OCH(CH 3) 2????OCH 2COOH ????H | ??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??CH 3??C 2H 5??H ??CH 3??CH 3 | ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H ????H |
The pyridazin-3-ketone derivant of general formula (7) has excellent weeding activity to following various injurious weeds when dry land is made blade face and soil treatment.
Polygalaceae:
Buckwheat knotweed (Polygonum convolvulus), Herb polygoni Lapathifolii (Polygonumlapathiolium), Binzhou knotweed (Polygonum pensylvanicum), lady's thumb (Polygonum persicaria), curled dock (Rumex crispus), Rheum obtusifolia Linn. (Rumex obtusifolius), giant knotweed (Polygonum cuspidatum)
Portulacaceae:
Purslane (Portulaca oleracea)
Caryophyllaceae:
Chickweed (Stellaria media)
Chenopodiaceae:
Lamb's-quarters (Chenopodium album), summer cypress (Kochia scoparia)
Amaranthaceae:
Redroot amaranth (Amaranthus retroflexus), slim amaranth (Amaranthushybridus)
Cruciferae:
Wild radish (Raphanus raphanistrum), charlock (Sinapisarvensis), shepherd's purse (Capsella brusa-pastoris)
Pulse family:
Big fruit sesbania (Sesbania exaltata), Cassia tora (Cassia obtusifolia), distortion acutifoliate podocarpium herb (Desmodium tortuosum), butch clover (Trifoliumrepens)
Malvaceae:
fiber crops (Abutilon theophrasti), thorn Radix sidae acutae (Sida spinosa)
Violaceae:
Field viola (Viola arvensis), circle wild pansy (Viola tricolor)
Rubiaceae:
Tender Catchweed Bedstraw Herb (cleavers) (Galium aparine)
Convolvulaceae:
Pharbitis nilChoisy (Ipomoea hederacea), Pharbitis purpurea (Ipomoeapurpurea), pharbitis nilChoisy (Ipomoea hederacea var.integriuscula), pitted morningglory (Ipomoea lacunosa), Herba seu Flos Convolvuli arvensis (Convolvulusarvensis)
Labiatae:
Deaf nettle (Lamium purpureum), benbie (Lamiumamplexicaule)
Solanaceae:
Thorn apple (Datura stramonium), black nightshade (Solanum nigrum)
Scrophulariaceae:
Birdseye speedwell (Veronica persica), Rhizoma Calystegiae Hederaceae veronica (Veronica hederaefolia)
Composite family:
Common cocklebur (Xanthium pensylvanicum), Sunflower Receptacle (Helianthus annuus), scentless mayweed (Matricaria perforata orinodora), Cornmarigold (Chrysanthemum segetum), pineappleweed (Matricariamatricarioides), american ragweed (Ambrosia artemisiifolia), great ragweed (Ambrosia trifida), Canada bitter fleabane (Erigeron canadensis), Japanesemugwort (Artemisia princeps) tall goldenrod (Solidagoaltissima)
Boraginaceae:
Field scorpion grass (Myosotis arvensis)
Asclepiadaceae:
Oblique Leah pleurisy foot (Asclepias syriaca)
Euphorbiaceae:
Wartwort (Euphorbia helioscopia), american euphorbia herb grass (Euphorbiamaculata)
Gramineae:
Barnyard grass (Echinochloa crus-galli), Herba Setariae Viridis (Setaria viridis), giantfoxtail (Setaria faberi), lady's-grass (Digitaria sanguinalis), yard grass (Eleusine indica), annual bluegrass (Poa annua), mouse tail amur foxtail (Alopecurusmyosuroides), wild avena sativa (Avena fatua), Ah thorn Bogao beam (Sorghumhalepense), Agropyron repens (Agropyron repens), downy brome (Bromustectorum), Bermuda grass (Cynodon dactylon), knucklegrass (Panicumdichotomiflorum), Texas panicnm (Panicum texanum), chinese sorghum (Sorghum vulgare)
Commelianaceae:
Herba Commelinae (Commelina communis)
Equisetaceae:
Meadow pine (Equisetum arvense)
Cyperaceae:
Cyperus iria L.scirpus maritimus (Cyperus iria), nutgrass flatsedge (Cyperus rotundus), chufa (Cyperus esculentus)
The pyridazin-3-ketone derivant of general formula (7) can obtain to prevent and kill off effectively injurious weed in soybean, corn and wheat no-tillage.
Gramineae:
Barnyard grass (Echinochloa oryzicola)
Scrophulariaceae:
common?falsepimpernel(Lindernia?procumbens)
Lythraceae:
Herba Clinopodii Polycephali, little three-coloured amaranth (Ammannia multiflora)
Elatinaceae:
Elatine?triandra
Cyperaceae:
Herba Cyperi Difformis (Cyperus difformis), firefly Lin (Scirpus juncoides), Herba Eleocharitis acicularis (Eleocharis acicularis), water rhizoma sparganic, water chestnut
Hai Shouke:
Sheathed Monochoria
Alismataceae:
Sagittaria pygmaea, arrowhead (sagittaria trifolia), narrow leaf rhizoma alismatis
Potamogetonaceae:
roundleaf?pondweed(Potamogeton?distinctus)
Umbelliferae:
A kind of Chinese celery (Oenanthe javanica)
Preventing and kill off that the pyridazin-3-ketone derivant of general formula (7) can be remained valid grows in orchards, pasture, lawn, forest, water route, the injurious weed in irrigation canals and ditches or other bare place.
