CN101605771B - 4-phenyl-pyrane-3,5-diones, 4-phenyl-thiopyrane-3,5-diones and cyclohexanetriones as novel herbicides - Google Patents
4-phenyl-pyrane-3,5-diones, 4-phenyl-thiopyrane-3,5-diones and cyclohexanetriones as novel herbicides Download PDFInfo
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- CN101605771B CN101605771B CN2007800511842A CN200780051184A CN101605771B CN 101605771 B CN101605771 B CN 101605771B CN 2007800511842 A CN2007800511842 A CN 2007800511842A CN 200780051184 A CN200780051184 A CN 200780051184A CN 101605771 B CN101605771 B CN 101605771B
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- 0 CC(C)(*)C(C(C1=CC(**)=C(*)CC=C1*)=C(C(*)(*)*)ON)=O Chemical compound CC(C)(*)C(C(C1=CC(**)=C(*)CC=C1*)=C(C(*)(*)*)ON)=O 0.000 description 46
- FIJOVYAGQVAMDQ-UHFFFAOYSA-N CCOC(C(C(C(C)(COC)OC1(C)C)=O)=C1O)=O Chemical compound CCOC(C(C(C(C)(COC)OC1(C)C)=O)=C1O)=O FIJOVYAGQVAMDQ-UHFFFAOYSA-N 0.000 description 1
- RMELANOVGLNKGL-UHFFFAOYSA-N CCc(cc1)c(B(O)O)cc1Br Chemical compound CCc(cc1)c(B(O)O)cc1Br RMELANOVGLNKGL-UHFFFAOYSA-N 0.000 description 1
- FRUYUNFYXFRAJV-UHFFFAOYSA-N CCc(ccc(-c(cc1)c(C)cc1Cl)c1)c1C(C(C(C)(C)OC1(C)C)=O)=C1O Chemical compound CCc(ccc(-c(cc1)c(C)cc1Cl)c1)c1C(C(C(C)(C)OC1(C)C)=O)=C1O FRUYUNFYXFRAJV-UHFFFAOYSA-N 0.000 description 1
- WJONVHLQPHYAAO-UHFFFAOYSA-N CCc(ccc(-c(ccc(Cl)c1)c1Cl)c1)c1C(C(C(C)(C)C(C1(C)C)=O)=O)=C1O Chemical compound CCc(ccc(-c(ccc(Cl)c1)c1Cl)c1)c1C(C(C(C)(C)C(C1(C)C)=O)=O)=C1O WJONVHLQPHYAAO-UHFFFAOYSA-N 0.000 description 1
- MPGAYANSXKPKHD-UHFFFAOYSA-N CCc(ccc(-c(ccc(Cl)c1)c1Cl)c1)c1C(C(C(C)(C)S(C1(C)C)=O)=O)=C1O Chemical compound CCc(ccc(-c(ccc(Cl)c1)c1Cl)c1)c1C(C(C(C)(C)S(C1(C)C)=O)=O)=C1O MPGAYANSXKPKHD-UHFFFAOYSA-N 0.000 description 1
- QLMVAIZOSSAFON-UHFFFAOYSA-N CCc(ccc(-c1ccc(C(F)F)cc1)c1)c1C(C(C(C)(C)OC1(C)C)=O)=C1O Chemical compound CCc(ccc(-c1ccc(C(F)F)cc1)c1)c1C(C(C(C)(C)OC1(C)C)=O)=C1O QLMVAIZOSSAFON-UHFFFAOYSA-N 0.000 description 1
Abstract
Pyrandione, thiopyrandione and cyclohexanetrione compounds, which are suitable for use as herbicides.
Description
The present invention relates to novel herbicidal active ring two ketones and verivate thereof; The preparation method who relates to them relates to and comprises these compound compositions, also relates to them in controlling weeds; Particularly the weeds in the useful plant crop perhaps suppress the purposes in the plant-growth.
Ring diketone class description with weeding activity in, for example, among the WO 01/74770.
Novel pyrans diketone, sulfo-pyrans diketone and the cyclohexanetriones compound of having found to have weeding and growth-inhibiting characteristic at present.
Therefore, the present invention relates to formula I compound.
Wherein
R
1Be halogen, C
1-C
4Alkyl, C
1-C
4Haloalkyl, C
3-C
6Naphthenic base, C
2-C
4Thiazolinyl, C
2-C
4Haloalkenyl group, C
2-C
4Alkynyl, C
1-C
4Alkoxyl group, C
1-C
4Halogenated alkoxy, C
1-C
4Alkylthio, C
1-C
4Alkyl sulphinyl, C
1-C
4Alkyl sulphonyl, nitro or cyanic acid;
R
2Be optional substituted aryl or optional substituted heteroaryl;
R is 0,1,2 or 3;
R
3If r is 1, be halogen, C
1-C
6Alkyl, C
1-C
6Haloalkyl, C
1-C
6Alkoxyl group, C
1-C
6Halogenated alkoxy, C
2-C
6Thiazolinyl, C
2-C
6Alkynyl, C
1-C
6Alkylthio, C
1-C
6Alkyl sulphinyl, C
1-C
6Alkyl sulphonyl, cyanic acid or nitro; Or said substituent R
3If r is 2 or 3, be halogen, C independently of one another
1-C
6Alkyl, C
1-C
6Haloalkyl, C
1-C
6Alkoxyl group, C
1-C
6Halogenated alkoxy, C
2-C
6Thiazolinyl, C
2-C
6Alkynyl, C
1-C
6Alkylthio, C
1-C
6Alkyl sulphinyl, C
1-C
6Alkyl sulphonyl, cyanic acid or nitro;
R
4, R
5, R
6And R
7Be hydrogen, C independently of one another
1-C
4Alkyl, C
1-C
4Haloalkyl, C
1-C
4Alkoxy C
1-C
4Alkyl, C
1-C
4Alkylthio C
1-C
4Alkyl, C
1-C
4Alkyl sulphinyl C
1-C
4Alkyl, C
1-C
4Alkyl sulphonyl C
1-C
4Alkyl, cyclopropyl or by C
1-or C
2Alkyl, C
1-or C
2The substituted cyclopropyl of haloalkyl or halogen; Cyclobutyl or by C
1-or C
2The substituted cyclobutyl of alkyl; Oxetanyl or by C
1-or C
2The substituted oxetanyl of alkyl; C
5-C
7Naphthenic base or by C
1-or C
2Alkyl or C
1-or C
2The substituted C of haloalkyl
5-C
7Naphthenic base, the methylene radical of wherein said cycloalkyl moiety are randomly by oxygen or sulphur atom or sulfinyl or alkylsulfonyl replacement; C
4-C
7Cycloalkenyl group or by C
1-or C
2Alkyl or C
1-or C
2The substituted C of haloalkyl
4-C
7Cycloalkenyl group, the methylene radical of wherein said cycloalkenyl group part are randomly by oxygen or sulphur atom or sulfinyl or alkylsulfonyl replacement; Cyclopropyl C
1-C
5Alkyl or by C
1-or C
2Alkyl, C
1-or C
2The substituted cyclopropyl C of haloalkyl or halogen
1-C
5Alkyl; Cyclobutyl C
1-C
5Alkyl or by C
1-C
2The substituted cyclobutyl C of alkyl
1-C
5Alkyl; Oxetanyl C
1-C
5Alkyl or by C
1-or C
2The substituted oxetanyl C of alkyl
1-C
5Alkyl; C
5-C
7Naphthenic base C
1-C
5Alkyl or by C
1-or C
2Alkyl or C
1-or C
2The substituted C of haloalkyl
5-C
7Naphthenic base C
1-C
5Alkyl, the methylene radical of wherein said cycloalkyl moiety are randomly by oxygen or sulphur atom or sulfinyl or alkylsulfonyl replacement; C
4-C
7Cycloalkenyl group C
1-C
5Alkyl or by C
1-or C
2Alkyl or C
1-or C
2The substituted C of haloalkyl
4-C
7Cycloalkenyl group C
1-C
5Alkyl, the methylene radical of wherein said cycloalkenyl group part are randomly by oxygen or sulphur atom or sulfinyl or alkylsulfonyl replacement; Phenyl or by C
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
1-C
4Haloalkyl, halogen, nitro, cyanic acid, C
1-C
4Alkylthio, C
1-C
4Alkyl sulphinyl, C
1-C
4Alkyl sulphonyl or C
1-C
4The substituted phenyl of alkyl-carbonyl; Benzyl or by C
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
1-C
4Haloalkyl, halogen, nitro, cyanic acid, C
1-C
4Alkylthio, C
1-C
4Alkyl sulphinyl, C
1-C
4Alkyl sulphonyl or C
1-C
4The substituted benzyl of alkyl-carbonyl; Heteroaryl or by C
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
1-C
4Haloalkyl, halogen, nitro, cyanic acid, C
1-C
4Alkylthio, C
1-C
4Alkyl sulphinyl, C
1-C
4Alkyl sulphonyl or C
1-C
4The substituted heteroaryl of alkyl-carbonyl; Perhaps
R
4With R
5, or R
6With R
7Form the saturated or undersaturated ring of 5-7 unit together, wherein methylene radical is randomly replaced by oxygen or sulphur atom, perhaps by C
1-or C
2Saturated or the undersaturated ring of alkyl substituted 5-7 unit, the methylene radical of wherein said ring is randomly replaced by oxygen or sulphur atom; Perhaps
R
4With R
7Form together without replacement or by substituted 5-7 saturated or undersaturated ring: the C of unit of following radicals
1-or C
2Alkyl, C
1-or C
2Alkoxyl group, C
1-C
2Alkoxy C
1-C
2Alkyl, hydroxyl, halogen, phenyl or by C
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
1-C
4Haloalkyl, halogen, nitro, cyanic acid, C
1-C
4Alkylthio, C
1-C
4Alkyl sulphinyl, C
1-C
4Alkyl sulphonyl or C
1-C
4The substituted phenyl of alkyl-carbonyl; Heteroaryl or by C
1-C
4Alkyl, C
1-C
4Alkoxyl group, C
1-C
4Haloalkyl, halogen, nitro, cyanic acid, C
1-C
4Alkylthio, C
1-C
4Alkyl sulphinyl, C
1-C
4Alkyl sulphonyl or C
1-C
4The substituted heteroaryl of alkyl-carbonyl;
Y is O, C=O, S (O)
mOr S (O)
nNR
8Condition be when Y be C=O, work as R
4Or R
5R when being hydrogen
6And R
7Not hydrogen, and work as R
6Or R
7R when being hydrogen
4And R
5Not hydrogen;
M be 01 or 2 and n be 0 or 1;
R
8Be hydrogen, C
1-C
6Alkyl, C
3-C
6Naphthenic base, C
1-C
6Alkoxy carbonyl, three (C
1-C
6Alkyl) silyl ethoxy carbonyl, C
1-C
6Halo alkoxy carbonyl, cyanic acid, C
1-C
6Haloalkyl, C
1-C
6Hydroxyalkyl, C
2-C
6Thiazolinyl, C
2-C
6Alkynyl, C
2-C
6Haloalkenyl group, C
1-C
6Alkyl-carbonyl, C
1-C
6Halogenated alkyl carbonyl, C
1-C
6Naphthene base carbonyl, phenylcarbonyl group or by R
9Substituted phenylcarbonyl group; Benzyloxycarbonyl group or by R
9Substituted benzyloxycarbonyl group; Pyridyl carbonyl or by R
9Substituted pyridyl carbonyl; Phenyloxycarbonyl or by R
9Substituted phenyloxycarbonyl; Benzyloxycarbonyl or by R
9Substituted benzyloxycarbonyl;
R
9Be C
1-C
6Haloalkyl, C
1-C
6Alkoxy carbonyl, nitro, cyanic acid, formyl radical, carboxyl or halogen and
G is the acceptable positively charged ion or (latentiating) group of hiding on hydrogen, the agricultural.
In the definition of the substituting group of formula I compound, have moieties preferably methyl, ethyl, propyl group, butyl, amyl group and the hexyl of alkyl substituent and alkoxyl group, the alkylthio etc. of 1-6 carbon atom, form is their straight chain and branched isomer.The senior alkyl of 10 carbon atoms preferably comprises octyl group, nonyl and decyl at the most, and form is their straight chain and branched isomer.Have 2-6 carbon atom and at the most thiazolinyl and the alkynyl group of 10 carbon atoms can be straight chain or branching and can comprise two keys or triple bond more than 1.Instance is vinyl, allyl group, propargyl, crotonyl, butynyl, pentenyl and pentynyl.Suitable naphthenic base comprises 3-7 carbon atom and is for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and suberyl.Preferred cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.Preferred halogen is fluorine, chlorine and bromine.The preferred embodiment of aryl is phenyl and naphthyl.Heteroaryl Preferred examples of thienyl, furyl, pyrrolyl, iso oxazolyl, oxazolyl, isothiazolyl, thiazolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyrazinyl, triazinyl, oxadiazolyl, thiadiazolyl and pyridazinyl groups, and when appropriate, its N-oxides and salts.These aryl and heteroaryl can be replaced by one or more substituting groups, and wherein preferred substituted is halogen, C
1-C
4Alkyl, C
1-C
4Haloalkyl, C
2-C
4Thiazolinyl, C
2-C
4Haloalkenyl group, C
2-C
4Alkynyl, C
1-C
4Alkoxyl group, C
1-C
4Halogenated alkoxy, C
1-C
4Alkylthio, C
1-C
4Alkyl sulphinyl, C
1-C
4Alkyl sulphonyl, C
1-C
4Halogenated alkylthio, C
1-C
4Haloalkyl sulfinyl, C
1-C
4Halogenated alkyl sulfonyl, nitro or cyanic acid.Group G representes that acceptable positively charged ion on hydrogen, the agricultural is (such as alkali metal cation, alkaline earth metal cation, sulphur positively charged ion (preferred three (C
1-C
6) alkyl sulfide positively charged ion, ammonium cation, C
1-C
6Alkyl ammonium cation, two (C
1-C
6Alkyl) ammonium cation, three (C
1-C
6Alkyl) ammonium cation or four (C
1-C
6) alkyl ammonium cation) or the group of hiding.Thereby select these group G of hiding make can before zone that is applied to processing or the plant, during or afterwards, be removed through a kind of or combination in biochemical, chemistry or the physical process that G is the formula I compound of H to produce wherein.The instance of said process comprises enzymatic lysis, chemical hydrolysis and photodissociation.The compound that has this group G can provide some advantages; Improved epidermis penetrance such as treated plant; The tolerance that crop increases; Comprise improved consistency and stability in the preparation mixture of other weedicide, herbicide-safener, plant-growth regulator, mycocide or sterilant, the soil eluviation that perhaps reduces.
It is C that the said group G of hiding is preferably selected from group G
1-C
8Alkyl, C
2-C
8Haloalkyl, phenyl C
1-C
8(wherein said phenyl can be randomly by C for alkyl
1-C
3Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group, C
1-C
3Halogenated alkoxy, C
1-C
3Alkylthio, C
1-C
3Alkyl sulphinyl, C
1-C
3Alkyl sulphonyl, halogen, cyanic acid or nitro replace), heteroaryl C
1-C
8(wherein said heteroaryl can be randomly by C for alkyl
1-C
3Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group, C
1-C
3Halogenated alkoxy, C
1-C
3Alkylthio, C
1-C
3Alkyl sulphinyl, C
1-C
3Alkyl sulphonyl, halogen, cyanic acid or nitro replace), C
3-C
8Thiazolinyl, C
3-C
8Haloalkenyl group, C
3-C
8Alkynyl, C (X
a)-R
a, C (X
b)-X
c-R
b, C (X
d)-N (R
c)-R
d,-SO
2-R
e,-P (X
e) (R
f)-R
gOr CH
2-X
f-R
h, X wherein
a, X
b, X
c, X
d, X
eAnd X
fBe the group of oxygen or sulphur independently of one another;
R
aBe H, C
1-C
18Alkyl, C
2-C
18Thiazolinyl, C
2-C
18Alkynyl, C
1-C
10Haloalkyl, C
1-C
10The cyanic acid alkyl, C
1-C
104-nitro alkyl, C
1-C
10Aminoalkyl group, C
1-C
5Alkylamino C
1-C
5Alkyl, two (C
2-C
8Alkyl) amino C
1-C
5Alkyl, C
3-C
7Naphthenic base C
1-C
5Alkyl, C
1-C
5Alkoxy C
1-C
5Alkyl, C
3-C
5Alkene oxygen base C
1-C
5Alkyl, C
3-C
5Alkynyloxy group C
1-C
5Alkyl, C
1-C
5Alkylthio C
1-C
5Alkyl, C
1-C
5Alkyl sulphinyl C
1-C
5Alkyl, C
1-C
5Alkyl sulphonyl C
1-C
5Alkyl, C
2-C
8Alkylidene group aminooxy C
1-C
5Alkyl, C
1-C
5Alkyl-carbonyl C
1-C
5Alkyl, C
1-C
5Alkoxy carbonyl C
1-C
5Alkyl, aminocarboxyl C
1-C
5Alkyl, C
1-C
5Alkyl amino-carbonyl C
1-C
5Alkyl, two (C
2-C
8Alkyl) aminocarboxyl C
1-C
5Alkyl, C
1-C
5Alkyl-carbonyl-amino C
1-C
5Alkyl, N-C
1-C
5Alkyl-carbonyl-N-C
1-C
5Alkylamino C
1-C
5Alkyl, three (C
3-C
6Alkyl) silyl C
1-C
5Alkyl, phenyl C
1-C
5(wherein said phenyl can be randomly by C for alkyl
1-C
3Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group, C
1-C
3Halogenated alkoxy, C
1-C
3Alkylthio, C
1-C
3Alkyl sulphinyl, C
1-C
3Alkyl sulphonyl, halogen, cyanic acid replace or are replaced by nitro), heteroaryl C
1-C
5Alkyl, (wherein said heteroaryl can be randomly by C
1-C
3Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group, C
1-C
3Halogenated alkoxy, C
1-C
3Alkylthio, C
1-C
3Alkyl sulphinyl, C
1-C
3Alkyl sulphonyl, halogen, cyanic acid replace or are replaced by nitro), C
2-C
5Haloalkenyl group, C
3-C
8Naphthenic base, phenyl or by C
1-C
3Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group, C
1-C
3The substituted phenyl of halogenated alkoxy, halogen, cyanic acid or nitro, heteroaryl or by C
1-C
3Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group, C
1-C
3The substituted heteroaryl of halogenated alkoxy, halogen, cyanic acid or nitro,
R
bBe C
1-C
18Alkyl, C
3-C
18Thiazolinyl, C
3-C
18Alkynyl, C
2-C
10Haloalkyl, C
1-C
10The cyanic acid alkyl, C
1-C
104-nitro alkyl, C
2-C
10Aminoalkyl group, C
1-C
5Alkylamino C
1-C
5Alkyl, two (C
2-C
8Alkyl) amino C
1-C
5Alkyl, C
3-C
7Naphthenic base C
1-C
5Alkyl, C
1-C
5Alkoxy C
1-C
5Alkyl, C
3-C
5Alkene oxygen base C
1-C
5Alkyl, C
3-C
5Alkynyloxy group C
1-C
5Alkyl, C
1-C
5Alkylthio C
1-C
5Alkyl, C
1-C
5Alkyl sulphinyl C
1-C
5Alkyl, C
1-C
5Alkyl sulphonyl C
1-C
5Alkyl, C
2-C
8Alkylidene group aminooxy C
1-C
5Alkyl, C
1-C
5Alkyl-carbonyl C
1-C
5Alkyl, C
1-C
5Alkoxy carbonyl C
1-C
5Alkyl, aminocarboxyl C
1-C
5Alkyl, C
1-C
5Alkyl amino-carbonyl C
1-C
5Alkyl, two (C
2-C
8Alkyl) aminocarboxyl C
1-C
5Alkyl, C
1-C
5Alkyl-carbonyl-amino C
1-C
5Alkyl, N-C
1-C
5Alkyl-carbonyl-N-C
1-C
5Alkylamino C
1-C
5Alkyl, three (C
3-C
6Alkyl) silyl C
1-C
5Alkyl, phenyl C
1-C
5(wherein said phenyl can be randomly by C for alkyl
1-C
3Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group, C
1-C
3Halogenated alkoxy, C
1-C
3Alkylthio, C
1-C
3Alkyl sulphinyl, C
1-C
3Alkyl sulphonyl, halogen, cyanic acid replace or are replaced by nitro), heteroaryl C
1-C
5Alkyl, (wherein said heteroaryl can be randomly by C
1-C
3Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group, C
1-C
3Halogenated alkoxy, C
1-C
3Alkylthio, C
1-C
3Alkyl sulphinyl, C
1-C
3Alkyl sulphonyl, halogen, cyanic acid replace or are replaced by nitro), C
3-C
5Haloalkenyl group, C
3-C
8Naphthenic base, phenyl or by C
1-C
3Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group, C
1-C
3Halogenated alkoxy, halogen, the substituted phenyl of cyanic acid or nitro, heteroaryl or by C
1-C
3Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group, C
1-C
3Halogenated alkoxy, halogen, the substituted heteroaryl of cyanic acid or nitro,
R
hBe C
1-C
10Alkyl, C
3-C
10Thiazolinyl, C
3-C
10Alkynyl, C
1-C
10Haloalkyl, C
1-C
10The cyanic acid alkyl, C
1-C
104-nitro alkyl, C
2-C
10Aminoalkyl group, C
1-C
5Alkylamino C
1-C
5Alkyl, two (C
2-C
8Alkyl) amino C
1-C
5Alkyl, C
3-C
7Naphthenic base C
1-C
5Alkyl, C
1-C
5Alkoxy C
1-C
5Alkyl, C
3-C
5Alkene oxygen base C
1-C
5Alkyl, C
3-C
5Alkynyloxy group C
1-C
5Alkyl, C
1-C
5Alkylthio C
1-C
5Alkyl, C
1-C
5Alkyl sulphinyl C
1-C
5Alkyl, C
1-C
5Alkyl sulphonyl C
1-C
5Alkyl, C
2-C
8Alkylidene group aminooxy C
1-C
5Alkyl, C
1-C
5Alkyl-carbonyl C
1-C
5Alkyl, C
1-C
5Alkoxy carbonyl C
1-C
5Alkyl, aminocarboxyl C
1-C
5Alkyl, C
1-C
5Alkyl amino-carbonyl C
1-C
5Alkyl, two (C
2-C
8Alkyl) aminocarboxyl C
1-C
5Alkyl, C
1-C
5Alkyl-carbonyl-amino C
1-C
5Alkyl, N-C
1-C
5Alkyl-carbonyl-N-C
1-C
5Alkylamino C
1-C
5Alkyl, three (C
3-C
6Alkyl) silyl C
1-C
5Alkyl, phenyl C
1-C
5(wherein said phenyl can be randomly by C for alkyl
1-C
3Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group, C
1-C
3Halogenated alkoxy, C
1-C
3Alkylthio, C
1-C
3Alkyl sulphinyl, C
1-C
3Alkyl sulphonyl, halogen, cyanic acid replace or are replaced by nitro), heteroaryl C
1-C
5(wherein said heteroaryl can be randomly by C for alkyl
1-C
3Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group, C
1-C
3Halogenated alkoxy, C
1-C
3Alkylthio, C
1-C
3Alkyl sulphinyl, C
1-C
3Alkyl sulphonyl, halogen, cyanic acid replace or are replaced by nitro), phenoxy C
1-C
5(wherein said phenyl can be randomly by C for alkyl
1-C
3Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group, C
1-C
3Halogenated alkoxy, C
1-C
3Alkylthio, C
1-C
3Alkyl sulphinyl, C
1-C
3Alkyl sulphonyl, halogen, cyanic acid replace or are replaced by nitro), heteroaryloxy C
1-C
5(wherein said heteroaryl can be randomly by C for alkyl
1-C
3Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group, C
1-C
3Halogenated alkoxy, C
1-C
3Alkylthio, C
1-C
3Alkyl sulphinyl, C
1-C
3Alkyl sulphonyl, halogen, cyanic acid replace or are replaced by nitro), C
3-C
5Haloalkenyl group, C
3-C
8Naphthenic base, phenyl or by C
1-C
3Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group, C
1-C
3Halogenated alkoxy, halogen replace or by the substituted phenyl of nitro, or heteroaryl or by C
1-C
3Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group, C
1-C
3Halogenated alkoxy, halogen, cyanic acid replace or by the substituted heteroaryl of nitro.
In the preferred group of formula I compound, R
1Be halogen, C
1-C
4Alkyl, C
1-C
4Haloalkyl, C
2-C
4Thiazolinyl or C
2-C
4Alkynyl.
In another preferred group of formula I compound, R
2Be aryl or heteroaryl; Perhaps by substituted aryl of following radicals or heteroaryl: halogen, C
1-C
4Alkyl, C
1-C
4Haloalkyl, C
2-C
4Thiazolinyl, C
2-C
4Haloalkenyl group, C
2-C
4Alkynyl, C
1-C
4Alkoxyl group, C
1-C
4Halogenated alkoxy, phenoxy, C
1-C
4Alkylthio, C
1-C
4Alkyl sulphinyl, C
1-C
4Alkyl sulphonyl, C
1-C
4Halogenated alkylthio, C
1-C
4Haloalkyl sulfinyl, C
1-C
4Halogenated alkyl sulfonyl, C
3-C
6Naphthenic base, C
1-C
4Alkyl sulphonyl oxygen base, C
1-C
4Halogenated alkyl sulfonyl oxygen base, C
1-C
4Alkoxy C
1-C
4Alkyl, C
1-C
4Alkylthio C
1-C
4Alkyl, C
1-C
4Alkyl sulphinyl C
1-C
4Alkyl, C
1-C
4Alkyl sulphonyl C
1-C
4Alkyl, nitro, cyanic acid, thiocyano, hydroxyl, amino, C
1-C
6Alkylamino, C
1-C
6Dialkyl amido, C
3-C
6Cycloalkyl amino, morpholino, thiomorpholine generation, C
1-C
6Alkyl-carbonyl-amino, C
1-C
6Alkoxycarbonyl amino, C
3-C
6Allyloxycarbonyl is amino, C
3-C
6Alkynyloxy group carbonylamino, C
1-C
6Alkyl amino-carbonyl is amino, two (C
1-6Alkyl) amino carbonyl amino, formyl radical, C
1-C
6Alkyl-carbonyl, C
2-C
6Alkenyl carbonyl, C
2-C
6Alkynyl carbonyl, carboxyl, C
1-C
6Alkoxy carbonyl, C
3-C
6Allyloxycarbonyl, C
3-C
6Alkynyloxy group carbonyl, carboxamide groups, C
1-C
6Alkyl amino-carbonyl, two (C
1-C
6Alkyl) aminocarboxyl, C
1-C
6Alkyl carbonyl oxy, C
1-C
6Alkyl amino carbonyl oxy, two (C
1-C
6Alkyl) amino carbonyl oxygen base or C
1-C
6The alkylthio carbonylamino;
Preferably, the R in the formula I compound
2Be aryl or heteroaryl; Perhaps by substituted aryl of following radicals or heteroaryl: halogen, C
1-C
4Alkyl, C
1-C
4Haloalkyl, phenoxy, C
2-C
4Thiazolinyl, C
2-C
4Haloalkenyl group, C
2-C
4Alkynyl, C
1-C
4Alkoxyl group, C
1-C
4Halogenated alkoxy, C
1-C
4Alkylthio, C
1-C
4Alkyl sulphinyl, C
1-C
4Alkyl sulphonyl, C
1-C
4Halogenated alkylthio, C
1-C
4Haloalkyl sulfinyl, C
1-C
4Halogenated alkyl sulfonyl, nitro or cyanic acid.
More preferably, R
2Be phenyl, thienyl, furyl, pyrryl 、 isoxazolyl 、 oxazolyl, isothiazolyl, thiazolyl, pyrazolyl, imidazolyl, triazolyl, tetrazyl, pyridyl, pyrimidyl, pyrazinyl, triazinyl, pyridazinyl 、 oxadiazole base and thiadiazolyl group; And N-oxide compound and salt, wherein these rings are without substituted or by halogen, C
1-C
4Alkyl, C
1-C
4Haloalkyl, C
2-C
4Thiazolinyl, C
2-C
4Haloalkenyl group, C
2-C
4Alkynyl, C
1-C
4Alkoxyl group, C
1-C
4Halogenated alkoxy, C
1-C
4Alkylthio, C
1-C
4Alkyl sulphinyl, C
1-C
4Alkyl sulphonyl, C
1-C
4Halogenated alkylthio, C
1-C
4Haloalkyl sulfinyl, C
1-C
4Halogenated alkyl sulfonyl, nitro or cyanic acid replace.
In addition preferred formula I compound in, R
2Be that phenyl or pyridyl are perhaps by halogen, nitro, cyanic acid, C
1-C
2Alkyl, C
1-C
2Haloalkyl, C
1-C
2Alkoxyl group or C
1-C
2Substituted phenyl of halogenated alkoxy or pyridyl.
In preferred especially compound group, R
2Be by the substituted phenyl of halogen (particularly chlorine), and randomly further by halogen, nitro, C in contraposition
1-C
2Alkyl, C
1-C
2Haloalkyl, C
1-C
2Alkoxyl group or C
1-C
2Halogenated alkoxy replaces.
Preferably, R
3Be hydrogen (r is 0), halogen or C
1-C
6Alkyl, particularly hydrogen.
Preferably, R
3If r is 1, be halogen or C
1-C
3Alkyl.
Preferably these formulas I compound, wherein R
4, R
5, R
6And R
7Be hydrogen, C independently of one another
1-C
4Alkyl, C
1-C
4Haloalkyl, C
1-C
4Alkoxy C
1-C
4Alkyl, C
1-C
4Alkylthio C
1-C
4Alkyl, C
1-C
4Alkyl sulphinyl C
1-C
4Alkyl, C
1-C
4Alkyl sulphonyl C
1-C
4Alkyl; C
5-C
7Naphthenic base or by C
1-or C
2Alkyl or C
1-or C
2The substituted C of haloalkyl
5-C
7Naphthenic base and wherein methylene radical randomly substituted by oxygen or sulphur atom or sulfinyl or alkylsulfonyl; C
5-C
7Naphthenic base C
1-C
5Alkyl or by C
1-C
2Alkyl or C
1-or C
2The substituted C of haloalkyl
5-C
7Naphthenic base C
1-C
5Alkyl and wherein methylene radical randomly replaced by oxygen or sulphur atom or sulfinyl or alkylsulfonyl.
More preferably, R
4, R
5, R
6And R
7Be hydrogen, C independently of one another
1-C
2Alkyl, C
1-C
2Haloalkyl or C
1-C
2Alkoxy C
1-C
2Alkyl.
The preferred meaning of Y is O, C=O and S.
Y is that O is preferred especially.
Preferably, G representes C (X
a)-R
aOr C (X
b)-X
c-R
b, X
a, R
a, X
b, X
cAnd R
bImplication such as preamble definition.Even more preferably, the said group G of hiding is selected from group C (X
a)-R
a, C (X
b)-X
c-R
b, X wherein
a, X
bAnd X
cBe oxygen, R
aBe C
1-C
6Alkyl, C
2-C
6Thiazolinyl, C
2-C
6Alkynyl, C
3-C
6Naphthenic base or C
1-C
4Alkoxy C
1-C
4Alkyl and R
bBe C
1-C
6Alkyl, C
3-C
6Thiazolinyl, C
3-C
6Alkynyl, C
3-C
6Naphthenic base or C
1-C
4Alkoxy C
1-C
4Alkyl.
Prior group G comprises hydrogen, basic metal or alkaline earth metal cation as acceptable positively charged ion on the agricultural, wherein preferred especially hydrogen.
In the preferred group of formula I compound, R
1Be C
1-C
4Alkyl, R
2It is phenyl or by halogen or C
1-C
2The substituted phenyl of alkyl, R
3Be hydrogen, R
4, R
5, R
6And R
7Be C independently of one another
1-C
2Alkyl, Y are that O and G are hydrogen.
The invention still further relates to the salt that formula I compound can form with amine, basic metal and alkaline earth metal alkali or quaternary ammonium hydroxide.
In basic metal and alkaline earth metal hydroxides, be to be noted that the oxyhydroxide of lithium, sodium, potassium, magnesium and calcium, more particularly the oxyhydroxide of sodium and potassium as the salify material.Formula I compound according to the present invention also comprises the hydrate that can during salify, form.
The instance that is suitable for forming the amine of ammonium salt comprises ammonia and primary, the second month in a season and uncle C
1-C
18Alkylamine, C
1-C
4Hydroxyalkyl amine and C
2-C
4Alkoxyalkyl amine; For example methylamine, ethamine, Tri N-Propyl Amine, Isopropylamine, four kinds of butylamine isomer, n-amylamine, isobutylcarbylamine, hexylamine, heptyl amice, octylame, nonyl amine, certain herbaceous plants with big flowers amine, pentadecyl amine, cetylamine, heptadecylamine (HDA), octadecane amine, methyl ethyl-amine, methyl isopropyl amine, tuaminoheptane, methyl nonyl amine, methyl pentadecyl amine, methyl octadecane amine, ethyl butyl amine, ethyl heptyl amice, ethyl octylame, hexyl heptyl amice, hexyl octylame, n n dimetylaniline, diethylamine, di-n-propylamine, Diisopropylamine, Di-n-Butyl Amine, two n-amylamines, di-iso-amylamine, dihexylamine, two heptyl amices, Di-Octyl amine, thanomin, n-propyl alcohol amine, Yi Bingchunan, N; N-diethylolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-but-2-ene amine, n-penta-2-enamine, 2,3-dimethyl butyrate-2-enamine, two but-2-ene amine, just oneself-2-enamine, tn, Trimethylamine 99, triethylamine, Tri-n-Propylamine, tri-isopropyl amine, tri-n-butylamine, tri-isobutylamine, tri sec-butylamine, tri-n-amyl amine, methoxyethyl amine and ethoxy ethyl amine; Heterocyclic amine, for example pyridine, quinoline, isoquinoline 99.9, morpholine, piperidines, tetramethyleneimine, indoline, rubane and azepine
Uncle arylamine, for example aniline, anisidine, phenetidine, o-, m-and p-Tolylamine, phenylenediamine, p-diaminodiphenyl, naphthylamines and o-, m-and p-chloroaniline; But particularly triethylamine, Isopropylamine and Diisopropylamine.
Preferably be suitable for salifiable quaternary ammonium hydroxide corresponding to, formula [N (R for example
aR
bR
cR
d)] OH, wherein R
a, R
b, R
cAnd R
dBe C separately independently of each other
1-C
4Alkyl.Can for example obtain other suitable tetra-allkylammonium and other anionic alkali through anion exchange reaction.
According to G, R
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8Implication, formula I compound can exist with different isomerization bodily form formula.When G was hydrogen, for example, formula I compound can exist with different tautomeric forms:
In addition, when Y be C=O and R
4When being hydrogen, other formula I compound can exist with different tautomeric forms:
In addition, when substituting group comprises two key, can select cis and trans-isomer(ide).All these isomer and tautomer of all proportions and composition thereof contained in the present invention.These isomer are also in the scope of the formula I compound that requires to protect.
Formula I compound, wherein G is C
1-C
8Alkyl, C
2-C
8Haloalkyl, phenyl C
1-C
8(wherein said phenyl can be randomly by C for alkyl
1-C
3Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group, C
1-C
3Halogenated alkoxy, C
1-C
3Alkylthio, C
1-C
3Alkyl sulphinyl, C
1-C
3Alkyl sulphonyl, halogen, cyanic acid replace or are replaced by nitro), heteroaryl C
1-C
8(wherein said heteroaryl can be randomly by C for alkyl
1-C
3Alkyl, C
1-C
3Haloalkyl, C
1-C
3Alkoxyl group, C
1-C
3Halogenated alkoxy, C
1-C
3Alkylthio, C
1-C
3Alkyl sulphinyl, C
1-C
3Alkyl sulphonyl, halogen, cyanic acid replace or are replaced by nitro), C
3-C
8Thiazolinyl, C
3-C
8Haloalkenyl group, C
3-C
8Alkynyl, C (X
a)-R
a, C (X
b)-X
c-R
b, C (X
d)-N (R
c)-R
d,-SO
2-R
e,-P (X
e) (R
f)-R
gOr CH
2-X
f-R
h, X wherein
a, X
b, X
c, X
d, X
e, X
f, R
a, R
b, R
c, R
d, R
e, R
f, R
gAnd R
hSuch as preamble definition, can be through with formula (A) compound, it is that wherein G is the formula I compound of H, with reagent G-Z processing, wherein G-Z is that (definition of haloalkane comprises simple halo C to alkylating reagent such as haloalkane
1-C
8Alkane such as methyl iodide and iodoethane are through substituted haloalkane such as chloromethyl alkyl oxide, C
1-CH
2-X
f-R
h, X wherein
fBe oxygen and chloromethyl alkyl thioether, C1-CH
2-X
f-R
h, X wherein
fBe sulphur), sulfonic acid C
1-C
8Alkyl ester, or sulfuric acid two (C
1-C
8Alkyl) ester is perhaps used halo C
3-C
8Alkene is handled, and perhaps uses halo C
3-C
8Alkynes is handled, perhaps handles with acylating reagent, and such as carboxylic acid, HO-C (X
a) R
a, X wherein
aBe oxygen, acyl chlorides, C1-C (X
a) R
a, X wherein
aBe oxygen, or acid anhydrides, [R
aC (X
a)]
2O, wherein X
aBe oxygen, or isocyanic ester, R
cN=C=O, or urea chloride, C1-C (X
d)-N (R
c)-R
d(X wherein
dBe that oxygen and condition are R
cOr R
dBe not hydrogen), or thiocarbamyl chlorine, C1-(X
d)-N (R
c)-R
d(X wherein
dBe that sulphur and condition are R
cOr R
dBe not hydrogen), or the carbonochloridic acid ester, C1-C (X
b)-X
c-R
b(X wherein
bAnd X
cBe oxygen), or the chloro thiocarboxylic, C1-C (X
b)-X
c-R
b(X wherein
bBe oxygen and X
cBe sulphur), or the chloro dithio formate, C1-C (X
b)-X
c-R
b(X wherein
bAnd X
cBe sulphur), or lsothiocyanates, R
cN=C=S perhaps handles with dithiocarbonic anhydride and alkylating reagent through order, perhaps handles with phosphorus esterification reagent, and such as phosphoryl chloride, C1-P (X
e) (R
f)-R
gPerhaps handle with sulfonylation agent, such as SULPHURYL CHLORIDE, C1-SO
2-R
e, preferably preparation in the presence of at least 1 equivalent alkali.In substituent R
4And R
5Be not equal to substituent R
6And R
7Situation under, these reactions can also produce second kind of formula (IA) compound except that formula (I) compound.Formula (I) compound and formula (IA) compound are contained in the present invention, and these compounds arbitrarily than mixture.
Ring 1, the O-alkylation of 3-diketone is known; Proper method is by for example T.Wheeler, and US4436666 describes.Alternative methods is by M.Pizzorno and S.Albonico, Chem.Ind. (London), (1972), 425-426; People such as H.Born, J.Chem.Soc., (1953), 1779-1782; People such as M.G.Constantino, Synth.Commun., (1992), 22 (19), 2859-2864; People such as Y.Tian, Synth.Commun., (1997), 27 (9), 1577-1582; People such as S.Chandra Roy, Chem.Letters, (2006), 35 (1), 16-17; People such as P.K.Zubaidha, Tetrahedron Lett., (2004), 45,7187-7188 report.
Ring 1, the O-alkylation of 3-diketone can through with for example R.Haines, US4175135 and T.Wheeler, US4422870, those similar methods of US4659372 and US4436666 description are carried out.Formula (A) diketone can be handled with acylating reagent usually, preferably in the presence of the suitable alkali of at least 1 equivalent, and randomly in the presence of suitable solvent.Said alkali can be mineral alkali, and such as alkaline carbonate or oxyhydroxide, or metal hydride, perhaps organic bases is such as tertiary amine or metal alkoxide.The instance of suitable mineral alkali comprises yellow soda ash, sodium hydroxide or Pottasium Hydroxide, sodium hydride; Suitable organic bases comprises trialkylamine; Such as Trimethylamine 99 and triethylamine; Pyridine or other amine alkali is such as 1,4-diazabicylo [2.2.2]-octane and 1,8-diazabicylo [5.4.0] 11-7-alkene.Preferred alkali comprises triethylamine and pyridine.Thereby selection is compatible and comprise ethers such as THF and 1 with reactant to this reaction The suitable solvent, and 2-glycol dimethyl ether and halogenated solvent are such as methylene dichloride and chloroform.Some alkali such as pyridine and triethylamine, can successfully be used as alkali and solvent.At acylating reagent is under the situation of carboxylic acid; Preferably in the presence of known coupling agent, carry out acidylate; Such as iodate 2-chloro-1-picoline, N, N '-NSC 57182,1-(3-dimethylaminopropyl)-3-ethyl carbodiimide and N, N '-carbonyl dimidazoles; Randomly in the presence of alkali such as triethylamine or pyridine, suitable solvent such as THF, methylene dichloride or acetonitrile in.Suitable method is by for example W.Zhang and G.Pugh, Tetrahedron Lett., (1999), 40 (43), 7595-7598; T.Isobe and T.Ishikawa, J.Org.Chem., (1999), and 64 (19), 6984-6988 and K.Nicolaou, T.Montagnon, G.Vassilikogiannakis, C.Mathison, J.Am.Chem.Soc., (2005), and 127 (24), 8872-8888 describes.
Ring 1, the phosphorylated of 3-diketone can use phosphoryl halogen or thiophosphoryl halogen and alkali through with for example L.Hodakowski, those similar methods of US4409153 description are carried out.
The sulfonylation of formula (A) compound can use the alkyl or aryl sulfonic acid halide, preferably in the presence of at least 1 equivalent alkali, and through for example C.Kowalski and K.Fields, J.Org.Chem., (1981), and 46, the method for 197-201 realizes.
Formula (A) compound, wherein Y is S (O)
mAnd m is 1 or 2, can through oxidation according to E.Fehnel and A.Paul, J.Am.Chem.Soc., (1955), 77, the similar method of 4241-4244, the preparation from formula (A) compound, wherein Y is S.
Formula (A) compound, wherein Y is O, S or C=O, can through with T.Wheeler, those similar methods that US4209532 describes prepare via the cyclisation of formula (B) compound, preferably in the presence of acid or alkali, choose wantonly in the presence of suitable solvent.Formula (B) compound is designed to the midbody of formula I compound in synthetic especially.Formula (B) compound, wherein R is hydrogen or C
1-C
4Alkyl, (particularly methyl, ethyl and the tertiary butyl) can preferably in the presence of strong acid such as sulfuric acid, Tripyrophosphoric acid or Eaton ' s reagent, be chosen wantonly in the presence of suitable solvent such as acetate, toluene or methylene dichloride and carry out in cyclisation under the acidic conditions.
Formula (B) compound; Wherein R is that alkyl (preferable methyl or ethyl) can cyclisation under acidity or alkaline condition; Preferably under alkaline condition; In the presence of at least 1 equivalent highly basic such as potassium tert.-butoxide, diisopropylamino lithium, two (trimethyl silyl) sodium amide or sodium hydride, at solvent such as THF, toluene, methyl-sulphoxide or N, in the dinethylformamide.
Formula (B) compound, wherein R is H, can under known conditions, (for example in the presence of acid catalyst, with alcohol, R-OH handles) esterification be formula (B) compound, wherein R is an alkyl.
Formula (B) compound; Wherein R is H, can by with for example T.Wheeler, those similar method through type (C) compounds that US4209532 describes; Wherein R is that H or alkyl and R ' are that the hydrolysis of alkyl (preferable methyl or ethyl) prepares, and acidified reaction mixture causes decarboxylation subsequently.Alternatively, formula (B) compound, wherein R is alkyl (preferable methyl); Can be decarboxylation method used (referring to for example G.Quallich, P.Morrissey, Synthesis through under known conditions, using the Krapcho of known agent; (1993), (1), 51-53); Preparation is from formula (C) compound, and wherein R is alkyl (preferable methyl).
Formula (C) compound, wherein R is an alkyl, can be that formula (E) acyl chlorides processing formula (D) compound of alkyl prepares through the wherein R that usefulness is suitable under alkaline condition.Suitable alkali comprises potassium tert.-butoxide, two (trimethyl silyl) sodium amide and diisopropylamino lithium, and reaction is preferably carried out under (such as THF or toluene) and-80 ℃-30 ℃ the temperature in suitable solvent:
Alternatively; Formula (C) compound; Wherein R is H; Can through in suitable solvent (such as THF or toluene) in optimal temperature (80 ℃-30 ℃) down with suitable alkali (such as potassium tert.-butoxide, two (trimethyl silyl) sodium amide and diisopropylamino lithium) processing formula (D) compound, and institute's negatively charged ion that obtains and formula (F) anhydride reaction that suits are prepared:
Formula (E) and formula (F) compound be known (referring to, for example T.Terasawa and T.Okada, J.Org.Chem.; (1977), 42 (7), 1163-1169 and G.Bennett; W.Houlihan, R.Mason and R.Engstrom, J.Med.Chem.; (1976), 19 (5), 709-14) perhaps can make through similar approach from commercially available raw material.
Use and above-mentioned those similar methods,, can prepare formula (H) compound from formula (G) benzene halide yl acetate (wherein Ha l is chlorine, bromine or iodine).Subsequently, through with coupling partner such as aryl or heteroaryl boric acid, R
2-B (OH)
2, or its suitable salt or ester react under the preferred Suzuki-Miyaura condition under the palladium catalytic condition, can above-claimed cpd be converted into formula (A) compound, wherein R
2Be aryl or heteroaryl.
Formula H compound is designed for the synthetic midbody of formula (I) compound especially.
Carry out formula (H) aryl halide and formula R
2-B (OH)
2The Suzuki-Miyaura link coupled suitable condition of aryl or heteroaryl boric acid or its suitable salt or ester be known in the document (referring to, for example K.Billingsley and S.Buchwald, J.Am.Chem.Soc., (2007), 129,3358-3366; H.Stefani, R.Cella and A.Vieira, Tetrahedron, (2007), 63,3623-3658; N.Kudo, M.Perseghini and G.Fu, Angew.Chem.Int.Ed., (2006), 45,1282-1284; A.Roglans, A.Pla-Quintana and M.
Chem.Rev., (2006), 106,4622-4643; J-H Li, Q-M Zhu and Y-X Xie, Tetrahedron (2006), 10888-10895; People such as S.Nolan, J.Org.Chem., (2006), 71,685-692; M.Lys é n and K.
Synthesis, (2006), 4,692-698; K.Anderson and S.Buchwald, Angew.Chem.Int.Ed., (2005), 44,6173-6177; Y.Wang and D.Sauer, Org.Lett., (2004), 6 (16), 2793-2796; I.Kondolff, H.Doucet and M, Santelli, Tetrahedron, (2004), 60,3813-3818; F.Bellina, A.Carpita and R.Rossi, Synthesis (2004), 15,2419-2440; H.Stefani, G.Molander, C-S Yun, M.Ribagorda and B.Biolatto, J.Org.Chem., (2003), 68,5534-5539; A.Suzuki, Journal of Organometallic Chemistry, (2002), 653,83; G.Molander and C-S Yun, Tetrahedron, (2002), 58,1465-1470; G.Zou, Y.K.Reddy and J.Falck, Tetrahedron Lett., (2001), 42,4213-7215; S.Darses, G.Michaud and J-P.Gen ê t, Eur.J.Org.Chem., (1999), 1877-1883; People such as M.Beavers, WO2005/012243; J.Org.Chem. (1994), 59,6095-6097; A.Collier and G.Wagner, Synthetic Communications, (2006), 36; 3713-3721).
Alternatively, formula (A) compound can pass through Suzuki-Miyaura coupling formula (I) compound, and wherein Hal is chlorine, bromine, iodine or pseudohalogen such as C
1-C
4Haloalkyl sulphonate, particularly trifluoromethane sulfonic acid ester are with formula R
2-B (OH)
2Aryl or heteroaryl boric acid or its suitable salt or ester, cyclisation prepares under the condition that preamble is described formula (B) compound subsequently.
In another approach, formula (A) compound, wherein R
2Be pyridine (azine) N-oxide compound such as pyridine N-oxides, pyrimidine N-oxide compound, pyridazine N-oxide compound or pyrazine N-oxide compound, can be through at L.Campeau, S.Rousseaux and K.Fagnou; J.Am. Chem.Soc., (2005), 127; 18020 and J-P.Leclerc and K.Fagnou, Angew.Chem.Int.Ed., (2006); 45, under the condition that 7781-7786 describes with suitable pyridine-N-oxide compound prepared in reaction from formula (H) compound.The N-oxide compound that obtains can be used known agent under known conditions, to handle (for example in the presence of suitable catalyzer, reducing with hydrogen or ammonium formiate) and produce other formula (I) compound.
Other formula (A) compound, wherein R
2Be the heteroaromatic rings that is connected to benzyl ring through nitrogen-atoms, can be by for example M.Taillefer, N.Xia and A.Ouali, Angew.Chem.Int.Ed., (2007), 46 (6), 934-936; H.Zhang, Q.Cai, D.Ma, J.Org.Chem., (2005), 70,5164-5173; J.Antilla, J.Baskin, T.Barder and S.Buchwald; J.Org.Chem., (2004), 69; 5578-5587 and A.Thomas and S.Ley; Angew.Chem.Int.Ed., 2003,42; Being described under suitable catalyzer, suitable part, the suitable alkali existence and in suitable solvent, in 5400-5449 and the reference wherein through Ullmann-type coupling (this is reflected at and is also referred to as the N-arylation in the document) formula (H) compound or formula (I) compound and the heteroaromatics R that comprises N-H
2-H obtains.
In another approach, formula (A) compound, wherein Y is O, S or C=O, can be in the presence of suitable part and in suitable solvent prepares through formula (J) compound and aryl tricarboxylic lead plumbate are reacted.Similarly the reaction be described in document (for example referring to J.Pinhey, B.Rowe, Aust.J.Chem., (1979), 32,1561-6; J.Morgan, J.Pinhey, J.Chem.Soc.Perkin Trans.1, (1990), 3,715-20).Preferred said aryl tricarboxylic lead plumbate is that formula (K) aryl nitrilotriacetic is plumbous.Preferably said part be nitrogen heterocyclic ring such as N, N-Dimethylamino pyridine, 1,10-phenanthroline pyridine, dipyridyl or imidazoles, and preferably use the normal part of relative formula (J) compound 1-10.Most preferably part is N, the N-Dimethylamino pyridine.Solvent is chloroform, methylene dichloride or toluene preferably, most preferably the mixture of chloroform or chloroform and toluene.Preferred this is reflected under-10 ℃-100 ℃ the temperature and carries out most preferably 40-90 ℃).
Formula (J) compound, wherein Y is O, be known compound maybe can through with document (referring to, for example, M.Morgan and E.Heyningen, J.Am.Chem Soc., (1957), 79,422-424; I.Korobitsyna and K.Pivnitskii, Russian Journal ofGeneral Chemistry, (1960), 30,4016-4023; T.Terasawa and T.Okada, J.Org.Chem., (1977), 42 (7), 1163-1169; People US5089046 such as R.Anderson; R.Altenbach, K.Agrios, I.Drizin and W.Carroll, Synth.Commun., (2004), 34 (4) 557-565; People such as R.Beaudegnies, WO2005/123667; W.Li, G.Wayne, J.Lallaman, S.Chang and S.Wittenberger, J.Org.Chem. (2006), 71,1725-1727; R.Altenbach, M.Brune, S.Buckner, M.Coghlan, A.Daza; A.Fabiyi, M.Gopalakrishnan, R.Henry, A.Khilevich, M.Kort; I.Milicic, V.Scott, J.Smith, K.Whiteaker and W.Carroll; J.Med.Chem, (2006), 49 (23), 6869-6887; People such as Carroll, WO 2001/083484A1; J.K.Crandall, W.W.Conover, J.Org.Chem. (1978), 43 (18), 3533-5; I.K.Korobitsyna, O.P.Studzinskii, Chemistry of HeterocyclicCompounds (1966), (6), 848-854) middle those similar approach of describing make.Formula (J) compound, wherein Y is S, be known compound maybe can through with document (referring to, for example, E.Fehnel and A.Paul, J.Am.Chem Soc., (1955), 77,4241-4244; E.Er and P.Margaretha, Helvetica Chimica Acta (1992), 75 (7), 2265-69; People such as H.Gayer, DE 3318648 A1) those similar approach of describing in make.Formula (J) compound; Wherein Y is C=O; Be known compound maybe can through with document (referring to; For example, R.
and N.
WO2001/060776R. people WO2000/075095 such as
; People such as M.Benbakkar, Synth.Commun. (1989) 19 (18) 3241-3247; A.Jain and T.Seshadri, Proc.Indian Acad.Sci.Sect.A, (1955), 42,279); People such as N.Ahmad, J.Org.Chem., (2007), 72 (13), 4803-4815); People such as F.Effenberger, Chem.Ber., (1986), 119,3394-3404 and wherein reference) in those similar approach of describing make.
Formula (K) compound can according to document (for example referring to, K.Shimi, G.Boyer, J-P.Finet and J-P.Galy, Letters in Organic Chemistry, (2005), 2,407-409; J.Morgan and J.Pinhey, J.Chem.Soc.Perkin Trans.1; (1990), 3,715-720) the middle method of describing in suitable solvent (for example chloroform), under 25 ℃-100 ℃ (preferred 25 ℃-50 ℃), is chosen wantonly in the presence of catalyzer such as oxalic acid mercury, makes through handle formula (L) compound with lead tetraacetate.
Formula (L) aryl boric acid can pass through currently known methods (referring to, for example, W.Thompson and J.Gaudino; J.Org.Chem, (1984), 49; People such as 5237-5243 and R.Hawkins, J.Am.Chem.Soc., (1960); 82,3053-3059) preparation is from formula (M) aryl halide, and wherein Hal is a bromine or iodine.Thus, formula (M) aryl halide can be handled with lithium alkylide or alkyl halide magnesium at low temperatures, makes gained aryl magnesium or aryl lithium and trialkylboron acid esters B (OR ")
3The reaction of preferred boric acid trimethyl produces the aryl boric acid dialkyl, and it can form formula (L) boric acid of hoping in hydrolysis under the acidic conditions.Alternatively; Compound (M) can use known agent through the catalytic boron acylation reaction of palladium under known conditions to the same general conversion of compound (L), realizes (referring to for example T.Ishiyama, M.Murata with posthydrolysis midbody boric acid ester; N.Miyaura; J.Org.Chem. (1995), 60,7508-7501; And K.L.Billingsley, T.E.Barder, S.L.Buchwald, Angew.Chem.Int.Ed. (2007), 46,5359-5363).
Formula (M) aryl halide is that known compound maybe can be through the currently known methods preparation from known compound.For example, formula (M) aryl halide can react through currently known methods such as Sandmeyer, via the preparation of corresponding diazonium salt from formula (N) aniline (referring to; For example, J.March, AdvancedOrganic Chemistry; The 3rd edition, John Wiley and Sons, 647-648 page or leaf and reference wherein.Additional embodiments is also referring to people such as W.Denney, J.Med.Chem., (1991), 34,217-222; People such as P.Knochel, Synthesis, (2007), No.1,81-84).
In addition; Formula (N) compound can use the palladium catalysis boron acidylate of known agent through midbody aryl diazonium salt under known conditions; Subsequently with the hydrolysis of said midbody boric acid ester be converted into formula (L) compound (referring to for example D.M.Willis, R.M.Strongin, Tetrahedron Lett. (2000); 41,8683-8686).
Formula (N) aniline is known compound or can prepares from known compound through currently known methods.For example, formula (N) aniline can through under the Suzuki-Miyaura condition with aryl-or heteroaryl-boric acid R
2-B (OH)
2Or its suitable salt or ester reaction, perhaps under N-arylation condition with contain N-H heteroaromatic rings R
2-H reaction, through standard method reduction nitro, (wherein Hal is that chlorine, bromine, iodine or pseudohalogen are such as C from formula (O) oil of mirbane in preparation subsequently
1-C
4Haloalkyl sulphonate, particularly trifluoromethane sulfonic acid ester).Alternatively, formula (O) compound can at first be reduced to aniline, said aniline under the Suzuki-Miyaura condition cross-coupling (referring to, A.Maj for example, L.Delaude, A.Demonceau and A.Noels, Tetrahedron, (2007), 63,2657-2663; F.Bellina, A.Carpita and R.Rossi, Synthesis (2004), 15,2419-2440 and A.Suzuki, Journal of OrganometallicChemistry, (2002), 653,83-90).
Formula (O) oil of mirbane is known compound, perhaps can be through the currently known methods preparation from known compound.
In another approach, formula (A) compound can be in the presence of suitable palladium catalyst and alkali, preferably in suitable solvent, through preparing from formula (P) compound with formula (L) aromatic yl acid reaction.Suitable palladium catalyst is palladium (II) or palladium (0) title complex normally; Dihalide palladium (II) for example, acid chloride (II), palladous sulfate (II), dichloride two (triphenylphosphine) palladium (II), dichloride two (three cyclopentyl phosphines) palladium (II), dichloride two (tricyclohexyl phosphine) palladium (II), two (dibenzalacetone) palladium (0) or four (triphenylphosphine)-palladiums (0).Said palladium catalyst also can make through cooperating with the part of hope from palladium (II) or palladium (0) compound " original position ", the palladium that for example will cooperate (II) salt, for example palladium chloride (II) (PdCl
2) or acid chloride (II) (Pd (OAc)
2) with the part of hope, for example triphenylphosphine (PPh
3), three cyclopentyl phosphines or tricyclohexyl phosphine and selected solvent, with formula (P) compound, formula (L) compound and alkali combination.Also suitable bidentate ligand is, 1,1 '-two (diphenylphosphino) ferrocene or 1 for example, 2-two (diphenylphosphino) ethane.Through the reacting by heating medium,, then cause said C-C linked reaction to the desirable palladium of C-C linked reaction (II) title complex or " original position " formation thus of palladium (0) title complex.
The consumption of said palladium catalyst is 0.001-50mol%, and preferred amounts is 0.1-15mol%, based on formula (P) compound.More preferably the palladium source is an acid chloride, and said alkali is that Lithium Hydroxide MonoHydrate and said solvent are 1,4 of 2-glycol dimethyl ether and water: 1-1: 4 mixtures.Said reaction also can for example be carried out under the Tetrabutylammonium bromide existence such as tetraalkylammonium salt at other additives:
Formula (P) compound can be according to K.Schank and C.Lick, Synthesis, (1983), and 392-395, perhaps people such as Z Yang, Org.Lett., (2002), and 4 (19), the method for 3333-3336 is through handling by formula (J) compound with (diacetoxy) iodobenzene:
In another approach; Formula (A) compound can make via the rearrangement of formula (Q) compound down such as metal alkoxide (preferred formula (Q) compound relatively is equal to or greater than 100% amount), cyanide anion ion (for example 0.001-25% Potssium Cyanide, 0.001-25% sodium cyanide) or cyanalcohol (preferred formula (Q) compound relatively is the acetone cyanohydrin of 0.001-25%) existence at the reagent that promotes rearrangement.This reaction randomly in suitable solvent (for example acetonitrile), is carried out down and with suitable alkali (such as triethylamine) in optimal temperature (being generally 25-100 ℃).
Formula (Q) compound can be in suitable solvent (for example acetonitrile); Under optimal temperature (normally 25 ℃-150 ℃); With choose wantonly under microwave radiation; Through the catalyzer (such as palladium chloride (II), gold trichloride (I) or silver carbonate) that lactonizes with promotion, the silver carbonate of preferred formula (R) compound 0.001-50% is relatively handled, and preparation is from formula (R) compound.Similarly lactonize be known in document (referring to for example P.Huang and W.Zhou, Tetrahedron Asymmetry (1991), 2 (9), 875-878; And H.Harkat, J-M.Weibel, P.Pale, Tetrahedron Letters (2006), 47 (35), 6273-6276).
Formula (R) compound can through hydrolysis wherein R ' be that formula (S) compound of alkyl (preferable methyl or ethyl) prepares; And formula (S) compound can be through in the presence of the suitable palladium catalyst of the amount of the 0.001-25% that is generally formula (T) compound (for example dichloride two (triphenylphosphine) palladium (II), tetrakis triphenylphosphine palladium (0) or acid chloride, in the presence of suitable part), chooses wantonly in the presence of the suitable copper promotor (for example cupric iodide (I)) of amount of 0.001-50% that is formula (T) compound; Also can be used as in the presence of the suitable alkali of solvent (such as diethylamine, triethylamine, piperidines or tetramethyleneimine); Or choose wantonly and selecting solvent else as 1,4-dioxane, DMAC N,N, N; In the dinethylformamide; Choose wantonly under microwave radiation, through with formula (M) compound S onogashira coupling, the preparation from formula (T) compound.Similarly the Sonogashira coupling is known in document (referring to for example J.Vara Prasad, F.Boyer, L.Chupak, M.Dermyer, Q.Ding; K.Gavardinas, S.Hagen, M.Huband, W.Jiao, T.Kaneko; S.N.Maiti, M.Melnick, K.Romero, M.Patterson, X.Wu; Bioorganicand Medicinal Chemistry Letters (2006), 16 (20), 5392-5397, N.Leadbeater and B.Tominack, Tetrahedron Lett.; (2003), 8653-8656, Z.Gan and R.Roy, Canadian Journal of Chemistry (2002), 80 (8); 908-916 and K.Sonogashira, J.Organomet.Chem., (2002), 653,46-49 and reference wherein) in.
Formula (T) compound be known compound or can through with document (referring to, for example, people such as I.Drizin, WO2001/066544; M.Yamamoto, Journal of ChemicalResearch, Synopses (1991), (7), 165; P.Machin, US 4774253; M.Morgan and E.Heyningen, J.Am.Chem Soc., (1957), 79,422-424; N.Petiniot, A.J.Anciaux, A.F.Noels, A.J.Hubert, P.Teyssie; Tetrahedron letters, 1978,14,1239-42; And A.F.Noels, A.Demonceau, N.Petiniot, A.J.Hubert; P.Teyssie, Tetrahedron (1982), 38 (17), those similar approach of 2733-9) describing make.
In another approach, formula (A) compound can be preferably in the presence of the acid catalyst example hydrochloric acid and choose wantonly in the presence of suitable solvent such as THF through the hydrolysis preparation from formula (I) or (1A) compound (wherein G is C
1-4Alkyl).Formula (1) or (1A) compound (G C preferably wherein
1-4Alkyl) can be in the presence of suitable palladium catalyst (the for example acid chloride (II) of the 0.001-50% of relativization compound (U)) and alkali (the for example 1-10 equivalent potassiumphosphate of relativization compound (U)) and preferably suitable part (for example (the 2-dicyclohexyl phosphino-)-2 of the 0.001-50% of relativization compound (U) '; 6 '-dimethoxy-biphenyl) exist down; And in suitable solvent (for example toluene), preferred 25 ℃-200 ℃ down through with formula (U) compound (G C preferably wherein
1-4Alkyl and Hal are halogens, preferred bromine or iodine) make with formula (L) aromatic yl acid reaction.Similar coupling be known in document (referring to for example, Y.Song, B.Kim and J.-N.Heo, Tetrahedron Letters (2005), 46 (36), 5987-5990) in.
Formula (U) compound can be used halo C subsequently through halogenation formula (J) compound under known conditions
1-4Alkane or tributyl three-C
1-4-alkyl ester alkylation gained formula V halogenide makes; For example through R.Shepherd and A.White (J.Chem.Soc.Perkin Trans.1 (1987); 2153-2155) and people (Bioorg.Med.Chem. (2002), 10, method 685-690) such as Y.-L.Lin.Alternatively, formula (U) compound can pass through with alkylating reagent such as halo C
1-4Alkane or tributyl three-C
1-4-alkyl ester alkylation formula (J) compound and under known conditions halogenation gained formula (W) ketenes make (referring to for example Y.Song, B.Kim and J.-N.Heo, Tetrahedron Letters (2005), 46 (36), 5987-5990).