The derivative of the pyridazin-3-one of general formula (7) will be for being grown in the water route, and the various deleterious aquatic weed of irrigation canals and ditches or other waterside for example water hyacinth has weeding activity.
The pyridazin-3-ketone derivant of general formula (7) is for staple crop for example corn, wheat, barley, paddy rice, Chinese sorghum, soybean, cotton, beet, peanut, Sunflower Receptacle and cassava; The flower garden crop is flowers for example, see and taste plant and vegetable crop; And show selectivity between injurious weed in the early rice of transplanting and the crop.
The pyridazin-3-ketone derivant of general formula (7) as the effective constituent of weedicide the time, usually with solid or liquid vehicle or thinner, tensio-active agent and the mixing of other auxiliary agent, to be processed into for example missible oil, wettable powder, flowing agent, granule, preparations such as emulsifiable concentrate or water-dispersible granules.
These preparations contain the pyridazin-3-ketone derivant of a kind of general formula as effective constituent (7) at least, and its content is 0.001% to 80% of total formulation weight amount, and preferred 0.005% to 70%.
The example of solid carrier or thinner can comprise the fine powder or the particle of following material: mineral substance is kaolin for example, attapulgite, wilkinite, carclazyte, pyrophyllite, talcum, diatomite and calcite; Organic substance is walnut shell flour for example; Water soluble organic substance matter is urea for example; Inorganic salt are ammonium sulfate for example; And the synthetic hydrated silica, the example of liquid vehicle or thinner can comprise methylnaphthalene, phenyl xylyl ethane, and alkylbenzene, for example, and dimethylbenzene; Alcohols is Virahol, ethylene glycol and cellosolvo for example; The ester class is bialkyl ortho phthalate for example; Ketone is acetone, pimelinketone and isophorone for example; Dormant oils is machinery oil for example; Rape oil is soybean oil and Oleum Gossypii semen for example; Dimethyl sulfoxide (DMSO), N, dinethylformamide, acetonitrile, N-methylpyrroline ketone, and water.
As emulsifying agent, the example of the tensio-active agent of dispersion agent and spreader-sticker can comprise aniorfic surfactant, for example the phosphoric acid salt of alkyl-sulphate, alkylsulfonate, alkylaryl sulphonate, dialkyl group sulfo-succinate and polyoxyethylene alkylaryl ether; And nonionic surface active agent, for example Voranol EP 2001, polyoxyethylene alkylaryl ether, polyoxyethylene polyoxypropylene block copolymer, fatty acid esters of sorbitan and Vykamol Sorbitol 8B.
The example of the auxiliary agent that is used to process can comprise sulfonated lignin, alginate, polyvinyl alcohol, gum arabic, carboxymethyl cellulose (CMC) and bisulphate isopropyl ester (PAP).
The pyridazin-3-ketone derivant of general formula (7) is prepared usually, and before the bud of injurious weed or behind the bud with soil, blade face or the processing of pouring water.Soil treatment can comprise native list processing and mix soil and handle.Foliar treatment can be included in to be used on the plant and directly uses, and in directly using, chemical only is applied to injurious weed and does not contact crop.
When the pyridazin-3-ketone derivant of general formula (7) is used as the effective constituent of weedicide, amount of application is usually at 0.01～10000g/ha, in the scope of preferred 1～8000g/ha, but it can be with weather condition, formulation, time of application, application process, edaphic condition, crop, injurious weed and other factors and change.Missible oil for example, wettable powder, flowing agent, various formulations such as emulsifiable concentrate or water-dispersible granules all will for example be used 10～1000 premium on currency dilution back of spreader-sticker with selecting to contain a kind of auxiliary agent arbitrarily with per hectare according to the amount of saying previously usually.For example the formulations such as flowing agent of granule or some type need not be diluted usually and can be used.
If desired, the example of used auxiliary agent also can comprise polyoxyethylene resinous acid (ester), sulfonated lignin except above-mentioned, rosin ester, dinaphthyl methane-disulfonic acid salt, dense dose of crop oil, and rape oil for example soybean oil, Semen Maydis oil, Oleum Gossypii semen and sunflower oil.
Embodiment
By following production example, processing and implementation example and experimental example will further specify the present invention; The present invention is not subjected to the restriction of these embodiment.
1) produces The compounds of this invention by technology 1
Production example 1-1
In room temperature, under the nitrogen protection, with 0.285g 3,3,3-three fluoro-2-oxo-propanal 1-(4-chloro-2-fluoro-5-isopropyl phenyl hydrazone) are dissolved in the 1.7ml pyridine.Add 0.086ml piperidines and 0.149g Methylpropanedioic acid mono ethyl ester in this solution, then with mixture heating up to 90 ℃ and stirred 2 hours.Reaction soln is reduced to room temperature and concentrating under reduced pressure.Residue dilutes with the 100ml ether.The solution of dilution is washed 2 times with 20ml 3N HCl, washes 1 time with the 30ml saturated sodium bicarbonate solution, uses dried over mgso, filtration, and under reduced pressure concentratedly obtain thick product.Thick product is handled through column chromatography and is obtained 0.224g The compounds of this invention 1 217, is following 2 mixture of isomers.Isomer 1
1H-NMR (300MHz, CDCl
3, TMS) δ (ppm): 1.25 (t, 3H), 1.31 (d, 3H), 1.37 (d, 3H), 1.38 (d, 3H), 3.24 (q, 1H), 4.16 (q, 2H), 4.49 (m, 1H), 4.68 (s, 1H), 7.02 (d, 1H), 7.05 (d, 1H), 7.48 (brs, 1H), 8.26 (brs, 1H). isomer 2
1H-NMR(300MHz，CDCl
3，TMS)δ(ppm)：1.26(t，3H)，1.36(d，9H)，3.20(q，1H)，4.20(m，2H)，4.47(m，1H)，4.84(s，1H)，6.98(d，1H)，7.04(d，1H)，7.20(brs，1H)，8.06(brs，1H).