In another approach; Formula (A) compound can suitable palladium catalyst (for example with respect to the 0.001-50% of formula (J) compound acid chloride (II)) and alkali the 1-10 equivalent potassiumphosphate of formula (J) compound (for example with respect to) down and preferred the part that suits (for example with respect to (the 2-dicyclohexyl phosphino-)-2 of the 0.001-50% of formula (J) compound '; 4 '; 6 '-tri isopropyl biphenyl) exist down; With in suitable solvent (for example dioxane), preferred 25 ℃-200 ℃ and randomly under microwave heating through the reaction of formula (J) compound and formula (M) compound is made.Similarly coupling be known in document (referring to for example, J.Fox, X.Huang, A.Chieffi, S.Buchwald, J.Am.Chem.Soc. (2000), 122,1360-1370; People WO 2005/000233 such as B.Hong) in.Alternatively; Formula (A) compound can be at suitable copper catalyst (for example with respect to the 0.001-50% of compound (J) cupric iodide (I)) and alkali the 1-10 equivalent cesium carbonate of compound (J) (for example with respect to) down and in the presence of the preferred part that is suiting (for example with respect to the 0.001-50% of compound (J) L-proline(Pro)); With in suitable solvent (for example methyl-sulphoxide), preferred 25 ℃-200 ℃ are descended through formula (J) compound and the reaction of formula (M) compound are made.Similarly coupling be known in document (referring to for example Y.Jiang, N.Wu, H.Wu, M.He, Synlett, (2005), 18,2731-2734, X.Xie, G.Cai, D.Ma, Organic Letters (2005), 7 (21), 4693-4695) in.
In another approach, formula (A) compound can through under the Suzuki-Miyaura condition of describing at preamble with aryl-or heteroaryl-halogen R
2-Hal cross-coupling, wherein Hal preferably chlorine, bromine, iodine or pseudohalogen such as C
1-C
4Haloalkyl sulphonate, particularly trifluoromethane sulfonic acid ester are perhaps at people such as for example P.Lam, Tetrahedron Lett.; (1998), 39 (19), 2941-2944, and P.Lam; G.Vincent, C.G.Clark, S.Deudon, P.K.Jadhav; Tetrahedron Lett., (2001), 42, the copper catalytic condition that 3415-3418 describes descends and the heteroaromatics R that contains N-H
2The preparation of-H cross-coupling is from formula (X) compound.Formula X compound is specifically designed the synthetic midbody of formula I compound.
Formula (X) compound can be through handling with suitable alkali (such as sodium hydride or potassium hydride KH) in suitable solvent (such as THF or Anaesthetie Ether); Carry out subsequently metal-halogen exchange reaction (preferably through with alkyl lithium reagents such as n-Butyl Lithium, s-butyl lithium or tert-butyl lithium, or organomagnesium reagent is handled such as isopropylmagnesium chloride) also use trialkyl borate B (OR ") subsequently
3(preferred boric acid trimethyl) handled production (Y) aryl-boric acid ester and prepared from formula (H) compound (wherein Hal preferably iodine or bromine).Formula (Y) compound can be at hydrolysis production (X) boric acid under the acidic conditions.Alternatively, formula (X) compound can with those similar known palladium catalysis boron acylation conditions of quoting of preparation compound (L) prepare down from formula (H) compound (wherein Hal preferably iodine, bromine, chlorine or pseudohalogen such as C
1-C
4Haloalkyl sulphonate, particularly trifluoromethane sulfonic acid ester.
Formula (H) compound can prepare by preamble is said.Alternatively, formula (H) compound can with under those used similar conditions of formula (K) compound formula (A) compound with formula (Z) compound prepared in reaction from formula (J) compound.
Formula (Z) compound can be through preparing from formula (Y) compound from described those the similar methods of formula (L) compound formula (K) compound with preamble.
Formula (Z) compound be known compound (referring to, for example, people such as R.Bhatt, US2004/0204386), perhaps can be through currently known methods preparation from known compound, according to for example to the description of preparation formula (L) compound.
Formula I compound of the present invention can be used as weedicide like the form of the synthetic unmodified that is able to, but uses the formulation auxiliary agents like carrier, solvent and surfactant in every way their preparations to be become herbicidal composition usually.Said preparation can be various physical form; But for example pulvis, gelifying agent, wettable powder, water-dispersible granules, water dispersed tablet, effervesce compressed tablets, dense dose of missible oil microemulsified, aqueous emulsion, the finish that can flow, water dispersant, oil dispersant, suspended emulsion agent, micro-capsule suspension, newborn granula, soluble concentrate, water-soluble dense dose (have as the water of carrier or can with water blended organic solvent), the form of polymers impregnated film or known from for example the Manual on Development and Use of FAO Specifications forPlant Protection Products; The 5th edition, other form of 1999.These preparations can directly use or dilution before use.The preparation of dilution can prepare with for example water, liquid fertilizer, micro-nutrients, organism, oil or solvent.
These preparations can prepare like this, for example through activeconstituents is mixed the compsn of the solid, particle, solution, dispersion liquid or the emulsion form that obtain segmenting with formulation auxiliary agents.Activeconstituents can also be with other auxiliary agent preparation, for example vegetables oil, organic solvent, water, surfactant or its combination of the solid of segmentation, MO, vegetables oil, modification.Activeconstituents can also be included in the very tiny microcapsule that comprise polymkeric substance.Microcapsule comprise activeconstituents in porous support.This makes activeconstituents to be released into its environment with controlled quatity (for example slowly-releasing).Microcapsule have 0.1 to 500 micron diameter usually.They comprise activeconstituents, by capsules weight about 25 to 95%.Activeconstituents can exist with particulate form in monoblock solid form, solid or the liquid dispersion or suitable solution form.Encapsulated membranes comprises; For example, the polymkeric substance of natural or synthetic gum, Mierocrystalline cellulose, styrene-butadiene copolymer, polyacrylonitrile, polyacrylic ester, polyester, polymeric amide, polyureas, urethane or chemical modification and starch xanthate or other related polymer well known by persons skilled in the art.Alternatively, can form very thin microcapsule, wherein activeconstituents exists with the finely divided particulate form in the basic substance solid matrix, but microcapsule are not sealed in the case.
The formulation auxiliary agents itself that is suitable for preparing the present composition is known.Can be used as having of liquid vehicle: water, toluene, YLENE, sherwood oil, vegetables oil, acetone, methylethylketone, pimelinketone, acid anhydrides, acetonitrile, methyl phenyl ketone, pentyl acetate, 2-butanone, butylene carbonate, chlorobenzene, hexanaphthene, hexalin, alkyl acetate, diacetone alcohol, 1; 2-propylene dichloride, diethylolamine, p-Diethylbenzene, glycol ether, glycol ether rosin ester, diethylene glycol butyl ether, diethylene glycol monoethyl ether, glycol ether methyl ether, N; Dinethylformamide, the inferior maple, 1 of diformazan; 4-dioxane, DPG, DPG methyl ether, DPG dibenzoate, diproxitol, alkyl pyrrolidone, ETHYLE ACETATE, 2-Ethylhexyl Alcohol, ethylene carbonate, 1; 1,1-trichloroethane, 2-heptanone, α-Pai Xi, d-PC 560, ethyl lactate, terepthaloyl moietie, ethylene glycol butyl ether, Ethylene Glycol Methyl ether, gamma-butyrolactone, glycerine, glycerol acetate, glyceryl diacetate, vanay, n-Hexadecane, pinakon, Isoamyl Acetate FCC, isobornyl acetate, octane-iso, isophorone, isopropyl benzene, Isopropyl myristate, lactic acid, amino dodecane, mesityl oxide, methoxypropanol, methyl isoamyl ketone, MIBK, Laurate methyl, methyl caprylate, Witconol 2301, methylene dichloride, m-xylene, normal hexane, NSC 9824, octadecanoic acid, octylame acetate, oleic acid, oleoyl amine, o-Xylol, phenol, polyoxyethylene glycol (PEG400), propionic acid, propyl lactate, Texacar PC, Ucar 35, methyl proxitol, p-Xylol, toluene, triethyl phosphate, triglycol, xylene monosulfonic acid, alkane, MO, trieline, tetrachloroethylene, ETHYLE ACETATE, pentyl acetate, butylacetate, methyl proxitol, glycol ether methyl ether, methyl alcohol, ethanol, Virahol and like the alcohol of the more amount of polymers of primary isoamyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, terepthaloyl moietie, Ucar 35, glycerine, N-N-methyl-2-2-pyrrolidone N-etc.For the dilution enriched material, generally select water to make carrier.Suitable solid carrier is; For example, talcum, titanium oxide, pyrophyllite clay, tripoli, attapulgite clay, zeyssatite, Wingdale, lime carbonate, wilkinite, smectite calcium, cotton seed hulls, sye middlings, soya flour, float stone, wood chip, the similar substance that grinds English walnut (ground walnut) shell, xylogen and for example describe among CFR 180.1001. (c) & (d).
The exhibiting high surface active substance can be advantageously utilised in solid and the liquid preparation, particularly in those preparations of available support dilution before use.Surfactant can be negatively charged ion, positively charged ion, nonionic or polymkeric substance, and they also can be used as emulsifying agent, wetting agent or suspension agent or are used for other purposes.Typical surfactant comprises that for example, alkyl-sulphate is such as lauryl sulfate di-alcohol ammonium; Alkylaryl sulphonate is such as calcium dodecylbenzene sulphonate; The adduct of alkylphenol-epoxy alkane is such as ethoxylated nonylphenol; The adduct of alcohol-epoxy alkane is such as the ethoxylation tridecyl alcohol; Soap is such as StNa; Sulfonated alkyl naphathalene is such as sodium dibutyl naphthalene sulfonate; The dialkyl of sulfosuccinate is such as sodium sulfosuccinate two (2-ethylhexyl) ester; Sorbitol ester is such as the Sorbitol Powder oleic acid ester; Quaternary ammonium, such as Trimethyllaurylammonium chloride, the polyglycerol fatty acid glycol ester is such as gathering glycol stearate; The segmented copolymer of oxyethane and propylene oxide; Single-with the salt of two-alkyl phosphate; Also have at for example " McCutcheon ' s Detergents and Emulsifiers Annual " MC Publishing Corp. Ridgewood New Jersey, other material of describing in 1981.
Other auxiliary agent that can be used in usually in the pesticide preparation can comprise crystallization inhibitor, viscosity modified material, suspension agent, dyestuff, inhibitor, pore forming material, light absorber, mixed aid, skimmer, coordination agent, neutralization or pH-modified material and buffer reagent, corrosion-suppressor factor, spices, wetting agent, absorption activator, micro-nutrients, softening agent, glidant, lubricant, dispersion agent, thickening material, frostproofer, microbiocide and liquid and solid fertilizer.
Said preparation can also comprise extra active substance, for example other weedicide, herbicide-safener, plant-growth regulator, mycocide or sterilant.
The present composition can also comprise additive, and it comprises alkyl ester or the such oil and the mixture of oily verivate of the oil, MO of plant or animal-origin, such oil.The amount that is used for the oil additive of the present composition generally is from 0.01 to 10%, based on the spray mixing thing.For example, can be after preparing the spray mixing thing can oil additive be added to spray cistern with the concentration of hope.Preferred oil additive comprises the oil of MO or plant origin, for example rapeseed oil, sweet oil or sunflower oil, the alkyl ester of emulsified vegetable oil oil of (
-Poulenc CanadaInc.), plant origin like
such as oil such as the fish oil or the tallow of methyl-derivatives or animal-origin.Preferred additives comprises, and for example, as activeconstituents the fish oil alkyl ester of 80% weight and the rapeseed oil that methylates of 15% weight basically, also has the habitual emulsifying agent and the pH properties-correcting agent of 5% weight.Preferred especially oil additive comprises C
8-C
22Effective for treatment of premature ejaculation, particularly C
12-C
18The methyl-derivatives of lipid acid, for example important LAURIC ACID 99 MIN, palmitinic acid and oleic methyl esters.These esters are known as Laurate methyl (CAS-111-82-0), Uniphat A60 (CAS-112-39-0) and Witconol 2301 (CAS-112-62-9).Preferred fatty acid methyl ester derivative is
2230 and 2231 (Cognis GmbH).These oily verivates are also known to the Compendium of Herbicide Adjuvants, the 5th edition, Southern Illinois University, 2000 with other oily verivate.
Using and acting on of oil additive can also improve through itself and surfactant such as nonionic, negatively charged ion or cats product are made up.The instance of suitable negatively charged ion, nonionic and cats product is shown in the 7th page and the 8th page of WO 97/34485.Preferred surfactant is the AS of dodecyl benzyl sulfonic acid salt, the nonionogenic tenside of particularly its calcium salt, and ethoxylized fatty alcohol class.Particularly preferably be ethoxylation C with 5 to 40 ethoxylation degrees
12-C
22Fatty Alcohol(C12-C14 and C12-C18).The instance of the tensio-active agent that can buy is Genapol type (Clariant AG).Silicone surfactant further preferably; Seven methyl trisiloxanes of many trialkylphosphine oxides modification particularly; It for example can be used as that SilwetL-
buys, and the perfluorination tensio-active agent.The surfactant concentration of total relatively additive is from 1 to 30% weight generally.The example additives that comprises oil or MO or derivatives thereof and surfactant mixtures is Edenor ME
(SyngentaAG; CH) and
(BP Oil UK Limited, GB).
Said surfactant can also be used for preparation, i.e. non-refuelling additive separately.
In addition, in oil additive/surfactant mixt, add organic solvent and can help the further enhancing that acts on.The suitable solvent is; For example,
(ESSO) and Aromatic
(Exxon Corporation).The concentration of this solvent can be 10 to 80% of gross weight.This for example can being described in the oil additive of solvent among the US-A-4834908, wherein disclosed commercially available oil additive is called
(BASFCorporation).Preferred another oil additive of the present invention is
(SyngentaCrop Protection Canada).
Except the top oil additive of listing; In order to strengthen the effect of the present composition, can also alkyl pyrrolidone preparation (for example
) be added the spray mixing thing.Can also use comprise network structure (latice) preparation; Such as, for example SEPIGEL 305, polyvinyl compound or gather-1-p-menthene (for example
or
).The solution that comprises propionic acid, for example Eurogkem Pen-e-
also can sneak in the spray mixing thing as active reinforcing agent.
Herbicidal formulations comprises the formula I compound of from 0.1 to 99% weight, particularly from 0.1 to 95% weight and the formulation auxiliary agents of from 1 to 99.9% weight usually, and it preferably includes the surfactant of from 0 to 25% weight.Though the commerical prod preferred formulation is an enriching agent, the terminal user adopts the preparation of dilution usually.
The rate of application of formula I compound can change in wide region and depend on that soil property, application process are (after emerging preceding or emerging; Seed dressing; In kind of furrow, use; No-tillage use etc.), crop plants, the weeds that will prevent and treat or gramineous grass, prevailing weather conditions and other receive factor, time of application and the target crop of application process control.Formula I compound of the present invention is used with the ratio of 1-4000g/ha, particularly 5-1000g/ha usually.
Preferred preparation has following composition especially:
(%=weight percent):
Missible oil:
Activeconstituents: 1-95%, preferred 60-90%
Tensio-active agent: 1-30%, preferred 5-20%
Liquid vehicle: 1-80%, preferred 1-35%
Pulvis:
Activeconstituents: 0.1-10%, preferred 0.1-5%
Solid carrier: 99.9-90%, preferred 99.9-99%
Suspension concentrates:
Activeconstituents: 5-75%, preferred 10-50%
Water: 94-24%, preferred 88-30%
Tensio-active agent: 1-40%, preferred 2-30%
Wettable powder:
Activeconstituents: 0.5-90%, preferred 1-80%
Tensio-active agent: 0.5-20%, preferred 1-15%
Solid carrier: 5-95%, preferred 15-90%
Granule:
Activeconstituents: 0.1-30%, preferred 0.1-15%
Solid carrier: 99.5-70%, preferred 97-85%
Following embodiment further illustrates rather than limits the present invention.
F1. missible oilA) d c b)))
Activeconstituents 5% 10% 25% 50%
Calcium dodecylbenzene sulphonate 6% 8% 6% 8%
Viscotrol C polyglycol ether 4%-4% 4%
(36mol oxyethane)
Octylphenol polyethylene glycol ether-4%-2%
(7-8mol oxyethane)
NMP - - 10％ 20％
The aromatic hydrocarbon mixture C
9-C
1285% 78% 55% 16%
The emulsion of concentration is hoped in this liquid concentrator preparation of dilutable water arbitrarily.
F2. solutionA) d c b)))
Activeconstituents 5% 10% 50% 90%
1-methoxyl group-3-(the 3-methoxyl group-
Propoxy-)-propane-20% 20%-
Polyethylene glycol MW 400 20% 10%--
NMP - - 30％ 10％
The aromatic hydrocarbon mixture C
9-C
1275% 60%--
This solution is suitable for using with droplet agent form.
F3. wettable powderA) d c b)))
Activeconstituents 5% 25% 50% 80%
Sodium lignosulfonate 4%-3%-
Sodium Lauryl Sulphate BP/USP 2% 3%-4%
Diisobutyl sodium naphthalene sulfonate-6% 5% 6%
Octylphenol polyethylene glycol ether-1% 2%-
(7-8mol oxyethane)
High dispersive silicic acid 1% 3% 5% 10%
Kaolin 88% 62% 35%-
This activeconstituents mixes with auxiliary agent fully, and said mixture fully grinds in suitable shredder, obtain wettable powder, but its thin up provides the suspension agent that requires concentration arbitrarily.
F4. coatedparticles agentA) c b))
Activeconstituents 0.1% 5% 15%
High dispersive silicic acid 0.9% 2% 2%
Inorganic carrier 99.0% 93% 83%
(diameter 0.1-1mm)
CaCO for example
3Or SiO
2
This activeconstituents is dissolved in methylene dichloride, and on carrier, then steaming desolventizes in a vacuum with solution spraying.
F5. coatedparticles agentA) c b))
Activeconstituents 0.1% 5% 15%
Polyethylene glycol MW 200 1.0% 2% 3%
High dispersive silicic acid 0.9% 1% 2%
Inorganic carrier 98.0% 92% 80%
(diameter 0.1-1mm)
CaCO for example
3Or SiO
2
In stirrer, the activeconstituents that fully grinds is applied to the moistening carrier of polyoxyethylene glycol equably.Obtain dustless coatedparticles agent in this way.
F6. extrude granuleA) d c b)))
Activeconstituents 0.1% 3% 5% 15%
Sodium lignosulfonate 1.5% 2% 3% 4%
CMC 99.5 1.4% 2% 2% 2%
Kaolin 97.0% 93% 90% 79%
Used additives mixes with activeconstituents and grinds, with this mixture of water-wet.It is dry in airflow that the mixture that obtains is extruded the back.
F7. pulvisA) c b))
Activeconstituents 0.1% 1% 5%
Talcum 39.9% 49% 35%
Kaolin 60.0% 50% 60%
Obtain promptly to use pulvis through mixed active composition and carrier and at the said mixture of suitable grinding machine for grinding.
F8. suspension concentratesA) d c b)))
Activeconstituents 3% 10% 25% 50%
Terepthaloyl moietie 5% 5% 5% 5%
Nonoxynol-9-1% 2%-
(15mol oxyethane)
Sodium lignosulfonate 3% 3% 4% 5%
CMC 99.5 1% 1% 1% 1%
37% formalin 0.2% 0.2% 0.2% 0.2%
Silicone oil emulsion 0.8% 0.8% 0.8% 0.8%
Water 87% 79% 62% 38%
Used additives and the activeconstituents intimate of fully grinding obtain suspension concentrates, and the dilute with water latter can prepare the suspension agent that requires concentration arbitrarily.
Invention also relates to gramineous grass and the method for weed in the selectivity control useful plant crop, and it comprises with the said useful plant of formula I compound treatment or its cultural area or place.
Wherein can use the useful plant crop of the present composition to comprise cereal, cotton, soybean, sugar beet, sugarcane, plantation crops, rape, corn and rice, and be used for non-selective control of weeds.The present composition is used in particular for selectivity control gramineous grass and weeds in cereal, corn and rice, particularly rice.Term " crop " should be understood that also to comprise the crop that makes its herbicide-tolerant or classes of herbicides (for example ALS, GS, EPSPS, PPO, ACCase and HPPD suppressor factor) through conventional breeding method or genetically engineered.Making its instance that tolerates the crop of imidazolone type for example such as imazamox through the conventional breeding method is
rape in summer (rape).The instance that makes it the crop of herbicide-tolerant through gene engineering method comprises resistance glyphosate and the corn that resists careless ammonium phosphine, and this kind can be buied according to trade(brand)name
and
.The weeds that prevent and treat can be unifacial leaf and broadleaf weed; Such as; For example, Stellaria (Stellaria), Nasturtium (Nasturtium), Agrostis (Agrostis), knotgrass (Digitaria), Avena (Avena), setaria (Setaria), sinapsis alba genus (Sinapis), lolium (Lolium), Solanum (Solanum), Echinochloa (Echinochloa), Scirpus (Scirpus), Monochoria (Monochoria), arrowhead belong to (Sagittaria), Brome (Bromus), amur foxtail belongs to (Alopecurus), Sorghum (Sorghum), Rottboellia exaltata L. F. genus (Rottboellia), Cyperus (Cyperus), abutilon (Abutilon), chrysanthemum sth. made by twisting genus (Sida), Xanthium (Xanthium), Amaranthus (Amaranthus), Chenopodium (Chenopodium), Ipomoea (Ipomoea), Chrysanthemum (Chrysanthemum), Bedstraw (Galium), Viola (Viola) and Veronica (Veronica).
Crop also is understood that to make it to harmful insect those of resistance, for example Bt corn (European corn borer is had resistance), Bt cotton (cotton boll has been resembled resistance) and Bt yam (colorado potato beetles are had resistance) arranged through gene engineering method.The instance of Bt corn is the Bt-176 hybrid maize of
(Syngenta Seeds).This Bt toxin is by the natural albumen that forms of Bacillus thuringiensis (Bacillus thuringiensis) soil bacteria.The case description of toxin and the transgenic plant that can synthesize this toxin is in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529.The transgenic plant instance that comprises one or more coded insect-killing resistances and the gene of expressing one or more toxin is that
(corn), Yield
(corn),
(cotton),
(cotton),
(yam),
He
plant crop are with its seed material can have resistance to weedicide, and simultaneously to the insect resistance (" synergetic " transgenic event) of having ingested.Seed for example can have the ability of expressing insecticidal activity Cry3 albumen and glyphosate tolerant being arranged at the same time.Term " crop " should be understood that also to comprise the crop that obtains through conventional breeding method or genetically engineered that it comprises so-called output characteristic (for example improved taste, storage stability, nutritive ingredient).
Cultural area should be understood to include the soil of the crop plants of wherein having grown and the soil that is intended for use the cultivation of these crop plants.
Formula I compound of the present invention can also use with one or more other combinations of herbicides.The following mixture particularly important of formula I compound.Preferably, in these mixtures, formula I compound is one of those compounds of listing of back literary composition table 1-294:
Reference example such as The Pesticide Manual, the 12nd edition (BCPC), the content in 2000, the mixed thing of formula I compound can also be the form of ester or salt.
Formula of the present invention (I) compound can also use with the safener combination.Preferably, in these mixtures, formula (I) compound is one of those compounds of listing of back literary composition table 1-294.The following mixture of special consideration and safener:
Formula (I) compound+cloquintocetmexyl, formula (I) compound+cloquintocetmexyl acid and salt thereof, formula (I) compound+fenchlorazole, formula (I) compound+fenchlorazole acid and salt thereof; Formula (I) compound+mefenpyrdiethyl, formula (I) compound+mefenpyrdiethyl (mefenpyr diacid), formula (I) compound+Shuan Ben oxazole acid-ethyl esters, the acid of formula (I) compound+Shuan Ben oxazoles; Formula (I) compound+furilazole, formula (I) compound+furilazole R isomer, formula (I) compound+benoxacor, formula (I) compound+dichlormide; Formula (I) compound+AD-67, formula (I) compound+oxabetrinil, formula (I) compound+cyometrinil; Formula (I) compound+cyometrinil Z-isomer, formula (I) compound+fenclorim, formula (I) compound+ring acyl sulphur grass amine (cyprosulfamide); Formula (I) compound+acid phthalic anhydride, formula (I) compound+flurazole, formula (I) compound+N-(2-anisoyl)-4-[(methylamino carbonyl) amino] benzsulfamide; Formula (I) compound+CL 304,415, the phonetic humulone of formula (I) compound+pyrrole (dicyclonon); Formula (I) compound+fluxofenim, formula (I) compound+DKA_24, formula (I) compound+R-29148 and formula (I) compound+PPG-1292.Can also observe formula (I) compound+daimuron, formula (I) compound+2 first, 4 chlorine, the safe effect of formula (I) compound+Vi par and formula (I) compound+mecopropP.
Above-mentioned safener of mentioning and weedicide are described in, the Pesticide Manual for example, the 12nd edition, British Crop Protection Council, 2000.R-29148 is for example by people such as P.B.Goldsbrough; Plant Physiology; (2002); The 130th volume 1497-1505 page or leaf and reference are wherein described, and PPG-1292 is known in WO 09211761 and N-(2-anisoyl)-4-[(methylamino carbonyl) amino] benzsulfamide is known in EP365484.
The preferred present composition removes and comprises formula I compound, also comprises other weedicides and safener as mixed thing.
Following embodiment further illustrates the present invention but does not limit the present invention.
It will be appreciated by those skilled in the art that some compounds that describe below are β-ketone enols; And itself can be used as single tautomer or exist as the mixture of ketone enol and two keto tautomers; J.March for example; Advanced Organic Chemistry, the third edition, the description among the John Wileyand Sons.Hereinafter and the independent enol tautomer of showing to show among T1 and the P1 of the artificial paintings of compound, but should be appreciated that this description comprises said diketone and can pass through any possible enol that tautomerism forms.In addition, some compounds that hereinafter and Table A, table B, table C and table show among the D draw for simplicity is merely single enantiomer, only if but being illustrated as single enantiomer, these structures are interpreted as representing the mixture of enantiomer.In addition, some compounds can be used as diastereomer and exist, and should understand mixture or any single diastereomer that they can represent diastereomer.At detailed experimental section,, still select two keto tautomers from the name purpose even main tautomer is the enol form.
Preparation embodiment:
Embodiment 1: preparation 4-(4 '-chloro-4-methyl diphenyl-3-yl)-2,2,6,6-tetramethyl-pyrans-3,5-diketone
Step 1: preparation 3-amino-4 '-chloro-4-methyl diphenyl
With tetrakis triphenylphosphine palladium (0) (3.7g, 0.003mol) with the 4-chlorophenylboronic acid (20.2g, 0.13mol) add to 5-bromo-2-aminotoluene (20g, 0.1mol) 1,2-glycol dimethyl ether (200ml) solution.After 15 minutes, (300ml) adds to mixture with 20% aqueous sodium carbonate at 20 ℃ of stirred reaction mixtures, and heating gained mixture is 24 hours under refluxing.Reaction mixture is cooled to room temperature,, uses ethyl acetate extraction with the dilution of (600ml) water.The organic extract that merges is dry on SODIUM SULPHATE ANHYDROUS 99PCT, filters vacuum concentrated filtrate.Further through column chromatography purifying resistates on silica gel, the ethyl acetate/hexane wash-out with 7%, provide 3-amino-4 '-chloro-4-methyl diphenyl (21.0g).
Step 2: preparation 3-bromo-4 '-chloro-4-methyl diphenyl
With Hydrogen bromide (48% weightaqueous solution, 120ml) drop to 3-amino-4 '-(21g, water 0.09mol) (80ml) suspension-s stirs the mixture and dissolves up to solid chloro-4-methyl diphenyl.Mixture is cooled to-5 ℃, (keeping temperature is 0-5 ℃ for 10.12g, the 0.14mol) aqueous solution (50ml) to drip Sodium Nitrite.Stirred reaction mixture 1 hour adds to 0 ℃ the cuprous bromide of refrigerative in advance (17.9g, Hydrogen bromide 0.12mol) (48% weightaqueous solution, 120ml) solution subsequently.Stirred reaction mixture makes it be warmed to ambient temperature overnight.Mixture is used ethyl acetate extraction, merges organic extract, and is dry on SODIUM SULPHATE ANHYDROUS 99PCT, filters vacuum concentrated filtrate.Further through column chromatography purifying resistates on silica gel, with 2% ethyl acetate/hexane wash-out, provide 3-bromo-4 '-chloro-4-methyl diphenyl (15.0g).
Step 3: preparation 4 '-chloro-4-methyl diphenyl-3-ylboronic acid
With 3-bromo-4 '-(5.0g 0.02mol) is dissolved in anhydrous tetrahydro furan (125ml) to chloro-4-methyl diphenyl, mixture is cooled to-78 ℃.(hexane solution of 1.33 volumetric molar concentrations, 17.3ml), temperature remains on approximately-78 ℃ in 30 minutes, to drip n-Butyl Lithium.-78 ℃ of stirred reaction mixtures 1.5 hours, (2.58g, 0.024mol), stirred reaction mixture 3.5 hours made it be warmed to 0 ℃ to drip trimethyl borate then.Drip 2N aqueous hydrochloric acid (50ml) then, mixture stirred 2 hours after being added dropwise to complete.Vacuum concentrated mixture is removed most of THF, then water (～80ml) dilute and use extracted with diethyl ether.Merge organic extract, dry on SODIUM SULPHATE ANHYDROUS 99PCT, filter vacuum concentrated filtrate.On silica gel, be further purified resistates through flash column chromatography, with 7% ethyl acetate/hexane wash-out, provide 4 '-chloro-4-methyl diphenyl-3-ylboronic acid (2.5g).
Step 4: preparation 4 '-chloro-4-methyl diphenyl-3-base nitrilotriacetic is plumbous
Step 4a:
(2.44g, 5.50mmol) (0.16g 0.50mmol) adds anhydrous chloroform (6ml) in the mixture with oxalic acid mercury to the lead tetraacetate with the nitrogen cleaning down.This mixture is warmed to 40 ℃, once add 4 '-(1.23g, 5.00mmol), this suspension-s heated 5 hours under this temperature chloro-4-methyl diphenyl-3-ylboronic acid.After being cooled to room temperature, mixture is concentrated into small volume, grinds with hexane subsequently, filter produce thick 4 '-chloro-4-methyl diphenyl-3-base nitrilotriacetic plumbous (2.93g).
Step 4b:
With thick 4 '-chloro-4-methyl-biphenyl-3-base nitrilotriacetic plumbous (1.50g) is dissolved in anhydrous chloroform (20ml), (0.59g 4.24mmol), then stirred 5 minutes fast to wherein adding powdered anhydrous salt of wormwood.Through solids removed by filtration, that concentrated organic solution provides is pure 4 '-chloro-4-methyl diphenyl-3-base nitrilotriacetic plumbous (1.121g), be the bright orange solid.
Step 5: preparation 4-(4 '-chloro-4-methyl diphenyl-3-yl)-2,2,6,6-tetramethyl-pyrans-3,5-diketone
To 2,2,6,6-tetramethyl-pyrans-3, (0.296g, 1.74mmol) and N, (1.06g, mixture 8.70mmol) adds anhydrous chloroform (20ml) to the N-dimethyl aminopyridine to 5-diketone (being described in US5089046A), at room temperature stirs until dissolving subsequently.In this solution, add dry toluene (5ml), once add 4 subsequently '-chloro-4-methyl diphenyl-3-base nitrilotriacetic plumbous (1.12g, 1.91mmol), in 80 ℃ of reacting by heating mixtures 1-2 hour.Make mixture be cooled to room temperature, use the dilution of methylene dichloride (150ml) and diluted hydrochloric acid aqueous solution (30ml) then, then stirred 5 minutes, remove inorganic residues (using solvent wash in addition) through diatomite filtration.Merge whole organic fractions, dry on anhydrous magnesium sulfate, vacuum concentration.Crude product is through column chromatography (hexane/ethyl acetate of 100% hexane-5: 1) purifying, and grinding with hexane then provides 4-(4 '-chloro-4-methyl diphenyl-3-yl)-2,2,6,6-tetramethyl-pyrans-3, and 5-diketone (0.318g) is an off-white powder.
Embodiment 2: preparation 4-(4 '-chloro-4-ethyl biphenyl-3-yl)-2,2,6,6-tetramethyl-pyrans-3,5-diketone
Step 1: preparation 4-ethyl-3-N-methyl-p-nitroaniline
(39.6g, 0.49mol) add to refrigerative (ice bath) 4-MEA (keeping temperature through externally cooled is-10 ℃-0 ℃ for 20g, vitriol oil 0.16mol) (100ml) solution in batches with an ammonium nitrate.Stirred reaction mixture 2 hours inclines to trash ice, through filtering collecting precipitation.Use water dispersible solid, add the dilute sodium hydroxide aqueous solution neutralization solution, use ethyl acetate extraction.Merge organic extract, dry on SODIUM SULPHATE ANHYDROUS 99PCT, filter, vacuum concentrated filtrate provides 4-ethyl-3-N-methyl-p-nitroaniline (20g).
Step 2: preparation 4-bromo-1-ethyl-2-oil of mirbane
(48% weightaqueous solution, (20g, water 0.12mol) (80ml) suspension-s stirs the mixture and dissolves until solid 240ml) to drop to 4-ethyl-3-N-methyl-p-nitroaniline with Hydrogen bromide.Mixture is cooled to-5 ℃, (keeping temperature is 0-5 ℃ for 19.8g, the 0.28mol) aqueous solution (100ml) to drip Sodium Nitrite.Add in case accomplish, remove cooling bath, at room temperature stirred reaction mixture is 1 hour.Mixture dropped to 0 ℃ the cuprous bromide of refrigerative in advance (22.4g, Hydrogen bromide 0.16mol) (48% weightaqueous solution) solution.Stirred reaction mixture also makes it in 3 hours, be warmed to room temperature.Use the extracted with diethyl ether mixture, merge organic extract, dry on SODIUM SULPHATE ANHYDROUS 99PCT, filter vacuum concentrated filtrate.On silica gel, be further purified resistates through column chromatography, use the hexane wash-out, provide 4-bromo-1-ethyl-2-oil of mirbane (18g)
Step 3: preparation 4 '-chloro-4-ethyl-3-nitrobiphenyl
At room temperature; To 150ml 1, (20.0g 0.087mol) adds 4-chlorophenylboronic acid (14.98g to the 4-bromo-1-ethyl-2-oil of mirbane in the 2-glycol dimethyl ether; 0.096mol) and tetrakis triphenylphosphine palladium (0) (2.0g 0.00174mol) passes through mixture with nitrogen bubble.After stirring 10 minutes under 20 ℃, add yellow soda ash (73.8g, aqueous solution 0.696mol) (350ml), backflow mixture 16 hours.Reaction mixture is cooled to room temperature, through diatomite filtration, washs with 200ml ETHYLE ACETATE.With mixture impouring separating funnel, two separate mutually.Use the ethyl acetate extraction water.Merge organic extract, dry on anhydrous magnesium sulfate, filter, vacuum-evaporation filtrating, provide 4 '-chloro-4-ethyl-3-nitrobiphenyl (23.84g), be brown oil, do not add to be further purified and be used for subsequent step.
Step 4: preparation 3-amino-4 '-chloro-4-ethyl biphenyl
With 4 '-(22.6g 0.086mol) is suspended in the methyl alcohol (250ml), at room temperature stirred reaction mixture chloro-4-ethyl-3-nitrobiphenyl.Add zero(ppm) water (100ml), add subsequently zinc powder (39.0g, 0.60mol) and ammonium chloride (13.8g, 0.26mol), with mixture heating up to refluxing 1 hour.Reaction mixture is cooled to room temperature, and through diatomite filtration, vacuum concentrated filtrate is removed most of methyl alcohol.Resistates phase-splitting between ETHYLE ACETATE (200ml) and water is with ETHYLE ACETATE (200ml) aqueous phase extracted once more.Merge organic extract, water and brine wash, dry on anhydrous magnesium sulfate, filter, vacuum-evaporation filtrating, provide 3-amino-4 '-chloro-4-ethyl biphenyl (15.0g), be colorless solid.Product does not add to be further purified and directly is used for step 5.
Step 5: preparation 3-bromo-4 '-chloro-4-ethyl biphenyl
Step 5a:
With 3-amino-4 '-chloro-4-ethyl biphenyl (60.0g, 0.26mol) add in batches Hydrogen bromide (48% weightaqueous solution, 350ml) with the mixture of water (250ml), accomplish adding after, with mixture heating up to 40 ℃, stirred 20 minutes.In ice bath, be cooled to 5 ℃ subsequently.(20.65g, aqueous solution 0.30mol) (100ml) are accomplished the adding back and under 5 ℃, were continued to stir the mixture 45 minutes in 45 minutes, to drip Sodium Nitrite.
Step 5b:
Simultaneously, (48% weightaqueous solution 400ml) and at 70 ℃ stirs a collection of adding Salzburg vitriol (74.75g down to the heating Hydrogen bromide; 0.30mol), under 70 ℃, stirred the mixture 2 minutes, provide deep purple solution; (26.44g 0.42mol), obtains pink colour suspension-s to a collection of then adding copper powder.
Step 5c
Under 70 ℃, the mixture that will comprise diazonium salt (being prepared in step 5a) added the mixture that is prepared in step 5b (the said diazonium salt that comprises keeps cooling during the adition process in ice bath) in stirring in batches in 70 minutes.After accomplishing adding, under 70 ℃, continued to stir the mixture 30 minutes, make it to be cooled to room temperature then, with ETHYLE ACETATE (3 * 500ml) extractions.Merge organic extract, water and brine wash, dry on anhydrous magnesium sulfate, filter vacuum-evaporation filtrating.Through column chromatography purifying on silica gel provide 3-bromo-4 '-chloro-4-ethyl biphenyl (52.1g), be yellow oil
Step 6: preparation 4 '-chloro-4-ethyl biphenyl-3-ylboronic acid
With 3-bromo-4 '-(10g 0.03mol) is dissolved in THF (250ml) to chloro-4-ethyl biphenyl, is cooled to temperature-78 ℃.(the hexanol solution of 1.33 volumetric molar concentrations, 34.6ml), temperature remains on approximately-78 ℃ in 30 minutes, to drip n-Butyl Lithium.Stirred reaction mixture 1.5 hours drips trimethyl borate (4.9g, 0.05 mole), stirred reaction mixture 2 hours then.Drip 2N aqueous hydrochloric acid (100ml), adding stirred the mixture 2 hours after accomplishing.Enriched mixture is removed most of THF, and dilute with water is used extracted with diethyl ether.Organic extract water and brine wash merge, and be dry on SODIUM SULPHATE ANHYDROUS 99PCT, filters vacuum-evaporation filtrating.On silica gel, be further purified resistates through flash column chromatography, with 7% ethyl acetate/hexane wash-out, provide 4 '-chloro-4-ethyl biphenyl-3-ylboronic acid (5.4g).
Step 7: preparation 4 '-chloro-4-ethyl biphenyl-3-base nitrilotriacetic is plumbous
Step 7a:
(2.15g, 4.85mmol) (0.15g adds anhydrous chloroform (6ml) in mixture 0.47mmol) with oxalic acid mercury to the lead tetraacetate with the nitrogen cleaning down.This mixture is warmed to 40 ℃, a collection of adding 4 '-(1.17g 4.50mmol), added hot suspension 5 hours to chloro-4-ethyl biphenyl-3-ylboronic acid under this temperature.Cooling mixture is concentrated into small volume to room temperature then, grinds with hexane, filters, produce thick 4 '-chloro-4-ethyl biphenyl-3-base nitrilotriacetic plumbous (2.70g).
Step 7b:
With thick 4 '-chloro-4-ethyl biphenyl-3-base nitrilotriacetic plumbous (1.50g) is dissolved in anhydrous chloroform (20ml), (0.58g 4.16mmol), stirred 5 minutes subsequently fast to wherein adding powdered anhydrous salt of wormwood.Solids removed by filtration concentrates organic solution, provide pure 4 '-chloro-4-ethyl biphenyl-3-base nitrilotriacetic plumbous (1.176g), be the bright orange solid.
Step 8: preparation 4-(4 '-chloro-4-ethyl biphenyl-3-yl)-2,2,6,6-tetramethyl-pyrans-3,5-diketone
To 2,2,6,6-tetramethyl-pyrans-3, (0.303g, 1.78mmol) and N, (1.09g adds anhydrous chloroform (20ml) to the N-dimethyl aminopyridine to 5-diketone (being described in US5089046A) in mixture 8.90mmol), at room temperature stir up to dissolving subsequently.In this solution, add dry toluene (5ml), a collection of subsequently adding 4 '-chloro-4-ethyl biphenyl-3-base nitrilotriacetic lead (1.17g, 1.96mmol), at 80 ℃ of following heated mixt 1-2 hours.Make mixture be cooled to room temperature,, stirred subsequently 5 minutes, remove inorganic residues (using solvent wash in addition) through diatomite filtration with methylene dichloride (150ml) and diluted hydrochloric acid aqueous solution (30ml) dilution.Merge whole organic fractions, dry on anhydrous magnesium sulfate, vacuum concentration.Through column chromatography (hexane/ethyl acetate of 100% hexane-5: 1 ratio) purifying crude product, grind with hexane then, 4-(4 '-chloro-4-ethyl biphenyl-3-yl)-2,2,6 is provided, 6-tetramethyl-pyrans-3,5-diketone (0.46g) is an off-white powder.
Embodiment 3: preparation 4-(3 ', 4 '-two fluoro-4-methyl diphenyl-3-yls)-2,2,6,6-tetramethyl-pyrans-3,5-diketone
Step 1: preparation 5-chloro-2-aminomethyl phenyl nitrilotriacetic is plumbous
(2.15g, 4.85mmol) (0.15g adds anhydrous chloroform (6ml) in mixture 0.47mmol) with oxalic acid mercury to the lead tetraacetate with the nitrogen cleaning down.This mixture is warmed to 40 ℃, and (0.76g, 4.46mmol), stirred suspension is 5 hours under this temperature for a collection of adding 5-chloro-2-aminomethyl phenyl boric acid.After being cooled to room temperature, enriched mixture grinds with hexane to small volume then, filters, and produces thick 5-chloro-2-aminomethyl phenyl nitrilotriacetic plumbous (2.27g).
Step 2: preparation 4-(5-chloro-2-aminomethyl phenyl)-2,2,6,6-tetramethyl-pyrans-3,5-diketone
To 2,2,6,6-tetramethyl-pyrans-3, (0.504g, 2.96mmol) and N, (1.45g adds anhydrous chloroform (40ml) to the N-dimethyl aminopyridine to 5-diketone (being described in US5089046A) in mixture 11.84mmol).(2.26g 4.44mmol), then at 40 ℃ of following heated mixt 17 hours (analysis), continues heating 23 hours down at 45-50 ℃ to a collection of adding 5-chloro-2-aminomethyl phenyl nitrilotriacetic lead in this solution then.Make mixture be cooled to room temperature, use ETHYLE ACETATE (100ml) dilution then, with diluted hydrochloric acid aqueous solution (3 * 30ml) washings.Organic phase is dry on anhydrous magnesium sulfate, concentrates then and provides yellow jelly, and it is through column chromatography (ethyl acetate/hexane/acetic acid of 8: 18: 1 ratios) purifying; Grind with hexane then, 4-(5-chloro-2-aminomethyl phenyl)-2,2 is provided; 6; 6-tetramethyl-pyrans-3,5-diketone (0.53g) is a white solid.
Step 3: preparation 4-(3 ', 4 '-two fluoro-4-methyl diphenyl-3-yls)-2,2,6,6-tetramethyl-pyrans-3,5-diketone
In the microwave bottle, add 4-(5-chloro-2-aminomethyl phenyl)-2,2,6; 6-tetramethyl--pyrans-3, and the 5-diketone (0.20g, 0.68mmol), 3; 4-two fluoro-phenyl-boron dihydroxides (0.107g, 0.68mmol), potassiumphosphate (0.722g, 3.40mmol), palladium (II) (1.6mg; 0.0068mmol) and S-phos-3 '-sodium sulfonate (7.0mg, 0.0136mmol).Then add water (0.75ml) (sweeping away any solid), stirred subsequently 5 minutes, use argon cleaning from the bottle wall through the distillation degassing.Then under 160 ℃ under microwave radiation heating this mixture 15 minutes, add subsequently extra 3,4-difluorophenyl boric acid (0.107g, 0.68mmol) and potassiumphosphate (0.144g, 0.68mmol), then under 160 ℃ under microwave radiation reheat 15 minutes.After being cooled to room temperature, reaction mixture is acidified to pH2 with ETHYLE ACETATE (3ml) dilution with diluted hydrochloric acid aqueous solution.Tell organic phase, water is further used ETHYLE ACETATE (3 * 3ml) extractions.Merge whole organic phases, filter through the silicon-dioxide plug, evaporation provides crude product; It is dissolved in N, dinethylformamide (2.5ml), through preparation type reversed-phase HPLC purifying, provide 4-(3 '; 4 '-two fluoro-4-methyl diphenyl-3-yls)-2,2,6; 6-tetramethyl-pyrans-3,5-diketone (0.190g) is a white solid.
Embodiment 4: preparation (1R*, 5S*)-3-(4 '-chloro-4-ethyl biphenyl-3-yl)-1-methyl-8-oxa--two ring [3.2.1] octane-2, the 4-diketone
Step 1: preparation (1R*, 5S*)-2,3,4,4-tetrachloro-1-methyl-8-oxabicyclo [3.2.1] suffering-2,6-diene
With the pentachloro-Trimetylene (100g, 0.467mol) add to Pottasium Hydroxide (31.4g, 0.56mol) 1,4-dioxane (3600ml) suspension-s in stirring at room mixture 30 minutes, was heated to 65 ℃ of restir 30 minutes then.(38.36g 0.467mol) adds to reaction mixture, and elevated temperature stirred the mixture 16 hours to 85-90 ℃ with the 2-methyl furan.Reaction mixture is cooled to room temperature, filters through plug of celite, and vacuum-evaporation filtrating, provide (1R*, 5S*)-2,3,4,4-tetrachloro-1-methyl-8-oxabicyclo [3.2.1] is hot-2, and 6-diene (83g) does not add to be further purified and is used for subsequent step.
Step 2: preparation (1R*, 5S*)-3,4-two chloro-5-methyl-8-oxabicyclo [3.2.1] suffering-3,6-diene-2-ketone
With Silver Nitrate (166g, 0.982mol) in add stirring (1R*, 5S*)-2; 3,4,4-tetrachloro-1-methyl-8-oxabicyclo [3.2.1] hot-2; The 6-diene (83g, 0.491mol), the mixture of acetone (1500ml) and water (1500ml), 65 ℃ of following heated mixt 16 hours.Reaction mixture is cooled to room temperature, adds saturated aqueous solution of sodium bicarbonate and regulates pH to 7-8.Mixture filters through plug of celite, and vacuum concentrated filtrate is removed most of acetone.(3 * 500ml) extractions merge organic extract to this aqueous mixture, and are dry on SODIUM SULPHATE ANHYDROUS 99PCT, filter evaporated filtrate with ETHYLE ACETATE.Through flash column chromatography purifying resistates on silica gel, provide (1R*, 5S*)-3,4-two chloro-5-methyl-8-oxabicyclo [3.2.1] suffering-3,6-diene-2-ketone (29.5g) is a yellow oil.
Step 3: preparation 3-chloro-1-methyl-4-oxo-spiral shell (1,3-dioxolane-2,2 '-[8] oxa--two ring [3.2.1] oct-6-ene)
(4.41g 0.204mol) adds terepthaloyl moietie (99.75g), dissolves fully up to sodium under nitrogen atmosphere, stirring the mixture under 35-40 ℃ with sodium carefully.In 30 minutes, drip (1R*, 5S*)-3,4-two chloro-5-methyl-8-oxabicyclo [3.2.1] is hot-3,6-diene-2-ketone (28g, THF 0.136mol) (200ml) solution, accomplish add after, in stirring at room mixture 90 minutes.Through adding 10% biphosphate sodium water solution neutralization reaction mixture, with ETHYLE ACETATE (3 * 100ml) extractions.Merge organic extract, dry on SODIUM SULPHATE ANHYDROUS 99PCT, filter evaporated filtrate.Through flash column chromatography purifying resistates on silica gel, provide 3-chloro-1-methyl-4-oxo-spiral shell (1,3-dioxolane-2,2 '-[8] oxabicyclo [3.2.1] oct-6-ene) (24.5g), be jelly.
Step 4: preparation (1R*, 5S*)-1-methyl-4-oxo-spiral shell (1,3-dioxolane-2,2 '-[8] oxa--two ring [3.2.1] oct-6-ene)
With zinc powder (13.88g; 0.212mol) adding 3-chloro-1-methyl-4-oxo-spiral shell (1,3-dioxolane-2,2 '-[8] oxabicyclo [3.2.1] oct-6-ene) (24.5g; 0.016mo acetate l) (122.5ml) solution, at room temperature stirred reaction mixture is 24 hours.Mixture water (612.5ml) dilution is with ETHYLE ACETATE (3 * 150ml) extractions.Merge organic extract, dry on SODIUM SULPHATE ANHYDROUS 99PCT, filter evaporated filtrate; Provide (1R*, 5S*)-1-methyl-4-oxo-spiral shell (1,3-dioxolane-2; 2 '-[8] oxabicyclo [3.2.1] oct-6-ene) (20g), be yellow oil, do not add to be further purified and be used for subsequent step.
Step 5: preparation (1R*, 5S*)-1-methyl-8-oxabicyclo [3.2.1] oct-6-ene-2, the 4-diketone
(50ml) adds to (1R* in three batches with hydrochloric acid; 5S*)-1-methyl-4-oxo-spiral shell (1,3-dioxolane-2,2 '-[8] oxabicyclo [3.2.1] oct-6-ene) (20g; 0.102mol) mixture in acetone (500ml)/water (250ml), 65-70 ℃ of following stirred reaction mixture 48 hours.Mixture is cooled to room temperature, removes most of acetone through reduction vaporization, obtained aqueous solution is with ETHYLE ACETATE (3 * 100ml) extractions.Merge organic extract, dry on SODIUM SULPHATE ANHYDROUS 99PCT, filter evaporated filtrate.Through flash column chromatography purifying resistates on silica gel, provide (1R*, 5S*)-1-methyl-8-oxabicyclo [3.2.1] oct-6-ene-2,4-diketone (10.0g) is a yellow oil.
Step 6: preparation (1R*, 5S*)-1-methyl-8-oxabicyclo [3.2.1] octane-2, the 4-diketone
To (1R*, 5S*)-1-methyl-8-oxabicyclo [3.2.1] oct-6-ene-2, (12.0g adds 10% palladium carbon (2.4g) to the 4-diketone in ETHYLE ACETATE 0.079mol) (100ml) solution, under 1 crust hydrogen atmosphere, stirred 24 hours subsequently.Reaction mixture concentrates then through diatomite filtration, provides crude product, and it passes through flash chromatography (hexane/ethyl acetate) purifying, provide (1R*, 5S*)-1-methyl-8-oxabicyclo [3.2.1] octane-2,4-diketone (6.90g) is a faint yellow solid.
Step 7: preparation (1R*, 5S*)-3-(4 '-chloro-4-ethyl biphenyl-3-yl)-1-methyl-8-oxa--two ring [3.2.1] octane-2, the 4-diketone
Under nitrogen atmosphere in stirring down, in the mixture of chloroform (2.0ml) and toluene (0.5ml), add (1R*, 5S*)-1-methyl-8-oxa--two encircles [3.2.1] octane-2; 4-diketone (0.10g; 0.6mmol) and N, and N-dimethylamino-pyridine (0.395g, 3.2mmol).A collection of adding 4 in this reaction mixture '-chloro-4-ethyl biphenyl-3-base nitrilotriacetic lead (0.42g, 0.70mmol), then at 80 ℃ of following heated mixt 1-2 hours.Reaction mixture is cooled to room temperature, uses the diluted hydrochloric acid aqueous solution acidifying, removes inorganic residues (using washed with dichloromethane subsequently) through diatomite filtration then.(2 * 5ml) extractions merge whole organic fractions to watery distillate, and are dry on sodium sulfate with methylene dichloride; Vacuum concentration provides crude product then, and it is through flash chromatography (hexane/ethyl acetate) purifying; Provide (1R*; 5S*)-3-(4 '-chloro-4-ethyl biphenyl-3-yl)-1-methyl-8-oxabicyclo [3.2.1] octane-2,4-diketone (0.150g) is a white solid.
Embodiment 5: preparation (1R*, 5S*)-3-(4 '-chloro-4-methyl diphenyl-3-yl)-1-methyl-8-oxa--two ring [3.2.1] octane-2, the 4-diketone
Under nitrogen atmosphere in stirring down, in the mixture of chloroform (3.5ml) and toluene (0.75ml), add (1R*, 5S*)-1-methyl-8-oxa--two encircles [3.2.1] octane-2; 4-diketone (0.25g; 1.62mmol) and N, and the N-dimethyl aminopyridine (0.99g, 8.11mmol).A collection of adding 4 in this reaction mixture then '-chloro-4-methyl diphenyl-3-base nitrilotriacetic lead (1.05g, 1.78mmol), then at 80 ℃ of following heated mixt 1-2 hours.Reaction mixture is cooled to room temperature, uses the diluted hydrochloric acid aqueous solution acidifying, removes inorganic resistates (using washed with dichloromethane subsequently) through diatomite filtration then.(2 * 10ml) extractions merge whole organic fractions to watery distillate then, and are dry on sodium sulfate with methylene dichloride; Vacuum concentration provides crude product, and it is through flash chromatography (hexane/ethyl acetate) purifying; Provide (1R*; 5S*)-3-(4 '-chloro-4-methyl diphenyl-3-yl)-1-methyl-8-oxabicyclo [3.2.1] octane-2,4-diketone (0.240g) is a white solid.
Embodiment 6: preparation 4-(4 '-chloro-4-methyl diphenyl-3-yl)-2,2-dimethyl-pyrans-3,5-diketone
Step 1: preparation [3-(4 '-chloro-4-methyl diphenyl-3-yl)-1,1-dimethyl propylene-2-alkynyloxy group] methyl acetate
To 3-bromo-4 '-chloro-4-methyl diphenyl (12.6g; 44.7mmol) and (1; 1-dimethyl propylene-2-alkynyloxy group) methyl acetate (according to the WO2001/066544 preparation) (8.4g; 53.8mmol) triethylamine (70ml) solution in add dichloride two (triphenylphosphine) palladium (II) (0.63g, 0.9mmol) and cupric iodide (I) (0.34g, 1.8mmol).Reaction mixture outgases and with nitrogen (x3) flushing, under nitrogen, was stirring 1 hour under 80 ℃.Remove catalyzer through the refrigerative mixture through diatomite filtration, vacuum-evaporation filtrating.Resistates is placed (under nitrogen, the 8.4g in the 70ml triethylamine (1,1-dimethyl propylene-2-alkynyloxy group) methyl acetate, 0.63g dichloride two (triphenylphosphine)-palladium (II), 0.34g cupric iodide (I)) under the identical reaction conditions, stirred 1 hour down at 80 ℃.Through diatomite filtration, vacuum concentration then is through flash chromatography (3: 1 hexane/ethyl acetate) purifying through the refrigerative mixture; Provide [3-(4 '-chloro-4-methyl diphenyl-3-yl)-1; 1-dimethyl propylene-2-alkynyloxy group] methyl acetate (6.70g) is an oily matter.
Step 2: preparation [3-(4 '-chloro-4-methyl diphenyl-3-yl)-1,1-dimethyl propylene-2-alkynyloxy group] acetate
(1.105g 19.7mmol) adds to [3-(4 '-chloro-4-methyl-biphenyl-3-yl)-1,1-dimethyl propylene-2-alkynyloxy group] methyl acetate (6.7g, dioxane 18.8mmol) (20ml)/water (20ml) solution with Pottasium Hydroxide.20 ℃ stir 4 hours after, reaction mixture is with twice of dichloromethane extraction.Under 0 ℃, with 1N aqueous hydrochloric acid acidifying water layer to pH 2-3, with twice of ethyl acetate extraction.The organic extract that merges is dry on SODIUM SULPHATE ANHYDROUS 99PCT, filters vacuum-evaporation filtrating.Resistates stirs at hexane, filters, provide [3-(4 '-chloro-4-methyl diphenyl-3-yl)-1,1-dimethyl propylene-2-alkynyloxy group] acetate (4.50g) is white solid (m.p.125 ℃).
Step 3: preparation 6-[1-(4 '-chloro-4-methyl diphenyl-3-yl) methylene radical]-5,5-dimethyl--[1,4] diox-2-ketone
(0.17g 0.61mmol) adds to [3-(4 '-chloro-4-methyl-biphenyl-3-yl)-1,1-dimethyl propylene-2-alkynyloxy group] acetate (2.1g, anhydrous acetonitrile 6.13mmol) (15ml) solution in the microwave bottle with silver carbonate.Stirred reaction mixture under microwave radiation, heating 40 minutes under 120 ℃, provides brown suspension-s.The vacuum-evaporation mixture, dilute with water is used ethyl acetate extraction then.The organic extract that merges is dry on SODIUM SULPHATE ANHYDROUS 99PCT, filters, and vacuum-evaporation filtrating provides 6-[1-(4 '-chloro-4-methyl diphenyl-3-yl) methylene radical]-5, and the 5-dimethyl--[1,4] diox-2-ketone (1.75g) is a solid.
Step 4: preparation 4-(4 '-chloro-4-methyl diphenyl-3-yl)-2,2-dimethyl-pyrans-3,5-diketone
To 6-[1-(4 '-chloro-4-methyl diphenyl-3-yl) methylene radical]-5, the 5-dimethyl--[1,4] diox-2-ketone (and 1.5g, add in anhydrous acetonitrile 4.38mmol) (22ml) suspension-s triethylamine (0.67ml, 4.81mmol) and Potssium Cyanide (30mg, 0.46mmol).Stirred reaction mixture is 2 hours under refluxing.Dilute with ETHYLE ACETATE through the refrigerative mixture, add the 0.5N aqueous hydrochloric acid down at 0 ℃.Tell organic layer, water is with twice of ethyl acetate extraction.The organic extract that merges is dry on SODIUM SULPHATE ANHYDROUS 99PCT, filters vacuum-evaporation filtrating.Through flash chromatography (heptane/ETHYLE ACETATE of 1: 1 ratio) purifying resistates, 4-(4 '-chloro-4-methyl diphenyl-3-yl)-2 is provided, 2-dimethyl-pyrans-3,5-diketone (1.35g) is a foam shape thing.The sample of this product is stirred in hexane/Di Iso Propyl Ether (ratio 4: 1), filter, provide white solid, fusing point is 186-188 ℃.
Embodiment 7: preparation 4-(4 '-chloro-4-ethyl-2 '-fluorine biphenyl-3-yl)-2,2,6,6-tetramethyl--pyrans-3,5-diketone
Step 1: preparation 5-bromo-2-MEA
(9.71g, (35.72g 225.71mmol), heated 2 hours down at 70 ℃ subsequently to add two hydration tin chlorides (II) in ethanol 230mmol) (125ml) solution to 2-ethyl-5-bromo nitrobenzene.After being cooled to room temperature, solution is inclined to trash ice (1 liter), use ETHYLE ACETATE (200ml) dilution then.Add solid sodium carbonate carefully up to reaching pH7, pass through diatomite filtration (further with ETHYLE ACETATE/aqueous sodium carbonate washing) heavy-gravity mixture, phase-splitting in this stage.After the aqueous phase extracted, merge whole organic phases in addition, drying, vacuum concentration then on anhydrous magnesium sulfate.Thick oily matter provides 5-bromo-2-MEA (7.89g) through flash column chromatography (8: 2 hexane/ethyl acetate of ratio) purifying on silica gel, is brown oil.
Step 2: preparation 4-bromo-1-ethyl-2-iodobenzene
(3.39g, 200mmol) mixture in zero(ppm) water (110ml) adds the vitriol oil (5.60ml) to 5-bromo-2-MEA in stirring, of short durationly under refluxing is heated to dissolving.Make mixture be cooled to room temperature, produce trickle deposition, in ice/salt bath, further be cooled to about 0 ℃ then.In 15 minutes, (1.17g, zero(ppm) water 16.94mmol) (10ml) solution keep temperature to be lower than 5 ℃, and restir is 30 minutes subsequently in these slurries, to be added dropwise to Sodium Nitrite.Then filter reaction mixture drips second kind of potassiumiodide (8.44g, zero(ppm) water 50.83mmol) (45ml) solution in room temperature then.After accomplishing adding, solution is heated to 80 ℃ momently, and then makes it to be cooled to room temperature.(3 * 50ml) extractions, organic phase is with 1M aqueous hydrochloric acid (30ml) and sodium thiosulfate solution (2 * 30ml) washings with ETHYLE ACETATE for reaction mixture.Behind dry on the anhydrous magnesium sulfate and vacuum concentration, 4-bromo-1-ethyl-2-iodobenzene (4.90g) is provided, be orange liquid.
Step 3: preparation 5-bromo-2-ethylphenyl boric acid
Under-78 ℃, (10.00g, anhydrous tetrahydro furan 32.20mmol) (60ml) drips of solution adds chlorination isopropyl-magnesium solution (16.90ml, 33.80mmol, 2M tetrahydrofuran solution), keeps temperature to be lower than-60 ℃ to 4-bromo-1-ethyl-2-iodobenzene.Stir after 20 minutes, make reaction mixture slowly be warmed to room temperature, restir is 1 hour subsequently.Solution is cooled to again-78 ℃, (7.18ml 64.32mmol), after this makes mixture be warmed to room temperature, restir 2 hours once more to drip trimethyl borate.Add diluted hydrochloric acid aqueous solution (30ml), crude product is extracted into ETHYLE ACETATE (100ml).(2 * 100ml) washings merge all organic phases to water, and dry on anhydrous magnesium sulfate, vacuum concentration provides light brown solid then, and it is ground with hexane, and 5-bromo-2-ethylphenyl boric acid (6.46g) is provided, and is off-white powder with ETHYLE ACETATE.
Step 4: preparation 5-bromo-2-ethylphenyl nitrilotriacetic is plumbous
(13.7g, 31.00mmol) (0.47g adds anhydrous chloroform (42ml) in mixture 1.50mmol) with oxalic acid mercury to the lead tetraacetate with the nitrogen cleaning down.This mixture is warmed to 40 ℃, and (6.50g, 28.00mmol), suspension-s heated 5 hours under this temperature a collection of adding 5-bromo-2-ethylphenyl boric acid.Make mixture be cooled to room temperature then, further be cooled to 0 ℃ subsequently, add powdered anhydrous salt of wormwood (3.22g) then, stirred 5 minutes fast simultaneously, filter then.Filtrating is concentrated into the half the of its volume, adds hexane subsequently and cause deposition.Further concentrate this mixture, inclining solvent, uses the hexane wash solid, provides 5-bromo-2-ethylphenyl nitrilotriacetic plumbous (10.69g), the coloured solid of chiltern.