Production example 1-2
At first, with 5.0g 3,3,3-three fluoro-2-oxo-propanal 1-(4-chloro-2-fluoro-5-o-phenyl-isopropyl hydrazone) are dissolved in the 20g toluene.Add 2.46g Methylpropanedioic acid mono ethyl ester and 3.1g triethylamine in this solution, this mixture heated 8 hours under refluxing.After reaction was finished, reaction soln was reduced to room temperature and is poured in the water, extracts this mixture with toluene again.Organic layer dilute hydrochloric acid washes with water then, drying, and concentrate.Residue is handled through column chromatography and is obtained 3.6g The compounds of this invention 1-217.
Production example 1-3
At first, with 5.0g 3,3,3-three fluoro-2-oxo-propanal 1-(4-chloro-2-fluoro-5-o-phenyl-isopropyl hydrazone) are dissolved in 20g 1, in the 4-dioxane.Add 2.46g Methylpropanedioic acid mono ethyl ester and 2.51g sodium acetate in this solution, this mixture heated 24 hours under refluxing.After reaction was finished, reaction soln was reduced to room temperature and is poured in the water, extracts this mixture with toluene again.Organic layer dilute hydrochloric acid washes with water then, drying, and concentrate.Residue obtains 3.95g The compounds of this invention 1-217 after column chromatography is handled.
Production example 1-4
At first, with 5.0g 3,3,3-three fluoro-2-oxo-propanal 1-(4-chloro-2-fluoro-5-o-phenyl-isopropyl hydrazone) are dissolved in 20g 1, in the 4-dioxane.Add 2.46g Methylpropanedioic acid mono ethyl ester and 4.22g salt of wormwood in this solution, this mixture heated 6 hours under refluxing.After reaction was finished, reaction soln was reduced to room temperature and is poured in the water, extracts this mixture with toluene again.Organic layer dilute hydrochloric acid washes with water then, and is dry and concentrated.Residue is handled through column chromatography, obtains 1.24g The compounds of this invention 1-217.
2) produce pyridazin-3-ketone derivant by technology 2 from The compounds of this invention.
Production example 2-1
Under nitrogen protection, 1-217 is dissolved in the 2.0ml toluene with the 0.224g The compounds of this invention.In this mixture, add 0.189g tosic acid monohydrate, this mixture heating up is refluxed stirred 3 hours.Reaction soln is reduced to room temperature and is diluted with the 100ml ether.The solution of dilution is washed 1 time with the 30ml saturated sodium bicarbonate aqueous solution, washes 1 time with the 30ml saturated sodium-chloride water solution again, uses dried over mgso, filtration, and under reduced pressure concentratedly obtain thick product.Thick product is handled through column chromatography and is obtained 0.126g 2-(2-fluoro-4-chloro-5-o-phenyl-isopropyl)-4-methyl-5-trifluoromethyl pyridazin-3-one, compound 5-2.
1H-NMR(300MHz，CDCl
3，TMS)δ(ppm)：1.38(d，6H，J＝6.3Hz)，2.43(q，3H，J＝2.0Hz)，4.47(m，1H)，6.99(d，1H，J＝5.0Hz)，7.29(d，1H，J＝9.5Hz)，8.00(s，1H).
Production example 2-2
At first, 1.0g The compounds of this invention 1-217 is dissolved in the 5.0g dimethylbenzene.In this solution, add 0.35g 1,8-diazabicyclo (5.4.0) 11 carbon-7-alkene, this is reflected at the heating down 2 hours that refluxes.After reaction was finished, reaction soln was reduced to room temperature and is poured in the water, extracts this mixture with toluene.Organic layer washes with water, drying, and concentrate.Residue is handled through column chromatography and is obtained 0.22g 2-(2-fluoro-4-chloro-5-o-phenyl-isopropyl)-4-methyl-5-trifluoromethyl pyridazin-3-one, compound 5-2.
The preparation of the starting raw material that adopts in technology 1 has been described below with reference to embodiment.
Reference example 1
Down with 6.6g (24.3 mmole) 1,1-two bromo-3,3,3-trifluoroacetone are added to 5.3g (53.5 mmole) sodium acetate and are dissolved in the solution in about 100ml water ice-cooled, and this is reflected at 70 ℃ and carried out 20 minutes.Reaction soln is placed and to be chilled to room temperature, is dissolved in solution in about 20ml ether toward wherein adding the different third oxygen phenylhydrazine of 5.8g (21.5 mmole) 2-fluoro-4-chloro-5-, and this mixture was stirring at room 1 hour.Tell organic layer,, use anhydrous magnesium sulfate drying, and evaporate and remove ether, obtain 6.5g (20.0 mmole) 3,3,3-three fluoro-2-oxo-propanal 1-(4-chloro-2-fluoro-5-o-phenyl-isopropyl hydrazone), compound 3-3 with 10ml saturated sodium-chloride water solution washing 1 time.
1H-NMR(250MHz，CDCl
3，TMS)δ(ppm)：1.39(d，6H，J＝6.0Hz)，4.38-4.52(m，1H)，7.15(d，1H，J＝10.5Hz)，7.22(d，1H，J＝7.3Hz)，7.43(q，1H，J＝1.7Hz)，9.18(brs，1H)
Reference example 2
Production technique based on following reaction formula:
Will be from the different third oxygen aniline of 20.3g 4-chloro-2-fluoro-5-, the 20ml concentrated hydrochloric acid, compound (I-1) the deutero-diazonium salt acidic solution of 20ml water and the preparation of 7.3g Sodium Nitrite, be added drop-wise to 20.1g 4 being lower than under 10 ℃ the temperature, 4,4-trifluoroacetic ethyl acetoacetate and 25g sodium acetate are dissolved in the solution in the 150ml water.After dripping, this mixture at room temperature stirred 1 hour, by filter collecting the crystallization that is produced, washed with water, and drying obtains the compound (II-1) (yield 85%) in the reaction formula in the above.
The 15.9g compound (II-1) and the single hydronium(ion) oxidation of the 1.7g lithium of above-mentioned reaction gained are added to 30ml 1, and in the mixture of 4-dioxane and 3ml water, this mixture heating up refluxed 6 hours.Reaction soln is poured in the frozen water,, used ethyl acetate extraction with the dilute hydrochloric acid neutralization.Organic layer is dry and concentrated, and the residue hexane wash obtains 11.3g compound (III-1) (yield 76.3%).
Then, the 7.4g compound (III-1) of above-mentioned reaction gained is dissolved in 42ml N, in the dinethylformamide.Reaction soln is heated to 100 ℃, and under same temperature, kept 30 minutes, be chilled to room temperature then.Reaction soln is poured in the water, and used ethyl acetate extraction.Organic layer washs with dilute hydrochloric acid, uses anhydrous magnesium sulfate drying, concentrates, and obtains 5.9g compound 3-3, the compound (IV-1) (yield 90%) in the promptly above-mentioned reaction formula.
Reference example 3
The production of malonic acid monoester compound
At first, the 20.0g methyl-malonic ester is dissolved in 30g water and the 30g alcoholic acid mixing solutions.The 9.6g 48%NaOH aqueous solution is added drop-wise in this solution, and this mixture is high degree of agitation 7 hours at room temperature.After reaction is finished, reaction soln is transferred to pH3, and under reduced pressure concentrate by adding 35% hydrochloric acid.In residue, add 80g water, use this mixture of 40g ethyl acetate extraction 2 times again.Merge organic layer and under reduced pressure concentrated.In residue, add the 100g normal hexane, by filtering the crystallization of collecting precipitation.Filtrate under reduced pressure concentrates, and obtains 16.1g Methylpropanedioic acid mono ethyl ester.
1H-NMR(250MHz，CDCl
3，TMS)δ(ppm)：1.29(t，3H，J＝7.1Hz)，1.44(d，3H，J＝7.3Hz)，3.48(q，1H，J＝7.3Hz)，4.22(q，2H，J＝7.1Hz)，10-13(brs，1H).
Following formulation processing and implementation example has illustrated the application of the pyridazin-3-ketone derivant of general formula (7) as the herbicidal activity composition.In these embodiments, these derivatives represent that with the compound number that is listed in top table 24 " part " is the weight meter.
Formulation processing and implementation example 1
Compound 5-1 to 5-9 respectively gets 50 parts, and 3 parts of calcium lignin sulphonates, 2 parts of Sodium Lauryl Sulphate BP/USPs and 45 parts of warps of synthetic hydrated silica are fully pulverized and mixed the wettable powder that promptly obtains each compound.
Formulation processing and implementation example 2
Compound 5-1 to 5-9 respectively gets 10 parts, 14 parts of polyoxyethylene styryl phenyl ethers, 6 parts of calcium dodecylbenzene sulphonates, 35 parts of dimethylbenzene and 35 portions of missible oil that promptly obtain each compound through thorough mixing of pimelinketone.
Formulation processing and implementation example 3
Each 2 parts of compound 5-1 to 5-9,2 parts of synthetic hydrated silicas, 2 parts of calcium lignin sulphonates, 30 parts of wilkinites and 64 parts of warps of kaolin are fully pulverized and are mixed, and toward wherein adding entry, this mixture are fully kneaded again again, granulation, and dry promptly obtains the granule of each compound.
Formulation processing and implementation example 4
Compound 5-1 to 5-9 respectively gets 25 parts, and 25 parts in 50 parts of 10% polyvinyl alcohol water solutions and water is through mixing, and grinds this mixture, is 5 μ m or littler until mean particle size, promptly obtains the flowing agent of each compound.
Following experimental example shows the activeconstituents of the pyridazin-3-ketone derivant useful as herbicides of general formula (7).
Weeding activity is estimated with 0 to 5 index 6 ranks, that is to say and use digital " 0 ", " 1 ", " 2 ", " 3 ", " 4 " or " 5 " represent that wherein the implication of " 0 " is to handle and untreated test plant, be germinate between injurious weed and the crop and extent of growth on do not have difference or difference very little, the implication of " 5 " is that dead fully or their germination or grow of the test plant of handling is suppressed fully.When classifying " 4 " or " 5 " as, weeding activity is excellent, when classifying " 3 " as or dissatisfied when lower.
Experimental example 1 is in the foliar treatment of dry land
With the soil diameter 10cm that packs into, in the cylindrical plastic basin of dark 10cm.In soil, test plant grew in the greenhouse 19 days with the planting seeds of the subspecies (integriuscula) of pharbitis nilChoisy and fiber crops.According to formulation processing and implementation example 2, test compound is processed into missible oil, and dilutes it to aforementioned concentration with the water that contains spreader-sticker.With the consumption of atomizer diluent is sprayed on the blade face of test plant equably by 1000 liters/hectare.After the dispenser, test plant grew in the greenhouse 19 days, and the mensuration weeding activity the results are shown in table 25.