Step 5: preparation 4-(5-bromo-2-ethylphenyl)-2,2,6,6-tetramethyl-pyrans-3,5-diketone
To 2,2,6,6-tetramethyl-pyrans-3, (3.57g, 21.00mmol) and N, (13.50g adds anhydrous chloroform (120ml) to the N-dimethyl aminopyridine to the 5-diketone in mixture 111.00mmol), at room temperature stir up to dissolving subsequently.In this solution, add dry toluene (37ml), a collection of adding 5-bromo-2-ethylphenyl nitrilotriacetic is plumbous, and (10.69g 24.00mmol), in 80 ℃ of following reacting by heating mixtures 2 hours, at room temperature places then and spends the night.Mixture is with methylene dichloride (185ml) and diluted hydrochloric acid aqueous solution (185ml) dilution, and vortex is 5 minutes subsequently, removes by filter inorganic residues (using washed with dichloromethane in addition).Merge whole organic fractions, use brine wash, dry on anhydrous magnesium sulfate, vacuum concentration provides thick oily matter then, and it further through flash column chromatography (5: 1 hexane/ethyl acetate of ratio) purifying, provides product, is yellow solid (4.47g).Plumbous resistates is through being dissolved in this solid chloroform (50ml) and removing with silica gel (5.50g, the 1.20mmol/g carrying capacity) stirred overnight of 3-sulfydryl propyl group-functionalization.After filtering and concentrating, 4-(5-bromo-2-ethylphenyl)-2,2,6 is provided, 6-tetramethyl-pyrans-3,5-diketone (4.36g) is an off-white powder.
Step 6: preparation 4-(4 '-chloro-4-ethyl-2 '-fluorine biphenyl-3-yl)-2,2,6,6-tetramethyl-pyrans-3,5-diketone
To 4-(5-bromo-2-ethylphenyl)-2,2,6; 6-tetramethyl-pyrans-3, and the 5-diketone (0.278g, 0.79mmol), cesium fluoride (1.19g; 7.90mmol), 4-chloro-2-fluorophenyl boric acid (0.194g, 1.11mmol) with [1,1 '-two (diphenylphosphino) ferrocene] two chloro-palladium (II) (0.102g; 0.12mmol) mixture in add glycol dimethyl ether (2ml) through the degassing, under nitrogen, stirred gained suspension-s 45 minutes, heated 20 hours down at 80 ℃ then.After being cooled to room temperature, reaction mixture distributes between ETHYLE ACETATE and 1M aqueous hydrochloric acid.Water is further used ethyl acetate extraction, merges whole organic fractions, and is dry on anhydrous magnesium sulfate, vacuum concentration.The material that obtains through column chromatography (hexane/ethyl acetate of 3: 1 ratios) purifying on silica gel, provide 4-(4 '-chloro-4-ethyl-2 '-fluorine biphenyl-3-yl)-2,2,6,6-tetramethyl--pyrans-3,5-diketone (0.248g) is a white solid.
Embodiment 8: preparation 4-(2 ', 4 '-two chloro-4-ethyl biphenyl-3-yls)-2,2,6,6-tetramethyl-pyrans-3,5-diketone
To 4-(5-bromo-2-ethylphenyl)-2,2,6; 6-tetramethyl-pyrans-3, and the 5-diketone (0.278g, 0.79mmol), cesium fluoride (1.19g; 7.90mmol) (0.30g adds the dioxane (2.5ml) through the degassing in mixture 1.58mmol) with the 2,4 dichloro benzene ylboronic acid; Under nitrogen, stirred gained suspension-s 45 minutes, the interior during this period cream that forms.A collection of adding in this suspension-s then [1,1 '-two (diphenylphosphino) ferrocene]-dichloro palladium (II) (0.102g, 0.12mmol), about 100 ℃ of following heated mixt 3 hours.After being cooled to room temperature, add methylene dichloride (150ml), with 1M hydrochloric acid (150ml) washing soln.Separate organic phase, dry on anhydrous magnesium sulfate, filter, vacuum concentrated filtrate provides thick oily matter, and it provides product through column chromatography (hexane/ethyl acetate of 5: 1 ratios) purifying, is foam shape thing.Grind with hexane, 4-(2 ', 4 '-two chloro-4-ethyl-biphenyl-3-yls)-2,2,6 is provided, 6-tetramethyl-pyrans-3,5-diketone (0.250g) is a white solid.
Embodiment 9: preparation 4-(4 '-chloro-4-ethyl-2 '-methyl diphenyl-3-yl)-2,2,6,6-tetramethyl--pyrans-3,5-diketone
In the microwave bottle, add acid chloride (II) (3.3mg, 0.015mmol), three (3-sulfo group phenyl) phosphine trisodium salt (22mg, 0.038mmol), 4-chloro-2-aminomethyl phenyl boric acid (0.152g; 0.89mmol), 4-(5-bromo-2-ethyl-phenyl)-2,2,6; 6-tetramethyl-pyrans-3; The 5-diketone (0.208g, 0.59mmol) and potassiumphosphate (0.625g, 2.95mmol).Then add acetonitrile/zero(ppm) water (1.5ml, 1: 1 ratio) mixing solutions (sweeping away any solid), stirred subsequently 5 minutes and use argon cleaning from the bottle wall through the degassing.Under microwave radiation, heating this mixture 15 minutes under 160 ℃ then.After being cooled to room temperature, reaction mixture is acidified to pH2 with ETHYLE ACETATE (3ml) dilution and with diluted hydrochloric acid aqueous solution.Separate organic phase, water is further used ETHYLE ACETATE (2 * 3ml) extractions.Merge whole organic phases, filter through the silicon-dioxide plug, evaporation provides crude product; It is dissolved in N, and dinethylformamide (2.5ml) is through preparation type reversed-phase HPLC purifying; Provide 4-(4 '-chloro-4-ethyl-2 '-methyl diphenyl-3-yl)-2,2,6; 6-tetramethyl-pyrans-3,5-diketone (0.139g) is a white powder.
Embodiment 10: preparation 4-(4 '-chloro-4-ethyl-3 '-trifluoromethyl-biphenyl-3-yl)-2,2,6,6-tetramethyl-pyrans-3,5-diketone
In the microwave bottle, add acid chloride (II) (3.3mg, 0.015mmol), three (3-sulfo group phenyl) phosphine trisodium salt (22mg, 0.038mmol), 4-chloro-3-trifluoromethyl phenyl boronic acid (0.200g; 0.89mmol), 4-(5-bromo-2-ethylphenyl)-2,2,6; 6-tetramethyl-pyrans-3; The 5-diketone (0.208g, 0.59mmol) and potassiumphosphate (0.625g, 2.95mmol).Then add acetonitrile/zero(ppm) water (1.5ml, 1: 1 ratio) mixing solutions (sweeping away any solid), stirred subsequently 5 minutes and use argon cleaning from the bottle wall through the degassing.Under microwave radiation, heating this mixture 15 minutes under 160 ℃ then.After being cooled to room temperature, reaction mixture is acidified to pH2 with ETHYLE ACETATE (3ml) dilution and with diluted hydrochloric acid aqueous solution.Separate organic phase, water is further used ETHYLE ACETATE (2 * 3ml) extractions.Merge whole organic phases, filter through the silicon-dioxide plug, evaporation provides crude product; It is dissolved in N, and dinethylformamide (2.5ml) is through preparation type reversed-phase HPLC purifying; Provide 4-(4 '-chloro-4-ethyl-3 '-trifluoromethyl-biphenyl-3-yl)-2,2,6; 6-tetramethyl-pyrans-3,5-diketone (0.143g) is a white powder.
Embodiment 11: preparation 4-(4 '-bromo-4-ethyl biphenyl-3-yl)-2,2,6,6-tetramethyl-pyrans-3,5-diketone
Step 1a
With 4-(4 '-amino-4-ethyl biphenyl-3-yl)-2,2,6; 6-tetramethyl-pyrans-3, (0.260g 0.71mmol) adds to Hydrogen bromide (48% quality to the 5-diketone in batches; The aqueous solution, 1.7ml) with the mixture of water (1.2ml), accomplish add after; With mixture heating up to 40 ℃ and stirred 20 minutes, in ice bath, be cooled to 5 ℃ subsequently.In 20 minutes, (0.099g, aqueous solution 1.40mmol) (1.2ml) are accomplished the adding back and under 5 ℃, were continued to stir the mixture 45 minutes to drip Sodium Nitrite.
Step 1b
Simultaneously, under 70 ℃ to Hydrogen bromide (48% weight, the aqueous solution; 3.3ml) in the solution a collection of adding Salzburg vitriol (0.388g 1.55mmol), stirred the mixture under 70 ℃ 2 minutes; Provide deep purple solution, (0.135g is 2.15mmol) with (0.030g to add copper powder then; 0.47mmol), obtain pink colour suspension-s.
Step 1c
Add to preparation in the stirring from the mixture of step 1b at 5 ℃ of mixtures that will comprise down diazonium salt (preparation is from step 1a) in batches, continue heating 45 minutes down at 70 ℃ subsequently.After being cooled to room temperature, reaction mixture is used ethyl acetate extraction, and water and brine wash are dry on anhydrous magnesium sulfate then, vacuum concentration.Through flash column chromatography (hexane/ethyl acetate of 3: 1 ratios) purifying, produce thick solid, itself and hexane/ether is ground, provide 4-(4 '-bromo-4-ethyl biphenyl-3-yl)-2,2,6,6-tetramethyl-pyrans-3,5-diketone (0.045g) is a white solid.
Embodiment 12: preparation 4-(4 '-iodo-4-ethyl biphenyl-3-yl)-2,2,6,6-tetramethyl-pyrans-3,5-diketone
(1.03g adds 4-(4 '-amino-4-ethyl biphenyl-3-yl)-2,2 in acetonitrile 5.40mmol) (11ml) solution to a hydration tosic acid; 6,6-tetramethyl--pyrans-3,5-diketone (0.65g; 1.80mmol), at room temperature stirred subsequently 10 minutes, be cooled to 10 ℃ then.In this mixture, add then second kind of Sodium Nitrite (0.25g, 3.60mmol) and potassiumiodide (0.76g, the 4.50mmol) mixing solutions in zero(ppm) water (1.3ml) stirred the mixture under 10 ℃ 20 minutes then, then at room temperature stirred 2 hours.Add sodium bicarbonate aqueous solution up to reaching pH 9-10, with the ETHYLE ACETATE dilution, wash subsequently with pyrosulphite saturated aqueous solution of sodium (20ml).After in addition with ETHYLE ACETATE (x2) aqueous phase extracted, merge whole organic fractions, dry on anhydrous magnesium sulfate then with zero(ppm) water and brine wash, vacuum concentration.This crude product produces orange jelly through flash column chromatography (hexane/ethyl acetate of 3: 1 ratios) purifying on silica gel, with itself and hexane grinding 4-(4 '-iodo-4-ethyl biphenyl-3-yl)-2 is provided; 2,6,6-tetramethyl-pyrans-3; 5-diketone (0.413g) is a white solid.
Embodiment 13: preparation 4-(4-ethyl-4 '-ethynyl biphenyl-3-yl)-2,2,6,6-tetramethyl-pyrans-3,5-diketone
Step 1: preparation 4-[4-ethyl-4 '-(trimethyl silyl ethynyl) biphenyl-3-yl]-2,2,6,6-tetramethyl--pyrans-3,5-diketone
Under microwave radiation, heating 4-(4 '-iodo-4-ethyl-biphenyl-3-yl)-2,2,6 under 120 ℃; 6-tetramethyl-pyrans-3, and the 5-diketone (0.200g, 0.42mmol), trimethyl silyl acetylene (0.10ml; 0.47mmol), cupric iodide (I) (4mg, 0.023mmol), chlorination two (triphenylphosphine) palladium (II) (0.016g, 0.023mmol), triphenylphosphine (0.022g; 0.084mmol) with diethylamine (0.65ml) at anhydrous N, the mixture in the dinethylformamide (0.25ml) 25 minutes.Make this mixture be cooled to room temperature then, through diatomite filtration (using washed with dichloromethane in addition).Removal of solvent under reduced pressure, (9: 1-3: the hexane/ethyl acetate of 1 ratio) purifying produces 4-[4-ethyl-4 '-(trimethyl silyl ethynyl) biphenyl-3-yl]-2 to resistates on silica gel through flash column chromatography; 2; 6,6-tetramethyl-pyrans-3,5-diketone (0.143g); Be white solid, it does not add to be further purified and is used for subsequent step.
Step 2: preparation 4-(4-ethyl-4 '-ethynyl biphenyl-3-yl)-2,2,6,6-tetramethyl-pyrans-3,5-diketone
To 4-[4-ethyl-4 '-(trimethyl silyl ethynyl) biphenyl-3-yl]-2,2,6; 6-tetramethyl--pyrans-3, (0.143g adds potassium carbonate powder (0.177g in methyl alcohol 0.32mmol) (6.5ml) solution to the 5-diketone; 1.28mmol), at room temperature stirred the mixture 1 hour.Whole inorganicss that are dissolved in water then, vacuum concentrated mixture.Add 2M hydrochloric acid and reach pH 2-3, the material of using ETHYLE ACETATE (x3) extraction to hope then.Merge whole organic phases, use brine wash, drying, vacuum concentration then on anhydrous magnesium sulfate.Resistates is further through flash column chromatography (hexane/ethyl acetate of 4: 1 ratios) purifying on silica gel, and 4-(4-ethyl-4 '-ethynyl biphenyl-3-yl)-2,2,6 is provided, 6-tetramethyl-pyrans-3, and 5-diketone (0.070g) is a yellow solid.
Embodiment 14: preparation 4-[5-(3,5-dichloropyridine-2-yl)-2-aminomethyl phenyl]-2,2,6,6-tetramethyl--pyrans-3,5-diketone
Step 1: preparation 5-bromo-2-aminomethyl phenyl nitrilotriacetic is plumbous
(11.25g, 25.40mmol) (0.40g adds anhydrous chloroform (35ml) in mixture 1.27mmol) with oxalic acid mercury to the lead tetraacetate with the nitrogen cleaning down.This mixture is warmed to 40 ℃, and (4.96g 23.10mmol), added hot suspension 5 hours to a collection of adding 5-bromo-2-aminomethyl phenyl boric acid under this temperature.Make mixture be cooled to room temperature then, further be cooled to 0 ℃ subsequently, add powdered anhydrous salt of wormwood (1.61g) then, stirred 5 minutes fast simultaneously.Filtering mixt is concentrated into the half the of its volume with filtrating, adds hexane and causes deposition.Further concentrate this mixture, inclining solvent, uses the hexane wash solid, provides 5-bromo-2-aminomethyl phenyl nitrilotriacetic plumbous (10.10g), is sandy coloured solid.
Step 2: preparation 4-(5-bromo-2-aminomethyl phenyl)-2,2,6,6-tetramethyl-pyrans-3,5-diketone
To 2,2,6,6-tetramethyl-pyrans-3, (6.00g, 35.29mmol) and N, (21.62g adds anhydrous chloroform (200ml) to the N-dimethyl aminopyridine to the 5-diketone in mixture 177.21mmol), at room temperature stir up to dissolving subsequently.In this solution, add dry toluene (55ml), a collection of subsequently adding 5-bromo-2-aminomethyl phenyl nitrilotriacetic plumbous (21.60g, 38.99mmol), in 80 ℃ of following reacting by heating mixtures 2 hours.Make mixture be cooled to room temperature, use the dilution of methylene dichloride (300ml) and aqueous hydrochloric acid (300ml) then, vortex mixed thing 5 minutes removes by filter inorganic residues.Filter cake is used washed with dichloromethane, merges whole organic phases, and is dry on anhydrous magnesium sulfate, filters, and vacuum concentrated filtrate provides thick solid, with its recrystallization in dichloromethane/hexane.This material is then further through flash column chromatography (hexane/ethyl acetate of 5: 1 ratios) purifying.Plumbous resistates is through being dissolved in chloroform (100ml) with obtaining solid (approximately 6.50g) and removing with silica gel (6.50g, the 1.20mmol/ carrying capacity) stirred overnight of 3-sulfydryl propyl group-functionalization.Filtering mixt, vacuum concentrated filtrate provides 4-(5-bromo-2-methyl-phenyl)-2,2,6,6-tetramethyl-pyrans-3,5-diketone (6.50g) is an off-white powder.
Step 3: preparation 4-methyl-3-(2,2,6,6-tetramethyl--3,5-dioxo tetrahydropyran-4-base) phenyl-boron dihydroxide
With 4-(5-bromo-2-methyl-phenyl)-2,2,6,6-tetramethyl--pyrans-3, (5g 0.0147mol) is dissolved in anhydrous tetrahydro furan (150ml) to the 5-diketone, and reaction mixture is cooled to 0 ℃, adds sodium hydride (708mg, 0.0294mol, 60% dispersion liquid in oil).Stirred the mixture 30 minutes, and be cooled to-78 ℃ then.In about 10 minutes, drip n-Butyl Lithium (14.7ml, 0.0294mol, the cyclohexane solution of 2M), stirred reaction mixture 15 minutes, then add trimethyl borate (4.95ml, 0.0442mol).Continued stirred reaction mixture 45 minutes, and made it to be warmed to envrionment temperature, and then stirred 1.5 hours, then with the cancellation of 2M aqueous hydrochloric acid.Stirred reaction mixture 1 hour is used dichloromethane extraction then.After separating organic phase, removal of solvent under reduced pressure provides faint yellow gluey thing.Grinding with isohexane, 4-methyl-3-(2,2,6,6-tetramethyl--3,5-dioxa-tetrahydropyran-4-base) is provided phenyl-boron dihydroxide (2.01g), is white solid.
Step 4: preparation 4-[5-(3,5-dichloropyridine-2-yl)-2-aminomethyl phenyl]-2,2,6,6-four-methyl pyrans-3,5-diketone
In the microwave bottle, add 4-methyl-3-(2,2,6; 6-tetramethyl--3,5-dioxo-tetrahydropyran-4-base) phenyl-boron dihydroxide (200mg, 0.657mmol), 2-bromo-3; The 5-dichloropyridine (149mg, 0.657mmol), acid chloride (3.7mg, 0.0164mmol), three (3-sulfo group phenyl) phosphine trisodium salt (22mg; 0.0394mmol) and potassiumphosphate (697mg 3.28mol) adds water/acetonitrile (1.6ml, 2: 1 ratios) solvent mixture through the degassing subsequently.Mixture is used nitrogen wash, stirs at ambient temperature then 5 minutes, then under microwave radiation, is heating 15 minutes under 160 ℃.After being cooled to room temperature, being reflected between 2M aqueous hydrochloric acid and methylene dichloride and distributing, tell organic phase.Water is further used dichloromethane extraction, merges whole organic fractions, then evaporation.Resistates provides 4-[5-(3,5-dichloropyridine-2-yl)-2-aminomethyl phenyl]-2,2,6,6-tetramethyl-pyrans-3,5-diketone (113mg) through preparation type reversed-phase HPLC purifying.
Embodiment 15: preparation 4-[2-methyl-5-(4-methylthiazol-2-yl) phenyl]-2,2,6,6-tetramethyl-pyrans-3,5-diketone
To 4-(5-bromo-2-aminomethyl phenyl)-2,2,6; 6-tetramethyl-pyrans-3, and the 5-diketone (200mg, 0.589mmol), 4-methylthiazol (70mg; 0.707mmol), silver carbonate (814mg, 2.94mmol), triphenylphosphine (15mg, 0.0589mmol) with chlorination [1; 1-two (diphenylphosphino)-ferrocene] (24mg adds water/acetonitrile (1.5ml, 1: the 1 ratio) solvent mixture through the degassing to palladium (II) in mixture 0.0294mmol); Use nitrogen wash subsequently, under vibration, heating 65 hours under 65 ℃ then.After being cooled to room temperature, reaction mixture distributes between 2M aqueous hydrochloric acid and methylene dichloride, tells organic phase.With another part washed with dichloromethane water layer, the organic layer vapourisation under reduced pressure of merging provides brown solid, with it through preparation type reversed-phase HPLC purifying; Provide 4-[2-methyl-5-(4-methylthiazol-2-yl) phenyl]-2,2,6; 6-tetramethyl-pyrans-3, the 5-diketone is faint yellow solid (36mg).
Embodiment 16: preparation 4-[2-methyl-5-(1-oxygen yl pyridines-2-yl) phenyl]-2,2,6,6-tetramethyl--pyrans-3,5-diketone
Under vibration, heating 4-(5-bromo-2-aminomethyl phenyl)-2,2,6 under 110 ℃; 6-tetramethyl--pyrans-3, and the 5-diketone (30mg, 0.0888mmol), pyridine-N-oxide (33.7mg; 0.355mmol), acid chloride (1mg; 0.0044mmol), (24.5mg, 0.1775mmol) (3.86mg, 0.0133mmol) mixture in toluene (1ml) is 18 hours with the tri-butyl phosphine a tetrafluoro borate for salt of wormwood.After being cooled to room temperature, reduction vaporization reaction mixture, resistates provide 4-[2-methyl-5-(1-oxygen base-pyridine-2-yl) phenyl]-2,2,6 through preparation type reversed-phase HPLC purifying, 6-tetramethyl-pyrans-3, and 5-diketone (5.2mg) is colourless jelly.
Embodiment 17: preparation 4-(4 '-difluoromethyl-4-ethyl biphenyl-3-yl)-2,2,6,6-tetramethyl--pyrans-3,5-diketone
Under 0 ℃, to 4-(4 '-formaldehyde-4-ethyl biphenyl-3-yl)-2,2,6,6-tetramethyl-pyrans-3, the 5-diketone (0.110g, 0.3mmol) drip in the solution in anhydrous methylene chloride (4ml) three fluoridize (diethylamino) sulphur (0.14ml, 1.06mmol).Stir 1 as a child, make mixture be warmed to room temperature, solution continues stirred overnight.Cooling solution in ice bath added yellow soda ash saturated aqueous solution (4ml) under high degree of agitation in 30 minutes then.Reaction mixture is with ETHYLE ACETATE (x2) dilution, tells two-layerly then, and water is further used ethyl acetate extraction.Merge organic extract, use brine wash, dry on anhydrous magnesium sulfate.Filtering mixt, vacuum-evaporation filtrating, resistates is through preparation type reverse-phase chromatography purifying, and 4-(4 '-difluoromethyl-4-ethyl biphenyl-3-yl)-2,2,6 is provided, 6-tetramethyl-pyrans-3,5-diketone (0.015g) is a white solid.
Embodiment 18: preparation 4-(4,4 '-DCBP-3-yl)-2,2,6,6-tetramethyl-pyrans-3,5-diketone
Step 1: preparation 4-bromo-1-chloro-2-iodobenzene
(3ml, (2.71g, the 20mmol) suspension-s in acetonitrile (60ml) is under agitation with mixture heating up to 60 ℃ 25mmol) to add to cupric chloride (II) with the nitrous acid tertiary butyl ester.(5g, acetonitrile 17mmol) (15ml) solution are accomplished the adding back and under 60 ℃, were stirred the mixture 2.5 hours to drip 4-bromo-2-Iodoaniline.Mixture is cooled to room temperature, and impouring 20% aqueous hydrochloric acid is used extracted with diethyl ether.Organic extract is dry on anhydrous magnesium sulfate, filters vacuum-evaporation filtrating.Resistates further through column chromatography purifying on silica gel, provides 4-bromo-1-chloro-2-iodobenzene (4.32g), is oily matter.
Step 2: preparation 5-bromo-2-chlorophenylboronic acid
(10.35g 33mmol) is dissolved in anhydrous tetrahydro furan (60ml), under argon atmospher, solution is cooled to-75 ℃ with 4-bromo-1-chloro-2-iodobenzene.In 30 minutes, drip isopropylmagnesium chloride (17.1ml, 34mmol, the tetrahydrofuran solution of 2M), keep internal temperature to be lower than-70 ℃ through externally cooled.After accomplish adding,, make it to be warmed to room temperature then and stirred 1 hour about-70 ℃ following stirred reaction mixture 30 minutes.Then reaction mixture is cooled to-78 ℃, and the dropping trimethyl borate (7.3ml, 65mmol).Under-78 ℃, stirred the mixture 30 minutes, and removed cooling bath then, at room temperature stirred the mixture 1.5 hours.Add 2M aqueous hydrochloric acid (30ml), crude product is used ethyl acetate extraction then.Organic phase water and brine wash, dry on anhydrous magnesium sulfate, filter vacuum-evaporation filtrating.Grinding with hexane, provide 5-bromo-2-chlorophenylboronic acid (6.16g), is pale solid.
Step 3: preparation 5-bromo-2-chloro-phenyl-nitrilotriacetic is plumbous
(1.46g, 3.3mmol) (42mg adds anhydrous chloroform (2.5ml) in mixture 0.13mmol), stirred reaction mixture also is heated to 40 ℃ with oxalic acid mercury to the lead tetraacetate with the nitrogen cleaning down.A collection of adding 5-bromo-2-chlorophenylboronic acid (0.62g, 2.6mmol), 40 ℃ of following stirred reaction mixtures 4 hours.After being cooled to room temperature, add salt of wormwood (0.18g), high degree of agitation mixture 5 minutes filters then.Vacuum concentrated filtrate provides 5-bromo-2-chloro-phenyl-nitrilotriacetic plumbous (1.23g), does not add to be further purified to be used for subsequent step.
Step 4: preparation 4-(5-bromo-2-chloro-phenyl-)-2,2,6,6-tetramethyl-pyrans-3,5-diketone
To 2,2,6,6-tetramethyl-pyrans-3, (2.78g, 16.3mmol) and N, (9.97g adds anhydrous chloroform (120ml) to the N-dimethyl aminopyridine to the 5-diketone in mixture 81.6mmol).In this solution, add dry toluene (30ml), a collection of subsequently adding 5-bromo-2-chloro-phenyl-nitrilotriacetic lead (10.32g, 18mmol), 80 ℃ of following reacting by heating mixture overnight.Make mixture be cooled to room temperature, use the dilution of methylene dichloride (120ml) and 2M aqueous hydrochloric acid (250ml) then, remove inorganic residues through diatomite filtration subsequently.Filter cake is used washed with dichloromethane, merges whole organic fractions, with 2M hydrochloric acid, water and brine wash, and at anhydrous magnesium sulfate drying, vacuum concentration then.This material through flash column chromatography purifying on silica gel, provides 4-(5-bromo-2-chloro-phenyl-)-2,2,6 at last, 6-tetramethyl-pyrans-3, and 5-diketone (0.44g), purity is enough to directly be used for subsequent step.
Step 5: preparation 4-(4,4 '-DCBP-3-yl)-2,2,6,6-tetramethyl-pyrans-3,5-diketone
At room temperature under nitrogen atmosphere, with 4-(5-bromo-2-chloro-phenyl-)-2,2; 6,6-tetramethyl-pyrans-3,5-diketone (0.22g; 0.6mmol), 4-chlorophenylboronic acid (0.14g; 0.9mmol) and cesium fluoride (0.28g, mixture 1.8mmol) be together 1, stirred 45 minutes in the 2-glycol dimethyl ether (2.4ml).Adding [1,1 '-two (phenylbenzene-phosphino-) ferrocene] dichloro palladium (II) (80mg, 0.098mmol), 80 ℃ of following reacting by heating mixture overnight.Reaction mixture is through diatomite filtration, and filter cake is with methylene dichloride (7ml) and water (3ml) washing.Through adding the 2M aqueous hydrochloric acid mixture is acidified to pH1, tells organic phase.Water is used dichloromethane extraction, merges whole organic extracts, and is dry on anhydrous magnesium sulfate, filters evaporated filtrate.Resistates is dissolved in N, and dinethylformamide (approximately 1ml) and through preparation type reversed-phase HPLC purifying provides 4-(4,4 '-DCBP-3-yl)-2,2,6,6-tetramethyl-pyrans-3,5-diketone (80mg).
Embodiment 19: preparation 4-(4-bromo-4 '-chlordiphenyl-3-yl)-2,2,6,6-tetramethyl-pyrans-3,5-diketone
Step 1: preparation 4 '-chloro-3-iodine biphenyl-4-base amine
To 4 '-chlordiphenyl-4-base amine (2.03g, 0.01mmol) in the solution in methyl alcohol (10ml) and zero(ppm) water (40ml) mixed solvent system, add Potcrate (0.830g, 6.77mmol) and potassiumiodide (3.32g, 0.02mol).After reaction mixture is heated to 80 ℃, add concentrated hydrochloric acid (0.60ml), under this temperature, continue heated mixt and spend the night.Solution is cooled to room temperature, and crude product extracts with ether (x3), the organic fraction that merges with 5% sodium thiosulfate solution and distilled water wash subsequently.Organic phase is dry on anhydrous magnesium sulfate, filters, and vacuum-evaporation filtrating provides dark solid, and itself and hexane are ground, provide 4 '-the basic amine (2.94g) of chloro-3-iodine biphenyl-4-, be light brown solid.
Step 2: preparation 4-bromo-4 '-chloro-3-iodine biphenyl
With 4 '-chloro-3-iodine biphenyl-(13.5g 0.041mol) wears into fine powder to 4-base amine, is suspended in the mixture of 48% hydrobromic acid aqueous solution (54ml) and zero(ppm) water (42ml).This suspension-s is heated to 45 ℃ then, continues 30 minutes, is cooled to 0-5 ℃ then, drip Sodium Nitrite (3.54 g, zero(ppm) water 0.0125mol) (6ml) solution, during keep internal temperature to be lower than 5 ℃.Under 80 ℃, this mixture is added to second kind of preformed Salzburg vitriol (II) in batches, and (15g, 0.06mol) (5.29g is 0.084mol) in the suspension-s in 48% hydrobromic acid aqueous solution (80ml) with copper powder then.After accomplish adding, 80 ℃ of following restir reaction mixtures 90 minutes.After being cooled to room temperature, add ETHYLE ACETATE, reaction mixture is inclined to zero(ppm) water, two-layer separating.Water is further used ETHYLE ACETATE (x2) extraction, the organic extract of merging with distilled water wash up to reaching neutral pH, drying on anhydrous magnesium sulfate then.Filtering mixt, vacuum-evaporation filtrating, resistates is further through flash column chromatography (hexane wash-out) purifying on silica gel, provide 4-bromo-4 '-chloro-3-iodine biphenyl (10.5g), be greenish orange look liquid.
Step 3: preparation 4-bromo-4 '-chlordiphenyl-3-ylboronic acid
Under-75 ℃; To 4-bromo-4 '-chloro-3-iodine biphenyl (8.00g; 20.40mmol) drip isopropyl-magnesium chloride (31.60ml in the solution in the mixed solvent system of anhydrous diethyl ether (80ml) and anhydrous tetrahydro furan (80ml); 15% tetrahydrofuran solution), keep the temperature of reaction mixture to be lower than-70 ℃.After accomplish adding,, make it to be warmed to-25 ℃ then in-75 ℃ of following restir mixtures 2 hours, drip this moment trimethyl borate (3.15g, 30.60mmol).After accomplishing adding, make reaction be warmed to room temperature and stirred overnight, in ice bath, cool off subsequently, with the acidifying of 2M aqueous hydrochloric acid.Crude product merges organic fraction with ETHYLE ACETATE (x3) extraction, uses brine wash, and is dry on anhydrous magnesium sulfate then.Filtering mixt, vacuum-evaporation filtrating provides solid, and it is further ground with hexane, provide 4-bromo-4 '-chlordiphenyl-3-ylboronic acid (5.20g), be white solid.
Step 4: preparation 4-bromo-4 '-chlordiphenyl-3-base nitrilotriacetic is plumbous
(3.76g, 8.49mmol) (0.27g adds anhydrous chloroform (25ml) in mixture 0.85mmol) with oxalic acid mercury to the lead tetraacetate with the nitrogen cleaning down.This mixture is warmed to 40 ℃, a collection of adding 4-bromo-4 '-(2.40g, 7.72mmol), stirring and heated mixt are 4 hours under this temperature for chlordiphenyl-3-base-boric acid.After being cooled to room temperature, mixture cools off in ice bath with chloroform (25ml) dilution, adds powdered anhydrous salt of wormwood (2.75g) fast, stirs fast subsequently 5 minutes.Solid by filtration is removed, and filtrating is concentrated into about 1/4 of its volume.Add hexane and cause crystallization, vacuum evaporating solvent.Grind with hexane, provide 4-bromo-4 '-chlordiphenyl-3-base nitrilotriacetic plumbous (3.25g), do not add to be further purified and be used for subsequent step.