Table 25
| Test compound | Activeconstituents amount of application (g/ha) | Weeding activity | |
| The subspecies of pharbitis nilChoisy | The fiber crops | ||
| ????5-2 | ????500 | ????5 | ????5 |
Experimental example 2 is in the native list processing of dry land
Soil is packed in the cylindrical plastic basin of diameter 10cm and dark 10cm.During the seed kind of the subspecies (integriucula) of pharbitis nilChoisy and fiber crops buried.According to formulation processing and implementation example 2 test compound is processed into missible oil, and is diluted with water to aforesaid concentration.With the consumption of atomizer, diluent evenly is sprayed on the soil table of basin by 1000 liters/hectare.After the dispenser, test plant grew in the greenhouse 19 days, and measured weeding activity.The results are shown in table 26.
Table 26
| Test compound | Activeconstituents amount of application (g/ha) | Weeding activity | |
| The subspecies of pharbitis nilChoisy | The fiber crops | ||
| ????5-2 | ????500 | ????5 | ????5 |
Experimental example 3 is in the processing of pouring water of dry land
Soil is packed in the cylindrical plastic basin of diameter 9cm and dark 11cm, and sow the seed of barnyard grass therein.These basins are all poured water into the paddy field, and test plant was greenhouse growth 7 days.According to formulation processing and implementation example 2 test compound is processed into missible oil, water is diluted to aforesaid concentration with it again.By 50 liters/acre amount diluent is imposed on water surface in the basin with syringe.After the dispenser, test plant grew in the greenhouse 19 days, and measured weeding activity, the results are shown in table 27.
Table 27
| Test compound | Activeconstituents amount of application (g/ha) | Weeding activity |
| Barnyard grass | ||
| ????5-2 | ????250 | ????5 |
Industrial usability
Carboxylic ester derivative disclosed herein easily is transformed into pyridazin-3-ketone derivant, and therefore, can be used as their important intermediate. With a kind of suitable method, the technique of producing pyridazin-3-ketone derivants from these intermediates is the contributions greatly to the exploitation of the pyridazine herbicides with excellent activity of weeding.
Claims (13)
1. the carboxylicesters of general formula (1):
Wherein R is C
1-C
6Alkyl, R
2And R
3Be respectively hydrogen or C
1-C
3Alkyl and Q phenyl for selecting to replace.
2. according to the carboxylicesters of claim 1, wherein Q is the Q-1 of general formula (2), Q-2, and Q-3, Q-4 or Q-5:
Wherein X is a hydrogen or halogen;
Y is halogen, nitro, cyano group or trifluoromethyl;
Z
1And Z
2Be respectively oxygen or sulphur;
N is 0 or 1;
R
4Be hydrogen or C
1-C
3Alkyl;
R
5Be C
1-C
6Alkyl, C
1-C
6Alkylhalide group, (C
3-C
6Cycloalkyl) C
1-C
6Alkyl, C
3-C
6Alkenyl, C
3-C
6Halogen alkenyl, C
3-C
6Alkynyl group, C
3-C
6Halogen alkynyl group, cyano group C
1-C
6Alkyl, C
1-C
4Alkoxy C
1-C
4Alkyl, C
1-C
3Alkoxy C
1-C
3Alkoxy C
1-C
3Alkyl, carboxyl C
1-C
6Alkyl, (C
1-C
6Alkoxyl group) carbonyl C
1-C
6Alkyl, { (C
1-C
4Alkoxyl group) C
1-C
4Alkoxyl group } carbonyl C
1-C
6Alkyl, (C
3-C
8Cycloalkyloxy) carbonyl C
1-C
6Alkyl ,-CH
2CON (R
12) R
13,-CH
2COON (R
12) R
13,-CH (C
1-C
4Alkyl) CON (R
12) R
13-CH (C
1-C
4Alkyl) COON (R
12) R
13, C
1-C
4Alkylthio C
1-C
4Alkyl or hydroxyl C
1-C
6Alkyl;
R
12And R
13Be respectively hydrogen, C
1-C
6Alkyl, C
3-C
8Cycloalkyl, C
1-C
6Alkylhalide group, C
3-C
6Alkenyl, C
3-C
6Alkynyl group, cyano group C
1-C
6Alkyl, C
1-C
4Alkoxy C
1-C
4Alkyl, C
1-C
4Alkylthio C
1-C
4Alkyl, carboxyl C
1-C
6Alkyl, (C
1-C
6Alkoxyl group) carbonyl C
1-C
6Alkyl, (C
3-C
8Cycloalkyloxy) carbonyl C
1-C
6Alkyl, (C
1-C
6Alkyl) ketonic oxygen C
2-C
6Alkyl, (C
1-C
6Alkyl) carbonylamino C
2-C
6Alkyl, hydroxyl C
2-C
6Alkyl, any benzyl of selecting replacement, the phenyl or the { (C of selection replacement arbitrarily
1-C
4Alkoxyl group) C
1-C
4Alkyl } carbonyl C
1-C
6Alkyl, or R
12And R
13Connect together and form trimethylene, tetramethylene, penta-methylene, vinyloxy group ethylene or ethene sulfenyl ethylene;
R
6Be C
1-C
6Alkyl, C
1-C
6Alkylhalide group, cyano group, carboxyl, hydroxyl C
1-C
6Alkyl, C
1-C
6Alcoxyl C
1-C
6Alkyl, C
1-C
6Alcoxyl C
1-C
6Alcoxyl C
1-C
6Alkyl, (C
1-C
6Alkyl) ketonic oxygen C
1-C
6Alkyl, (C
1-C
6Alkylhalide group) ketonic oxygen C
1-C
6Alkyl or (C
1-C
6Alcoxyl) carbonyl;
R
7Be hydrogen or C
1-C
6Alkyl;
R
8Be C
1-C
6Alkyl, C
1-C
6Alkylhalide group, hydroxyl C
1-C
6Alkyl, C
1-C
4Alcoxyl C
1-C
4Alkyl, C
1-C
3Alcoxyl C
1-C
3Alcoxyl C
1-C
3Alkyl, (C
1-C
6Alkyl) ketonic oxygen C
1-C
6Alkyl, (C
1-C
6Alkylhalide group) carbonyl C
1-C
6Alkyl, carboxyl, carboxyl C
1-C
6Alkyl, (C
1-C
8Alcoxyl) carbonyl, (C
1-C
6Alkyl halide oxygen) carbonyl, (C
3-C
10Cycloalkanes oxygen) carbonyl, (C
3-C
8Alkene oxygen) carbonyl, (C
3-C
8Alkyne oxygen) carbonyl, (C
1-C
6Alkyl) aminocarboxyl, two (C
1-C
6Alkyl) aminocarboxyl, (C
1-C
6Alkyl) aminocarboxyl oxygen C
1-C
6Alkyl or two (C
1-C
6Alkyl) aminocarboxyl oxygen C
1-C
6Alkyl;
B is hydrogen, halogen, nitro, cyano group, chlorosulfonyl, OR
1, SR
1, SO
2OR
21, COOR
22, CR
23=CR
24COOR
25, or CH
2CHWCOOR
25
W is hydrogen, chlorine or bromine;
R
1For hydrogen, C1-C
6Alkyl, C1-C
6Alkylhalide group, C3-C
8Cycloalkyl, benzyl, C3-C
6Alkenyl, C3-C
6Halogen alkenyl, C3-C
6Alkynyl group, C3-C
6Halogen alkynyl group, cyano group C1-C
6Alkyl, C1-C
4Alkoxy C1-C
4Alkyl, C1-C
4Alkylthio group C1-C
4Alkyl, carboxyl C1-C
6Alkyl, (C1-C
8Alcoxyl) carbonyl C1-C
6Alkyl, (C1-C
6Alkyl halide oxygen) carbonyl C1-C
6Alkyl, { (C1-C
4Alcoxyl) C1-C
4Alcoxyl } carbonyl C1-C
6Alkyl, (C3-C
8Cycloalkanes oxygen) carbonyl C1-C
6Alkyl, (C3
-C
8Cycloalkyl) C1-C
6Alkoxy carbonyl group C1-C
6Alkyl ,-CH2COON(R
12)R
13、-CH-(C
1-C
4Alkyl) COON (R12)R
13、
-CH
2CON(R
12)R
13、-CH(C
1-C
4Alkyl) CON (R12)R
13、C
2-C
6Alkenyl oxygen carbonyl C1-C
6Alkyl, C3-C
6Halogen alkenyl oxygen carbonyl C1-C
6Alkyl, C3
-C
6Chain oxy-acetylene carbonyl C1-C
6Alkyl, C3-C
6Halogen alkynyl group oxygen carbonyl C1-C
6Alkyl, (C1-C
6Alkylthio group) carbonyl C1-C
6Alkyl, (C1-C
6Alkyl halide sulphur) carbonyl C1-C
6Alkyl, (C3-C
6Alkenyl sulphur) carbonyl C1-C
6Alkyl, (C3-C
6Halogen alkene sulphur) carbonyl C1-C
6Alkyl, (C3-C
6Alkyne sulphur) carbonyl C1-C
6Alkyl, (C3-C
6Halogen alkyne sulphur) carbonyl C1-C
6Alkyl, (C3-C
8Cycloalkanes sulphur) carbonyl C1
-C
6Alkyl, (C3-C
8Ring alkyl halide sulphur) carbonyl C1-C
6Alkyl, ((C3-C
8Cycloalkyl) C1-C
6Alkane sulphur) carbonyl C1-C
6Alkyl, two (C1-C
6Alkyl) C=NO carbonyl C1-C
6Alkyl, (selecting arbitrarily the benzyl sulphur that replaces) carbonyl C1-C
6Alkyl, (selecting arbitrarily the benzene sulphur that replaces) carbonyl C1-C
6Alkyl, hydroxyl C2-C
6Alkoxy carbonyl group C1-C
6Alkyl, (C1-C
6Alkyl) carbonyl oxygen C2-C
6Alkoxy carbonyl group C1-C
6Alkyl, (C1-C
6Alkyl) carbonyl amino C2-C
6Alkoxy carbonyl group C1-C
6Alkyl, { (C1-C
6Alcoxyl) carbonyl C1-
C
6Alkyl } oxygen carbonyl C1-C
6Alkyl, hydroxyl C1-C
6Alkyl, C1-C
6Alkoxy carbonyl group, C1-C
6Alkylhalide group oxygen carbonyl, C3-C
8Cycloalkyloxy group carbonyl, C3-C
6Chain ene keto carbonyl, benzyloxycarbonyl group, C1-C
6Alkyl-carbonyl, any benzyloxycarbonyl group C that replaces that selects1-C
6Alkyl, any carbobenzoxy C that replaces that selects1-C
6Alkyl, any furans oxygen carbonyl C that replaces that selects1
-C
6Alkyl, any furyl C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any thiophene oxygen carbonyl C that replaces that selects1-C
6Alkyl, any thiophene C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any pyrroles's oxygen carbonyl C that replaces that selects1-C
6Alkyl, any pyrrole radicals C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any imidazoles oxygen carbonyl C that replaces that selects1-C
6Alkyl, any imidazole radicals C that replaces that selects1-C
6Alkoxy carbonyl group C1
-C
6Alkyl, any pyrazoles oxygen carbonyl C that replaces that selects1-C
6Alkyl, any pyrazolyl C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any thiazole oxygen carbonyl C that replaces that selects1