Step 5: preparation 4-(4-bromo-4 '-chlordiphenyl-3-yl)-2,2,6,6-tetramethyl-pyrans-3,5-diketone
To 2,2,6,6-tetramethyl-pyrans-3, (0.75g, 4.9mmol) and N, (2.52g adds anhydrous chloroform (40ml) to the N-dimethyl aminopyridine to the 5-diketone in mixture 20.6mmol), at room temperature stir until dissolving subsequently.In this solution, add dry toluene (12ml), a collection of subsequently adding 4-bromo-4 '-chlordiphenyl-3-base nitrilotriacetic plumbous (3.25g, 5.1mmol), in 80 ℃ of following reacting by heating mixtures 2 hours.Mixture is cooled to room temperature,, stirred the mixture 5 minutes with chloroform (50ml) and 1M aqueous hydrochloric acid (50ml) dilution.Deposition is told two phases through removing by filter, and organic phase is used brine wash, and is dry on anhydrous magnesium sulfate, filters vacuum-evaporation filtrating.Resistates merges and comprises the cut of hoping compound through flash column chromatography purifying on silica gel, and evaporation provides resistates; It is further through preparation type reversed-phase HPLC purifying, provides 4-(4-bromo-4 '-chlordiphenyl-3-yl)-2,2; 6,6-tetramethyl-pyrans-3,5-diketone (0.013g).
Embodiment 20: preparation 4-(4 '-chloro-4-cyclopropyl biphenyl-3-yl)-2,2,6,6-tetramethyl--pyrans-3,5-diketone
4-in stirring (4-bromo-4 '-chlordiphenyl-3-yl)-2,2,6; 6-tetramethyl-pyrans-3, and the 5-diketone (0.390g, 0.90mmol), cyclopropylboronic acid (0.100g; 1.16mmol), potassiumphosphate (0.665g; 3.14mmol) and tricyclohexyl phosphine (0.025g, 0.09mmol) add in the solution in the mixed solvent system of toluene (4ml) and zero(ppm) water (0.2ml) acid chloride (0.010g, 0.044mmol).After 100 ℃ this mixture overnight of heating is cooled to room temperature down,, filter through zeyssatite (using ETHYLE ACETATE/distilled water wash in addition) then then with ETHYLE ACETATE and distilled water diluting solution.Water is acidified to pH3 with the 2M aqueous hydrochloric acid, tells organic phase, and water is used ETHYLE ACETATE (x2) extraction once more.Merge whole organic fractions, use brine wash, dry on anhydrous magnesium sulfate then, filter.Behind the vacuum concentration, thick oily matter is through preparation type reversed-phase HPLC purifying, then with the hexane grinding, 4-(4 '-chloro-4-cyclopropyl biphenyl-3-yl)-2,2,6 is provided, 6-tetramethyl-pyrans-3, and 5-diketone (0.011g) is a white solid.
Embodiment 21: preparation 4-(4 '-chloro-4-vinyl biphenyl-3-yl)-2,2,6,6-tetramethyl-pyrans-3,5-diketone
Under 80 ℃ with 4-(4-bromo-4 '-chlordiphenyl-3-yl)-2,2,6; 6-tetramethyl-pyrans-3, and the 5-diketone (0.314g, 0.72mmol), vinyl boron trioxide pyridine complex (0.175g; 0.73mmol), a hydronium(ion) oxidation lithium (0.177g, 4.22mmol), 1,3-two (diphenylphosphino) propane (0.015g; 0.036mmol) and acid chloride (0.010g, 0.044mmol) 1, the solution stirring in the mixed solvent system of 2-glycol dimethyl ether (5ml) and zero(ppm) water (1ml) 3 hours.After being cooled to room temperature, mixture is used ETHYLE ACETATE and distilled water wash subsequently through diatomite filtration.Water is acidified to pH3 with the 2M aqueous hydrochloric acid, tells organic phase then, and water is used ethyl acetate extraction once more.Merge whole organic fractions, dry on anhydrous magnesium sulfate then, filter.Behind the vacuum concentration, thick oily matter is through preparation type reversed-phase HPLC purifying, then with the hexane grinding, 4-(4 '-chloro-4-vinyl biphenyl-3-yl)-2,2,6 is provided, 6-tetramethyl-pyrans-3, and 5-diketone (0.038g) is a white solid.
Embodiment 22: preparation 4-(4 '-chloro-4-ethyl biphenyl-3-yl)-2-methoxymethyl-2,6,6-trimethylammonium pyrans-3,5-diketone
Step 1: preparation 1-methoxyl group-2, the 5-dimethyl-oneself-3-alkynes-2, the 5-glycol
Under 0-5 ℃, in anhydrous ether solution, add ethylmagnesium bromide (37.33ml, 112mmol, the diethyl ether solution of 3M), drip then 2-methyl-3-butyne-2-alcohol (4.70g, 55.87mmol).Make mixture be warmed to room temperature, under this temperature, stirred 30 minutes subsequently, stirring stops to emit (about 1 hour) up to gas under 40 ℃ then.Then this viscous mixture is cooled to room temperature, (3.78g, 42.90mmol), postheating to 40 ℃ continues 1 hour to drip methoxy acetone.After being cooled to room temperature, with the mixture of suspension-s impouring ice and ammonium chloride saturated aqueous solution, (methylene dichloride (2 * 50ml, 2 * 100ml) extractions are used in 2 * 50ml) extractions to product then with ether.Merge organic extract, use brine wash, dry on anhydrous magnesium sulfate, vacuum concentration provides 1-methoxyl group-2 then, and the 5-dimethyl-is own-3-alkynes-2,5-glycol (6.98g) is transparent oily matter.
Step 2: preparation 5-methoxymethyl-2,2,5-trimethylammonium dihydrofuran--3-ketone and 2-methoxymethyl-2,5,5-trimethylammonium dihydrofuran--3-ketone
To red precipitate (0.05g, add in 0.231mmol) trichoroacetic acid(TCA) (0.02g, methyl alcohol 0.122mmol) (0.053ml) solution, add then the diethyl boron-trifluoride etherate (0.053ml, 0.37mmol).Stir the mixture momently, heat then, use extra methyl alcohol (1ml) dilution subsequently up to producing oyster white mashed prod (about 5 minutes).In this suspension-s, drip 1-methoxyl group-2 then, the 5-dimethyl-oneself-3-alkynes-2, (1.22g, methyl alcohol 7.09mmol) (1ml) solution was 50 ℃ of following heated mixt 3 hours for the 5-glycol.After being cooled to room temperature, reaction mixture concentrates down at 40 ℃/150 millibars through diatomite filtration (with extra methanol wash) then, provides thick oily matter.This material further with the ether washing, stirs on solid sodium bicarbonate, filters then; Concentrate down at 40 ℃/150 millibars, 5-methoxymethyl-2,2 is provided; 5-trimethylammonium dihydrofuran--3-ketone and 2-methoxymethyl-2,5, the mixture of 5-trimethylammonium dihydrofuran--3-ketone (0.73g); Be brown oil, do not add to be further purified and be used for subsequent step.
Step 3: preparation 2-methoxymethyl-2,5,5-trimethylammonium furans-3,4-diketone
With the tin anhydride in stirring (2.10g, moisture dioxane 18.91mmol) (17ml comprises the zero(ppm) water of 0.5% volume) solution is heated to 100 ℃; In 30 minutes, drip second kind of 5-methoxymethyl-2,2,5-trimethylammonium dihydrofuran--3-ketone and 2-methoxymethyl-2 this moment; 5, (2.55g is 14.82mmol) at moisture dioxane (5ml for 5-trimethylammonium dihydrofuran--3-ketone; The zero(ppm) water that comprises 0.5% volume) (mixing) solution in heated 3 hours under this temperature then.After being cooled to room temperature, mixture removes down at 40 ℃/50 millibars then and desolvates through diatomite filtration (washing with ether), provides heavy-gravity sorrel oily matter.This material provides 2-methoxymethyl-2,5 through bottle to bottle distillation purifying, 5-trimethylammonium furans-3, and 4-diketone (2.15g) is a shiny red oily matter.
Step 4: preparation 2-methoxymethyl-2,6,6-trimethylammonium-3,5-dioxo tetrahydropyrans-4-ethyl formate
Under 8 ℃, in zinc chloride (11.80ml, 11.80mmol, the diethyl ether solution of 1M), add second kind of 2-methoxymethyl-2,5 carefully, 5-trimethylammonium furans-3,4-diketone (2.15g, t-butyl methyl ether 11.56mmol) (8ml) solution.Make this mixture be warmed to 15 ℃, (1.35g, t-butyl methyl ether 11.84mmol) (6ml) solution keep internal temperature to be lower than 21 ℃ and also at room temperature continue stirred overnight in 1 hour, to drip ethyl diazoacetate in this stage.Mixture is with t-butyl methyl ether (15ml) dilution, and (3 * 20ml) washings are with (2 * 100ml) extractions of 1M sodium hydroxide with 1M hydrochloric acid.Add solid sodium chloride to this aqueous phase, use the concentrated hydrochloric acid acidifying subsequently, use the dichloromethane extraction mixture then.Organic extract is dry on anhydrous magnesium sulfate, filters, and vacuum concentrated filtrate provides 2-methoxymethyl-2,6,6-trimethylammonium-3, and 5-dioxo-tetrahydropyrans-4-ethyl formate (2.11g) is a pink colour oily matter.
Step 5: preparation 2-methoxymethyl-2,6,6-trimethylammonium pyrans-3,5-diketone
To 2-methoxymethyl-2,6,6-trimethylammonium-3, (2.11g added 20% aqueous sulfuric acid (2.5ml) to 5-oxo tetrahydropyrans-4-ethyl formate in dioxane 7.72mmol) (2.5ml) solution, 110 ℃ of following heated mixt 2.5 hours.Mixture is cooled to room temperature, with the saturated brine dilution, uses dichloromethane extraction.With thick extracting substances such as aqueous sodium hydroxide solution, the water washed with dichloromethane is used the concentrated hydrochloric acid acidifying then, is extracted into methylene dichloride (2 * 15ml).The vacuum concentration organic phase provides thick oily matter, through flash column chromatography (isohexane/ether of 7.5: 1.5 ratios) purifying on silica gel, 2-methoxymethyl-2,6 is provided with it, 6-trimethylammonium pyrans-3, and 5-diketone (0.250g) is a pink solid.
Step 6: preparation 4-(4 '-chloro-4-ethyl biphenyl-3-yl)-2-methoxymethyl-2,6,6-trimethylammonium-pyrans-3,5-diketone
To 2-methoxymethyl-2,6,6-trimethylammonium pyrans-3; 5-diketone (0.141g; 0.705mmol) and N, the N-dimethyl aminopyridine (0.43g, 3.52mmol) a collection of adding 4 in the mixture in the mixed solvent system of anhydrous chloroform (7.5ml) and dry toluene (1.75ml) '-chloro-4-ethyl biphenyl-plumbous (0.465g of 3-base nitrilotriacetic; 0.775mmol), 80 ℃ of following heated mixt 2 hours.Make mixture be cooled to room temperature,, stirred 5 minutes, remove inorganic residues (using solvent wash in addition) through diatomite filtration then with methylene dichloride and diluted hydrochloric acid aqueous solution dilution.Merge organic fraction, dry on anhydrous magnesium sulfate, filter vacuum concentrated filtrate.Resistates is through column chromatography (hexane/ethyl acetate of 4: 1 ratios) purifying on silica gel.Merge and comprise the cut of hoping product, vacuum-evaporation.With hexane development, 4-(4 '-chloro-4-ethyl biphenyl-3-yl)-2-methoxymethyl-2,6 is provided, 6-trimethylammonium pyrans-3,5-diketone (0.070g) is a white solid.
Other compound in the Table A makes from proper raw material through similar approach.It should be noted that and be used for acquisition
1Under the condition of H nmr data, compounds more of the present invention exist as atropisomer or above-mentioned other mixture of isomers.When this thing happens, report single isomer, i.e. the characterization data of isomer A and isomer B, its common representative is existing atropisomer or other mixture of isomers in specific solvent at ambient temperature.
Table A:
Embodiment 23: preparation 6-(4 '-two chloro-4-ethyl biphenyl-3-yl)-2,2,4,4-tetramethyl--hexanaphthene-1,3,5-triketone
To 2,2,4,4-tetramethyl-ring hexane-1,3, (0.100g, 0.55mmol) and N, (0.33g adds anhydrous chloroform (3.60ml) to the N-dimethyl aminopyridine to the 5-triketone in mixture 2.70mmol), at room temperature stir until dissolving subsequently.In this solution, add dry toluene (1.00ml) then, a collection of then adding 4 '-chloro-4-ethyl biphenyl-3-base nitrilotriacetic lead (0.36g, 0.60mmol).80 ℃ of following heated solns 1 hour, be cooled to room temperature then, add methylene dichloride (200ml) subsequently, use 1M hydrochloric acid (200ml) washing then.Tell organic phase,, filter vacuum concentrated filtrate at anhydrous magnesium sulfate drying.Resistates provides 6-(4 '-two chloro-4-ethyl biphenyl-3-yl)-2,2,4 through flash column chromatography (hexane/ethyl acetate of 5: 1 ratios) purifying on silica gel, 4-four-methylcyclohexane-1,3, and 5-triketone (0.17g) is a white crystalline solid.
Embodiment 24: preparation 6-(2 ', 4 '-two chloro-4-ethyl biphenyl-3-yls)-2,2,4,4-tetramethyl--hexanaphthene-1,3,5-triketone
Step 1 preparation 6-(5-bromo-2-ethylphenyl)-2,2,4,4-tetramethyl-ring hexane-1,3,5-triketone
To 2,2,4; 4-tetramethyl-ring hexane-1,3,5-triketone (0.6g; 3.6mmol), 5-bromo-2-ethylphenyl nitrilotriacetic plumbous (2.27g, 4.00mmol) and N, N-dimethyl aminopyridine (2.22g; Add anhydrous chloroform (25ml) and toluene (6.3ml) in mixture 18mmol), in 80 ℃ of reacting by heating mixtures 3 hours.Mixture is removed inorganic residues with methylene dichloride (50ml) and 2M aqueous hydrochloric acid (100ml) dilution through diatomite filtration.Filter cake is used washed with dichloromethane, merges whole organic fractions, uses brine wash, and is dry on anhydrous magnesium sulfate, filters then.Vacuum concentrated filtrate, resistates provides 6-(5-bromo-2-ethylphenyl)-2,2,4 through the flash column chromatography purifying, 4-tetramethyl-ring hexane-1,3, the 5-triketone is white solid (0.84g).
Step 2: preparation 6-(2 ', 4 '-two chloro-4-ethyl biphenyl-3-yls)-2,2,4,4-tetramethyl-ring-hexane-1,3,5-triketone
In the microwave bottle, add acid chloride (II) (1.1mg, 0.0049mmol), three (3-sulfo group phenyl) phosphine trisodium salt (5.1mg, 0.0099mmol), 2; 4-dichlorophenyl boric acid (0.099g, 0.5mmol), 6-(5-bromo-2-ethylphenyl)-2,2; 4,4-tetramethyl-ring hexane-1,3; The 5-triketone (0.19g, 0.5mmol) and potassiumphosphate (0.53g, 2.5mmol).Then add water (0.75ml) (washing any solid), stirred subsequently 5 minutes, use argon cleaning from the bottle wall through the degassing.Under microwave radiation, heating this mixture 15 minutes under 160 ℃ then.(0.099g, 0.5mmol) (0.095g, 0.5mmol), reaction mixture is protected under the argon atmospher once more, at 160 ℃ of continuation heated mixt 15 minutes down with potassiumphosphate to add the 2,4 dichloro benzene ylboronic acid of additional quantity.After being cooled to room temperature, reaction mixture is with methylene dichloride (5ml) dilution, with the acidifying of 2M aqueous hydrochloric acid.Tell organic phase, dry on anhydrous magnesium sulfate, filter through silica gel plug.Concentrating under reduced pressure filtrating is dissolved in N with resistates, and dinethylformamide (approximately 1ml) is through preparation type reversed-phase HPLC purifying; 6-(2 ', 4 '-two chloro-4-ethyl biphenyl-3-yls)-2,2,4 is provided; 4-tetramethyl--hexanaphthene-1,3, the 5-triketone is colorless oil (80.6mg).
Embodiment 25: preparation 6-[5-(6-chloro-2-picoline-3-yl)-2-ethylphenyl]-2,2,4,4-tetramethyl-ring hexane-1,3,5-triketone
At room temperature under nitrogen, stir 6-(5-bromo-2-ethylphenyl)-2,2; 4,4-tetramethyl-ring hexane-1,3; The 5-triketone (0.19g, 0.5mmol), cesium fluoride (0.24g, 1.6mmol), 6-chloro-2-picoline-3-ylboronic acid (0.13g; 0.8mmol) and through 1 of the degassing, the mixture of 2-glycol dimethyl ether (1.7ml) 30 minutes.(0.034g 0.042mmol), at room temperature stirred the mixture 10 minutes, then 80 ℃ of following heated overnight to add [1,1 '-two-(diphenylphosphino) ferrocene] two chloro-palladiums (II).After being cooled to room temperature, reaction mixture is with methylene dichloride (5ml) and water dilution, through diatomite filtration.Filtrating is told organic phase with the acidifying of 2M aqueous hydrochloric acid, and is dry on anhydrous magnesium sulfate, vacuum concentration.Resistates is dissolved in N, and dinethylformamide (approximately 1ml) through preparation type reversed-phase HPLC purifying, provides 6-[5-(6-chloro-2-picoline-3-yl)-2-ethylphenyl]-2,2,4,4-tetramethyl-ring hexane-1,3, and the 5-triketone is filbert solid (75.3mg).
Embodiment 26: preparation 3-(4 '-two chloro-4-ethyl biphenyl-3-yl) two ring [3.2.1] nonanes-2,4,9-triketone
Under 80 ℃, with 4 '-chloro-4-ethyl biphenyl-3-base nitrilotriacetic is plumbous, and (0.94g 1.57mmol) adds to two ring [3.2.1] nonanes-2 carefully; 4, (according to people such as F.Effenberger, Chem Ber. (1986) 119 for the 9-triketone; The method preparation of 3394-3404) (0.237g; 1.42mmol) and N, (0.87g is 7.13mmol) in the solution in anhydrous chloroform (10ml) and toluene (2.5ml) mixture for the N-dimethyl aminopyridine.Under 80 ℃, stirred the mixture 3 hours, and be cooled to room temperature then,, add the 2M aqueous hydrochloric acid with the methylene dichloride dilution.Mixture is removed inorganic residues through diatomite filtration.Filter cake is used washed with dichloromethane, and merging filtrate is used brine wash, and is dry on anhydrous magnesium sulfate, filters.Vacuum concentrated filtrate, resistates is through flash column chromatography purifying on silica gel, then further through preparation type reversed-phase HPLC purifying; Provide 3-(4 '-two chloro-4-ethyl biphenyl-3-yl) two ring [3.2.1] nonanes-2; 4,9-triketone (0.087g) is a pale solid.
Other compound among the table B makes from proper raw material through similar approach.
Table B:
Embodiment 27: preparation 4-(2 ', 4 '-two chloro-4-ethyl biphenyl-3-yls)-2,2,6,6-tetramethyl--thiapyran-3,5-diketone
Step 1: preparation 4-(5-bromo-2-ethylphenyl)-2,2,6,6-tetramethyl-sulfo-pyrans-3,5-diketone
To 2,2,6,6-tetramethyl-sulfo-pyrans-3; The 5-diketone (according to E.Er and P.Margaretha, Helvetica Chimica Acta (1992), 75 (7); The preparation of the method for 2265-69) (1.8g, 9.9mmol) and N, N-dimethyl aminopyridine (5.3g; 4.34mmol) chloroform (60ml) solution in add toluene (18ml), a collection of then adding 5-bromo-2-ethylphenyl nitrilotriacetic plumbous (6.2g, 1.09mmol).Heating gained mixture is 2 hours under refluxing, and makes it to be cooled to envrionment temperature then, with methylene dichloride and the dilution of 1M aqueous hydrochloric acid, tells organic phase.The concentrating under reduced pressure organic phase, resistates through flash chromatography on silica gel (95: 5-7: the hexane/ethyl acetate of 3 ratios) purifying, provide 4-(5-bromo-2-ethylphenyl)-2,2,6,6-tetramethyl-sulfo-pyrans-3,5-diketone (2.42g) is an orange solids.
Step 2: preparation 4-(2 ', 4 '-two chloro-4-ethyl biphenyl-3-yls)-2,2,6,6-tetramethyl--thiapyran-3,5-diketone
Under nitrogen atmosphere, add 4-(5-bromo-2-aminomethyl phenyl)-2,2,6 to the microwave bottle; 6-tetramethyl-sulfo-pyrans-3, and the 5-diketone (500mg, 1.36mmol), 2,4 dichloro benzene ylboronic acid (389mg; 2.05mmol), chlorination [1,1-two (phenylbenzene-phosphino-) ferrocene] palladium (II) (111mg, 0.000136mol) and cesium fluoride (620mg; 0.00408mol), add through 1 of the degassing, 2-glycol dimethyl ether (3ml) subsequently.Stirred the mixture at ambient temperature then 5 minutes, and under microwave radiation, heating 15 minutes under 160 ℃ then.Reaction mixture is cooled to room temperature, between 2M aqueous hydrochloric acid and methylene dichloride, distributes.Tell organic phase and concentrating under reduced pressure.Resistates is through preparation type reversed-phase HPLC purifying, provides 4-(2 ', 4 '-two chloro-4-ethyl biphenyl-3-yls)-2,2,6,6-tetramethyl--thiapyran-3, and 5-diketone (264mg) is the brown jelly.
Embodiment 28: preparation 4-(2 ', 4 '-two chloro-4-ethyl biphenyl-3-yls)-2,2,6,6-tetramethyl--1-oxo sulfo--pyrans-3,5-diketone
At ambient temperature, stirring 4-(2 ', 4 '-two chloro-4-ethyl biphenyl-3-yls)-2,2; 6,6-tetramethyl-sulfo-pyrans-3,5-diketone (79mg; 0.1816mmol), the mixture of peroxy acetic acid (1.8g, 7.2mmol, the acetic acid soln of 36-40%) and methylene dichloride (0.23ml) 4 hours.Reaction mixture distributes between water and methylene dichloride, tells organic phase, then concentrating under reduced pressure.Resistates is through preparation type reversed-phase HPLC purifying, provides 4-(2 ', 4 '-two chloro-4-ethyl biphenyl-3-yls)-2,2,6,6-tetramethyl--1-oxo sulfo-pyrans-3, and 5-diketone (32.9mg) is transparent jelly.
Embodiment 29: preparation 4-(2 ', 4 '-two chloro-4-ethyl biphenyl-3-yls)-2,2,6,6-tetramethyl--1,1-dioxo sulfo-pyrans-3,5-diketone
At ambient temperature, stirring 4-(2 ', 4 '-two chloro-4-ethyl biphenyl-3-yls)-2,2; 6,6-tetramethyl-sulfo-pyrans-3, (79mg is 0.1816mmol) with potassium hydrogen peroxymonosulfate (446mg for the 5-diketone; 0.726mmol) mixture 20 hours, as methanol (1ml, 1: 1 ratio) solution.Reaction mixture distributes between water and methylene dichloride then, tells organic phase, concentrating under reduced pressure.Resistates is through preparation type reversed-phase HPLC purifying, provides 4-(2 ', 4 '-two chloro-4-ethyl biphenyl-3-yls)-2,2,6,6-tetramethyl--1, and 1-dioxy-thiapyran-3,5-diketone (24.6mg) is transparent jelly.
Other compound among the table C makes from proper raw material through similar approach.
Table C:
The compound of hereinafter table 1-294 can obtain in a similar manner.