-C
6Alkyl, any thiazolyl C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any replacement De oxazole oxygen carbonyl C that selects1-C
6Alkyl, any replacement De oxazolyl C that selects1-
C
6Alkoxy carbonyl group C1-C
6Alkyl, any isothiazole oxygen carbonyl C that replaces that selects1-C
6Alkyl, any isothiazolyl C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any replacement De isoxazole oxygen carbonyl C that selects1-C
6Alkyl, any replacement De isoxazolyl C that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any pyridine oxygen carbonyl C that replaces that selects1-C
6Alkyl, any pyridine radicals C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any pyrazine oxygen carbonyl C that replaces that selects1-C
6Alkyl, any pyrazinyl C that replaces that selects1-C
6Alkoxy carbonyl group C1-
C
6Alkyl, any pyrimidine oxygen carbonyl C that replaces that selects1-C
6Alkyl, any pyrimidine radicals C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any pyridazine oxygen carbonyl C that replaces that selects1-
C
6Alkyl, any pyridazinyl C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any indoline oxygen carbonyl C that replaces that selects1-C
6Alkyl, any indolinyl C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any indoles oxygen carbonyl C that replaces that selects1-C
6Alkyl, any indyl C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any indazole oxygen carbonyl C that replaces that selects1-C
6Alkyl, any indazolyl C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any quinoline oxygen carbonyl C that replaces that selects1-C
6Alkyl, any quinolyl C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, any isoquinolin oxygen carbonyl C that replaces that selects1-C
6Alkyl, any isoquinolyl C that replaces that selects1-C
6Alkoxy carbonyl group C1-C
6Alkyl, or the group of general formula (3):
R wherein14For C1-C
5Alkyl, R15For hydrogen, hydroxyl or-O-COR16Group; And R16For C1-C
6Alkyl, C1-C
6Alkylhalide group, C3-C
6Alkenyl, C3-C
8Cycloalkyl, the benzyl or the C that select the phenyl that replaces, any selection to replace arbitrarily1-C
6Alkoxyl, or
The group of general formula (4):
R wherein
17Be hydrogen, halogen or C
1-C
6Alkyl; R
18Be C
3-C
8Cycloalkyl, benzyl, with the C of an epoxy group(ing)
2-C
10Alkyl, C
3-C
8Cycloalkyl C
1-C
6Alkyl, C
3-C
8Cycloalkyl C
2-C
6Alkenyl, on same carbon atom, be with OR
19And OR
20Substituent C
1-C
6Alkyl, on same carbon atom, be with OR
19And OR
20Substituent C
2-C
6Alkenyl, on same carbon atom, be with SR
19And SR
20Substituent C
1-C
6Alkyl, on same carbon atom, be with SR
19And SR
20Substituent C
2-C
6Alkenyl, carboxyl C
2-C
6Alkenyl, (C
1-C
8Alcoxyl) carbonyl C
2-C
6Alkenyl, (C
1-C
8Alkyl halide oxygen) carbonyl C
2-C
6Alkenyl, { (C
1-C
4Alcoxyl) C
1-C
4Alcoxyl } carbonyl C
2-C
6Alkenyl or (C
3-C
8Cycloalkanes oxygen) carbonyl C
2-C
6Alkenyl; R
19And R
20Be respectively C
1-C
6Alkyl or C
1-C
6Alkylhalide group, or R
19And R
20Connect together the trimethylene that forms the ethylene selecting arbitrarily to replace with halogen, select arbitrarily to replace with halogen, the tetramethylene of selecting arbitrarily to replace with halogen, select the penta-methylene that replaces arbitrarily with halogen, or select the vinyloxy group ethylene that replaces arbitrarily with halogen;
R
21Be C
1-C
6Alkyl, C
1-C
6Alkylhalide group, C
3-C
8Cycloalkyl, C
3-C
6Alkenyl, C
3-C
6Halogen alkenyl, C
3-C
6Alkynyl group, C
3-C
6Halogen alkynyl group or benzyl;
R
22Be hydrogen, C
1-C
6Alkyl, C
1-C
6Alkylhalide group, C
3-C
8Cycloalkyl, benzyl, C
3-C
6Alkenyl, C
3-C
6Halogen alkenyl, C
3-C
6Alkynyl group, C
3-C
6Halogen alkynyl group, cyano group C
1-C
6Alkyl, C
1-C
4Alcoxyl C
1-C
4Alkyl, C
1-C
4Alkane sulphur C
1-C
4Alkyl, carboxyl C
1-C
6Alkyl, (C
1-C
8Alcoxyl) carbonyl C
1-C
6Alkyl, (C
1-C
6The halogen alkoxyl group) carbonyl C
1-C
6Alkyl, { (C
1-C
4Alcoxyl) C
1-C
4Alcoxyl } carbonyl C
1-C
6Alkyl, (C
3-C
8Cycloalkanes oxygen) carbonyl C
1-C
6Alkyl, (C
1-C
6Alkyl) carbonyl C
1-C
6Alkyl, (C