Table 1:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be methyl, R
4, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as hereinafter definition:
| Compound number | R 2 | R 3 |
| 1.001 | Phenyl | H |
| 1.002 | The 2-fluorophenyl | H |
| 1.003 | The 3-fluorophenyl | H |
| 1.004 | The 4-fluorophenyl | H |
| 1.005 | The 2-chloro-phenyl- | H |
| 1.006 | The 3-chloro-phenyl- | H |
| 1.007 | The 4-chloro-phenyl- | H |
| 1.008 | The 2-bromophenyl | H |
| 1.009 | The 3-bromophenyl | H |
| 1.010 | The 4-bromophenyl | H |
| 1.011 | The 4-tertiary butyl | H |
| 1.012 | The 2-iodophenyl | H |
| 1.013 | The 3-iodophenyl | H |
| 1.014 | The 4-iodophenyl | H |
| 1.015 | The 2-aminomethyl phenyl | H |
| 1.016 | The 3-aminomethyl phenyl | H |
| 1.017 | The 4-aminomethyl phenyl | H |
| 1.018 | The 2-cyano-phenyl | H |
| 1.019 | The 3-cyano-phenyl | H |
| 1.020 | The 4-cyano-phenyl | H |
| 1.021 | The 2-p-methoxy-phenyl | H |
| 1.022 | The 3-p-methoxy-phenyl | H |
| 1.023 | The 4-p-methoxy-phenyl | H |
| 1.024 | 2-difluoro-methoxy phenyl | H |
| 1.025 | 3-difluoro-methoxy phenyl | H |
| 1.026 | 4-difluoro-methoxy phenyl | H |
| 1.027 | 2-difluoromethyl phenyl | H |
| 1.028 | 3-difluoromethyl phenyl | H |
| 1.029 | 4-difluoromethyl phenyl | H |
| 1.030 | The 2-trifluoromethyl | H |
| 1.031 | The 3-trifluoromethyl | H |
| 1.032 | The 4-trifluoromethyl | H |
| 1.033 | The 2-Trifluoromethoxyphen-l | H |
| 1.034 | The 3-Trifluoromethoxyphen-l | H |
| 1.035 | The 4-Trifluoromethoxyphen-l | H |
| 1.036 | 4-methylthio group phenyl | H |
| 1.037 | 4-methylsulfinyl phenyl | H |
| 1.038 | 4-methyl sulphonyl phenyl | H |
| 1.039 | 4-trifluoromethylthio phenyl | H |
| 1.040 | 4-trifluoromethyl sulphinyl base phenyl | H |
| 1.041 | 4-trifluoromethyl sulfonyl phenyl | H |
| 1.042 | 2, the 3-difluorophenyl | H |
| 1.043 | The 2,4 difluorobenzene base | H |
| 1.044 | 2, the 5-difluorophenyl | H |
| 1.045 | 2, the 6-difluorophenyl | H |
| 1.046 | 3, the 4-difluorophenyl | H |
| 1.047 | 3, the 5-difluorophenyl | H |
| 1.048 | 2, the 3-dichlorophenyl | H |
| 1.049 | The 2,4 dichloro benzene base | H |
| 1.050 | 2, the 5-dichlorophenyl | H |
| 1.051 | 2, the 6-dichlorophenyl | H |
| 1.052 | 3, the 4-dichlorophenyl | H |
| 1.053 | 3, the 5-dichlorophenyl | H |
| 1.054 | 4-chloro-2-cyano-phenyl | H |
| 1.055 | 4-chloro-3-cyano-phenyl | H |
| 1.056 | 4-chloro-2-fluorophenyl | H |
| 1.057 | 4-chloro-3-fluorophenyl | H |
| 1.058 | 4-chloro-2-p-methoxy-phenyl | H |
| 1.059 | 4-chloro-3-p-methoxy-phenyl | H |
| 1.060 | 4-chloro-2-aminomethyl phenyl | H |
| 1.061 | 4-chloro-3-aminomethyl phenyl | H |
| 1.062 | 4-chloro-2-difluoro-methoxy phenyl | H |
| 1.063 | 4-chloro-3-difluoro-methoxy phenyl | H |
| 1.064 | 4-chloro-2-Trifluoromethoxyphen-l | H |
| 1.065 | 4-chloro-3-Trifluoromethoxyphen-l | H |
| 1.066 | 4-chloro-2-difluoromethyl phenyl | H |
| 1.067 | 4-chloro-3-difluoromethyl phenyl | H |
| 1.068 | 4-chloro-2-trifluoromethyl | H |
| 1.069 | 4-chloro-3-trifluoromethyl | H |
| 1.070 | 4-chloro-2, the 3-difluorophenyl | H |
| 1.071 | 4-chloro-2, the 5-difluorophenyl | H |
| 1.072 | 4 ,-chloro-2,6-difluorophenyl | H |
| 1.073 | 2,4-two chloro-3-fluorophenyls | H |
| 1.074 | 2,4-two chloro-5-fluorophenyls | H |
| 1.075 | 2,4-two chloro-6-fluorophenyls | H |
| 1.076 | 2,3, the 4-trichlorophenyl | H |
| 1.077 | 2,3, the 5-trichlorophenyl | H |
| 1.078 | 2,3, the 6-trichlorophenyl | H |
| 1.079 | 2,4, the 5-trichlorophenyl | H |
| 1.080 | 2,4, the 6-trichlorophenyl | H |
| 1.081 | 2,3, the 4-trifluorophenyl | H |
| 1.082 | 2,3, the 5-trifluorophenyl | H |
| 1.083 | 2,3, the 6-trifluorophenyl | H |
| 1.084 | 2,4, the 5-trifluorophenyl | H |
| 1.085 | 2,4, the 6-trifluorophenyl | H |
| 1.086 | 2-fluoro-4-trifluoromethyl | H |
| 1.087 | 3-fluoro-4-trifluoromethyl | H |
| 1.088 | 2-chloropyridine-5-base | H |
| 1.089 | 3-chloropyridine-5-base | H |
| 1.090 | 2-picoline-5-base | H |
| 1.091 | 3-picoline-5-base | H |
| 1.092 | 2-5-flumethiazine-5-base | H |
| 1.093 | 3-5-flumethiazine-5-base | H |
| 1.094 | 2-chloro-3-picoline-5-base | H |
| 1.095 | 2-chloro-4-picoline-5-base | H |
| 1.096 | 6-chloro-2-picoline-3-base | H |
| 1.097 | 2,3-dichloropyridine-5-base | H |
| 1.098 | 2,4-dichloropyridine-5-base | H |
| 1.099 | 2,6-dichloropyridine-3-base | H |
| 1.100 | Pyrazine-2-base | H |
| 1.101 | 2-chloropyrazine-5-base | H |
| 1.102 | 2-bromo-pyrazine-5-base | H |
| 1.103 | Pyridazine-3-base | H |
| 1.104 | 6-bromine pyridazine-3-base | H |
| 1.105 | 6-chlorine pyridazine-3-base | H |
| 1.106 | Pyrimidine-5-base | H |
| 1.107 | 2-bromo pyrimi piperidine-5-base | H |
| 1.108 | 5-bromo pyrimi piperidine-2-base | H |
| 1.109 | 2-chloropyrimide-5-base | H |
| 1.110 | 5-chloropyrimide-2-base | H |
| 1.111 | The 2-furyl | H |
| 1.112 | The 3-furyl | H |
| 1.113 | The 2-thienyl | H |
| 1.114 | The 3-thienyl | H |
| 1.115 | 4-bromothiophene-2-base | H |
| 1.116 | 5-bromothiophene-2-base | H |
| 1.117 | 4-chlorothiophene-2-base | H |
| 1.118 | 5-chlorothiophene-2-base | H |
| 1.119 | Pyrazol-1-yl | H |
| 1.120 | 3-chlorine pyrazol-1-yl | H |
| 1.121 | 4-chlorine pyrazol-1-yl | H |
| 1.122 | The 1-methyl-pyrazol-4-yl | H |
| 1.123 | 1-methyl-3-trifluoromethyl pyrazol-5-base | H |
| 1.124 | The 2-thiazolyl | H |
| 1.125 | 4-methylthiazol-2-base | H |
| 1.126 | 5-methylthiazol-2-base | H |
| 1.127 | Phenyl | CH 3 |
| 1.128 | The 2-fluorophenyl | CH 3 |
| 1.129 | The 3-fluorophenyl | CH 3 |
| 1.130 | The 4-fluorophenyl | CH 3 |
| 1.131 | The 2-chloro-phenyl- | CH 3 |
| 1.132 | The 3-chloro-phenyl- | CH 3 |
| 1.133 | The 4-chloro-phenyl- | CH 3 |
| 1.134 | The 2-bromophenyl | CH 3 |
| 1.135 | The 3-bromophenyl | CH 3 |
| 1.136 | The 4-bromophenyl | CH 3 |
| 1.137 | The 4-tertiary butyl | CH 3 |
| 1.138 | The 2-iodophenyl | CH 3 |
| 1.139 | The 3-iodophenyl | CH 3 |
| 1.140 | The 4-iodophenyl | CH 3 |
| 1.141 | The 2-aminomethyl phenyl | CH 3 |
| 1.142 | The 3-aminomethyl phenyl | CH 3 |
| 1.143 | The 4-aminomethyl phenyl | CH 3 |
| 1.144 | The 2-cyano-phenyl | CH 3 |
| 1.145 | The 3-cyano-phenyl | CH 3 |
| 1.146 | The 4-cyano-phenyl | CH 3 |
| 1.147 | The 2-p-methoxy-phenyl | CH 3 |
| 1.148 | The 3-p-methoxy-phenyl | CH 3 |
| 1.149 | The 4-p-methoxy-phenyl | CH 3 |
| 1.150 | 2-difluoro-methoxy phenyl | CH 3 |
| 1.151 | 3-difluoro-methoxy phenyl | CH 3 |
| 1.152 | 4-difluoro-methoxy phenyl | CH 3 |
| 1.153 | 2-difluoromethyl phenyl | CH 3 |
| 1.154 | 3-difluoromethyl phenyl | CH 3 |
| 1.155 | 4-difluoromethyl phenyl | CH 3 |
| 1.156 | The 2-trifluoromethyl | CH 3 |
| 1.157 | The 3-trifluoromethyl | CH 3 |
| 1.158 | The 4-trifluoromethyl | CH 3 |
| 1.159 | The 2-Trifluoromethoxyphen-l | CH 3 |
| 1.160 | The 3-Trifluoromethoxyphen-l | CH 3 |
| 1.161 | The 4-Trifluoromethoxyphen-l | CH 3 |
| 1.162 | 4-methylthio group phenyl | CH 3 |
| 1.163 | 4-methylsulfinyl phenyl | CH 3 |
| 1.164 | 4-methyl sulphonyl phenyl | CH 3 |
| 1.165 | 4-trifluoromethylthio phenyl | CH 3 |
| 1.166 | 4-trifluoromethyl sulphinyl base phenyl | CH 3 |
| 1.167 | 4-trifluoromethyl sulfonyl phenyl | CH 3 |
| 1.168 | 2, the 3-difluorophenyl | CH 3 |
| 1.169 | The 2,4 difluorobenzene base | CH 3 |
| 1.170 | 2, the 5-difluorophenyl | CH 3 |
| 1.171 | 2, the 6-difluorophenyl | CH 3 |
| 1.172 | 3, the 4-difluorophenyl | CH 3 |
| 1.173 | 3, the 5-difluorophenyl | CH 3 |
| 1.174 | 2, the 3-dichlorophenyl | CH 3 |
| 1.175 | The 2,4 dichloro benzene base | CH 3 |
| 1.176 | 2, the 5-dichlorophenyl | CH 3 |
| 1.177 | 2, the 6-dichlorophenyl | CH 3 |
| 1.178 | 3, the 4-dichlorophenyl | CH 3 |
| 1.179 | 3, the 5-dichlorophenyl | CH 3 |
| 1.180 | 4-chloro-2-cyano-phenyl | CH 3 |
| 1.181 | 4-chloro-3-cyano-phenyl | CH 3 |
| 1.182 | 4-chloro-2-fluorophenyl | CH 3 |
| 1.183 | 4-chloro-3-fluorophenyl | CH 3 |
| 1.184 | 4-chloro-2-p-methoxy-phenyl | CH 3 |
| 1.185 | 4-chloro-3-p-methoxy-phenyl | CH 3 |
| 1.186 | 4-chloro-2-aminomethyl phenyl | CH 3 |
| 1.187 | 4-chloro-3-aminomethyl phenyl | CH 3 |
| 1.188 | 4-chloro-2-difluoro-methoxy phenyl | CH 3 |
| 1.189 | 4-chloro-3-difluoro-methoxy phenyl | CH 3 |
| 1.190 | 4-chloro-2-Trifluoromethoxyphen-l | CH 3 |
| 1.191 | 4-chloro-3-Trifluoromethoxyphen-l | CH 3 |
| 1.192 | 4-chloro-2-difluoromethyl phenyl | CH 3 |
| 1.193 | 4-chloro-3-difluoromethyl phenyl | CH 3 |
| 1.194 | 4-chloro-2-trifluoromethyl | CH 3 |
| 1.195 | 4-chloro-3-trifluoromethyl | CH 3 |
| 1.196 | 4-chloro-2, the 3-difluorophenyl | CH 3 |
| 1.197 | 4-chloro-2, the 5-difluorophenyl | CH 3 |
| 1.198 | 4 ,-chloro-2,6-difluorophenyl | CH 3 |
| 1.199 | 2,4-two chloro-3-fluorophenyls | CH 3 |
| 1.200 | 2,4-two chloro-5-fluorophenyls | CH 3 |
| 1.201 | 2,4-two chloro-6-fluorophenyls | CH 3 |
| 1.202 | 2,3, the 4-trichlorophenyl | CH 3 |
| 1.203 | 2,3, the 5-trichlorophenyl | CH 3 |
| 1.204 | 2,3, the 6-trichlorophenyl | CH 3 |
| 1.205 | 2,4, the 5-trichlorophenyl | CH 3 |
| 1.206 | 2,4, the 6-trichlorophenyl | CH 3 |
| 1.207 | 2,3, the 4-trifluorophenyl | CH 3 |
| 1.208 | 2,3, the 5-trifluorophenyl | CH 3 |
| 1.209 | 2,3, the 6-trifluorophenyl | CH 3 |
| 1.210 | 2,4, the 5-trifluorophenyl | CH 3 |
| 1.211 | 2,4, the 6-trifluorophenyl | CH 3 |
| 1.212 | 2-fluoro-4-trifluoromethyl | CH 3 |
| 1.213 | 3-fluoro-4-trifluoromethyl | CH 3 |
| 1.214 | 2-chloropyridine-5-base | CH 3 |
| 1.215 | 3-chloropyridine-5-base | CH 3 |
| 1.216 | 2-picoline-5-base | CH 3 |
| 1.217 | 3-picoline-5-base | CH 3 |
| 1.218 | 2-5-flumethiazine-5-base | CH 3 |
| 1.219 | 3-5-flumethiazine-5-base | CH 3 |
| 1.220 | 2-chloro-3-picoline-5-base | CH 3 |
| 1.221 | 2-chloro-4-picoline-5-base | CH 3 |
| 1.222 | 6-chloro-2-picoline-3-base | CH 3 |
| 1.223 | 2,3-dichloropyridine-5-base | CH 3 |
| 1.224 | 2,4-dichloropyridine-5-base | CH 3 |
| 1.225 | 2,6-dichloropyridine-3-base | CH 3 |
| 1.226 | Pyrazine-2-base | CH 3 |
| 1.227 | 2-chloropyrazine-5-base | CH 3 |
| 1.228 | 2-bromo-pyrazine-5-base | CH 3 |
| 1.229 | Pyridazine-3-base | CH 3 |
| 1.230 | 6-bromine pyridazine-3-base | CH 3 |
| 1.231 | 6-chlorine pyridazine-3-base | CH 3 |
| 1.232 | Pyrimidine-5-base | CH 3 |
| 1.233 | 2-bromo pyrimi piperidine-5-base | CH 3 |
| 1.234 | 5-bromo pyrimi piperidine-2-base | CH 3 |
| 1.235 | 2-chloropyrimide-5-base | CH 3 |
| 1.236 | 5-chloropyrimide-2-base | CH 3 |
| 1.237 | The 2-furyl | CH 3 |
| 1.238 | The 3-furyl | CH 3 |
| 1.239 | The 2-thienyl | CH 3 |
| 1.240 | The 3-thienyl | CH 3 |
| 1.241 | 4-bromothiophene-2-base | CH 3 |
| 1.242 | 5-bromothiophene-2-base | CH 3 |
| 1.243 | 4-chlorothiophene-2-base | CH 3 |
| 1.244 | 5-chlorothiophene-2-base | CH 3 |
| 1.245 | Pyrazol-1-yl | CH 3 |
| 1.246 | 3-chlorine pyrazol-1-yl | CH 3 |
| 1.247 | 4-chlorine pyrazol-1-yl | CH 3 |
| 1.248 | The 1-methyl-pyrazol-4-yl | CH 3 |
| 1.249 | 1-methyl-3-trifluoromethyl pyrazol-5-base | CH 3 |
| 1.250 | The 2-thiazolyl | CH 3 |
| 1.251 | 4-methylthiazol-2-base | CH 3 |
| 1.252 | 5-methylthiazol-2-base | CH 3 |
| 1.253 | Phenyl | Cl |
| 1.254 | The 2-fluorophenyl | Cl |
| 1.255 | The 3-fluorophenyl | Cl |
| 1.256 | The 4-fluorophenyl | Cl |
| 1.257 | The 2-chloro-phenyl- | Cl |
| 1.258 | The 3-chloro-phenyl- | Cl |
| 1.259 | The 4-chloro-phenyl- | Cl |
| 1.260 | The 2-bromophenyl | Cl |
| 1.261 | The 3-bromophenyl | Cl |
| 1.262 | The 4-bromophenyl | Cl |
| 1.263 | The 4-tertiary butyl | Cl |
| 1.264 | The 2-iodophenyl | Cl |
| 1.265 | The 3-iodophenyl | Cl |
| 1.266 | The 4-iodophenyl | Cl |
| 1.267 | The 2-aminomethyl phenyl | Cl |
| 1.268 | The 3-aminomethyl phenyl | Cl |
| 1.269 | The 4-aminomethyl phenyl | Cl |
| 1.270 | The 2-cyano-phenyl | Cl |
| 1.271 | The 3-cyano-phenyl | Cl |
| 1.272 | The 4-cyano-phenyl | Cl |
| 1.273 | The 2-p-methoxy-phenyl | Cl |
| 1.274 | The 3-p-methoxy-phenyl | Cl |
| 1.275 | The 4-p-methoxy-phenyl | Cl |
| 1.276 | 2-difluoro-methoxy phenyl | Cl |
| 1.277 | 3-difluoro-methoxy phenyl | Cl |
| 1.278 | 4-difluoro-methoxy phenyl | Cl |
| 1.279 | 2-difluoromethyl phenyl | Cl |
| 1.280 | 3-difluoromethyl phenyl | Cl |
| 1.281 | 4-difluoromethyl phenyl | Cl |
| 1.282 | The 2-trifluoromethyl | Cl |
| 1.283 | The 3-trifluoromethyl | Cl |
| 1.284 | The 4-trifluoromethyl | Cl |
| 1.285 | The 2-Trifluoromethoxyphen-l | Cl |
| 1.286 | The 3-Trifluoromethoxyphen-l | Cl |
| 1.287 | The 4-Trifluoromethoxyphen-l | Cl |
| 1.288 | 4-methylthio group phenyl | Cl |
| 1.289 | 4-methylsulfinyl phenyl | Cl |
| 1.290 | 4-methyl sulphonyl phenyl | Cl |
| 1.291 | 4-trifluoromethylthio phenyl | Cl |
| 1.292 | 4-trifluoromethyl sulphinyl base phenyl | Cl |
| 1.293 | 4-trifluoromethyl sulfonyl phenyl | Cl |
| 1.294 | 2, the 3-difluorophenyl | Cl |
| 1.295 | The 2,4 difluorobenzene base | Cl |
| 1.296 | 2, the 5-difluorophenyl | Cl |
| 1.297 | 2, the 6-difluorophenyl | Cl |
| 1.298 | 3, the 4-difluorophenyl | Cl |
| 1.299 | 3, the 5-difluorophenyl | Cl |
| 1.300 | 2, the 3-dichlorophenyl | Cl |
| 1.301 | The 2,4 dichloro benzene base | Cl |
| 1.302 | 2, the 5-dichlorophenyl | Cl |
| 1.303 | 2, the 6-dichlorophenyl | Cl |
| 1.304 | 3, the 4-dichlorophenyl | Cl |
| 1.305 | 3, the 5-dichlorophenyl | Cl |
| 1.306 | 4-chloro-2-cyano-phenyl | Cl |
| 1.307 | 4-chloro-3-cyano-phenyl | Cl |
| 1.308 | 4-chloro-2-fluorophenyl | Cl |
| 1.309 | 4-chloro-3-fluorophenyl | Cl |
| 1.310 | 4-chloro-2-p-methoxy-phenyl | Cl |
| 1.311 | 4-chloro-3-p-methoxy-phenyl | Cl |
| 1.312 | 4-chloro-2-aminomethyl phenyl | Cl |
| 1.313 | 4-chloro-3-aminomethyl phenyl | Cl |
| 1.314 | 4-chloro-2-difluoro-methoxy phenyl | Cl |
| 1.315 | 4-chloro-3-difluoro-methoxy phenyl | Cl |
| 1.316 | 4-chloro-2-Trifluoromethoxyphen-l | Cl |
| 1.317 | 4-chloro-3-Trifluoromethoxyphen-l | Cl |
| 1.318 | 4-chloro-2-difluoromethyl phenyl | Cl |
| 1.319 | 4-chloro-3-difluoromethyl phenyl | Cl |
| 1.320 | 4-chloro-2-trifluoromethyl | Cl |
| 1.321 | 4-chloro-3-trifluoromethyl | Cl |
| 1.322 | 4-chloro-2, the 3-difluorophenyl | Cl |
| 1.323 | 4-chloro-2, the 5-difluorophenyl | Cl |
| 1.324 | 4 ,-chloro-2,6-difluorophenyl | Cl |
| 1.325 | 2,4-two chloro-3-fluorophenyls | Cl |
| 1.326 | 2,4-two chloro-5-fluorophenyls | Cl |
| 1.327 | 2,4-two chloro-6-fluorophenyls | Cl |
| 1.328 | 2,3, the 4-trichlorophenyl | Cl |
| 1.329 | 2,3, the 5-trichlorophenyl | Cl |
| 1.330 | 2,3, the 6-trichlorophenyl | Cl |
| 1.331 | 2,4, the 5-trichlorophenyl | Cl |
| 1.332 | 2,4, the 6-trichlorophenyl | Cl |
| 1.333 | 2,3, the 4-trifluorophenyl | Cl |
| 1.334 | 2,3, the 5-trifluorophenyl | Cl |
| 1.335 | 2,3, the 6-trifluorophenyl | Cl |
| 1.336 | 2,4, the 5-trifluorophenyl | Cl |
| 1.337 | 2,4, the 6-trifluorophenyl | Cl |
| 1.338 | 2-fluoro-4-trifluoromethyl | Cl |
| 1.339 | 3-fluoro-4-trifluoromethyl | Cl |
| 1.340 | 2-chloropyridine-5-base | Cl |
| 1.341 | 3-chloropyridine-5-base | Cl |
| 1.342 | 2-picoline-5-base | Cl |
| 1.343 | 3-picoline-5-base | Cl |
| 1.344 | 2-5-flumethiazine-5-base | Cl |
| 1.345 | 3-5-flumethiazine-5-base | Cl |
| 1.346 | 2-chloro-3-picoline-5-base | Cl |
| 1.347 | 2-chloro-4-picoline-5-base | Cl |
| 1.348 | 6-chloro-2-picoline-3-base | Cl |
| 1.349 | 2,3-dichloropyridine-5-base | Cl |
| 1.350 | 2,4-dichloropyridine-5-base | Cl |
| 1.351 | 2,6-dichloropyridine-3-base | Cl |
| 1.352 | Pyrazine-2-base | Cl |
| 1.353 | 2-chloropyrazine-5-base | Cl |
| 1.354 | 2-bromo-pyrazine-5-base | Cl |
| 1.355 | Pyridazine-3-base | Cl |
| 1.356 | 6-bromine pyridazine-3-base | Cl |
| 1.357 | 6-chlorine pyridazine-3-base | Cl |
| 1.358 | Pyrimidine-5-base | Cl |
| 1.359 | 2-bromo pyrimi piperidine-5-base | Cl |
| 1.360 | 5-bromo pyrimi piperidine-2-base | Cl |
| 1.361 | 2-chloropyrimide-5-base | Cl |
| 1.362 | 5-chloropyrimide-2-base | Cl |
| 1.363 | The 2-furyl | Cl |
| 1.364 | The 3-furyl | Cl |
| 1.365 | The 2-thienyl | Cl |
| 1.366 | The 3-thienyl | Cl |
| 1.367 | 4-bromothiophene-2-base | Cl |
| 1.368 | 5-bromothiophene-2-base | Cl |
| 1.369 | 4-chlorothiophene-2-base | Cl |
| 1.370 | 5-chlorothiophene-2-base | Cl |
| 1.371 | Pyrazol-1-yl | Cl |
| 1.372 | 3-chlorine pyrazol-1-yl | Cl |
| 1.373 | 4-chlorine pyrazol-1-yl | Cl |
| 1.374 | The 1-methyl-pyrazol-4-yl | Cl |
| 1.375 | 1-methyl-3-trifluoromethyl pyrazol-5-base | Cl |
| 1.376 | The 2-thiazolyl | Cl |
| 1.377 | 4-methylthiazol-2-base | Cl |
| 1.378 | 5-methylthiazol-2-base | Cl |
Table 2:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be ethyl, R
4, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 3:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be chlorine, R
4, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 4:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be methyl, R
4Be methyl, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 5:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be ethyl, R
4Be methyl, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 6:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be chlorine, R
4Be methyl, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 7:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be methyl, R
4And R
5Be methyl, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 8:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be ethyl, R
4And R
5Be methyl, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 9:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be chlorine, R
4And R
5Be methyl, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 10:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be methyl, R
4And R
6Be methyl, R
5And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 11:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be ethyl, R
4And R
6Be methyl, R
5And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 12:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be chlorine, R
4And R
6Be methyl, R
5And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 13:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be methyl, R
4, R
5And R
6Be methyl, R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 14:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be ethyl, R
4, R
5And R
6Be methyl, R
7Be hydrogen, G is hydrogen and R2 and R
3Such as table 1 definition.
Table 15:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be chlorine, R
4, R
5And R
6Be methyl, R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 16:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be methyl, R
4, R
5, R
6And R
7Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 17:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be ethyl, R
4, R
5, R
6And R
7Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 18:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be chlorine, R
4, R
5, R
6And R
7Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 19:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be methyl, R
4, R
5And R
6Be methyl, R
7Be methoxymethyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 20:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be ethyl, R
4, R
5And R
6Be methyl, R
7Be methoxymethyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 21:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be chlorine, R
4, R
5And R
6Be methyl, R
7Be methoxymethyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 22:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be methyl, R
4, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 23:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be ethyl, R
4, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 24:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be chlorine, R
4, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 25:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be methyl, R
4Be methyl, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 26:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be ethyl, R
4Be methyl, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 27:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be chlorine, R
4Be methyl, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 28:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be methyl, R
4And R
5Be methyl, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 29:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be ethyl, R
4And R
5Be methyl, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 30:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be chlorine, R
4And R
5Be methyl, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 31:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be methyl, R
4And R
6Be methyl, R
5And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 32:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be ethyl, R
4And R
6Be methyl, R
5And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 33:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be chlorine, R
4And R
6Be methyl, R
5And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 34:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be methyl, R
4, R
5And R
6Be methyl, R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 35:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be ethyl, R
4, R
5And R
6Be methyl, R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 36:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be chlorine, R
4, R
5And R
6Be methyl, R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 37:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be methyl, R
4, R
5, R
6And R
7Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 38:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be ethyl, R
4, R
5, R
6And R
7Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 39:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be chlorine, R
4, R
5, R
6And R
7Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 40:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be methyl, R
4, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 41:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be ethyl, R
4, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 42:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be chlorine, R
4, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 43:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be methyl, R
4Be methyl, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 44:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be ethyl, R
4Be methyl, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 45:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be chlorine, R
4Be methyl, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 46:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be methyl, R
4And R
5Be methyl, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 47:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be ethyl, R
4And R
5Be methyl, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 48:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be chlorine, R
4And R
5Be methyl, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 49:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be methyl, R
4And R
6Be methyl, R
5And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 50:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be ethyl, R
4And R
6Be methyl, R
5And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 51:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be chlorine, R
4And R
6Be methyl, R
5And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 52:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be methyl, R
4, R
5And R
6Be methyl, R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 53:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be ethyl, R
4, R
5And R
6Be methyl, R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 54:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be chlorine, R
4, R
5And R
6Be methyl, R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 55:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be methyl, R
4, R
5, R
6And R
7Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 56:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be ethyl, R
4, R
5, R
6And R
7Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 57:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be chlorine, R
4, R
5, R
6And R
7Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 58:
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be methyl, R
4, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 59:
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be ethyl, R
4, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 60:
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be chlorine, R
4, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 61:
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be methyl, R
4Be methyl, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 62:
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be ethyl, R
4Be methyl, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 63:
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be chlorine, R
4Be methyl, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 64:
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be methyl, R
4And R
5Be methyl, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 65:
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be ethyl, R
4And R
5Be methyl, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 66:
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be chlorine, R
4And R
5Be methyl, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 67:
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be methyl, R
4And R
6Be methyl, R
5And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 68:
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be ethyl, R
4And R
6Be methyl, R
5And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 69:
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be chlorine, R
4And R
6Be methyl, R
5And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 70:
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be methyl, R
4, R
5And R
6Be methyl, R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 71:
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be ethyl, R
4, R
5And R
6Be methyl, R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 72:
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be chlorine, R
4, R
5And R
6Be methyl, R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 73:
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be methyl, R
4, R
5, R
6And R
7Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 74:
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be ethyl, R
4, R
5, R
6And R
7Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 75:
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be chlorine, R
4, R
5, R
6And R
7Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 76:
This table comprises 378 compounds of following type:
Wherein Y is C=O, R
1Be methyl, R
4And R
5Be methyl, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 77:
This table comprises 378 compounds of following type:
Wherein Y is C=O, R
1Be ethyl, R
4And R
5Be methyl, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 78:
This table comprises 378 compounds of following type:
Wherein Y is C=O, R
1Be ethyl, R
4And R
5Be methyl, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 79:
This table comprises 378 compounds of following type:
Wherein Y is C=O, R
1Be methyl, R
4, R
5And R
6Be methyl, R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 80:
This table comprises 378 compounds of following type:
Wherein Y is C=O, R
1Be ethyl, R
4, R
5And R
6Be methyl, R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 81:
This table comprises 378 compounds of following type:
Wherein Y is C=O, R
1Be chlorine, R
4, R
5And R
6Be methyl, R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 82:
This table comprises 378 compounds of following type:
Wherein Y is C=O, R
1Be methyl, R
4, R
5, R
6And R
7Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 83:
This table comprises 378 compounds of following type:
Wherein Y is C=O, R
1Be ethyl, R
4, R
5, R
6And R
7Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 84:
This table comprises 378 compounds of following type:
Wherein Y is C=O, R
1Be chlorine, R
4, R
5, R
6And R
7Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 85:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1Be methyl, R
4, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3' such as hereinafter definition:
| Compound number | R 2 | R 3 |
| 85.001 | Phenyl | CH 3 |
| 85.002 | The 2-fluorophenyl | CH 3 |
| 85.003 | The 3-fluorophenyl | CH 3 |
| 85.004 | The 4-fluorophenyl | CH 3 |
| 85.005 | The 2-chloro-phenyl- | CH 3 |
| 85.006 | The 3-chloro-phenyl- | CH 3 |
| 85.007 | The 4-chloro-phenyl- | CH 3 |
| 85.008 | The 2-bromophenyl | CH 3 |
| 85.009 | The 3-bromophenyl | CH 3 |
| 85.010 | The 4-bromophenyl | CH 3 |
| 85.011 | The 4-tertiary butyl | CH 3 |
| 85.012 | The 2-iodophenyl | CH 3 |
| 85.013 | The 3-iodophenyl | CH 3 |
| 85.014 | The 4-iodophenyl | CH 3 |
| 85.015 | The 2-aminomethyl phenyl | CH 3 |
| 85.016 | The 3-aminomethyl phenyl | CH 3 |
| 85.017 | The 4-aminomethyl phenyl | CH 3 |
| 85.018 | The 2-cyano-phenyl | CH 3 |
| 85.019 | The 3-cyano-phenyl | CH 3 |
| 85.020 | The 4-cyano-phenyl | CH 3 |
| 85.021 | The 2-p-methoxy-phenyl | CH 3 |
| 85.022 | The 3-p-methoxy-phenyl | CH 3 |
| 85.023 | The 4-p-methoxy-phenyl | CH 3 |
| 85.024 | 2-difluoro-methoxy phenyl | CH 3 |
| 85.025 | 3-difluoro-methoxy phenyl | CH 3 |
| 85.026 | 4-difluoro-methoxy phenyl | CH 3 |
| 85.027 | 2-difluoromethyl phenyl | CH 3 |
| 85.028 | 3-difluoromethyl phenyl | CH 3 |
| 85.029 | 4-difluoromethyl phenyl | CH 3 |
| 85.030 | The 2-trifluoromethyl | CH 3 |
| 85.031 | The 3-trifluoromethyl | CH 3 |
| 85.032 | The 4-trifluoromethyl | CH 3 |
| 85.033 | The 2-Trifluoromethoxyphen-l | CH 3 |
| 85.034 | The 3-Trifluoromethoxyphen-l | CH 3 |
| 85.035 | The 4-Trifluoromethoxyphen-l | CH 3 |
| 85.036 | 4-methylthio group phenyl | CH 3 |
| 85.037 | 4-methylsulfinyl phenyl | CH 3 |
| 85.038 | 4-methyl sulphonyl phenyl | CH 3 |
| 85.039 | 4-trifluoromethylthio phenyl | CH 3 |
| 85.040 | 4-trifluoromethyl sulphinyl base phenyl | CH 3 |
| 85.041 | 4-trifluoromethyl sulfonyl phenyl | CH 3 |
| 85.042 | 2, the 3-difluorophenyl | CH 3 |
| 85.043 | The 2,4 difluorobenzene base | CH 3 |
| 85.044 | 2, the 5-difluorophenyl | CH 3 |
| 85.045 | 2, the 6-difluorophenyl | CH 3 |
| 85.046 | 3, the 4-difluorophenyl | CH 3 |
| 85.047 | 3, the 5-difluorophenyl | CH 3 |
| 85.048 | 2, the 3-dichlorophenyl | CH 3 |
| 85.049 | The 2,4 dichloro benzene base | CH 3 |
| 85.050 | 2, the 5-dichlorophenyl | CH 3 |
| 85.051 | 2, the 6-dichlorophenyl | CH 3 |
| 85.052 | 3, the 4-dichlorophenyl | CH 3 |
| 85.053 | 3, the 5-dichlorophenyl | CH 3 |
| 85.054 | 4-chloro-2-cyano-phenyl | CH 3 |
| 85.055 | 4-chloro-3-cyano-phenyl | CH 3 |
| 85.056 | 4-chloro-2-fluorophenyl | CH 3 |
| 85.057 | 4-chloro-3-fluorophenyl | CH 3 |
| 85.058 | 4-chloro-2-p-methoxy-phenyl | CH 3 |
| 85.059 | 4-chloro-3-p-methoxy-phenyl | CH 3 |
| 85.060 | 4-chloro-2-aminomethyl phenyl | CH 3 |
| 85.061 | 4-chloro-3-aminomethyl phenyl | CH 3 |
| 85.062 | 4-chloro-2-difluoro-methoxy phenyl | CH 3 |
| 85.063 | 4-chloro-3-difluoro-methoxy phenyl | CH 3 |
| 85.064 | 4-chloro-2-Trifluoromethoxyphen-l | CH 3 |
| 85.065 | 4-chloro-3-Trifluoromethoxyphen-l | CH 3 |
| 85.066 | 4-chloro-2-difluoromethyl phenyl | CH 3 |
| 85.067 | 4-chloro-3-difluoromethyl phenyl | CH 3 |
| 85.068 | 4-chloro-2-trifluoromethyl | CH 3 |
| 85.069 | 4-chloro-3-trifluoromethyl | CH 3 |
| 85.070 | 4-chloro-2, the 3-difluorophenyl | CH 3 |
| 85.071 | 4-chloro-2, the 5-difluorophenyl | CH 3 |
| 85.072 | 4 ,-chloro-2,6-difluorophenyl | CH 3 |
| 85.073 | 2,4-two chloro-3-fluorophenyls | CH 3 |
| 85.074 | 2,4-two chloro-5-fluorophenyls | CH 3 |
| 85.075 | 2,4-two chloro-6-fluorophenyls | CH 3 |
| 85.076 | 2,3, the 4-trichlorophenyl | CH 3 |
| 85.077 | 2,3, the 5-trichlorophenyl | CH 3 |
| 85.078 | 2,3, the 6-trichlorophenyl | CH 3 |
| 85.079 | 2,4, the 5-trichlorophenyl | CH 3 |
| 85.080 | 2,4, the 6-trichlorophenyl | CH 3 |
| 85.081 | 2,3, the 4-trifluorophenyl | CH 3 |
| 85.082 | 2,3, the 5-trifluorophenyl | CH 3 |
| 85.083 | 2,3, the 6-trifluorophenyl | CH 3 |
| 85.084 | 2,4, the 5-trifluorophenyl | CH 3 |
| 85.085 | 2,4, the 6-trifluorophenyl | CH 3 |
| 85.086 | 2-fluoro-4-trifluoromethyl | CH 3 |
| 85.087 | 3-fluoro-4-trifluoromethyl | CH 3 |
| 85.088 | 2-chloropyridine-5-base | CH 3 |
| 85.089 | 3-chloropyridine-5-base | CH 3 |
| 85.090 | 2-picoline-5-base | CH 3 |
| 85.091 | 3-picoline-5-base | CH 3 |
| 85.092 | 2-5-flumethiazine-5-base | CH 3 |
| 85.093 | 3-5-flumethiazine-5-base | CH 3 |
| 85.094 | 2-chloro-3-picoline-5-base | CH 3 |
| 85.095 | 2-chloro-4-picoline-5-base | CH 3 |
| 85.096 | 6-chloro-2-picoline-3-base | CH 3 |
| 85.097 | 2,3-dichloropyridine-5-base | CH 3 |
| 85.098 | 2,4-dichloropyridine-5-base | CH 3 |
| 85.099 | 2,6-dichloropyridine-3-base | CH 3 |
| 85.100 | Pyrazine-2-base | CH 3 |
| 85.101 | 2-chloropyrazine-5-base | CH 3 |
| 85.102 | 2-bromo-pyrazine-5-base | CH 3 |
| 85.103 | Pyridazine-3-base | CH 3 |
| 85.104 | 6-bromine pyridazine-3-base | CH 3 |
| 85.105 | 6-chlorine pyridazine-3-base | CH 3 |
| 85.106 | Pyrimidine-5-base | CH 3 |
| 85.107 | 2-bromo pyrimi piperidine-5-base | CH 3 |
| 85.108 | 5-bromo pyrimi piperidine-2-base | CH 3 |
| 85.109 | 2-chloropyrimide-5-base | CH 3 |
| 85.110 | 5-chloropyrimide-2-base | CH 3 |
| 85.111 | The 2-furyl | CH 3 |
| 85.112 | The 3-furyl | CH 3 |
| 85.113 | The 2-thienyl | CH 3 |
| 85.114 | The 3-thienyl | CH 3 |
| 85.115 | 4-bromothiophene-2-base | CH 3 |
| 85.116 | 5-bromothiophene-2-base | CH 3 |
| 85.117 | 4-chlorothiophene-2-base | CH 3 |
| 85.118 | 5-chlorothiophene-2-base | CH 3 |
| 85.119 | Pyrazol-1-yl | CH 3 |
| 85.120 | 3-chlorine pyrazol-1-yl | CH 3 |
| 85.121 | 4-chlorine pyrazol-1-yl | CH 3 |
| 85.122 | The 1-methyl-pyrazol-4-yl | CH 3 |
| 85.123 | 1-methyl-3-trifluoromethyl pyrazol-5-base | CH 3 |
| 85.124 | The 2-thiazolyl | CH 3 |
| 85.125 | 4-methylthiazol-2-base | CH 3 |
| 85.126 | 5-methylthiazol-2-base | CH 3 |
Table 86:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1Be ethyl, R
4, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 87:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1Be methyl, R
4Be methyl, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 88:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1Be ethyl, R
4Be methyl, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 89:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1Be methyl, R
4And R
5Be methyl, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 90:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1Be ethyl, R
4And R
5Be methyl, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 91:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1Be methyl, R
4And R
6Be methyl, R
5And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 92:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1Be ethyl, R
4And R
6Be methyl, R
5And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 93:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1Be methyl, R
4, R
5And R
6Be methyl, R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 94:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1Be ethyl, R
4, R
5And R
6Be methyl, R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 95:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1Be methyl, R
4, R
5, R
6And R
7Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 96:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1Be ethyl, R
4, R
5, R
6And R
7Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 97:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1Be methyl, R
4, R
5, R
6Be methyl, R
7Be methoxymethyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 98:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1Be ethyl, R
4, R
5, R
6Be methyl, R
7Be methoxymethyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 99:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1Be methyl, R
4, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 100:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1Be ethyl, R
4, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 101:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1Be methyl, R
4Be methyl, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 102:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1Be ethyl, R
4Be methyl, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 103:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1Be methyl, R
4And R
5Be methyl, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 104:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1Be ethyl, R
4And R
5Be methyl, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 105:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1Be methyl, R
4And R
6Be methyl, R
5And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 106:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1Be ethyl, R
4And R
6Be methyl, R
5And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 107:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1Be methyl, R
4, R
5And R
6Be methyl, R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 108:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1Be ethyl, R
4, R
5And R
6Be methyl, R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 109:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1Be methyl, R
4, R
5, R
6And R
7Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 110:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1Be ethyl, R
4, R
5, R
6And R
7Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 111:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1Be methyl, R
4, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 112:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1Be ethyl, R
4, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 113:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1Be methyl, R
4Be methyl, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 114:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1Be ethyl, R
4Be methyl, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 115:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1Be methyl, R
4And R
5Be methyl, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 116:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1Be ethyl, R
4And R
5Be methyl, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 117:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1Be methyl, R
4And R
6Be methyl, R
5And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 118:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1Be ethyl, R
4And R
6Be methyl, R
5And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 119:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1Be methyl, R
4, R
5And R
6Be methyl, R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 120:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1Be ethyl, R
4, R
5And R
6Be methyl, R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 121:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1Be methyl, R
4, R
5, R
6And R
7Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 122:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1Be ethyl, R
4, R
5, R
6And R
7Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 123:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1Be methyl, R
4, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 124:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1Be ethyl, R
4, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 125:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1Be methyl, R
4Be methyl, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 126:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1Be ethyl, R
4Be methyl, R
5, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 127:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1Be methyl, R
4And R
5Be methyl, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 128:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1Be ethyl, R
4And R
5Be methyl, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 129:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1Be methyl, R
4And R
6Be methyl, R
5And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 130:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1Be ethyl, R
4And R
6Be methyl, R
5And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 131:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1Be methyl, R
4, R
5And R
6Be methyl, R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 132:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1Be ethyl, R
4, R
5And R
6Be methyl, R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 133:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1Be methyl, R
4, R
5, R
6And R
7Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 134:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1Be ethyl, R
4, R
5, R
6And R
7Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 135:
This table comprises 126 compounds of following type:
Wherein Y is C=O, R
1Be methyl, R
4And R
5Be methyl, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 136:
This table comprises 126 compounds of following type:
Wherein Y is C=O, R
1Be ethyl, R
4And R
5Be methyl, R
6And R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 137:
This table comprises 126 compounds of following type:
Wherein Y is C=O, R
1Be methyl, R
4, R
5And R
6Be methyl, R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 138:
This table comprises 126 compounds of following type:
Wherein Y is C=O, R
1Be ethyl, R
4, R
5And R
6Be methyl, R
7Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 139:
This table comprises 126 compounds of following type:
Wherein Y is C=O, R
1Be methyl, R
4, R
5, R
6And R
7Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 140:
This table comprises 126 compounds of following type:
Wherein Y is C=O, R
1Be ethyl, R
4, R
5, R
6And R
7Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 141
This table comprises 126 compounds of following type:
Wherein Y is O and R
1And R
3aBe methyl, R
4, R
5, R
6And R
7Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 142:
This table comprises 126 compounds of following type:
Wherein Y is S and R
1And R
3aBe methyl, R
4, R
5, R
6And R
7Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 143:
This table comprises 126 compounds of following type:
Wherein Y is S=O and R
1And R
3aBe methyl, R
4, R
5, R
6And R
7Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 144:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2And R
1And R
3aBe methyl, R
4, R
5, R
6And R
7Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 145:
This table comprises 126 compounds of following type:
Wherein Y is C=O, R
1And R
3aBe methyl, R
4, R
5, R
6And R
7Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 146:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1Be ethyl, R
3aBe methyl, R
4, R
5, R
6And R
7Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 147:
This table comprises 126 compounds of following type:
Wherein Y is S and R
1Be ethyl and R
3aBe methyl, R
4, R
5, R
6And R
7Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 148:
This table comprises 126 compounds of following type:
Wherein Y is S=O and R
1Be ethyl and R
3aBe methyl, R
4, R
5, R
6And R
7Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 149:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2And R
1Be ethyl and R
3aBe methyl, R
4, R
5, R
6And R
7Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 150:
This table comprises 126 compounds of following type:
Wherein Y is C=O and R
1Be ethyl and R
3aBe methyl, R
4, R
5, R
6And R
7Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 151:
This table comprises 126 compounds of following type:
Wherein Y is O and R
1And R
3aBe ethyl, R
4, R
5, R
6And R
7Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 152:
This table comprises 126 compounds of following type:
Wherein Y is S and R
1And R
3aBe ethyl, R
4, R
5, R
6And R
7Be methyl, R
3bBe that methyl and G are hydrogen and R
2Such as table 85 definition.