1-C
6Alkylhalide group) carbonyl C
1-C
6Alkyl, { (C
1-C
4Alcoxyl) C
1-C
4Alkyl } carbonyl C
1-C
6Alkyl, (C
3-C
8Cycloalkyl) carbonyl C
1-C
6Alkyl ,-CH
2COON (R
26) R
27,-CH (C
1-C
4Alkyl) COON (R
26) R
27,-CH
2CON (R
26) R
27,-CH-(C
1-C
4Alkyl) CON (R
26) R
27, { (C
1-C
6Alcoxyl) carbonyl C
1-C
6Alkyl } oxygen carbonyl C
1-C
6Alkyl or hydroxyl C
1-C
6Alkyl;
R
26And R
27Be respectively hydrogen, C
1-C
6Alkyl, C
1-C
6Alkylhalide group, C
3-C
6Alkenyl, C
3-C
6Alkynyl group, cyano group C
1-C
6Alkyl, C
1-C
4Alcoxyl C
1-C
4Alkyl, C
1-C
4Alkylthio C
1-C
4Alkyl, carboxyl C
1-C
6Alkyl, (C
1-C
6Alcoxyl) carbonyl C
1-C
6Alkyl, (C
3-C
8Cycloalkanes oxygen) carbonyl C
1-C
6Alkyl or { (C
1-C
4Alcoxyl) C
1-C
4Alkyl } carbonyl C
1-C
6Alkyl, or R
26And R
27Connect together and form tetramethylene, penta-methylene or vinyloxy group ethylene;
R
23And R
24Be respectively hydrogen, halogen or C
1-C
6Alkyl; With
R
25Be hydrogen, C
1-C
6Alkyl, C
1-C
6Alkylhalide group, C
3-C
8Cycloalkyl or C
3-C
6Alkenyl.
3. according to the carboxylicesters of claim 2, wherein Q is Q-1.
4. according to the carboxylicesters of claim 3, wherein B is a hydrogen, OR
1Or SR
1, and R
1As the definition in the claim 2.
5. according to the carboxylicesters of claim 3, wherein Y is a halogen, and B is a hydrogen, C
1-C
6Carbalkoxy, OR
1Or SR
1, and R
1Be hydrogen, C
1-C
6Alkyl, C
1-C
6Alkylhalide group, C
3-C
8Cycloalkyl, benzyl, C
3-C
6Alkenyl, C
3-C
6The halogen alkenyl, C
3-C
6Alkynyl group, C
3-C
6The halogen alkynyl group, cyano group C
1-C
6Alkyl, C
1-C
4Alcoxyl C
1-C
4Alkyl, C
1-C
4Alkane sulphur C
1-C
4Alkyl, carboxyl C
1-C
6Alkyl, (C
1-C
8Alcoxyl) carbonyl C
1-C
6Alkyl, (C
1-C
6Alkyl halide oxygen) carbonyl C
1-C
6Alkyl, { (C
1-C
4Alcoxyl) C
1-C
4Alcoxyl } carbonyl C
1-C
6Alkyl, (C
3-C
8Cycloalkanes oxygen) carbonyl C
1-C
6Alkyl, C
1-C
6Carbalkoxy, C
1-C
6Alkyl halide oxygen carbonyl, C
3-C
8Cycloalkoxycarbonyl, C
3-C
6Chain ene keto carbonyl, carbobenzoxy-(Cbz) or C
1-C
6Alkyl-carbonyl.
6. according to the carboxylicesters of claim 3, wherein Y is a halogen, and B is OR
1Or SR
1, and R
1Be hydrogen or C
1-C
6Alkyl.
7. according to the carboxylicesters of claim 5, wherein B is OR
1
8. according to the carboxylicesters of claim 6, wherein B is OR
1
9. according to claim 1, each carboxylicesters in 2,3,4,5,6,7 or 8, wherein R is methyl or ethyl.
10. produce the technology of general formula (1) compound, be included in alkali and have down the hydrazone compound of general formula (5):
Wherein Q and R
3As defined in claim 1, with the malonic acid monoester derivatives reaction of general formula (6)
Wherein R and R
2As defined in claim 1.
11. according to the technology of claim 10, wherein alkali is sodium acetate, salt of wormwood, 1,8-diazabicyclo (5.4.0) 11 carbon-7-alkene or triethylamine.
12. produce the technology of the pyridazin-3-ketone derivant of general formula (7):
Q wherein, R
2And R
3As defined in claim 1, this technology is included in sulfonic acid and exists down, the pass ring of general formula (1) compound.
13. produce the technology of the pyridazin-3-ketone derivant of general formula (7), this technology is included in 1, there is the pass ring of general formula (1) compound down in 8-diazabicyclo (5.4.0) 11 carbon-7-alkene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97180772 CN1240422A (en) | 1996-10-21 | 1997-10-16 | Production of pyridazine herbicides |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP278256/96 | 1996-10-21 | ||
| CN 97180772 CN1240422A (en) | 1996-10-21 | 1997-10-16 | Production of pyridazine herbicides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1240422A true CN1240422A (en) | 2000-01-05 |
Family
ID=5177861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97180772 Pending CN1240422A (en) | 1996-10-21 | 1997-10-16 | Production of pyridazine herbicides |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1240422A (en) |
-
1997
- 1997-10-16 CN CN 97180772 patent/CN1240422A/en active Pending
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