Table 153:
This table comprises 126 compounds of following type:
Wherein Y is S=O and R
1And R
3aBe ethyl, R
4, R
5, R
6And R
7Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 154:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2And R
1And R
3aBe ethyl, R
4, R
5, R
6And R
7Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 155:
This table comprises 126 compounds of following type:
Wherein Y is C=O and R
1And R
3aBe ethyl, R
4, R
5, R
6And R
7Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 156:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be methyl, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 157
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be ethyl, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 158
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be chlorine, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 159:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be methyl, R
5Be hydrogen and R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 160:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be ethyl, R
5Be hydrogen and R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 161:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be chlorine, R
5Be hydrogen and R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 162:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be methyl, R
5And R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 163:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be ethyl, R
5And R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 164:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be chlorine, R
5And R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 165:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be methyl, R
5Be hydrogen and R
6Be methoxymethyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 166:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be ethyl, R
5Be hydrogen and R
6Be methoxymethyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 167:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be chlorine, R
5Be hydrogen and R
6Be methoxymethyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 168:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be methyl, R
5Be hydrogen and R
6Be ethoxyl methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 169:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be ethyl, R
5Be hydrogen and R
6Be ethoxyl methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 170:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be chlorine, R
5Be hydrogen and R
6Be ethoxyl methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 171:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be methyl, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 172:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be ethyl, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 173:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be chlorine, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 174:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be methyl, R
5Be methyl, R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 175:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be ethyl, R
5Be methyl, R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 176:
This table comprises 378 compounds of following type:
Wherein Y is O, R
1Be chlorine, R
5Be methyl, R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 177:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1Be methyl, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 178:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1Be ethyl, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 179:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1Be methyl, R
5Be hydrogen and R
6Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 180:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1Be ethyl, R
5Be hydrogen and R
6Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 181:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1Be methyl, R
5And R
6Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 182:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1Be ethyl, R
5And R
6Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 183:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1And R
3aBe methyl, R
5And R
6Be hydrogen, R
3bBe that methyl and G are hydrogen and R
2Such as table 85 definition.
Table 184:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1Be ethyl and R
3aBe methyl, R
5And R
6Be hydrogen, R
3bBe that methyl and G are hydrogen and R
2Such as table 85 definition.
Table 185:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1And R
3aBe ethyl, R
5And R
6Be hydrogen, R
3bBe that methyl and G are hydrogen and R
2Such as table 85 definition.
Table 186:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1And R
3aBe methyl, R
5Be hydrogen and R
6Be methyl, R
3bBe that methyl and G are hydrogen and R
2Such as table 85 definition.
Table 187:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1Be ethyl and R
3aBe methyl, R
5Be hydrogen and R
6Be methyl, R
3bBe that methyl and G are hydrogen and R
2Such as table 85 definition.
Table 188:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1And R
3aBe ethyl, R
5Be hydrogen and R
6Be methyl, R
3bBe that methyl and G are hydrogen and R
2Such as table 85 definition.
Table 189:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1And R
3aBe methyl, R
5Be R
6Be methyl, R
3bBe that methyl and G are hydrogen and R
2Such as table 85 definition.
Table 190:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1Be ethyl and R
3aBe methyl, R
5Be R
6Be methyl, R
3bBe that methyl and G are hydrogen and R
2Such as table 85 definition.
Table 191:
This table comprises 126 compounds of following type:
Wherein Y is O, R
1And R
3aBe ethyl, R
5Be R
6Be methyl, R
3bBe that methyl and G are hydrogen and R
2Such as table 85 definition.
Table 192:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be methyl, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 193:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be ethyl, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 194:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be chlorine, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 195:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be methyl, R
5Be hydrogen and R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 196:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be ethyl, R
5Be hydrogen and R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 197:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be chlorine, R
5Be hydrogen and R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 198:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be methyl, R
5And R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 199:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be ethyl, R
5And R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 200:
This table comprises 378 compounds of following type:
Wherein Y is S, R
1Be chlorine, R
5And R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 201:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1Be methyl, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 202:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1Be ethyl, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 203:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1Be methyl, R
5Be hydrogen and R
6Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 204:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1Be ethyl, R
5Be hydrogen and R
6Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 205:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1Be methyl, R
5And R
6Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 206:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1Be ethyl, R
5And R
6Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 207:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1And R
3aBe methyl, R
5And R
6Be hydrogen, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 208:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1Be ethyl and R
3aBe methyl, R
5And R
6Be hydrogen, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 209:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1And R
3aBe ethyl, R
5And R
6Be hydrogen, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 210:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1And R
3aBe methyl, R
5Be hydrogen and R
6Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 211:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1Be ethyl and R
3aBe methyl, R
5Be hydrogen and R
6Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 212:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1And R
3aBe ethyl, R
5Be hydrogen and R
6Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 213:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1And R
3aBe methyl, R
5Be R
6Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 214:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1Be ethyl R
3aBe methyl, R
5Be R
6Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 215:
This table comprises 126 compounds of following type:
Wherein Y is S, R
1And R
3aBe ethyl, R
5Be R
6Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 216:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be methyl, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 217:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be ethyl, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 218:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be chlorine, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 219:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be methyl, R
5Be hydrogen and R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 220:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be ethyl, R
5Be hydrogen and R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 221:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be chlorine, R
5Be hydrogen and R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 222:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be methyl, R
5And R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 223:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be ethyl, R
5And R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 224:
This table comprises 378 compounds of following type:
Wherein Y is S=O, R
1Be chlorine, R
5And R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 225:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1Be methyl, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 226:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1Be ethyl, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 227:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1Be methyl, R
5Be hydrogen and R
6Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 228:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1Be ethyl, R
5Be hydrogen and R
6Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 229:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1Be methyl, R
5And R
6Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 230:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1Be ethyl, R
5And R
6Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 231:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1And R
3aBe methyl, R
5And R
6Be hydrogen, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 232:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1Be ethyl and R
3aBe methyl, R
5And R
6Be hydrogen, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 233:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1And R
3aBe ethyl, R
5And R
6Be hydrogen, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 234:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1And R
3aBe methyl, R
5Be hydrogen and R
6Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 235:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1Be ethyl and R
3aBe methyl, R
5Be hydrogen and R
6Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 236:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1And R
3aBe ethyl, R
5Be hydrogen and R
6Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 237:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1And R
3aBe methyl, R
5Be R
6Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 238:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1Be ethyl and R
3aBe methyl, R
5Be R
6Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 239:
This table comprises 126 compounds of following type:
Wherein Y is S=O, R
1And R
3aBe ethyl, R
5Be R
6Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 240:
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be methyl, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 241:
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be ethyl, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 242:
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be chlorine, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 243
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be methyl, R
5Be hydrogen and R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 244:
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be ethyl, R
5Be hydrogen and R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 245:
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be chlorine, R
5Be hydrogen and R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 246:
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be methyl, R
5And R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 247:
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be ethyl, R
5And R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 248:
This table comprises 378 compounds of following type:
Wherein Y be S (=O)
2, R
1Be chlorine, R
5And R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 249:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1Be methyl, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 250:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1Be ethyl, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 251:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1Be methyl, R
5Be hydrogen and R
6Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 252:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1Be ethyl, R
5Be hydrogen and R
6Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 253:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1Be methyl, R
5And R
6Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 254:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1Be ethyl, R
5And R
6Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 255:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1And R
3aBe methyl, R
5And R
6Be hydrogen, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 256:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1Be ethyl and R
3aBe methyl, R
5And R
6Be hydrogen, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 257:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1And R
3aBe ethyl, R
5And R
6Be hydrogen, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 258:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1And R
3aBe methyl, R
5Be hydrogen and R
6Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 259:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1Be ethyl and R
3aBe methyl, R
5Be hydrogen and R
6Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 260:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1And R
3aBe ethyl, R
5Be hydrogen and R
6Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 261:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1And R
3aBe methyl, R
5Be R
6Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 262:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1Be ethyl and R
3aBe methyl, R
5Be R
6Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 263:
This table comprises 126 compounds of following type:
Wherein Y be S (=O)
2, R
1And R
3aBe ethyl, R
5Be R
6Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 264:
This table comprises 378 compounds of following type:
Wherein Y is C=O, R
1Be methyl, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 265:
This table comprises 378 compounds of following type:
Wherein Y is C=O, R
1Be ethyl, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 266:
This table comprises 378 compounds of following type:
Wherein Y is C=O, R
1Be chlorine, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 267:
This table comprises 378 compounds of following type:
Wherein Y is C=O, R
1Be methyl, R
5Be hydrogen and R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 268:
This table comprises 378 compounds of following type:
Wherein Y is C=O, R
1Be ethyl, R
5Be hydrogen and R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 269:
This table comprises 378 compounds of following type:
Wherein Y is C=O, R
1Be chlorine, R
5Be hydrogen and R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 270:
This table comprises 378 compounds of following type:
Wherein Y is C=O, R
1Be methyl, R
5And R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 271:
This table comprises 378 compounds of following type:
Wherein Y is C=O, R
1Be ethyl, R
5And R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 272:
This table comprises 378 compounds of following type:
Wherein Y is C=O, R
1Be chlorine, R
5And R
6Be methyl, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 273:
This table comprises 378 compounds of following type:
Wherein Y is C=O, R
1Be methyl, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 274:
This table comprises 378 compounds of following type:
Wherein Y is C=O, R
1Be ethyl, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 275:
This table comprises 378 compounds of following type:
Wherein Y is C=O, R
1Be chlorine, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 1 definition.
Table 276:
This table comprises 126 compounds of following type:
Wherein Y is C=O, R
1Be methyl, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 277:
This table comprises 126 compounds of following type:
Wherein Y is C=O, R
1Be ethyl, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 278:
This table comprises 126 compounds of following type:
Wherein Y is C=O, R
1Be methyl, R
5Be hydrogen and R
6Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 279:
This table comprises 126 compounds of following type:
Wherein Y is C=O, R
1Be ethyl, R
5Be hydrogen and R
6Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 280:
This table comprises 126 compounds of following type:
Wherein Y is C=O, R
1Be methyl, R
5And R
6Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 281:
This table comprises 126 compounds of following type:
Wherein Y is C=O, R
1Be ethyl, R
5And R
6Be methyl, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 282:
This table comprises 126 compounds of following type:
Wherein Y is C=O, R
1Be methyl, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 283:
This table comprises 126 compounds of following type:
Wherein Y is C=O, R
1Be ethyl, R
5And R
6Be hydrogen, G is hydrogen and R
2And R
3Such as table 85 definition.
Table 284:
This table comprises 126 compounds of following type:
Wherein Y is C=O, R
1And R
3aBe methyl, R
5And R
6Be hydrogen, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 285:
This table comprises 126 compounds of following type:
Wherein Y is C=O, R
1Be ethyl and R
3aBe methyl, R
5And R
6Be hydrogen, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 286:
This table comprises 126 compounds of following type:
Wherein Y is C=O, R
1And R
3aBe ethyl, R
5And R
6Be hydrogen, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 287:
This table comprises 126 compounds of following type:
Wherein Y is C=O, R
1And R
3aBe methyl, R
5Be hydrogen and R
6Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 288:
This table comprises 126 compounds of following type:
Wherein Y is C=O, R
1Be ethyl and R
3aBe methyl, R
5Be hydrogen and R
6Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 289:
This table comprises 126 compounds of following type:
Wherein Y is C=O, R
1And R
3aBe ethyl, R
5Be hydrogen and R
6Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 290:
This table comprises 126 compounds of following type:
Wherein Y is C=O, R
1And R
3aBe methyl, R
5Be R
6Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 291:
This table comprises 126 compounds of following type:
Wherein Y is C=O, R
1Be ethyl and R
3aBe methyl, R
5Be R
6Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 292:
This table comprises 126 compounds of following type:
Wherein Y is C=O, R
1And R
3aBe ethyl, R
5Be R
6Be methyl, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 293:
This table comprises 126 compounds of following type:
Wherein Y is C=O, R
1And R
3aBe methyl, R
5And R
6Be hydrogen, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Table 294:
This table comprises 126 compounds of following type:
Wherein Y is C=O, R
1Be ethyl and R
3aBe methyl, R
5And R
6Be hydrogen, R
3bBe methyl, and G is hydrogen and R
2Such as table 85 definition.
Embodiment 30: preparation 2,2-neopentanoic acid 4-(4 '-chloro-4-ethyl biphenyl-3-yl)-2,2,6,6-tetramethyl--5-oxo-5,6-dihydro-2H-pyrans-3-base ester
To 4-(4 '-chloro-4-ethyl biphenyl-3-yl)-2,2,6; 6-tetramethyl-pyrans-3, and the 5-diketone (0.077g, the solution that 0.20mmol) is dissolved in the anhydrous methylene chloride (3ml) adds triethylamine (0.031ml; 0.22mmol), add then pivalyl chloride (0.027ml, 0.22mmol).At room temperature stirred this mixture 3 hours, and used methylene dichloride (15ml) dilution then, with zero(ppm) water (2 * 10ml) washings.Merge organic fraction, dry on sal epsom, concentrate then; Provide thick oily matter, it provides 2 through flash chromatography (100% hexane-9: 1 hexane/ethyl acetate of ratio) purifying; 2-neopentanoic acid 4-(4 '-chloro-4-ethyl biphenyl-3-yl)-2,2,6; 6-tetramethyl--5-oxo-5,6-dihydro-2H-pyrans-3-base ester (0.090g) is colourless jelly.
Embodiment 31: preparation carbonic acid 4-(4 '-chloro-4-ethyl biphenyl-3-yl)-2,2,6,6-tetramethyl--5-oxo-5,6-dihydro-2H-pyrans-3-base METH ester
To 4-(4 '-chloro-4-ethyl biphenyl-3-yl)-2,2,6; 6-tetramethyl-pyrans-3, (0.141g adds triethylamine (0.152ml in anhydrous chloroform 0.366mmol) (3ml) solution to the 5-diketone; 1.09mmol) and methyl-chloroformate (0.084ml 1.09mmol), at room temperature stirred the mixture 2 hours.Remove and to desolvate,, carbonic acid 4-(4 '-chloro-4-ethyl biphenyl-3-yl)-2 is provided directly through column chromatography (hexane/ethyl acetate of 5: 1 ratios) purifying resistates; 2,6,6-tetramethyl--5-oxo-5; 6-dihydro-2H-pyrans-3-base METH ester (0.150g) is a white solid.
Embodiment 32: preparation carbonic acid 4-[5-(4-chlorine pyrazol-1-yl)-2-ethylphenyl]-2,2,6,6-tetramethyl--5-oxo-5,6-dihydro-2H-pyrans-3-base METH ester
To 4-(5-bromo-2-ethylphenyl)-2,2,6; 6-tetramethyl-pyrans-3, and the 5-diketone (0.15g, 0.42mmol), 4-chlorine pyrazoles (0.065g; 0.63mmol), L-proline(Pro) (0.049g; 0.42mmol), (0.080g, 0.42mmol) (0.36g adds the anhydrous dimethyl sulfoxide (1.5ml) through the degassing to cupric iodide (I) in mixture 1.68mmol) with the anhydrous powder potassiumphosphate.Under microwave radiation, heating this mixture 30 minutes under 160 ℃, be cooled to room temperature subsequently then, with methylene dichloride (150ml) dilution, with (2 * 50ml) washings of 1M aqueous hydrochloric acid.Merge organic fraction, drying, vacuum concentration then on anhydrous magnesium sulfate.Then ether is added to thick oily matter so that the product deposition also is dissolved in methylene dichloride (20ml) once more with its filtration.(0.16ml, 1.16mmol), (0.090ml 1.16mmol), at room temperature stirred 3 hours to add methyl-chloroformate subsequently in this solution, to add triethylamine then.Removal of solvent under reduced pressure; Through column chromatography (hexane/ethyl acetate of 3: 1 ratios) direct purification resistates on silica gel, carbonic acid 4-[5-(4-chlorine pyrazol-1-yl)-2-ethylphenyl]-2,2 is provided; 6; 6-tetramethyl--5-oxo-5,6-dihydro-2H-pyrans-3-base METH ester (0.075g) is a colorless oil.
Other compound among the table D can use proper raw material to make through similar approach.
Table D:
Biological Examples
Embodiment A
With being seeded in the standard soil in the basin of the seed of multiple test species.Cultivate after 1 day (before the seedling) or cultivate after 10 days (behind the seedling); In the greenhouse under controlled condition; With the aqueous spray solution plant of spraying, said spray solution derives from the preparation of technical grade activeconstituents in 0.6ml acetone and the 45ml formulation soln that contains 10.6%Emulsogen EL (accession number 61791-12-6), 42.2%N-SL 1332,42.2% dipropylene glycol monomethyl ether (accession number 34590-94-8) and 0.2%X-77 (accession number 11097-66-8).Test plants is grown under top condition in the greenhouse then, and after 15 days (behind the seedling) and 20 days (before the seedling), (the 100=plant damages fully to estimate the confession test plants; The 0=plant does not damage).
Test plants:
Big fringe amur foxtail (Alopecurus myosuroides) (ALOMY), ild avena sativa (Avenafatua) (AVEFA), lolium (Lolium perenne) (LOLPE), French dog hair grass (Setaria faberi) (SETFA), lady's-grass (Digitaria sanguinalis) (DIGSA), the west comes barnyard grass (Echinochioa crus-Calli) (ECHCG)
Active before the seedling
| Compound number | Ratio g/ha | ALOMY | AVEFA | LOLPE | SETFA | DIGSA | ECHCG |
| A-1 | 500 | 40 | 10 | 10 | 70 | 70 | 50 |
| A-2 | 500 | 50 | 50 | 60 | 70 | 10 | 100 |
| A-3 | 500 | 30 | 20 | 20 | 50 | 70 | 70 |
| A-5 | 500 | 60 | 50 | 50 | 100 | 100 | 100 |
| A-9 | 500 | 20 | 30 | 20 | 60 | 50 | 50 |
| A-10 | 250 | 40 | 50 | 60 | 100 | 100 | 100 |
| A-34 | 250 | 60 | 50 | 100 | 100 | 100 | 100 |
| A-35 | 250 | 70 | 70 | 80 | 100 | 80 | 100 |
| A-36 | 250 | 60 | 60 | 80 | 90 | 100 | 100 |
| A-38 | 250 | 50 | 10 | 60 | 90 | 30 | 70 |
| A-40 | 250 | 30 | 10 | 20 | 70 | 70 | 70 |
| A-42 | 250 | 100 | 30 | 50 | 100 | 100 | 80 |
| A-43 | 250 | 80 | 90 | 80 | 100 | 100 | 100 |
| A-44 | 250 | 60 | 20 | 80 | 50 | 100 | 70 |
| A-45 | 250 | 50 | 50 | 80 | 90 | 100 | 70 |
| A-47 | 250 | 30 | 20 | 30 | 60 | 70 | 70 |
| A-48 | 250 | 30 | 10 | 0 | 60 | 60 | 100 |
| A-49 | 250 | 0 | 20 | 20 | 50 | 50 | 100 |
| A-51 | 250 | 0 | 0 | 40 | 10 | 50 | 50 |
| A-52 | 250 | 0 | 0 | 10 | 80 | 100 | 70 |
| A-53 | 250 | 10 | 0 | 0 | 10 | 60 | 10 |
| B-1 | 500 | 40 | 60 | 60 | 100 | 100 | 100 |
| C-1 | 500 | 20 | 20 | 30 | 30 | 30 | 50 |
| C-2 | 250 | 10 | 10 | 10 | 70 | 100 | 100 |
| C-3 | 250 | 60 | 80 | 10 | 60 | 90 | 70 |
| D-2 | 500 | 30 | 60 | 80 | 100 | 100 | 80 |
| D-5 | 500 | 0 | 20 | 0 | 20 | 60 | 50 |
Active behind the seedling
| Compound number | Ratio g/ha | ALOMY | AVEFA | LOLPE | SETFA | DIGSA | ECHCG |
| A-1 | 125 | 10 | 0 | 80 | 50 | 0 | 70 |
| A-2 | 125 | 20 | 20 | 0 | 80 | 50 | 80 |
| A-3 | 125 | 0 | 0 | 0 | 60 | 40 | 70 |
| A-5 | 125 | 70 | 70 | 70 | 80 | 100 | 100 |
| A-9 | 125 | 50 | 0 | 30 | 80 | 80 | 80 |
| A-10 | 125 | 30 | 20 | 0 | 50 | 100 | 100 |
| A-34 | 125 | 70 | 20 | 80 | 90 | 90 | 100 |
| A-35 | 125 | 80 | 50 | 70 | 80 | 80 | 100 |
| A-36 | 125 | 40 | 0 | 70 | 60 | 70 | 70 |
| A-38 | 125 | 50 | 60 | 0 | 80 | 70 | 90 |
| A-40 | 125 | 70 | 60 | 60 | 70 | 70 | 100 |
| A-42 | 125 | 80 | 90 | 70 | 100 | 100 | 100 |
| A-43 | 125 | 80 | 90 | 80 | 100 | 100 | 100 |
| A-44 | 125 | 40 | 60 | 60 | 30 | 70 | 100 |
| A-45 | 125 | 20 | 70 | 70 | 80 | 100 | 100 |
| A-47 | 125 | 90 | 90 | 70 | 50 | 80 | 100 |
| A-48 | 125 | 70 | 40 | 0 | 40 | 40 | 40 |
| A-49 | 125 | 50 | 70 | 80 | 50 | 70 | 80 |
| A-51 | 125 | 10 | 20 | 0 | 40 | 60 | 80 |
| A-52 | 125 | 90 | 70 | 30 | 60 | 70 | 90 |
| A-53 | 125 | 30 | 10 | 10 | 0 | 50 | 90 |
| B-1 | 125 | 30 | 30 | 80 | 90 | 100 | 100 |
| C-1 | 125 | 50 | 70 | 30 | 80 | 100 | 100 |
| C-2 | 125 | 70 | 70 | 60 | 90 | 90 | 100 |
| C-3 | 125 | 70 | 80 | 50 | 90 | 100 | 100 |
| D-2 | 125 | 20 | 10 | 20 | 90 | 90 | 90 |
| D-5 | 125 | 10 | 40 | 40 | 70 | 20 | 60 |
Embodiment B
With being seeded in the standard soil in the basin of the seed of multiple test species.In glass room, under controlled condition (24/16 ℃ (day/night); Illumination in 14 hours; 65% humidity) cultivation is after 1 day (before the seedling) or cultivate after 8 days (behind the seedling); Use to such an extent that contain the aqueous spray solutions spraying plant of preparation of acetone (50: 50) solution of the former medicine of activeconstituents of 0.5% polysorbas20 (polyoxyethylene sorbitan mono-laurate, CAS RN 9005-64-5).Test plants is grown in the greenhouse, in the greenhouse under controlled condition (24/16 ℃, daytime/night; Illumination in 14 hours; 65% humidity), water every day twice.After 13 days (before the seedling and behind the seedling), (the 100=plant damages fully in evaluation test; The 0=plant does not damage).
Test plants:
Big fringe amur foxtail (Alopecurus myosuroides) (ALOMY), ild avena sativa (Avenafatua) (AVEFA), French dog hair grass (Setaria faberi) (SETFA), the west come barnyard grass (Echinochloa crus-galli) (ECHCG), black nightshade (Solanum nigrum) (SOLNI) and Amaranthus retroflexus (Amaranthus retroflexus) (AMARE)
Active before the seedling
| Compound number | Ratio g/ha | SOLNI | AMARE | SETFA | ALOMY | ECHCG | AVEFA |
| A-4 | 250 | - | 20 | 100 | 70 | 100 | 70 |
| A-15 | 1000 | 100 | 100 | 50 | 50 | 100 | 50 |
| A-16 | 1000 | 0 | 0 | 100 | 30 | 100 | 20 |
| A-20 | 1000 | 40 | 0 | 100 | 90 | 100 | 60 |
| A-21 | 1000 | 50 | 60 | 100 | 100 | 90 | 50 |
| A-22 | 1000 | 60 | 30 | 40 | 40 | 90 | 20 |
| A-24 | 1000 | 20 | 20 | 90 | 80 | 100 | 60 |
| A-25 | 1000 | 0 | 0 | 20 | 70 | 80 | 30 |
| A-26 | 1000 | 0 | 0 | 100 | 80 | 100 | 80 |
| A-27 | 1000 | 20 | 10 | 90 | 80 | 100 | 60 |
| A-29 | 1000 | 0 | 0 | 100 | 90 | 100 | 80 |
| A-30 | 1000 | 0 | 0 | 100 | 80 | 100 | 70 |
| A-31 | 1000 | 0 | 0 | 100 | 50 | 100 | 0 |
| A-37 | 1000 | 0 | 0 | 20 | 40 | 30 | 20 |
| A-54 | 1000 | 0 | 20 | 90 | 70 | 100 | 80 |
| A-56 | 1000 | 20 | 0 | 0 | 10 | 30 | 40 |
| A-58 | 1000 | 20 | 20 | 100 | 80 | 100 | 60 |
| A-59 | 250 | - | 0 | 40 | 30 | 90 | 40 |
| A-60 | 250 | - | 0 | 20 | 0 | 20 | 0 |
| A-62 | 250 | - | 0 | 60 | 20 | 0 | 20 |
| A-63 | 250 | - | 0 | 30 | 0 | 0 | 0 |
| A-64 | 250 | - | 0 | 40 | 0 | 40 | 20 |
| A-65 | 250 | - | 0 | 0 | 0 | 90 | 0 |
| Compound number | Ratio g/ha | SOLNI | AMARE | SETFA | ALOMY | ECHCG | AVEFA |
| A-66 | 250 | - | 0 | 50 | 0 | 60 | 40 |
| A-67 | 250 | - | 0 | 90 | 40 | 60 | 0 |
| A-69 | 250 | - | 0 | 80 | 0 | 60 | 0 |
| A-71 | 250 | - | 0 | 100 | 40 | 80 | 20 |
| A-72 | 250 | - | 0 | 0 | 0 | 40 | 0 |
| A-73 | 250 | - | 0 | 20 | 0 | 10 | 0 |
| A-74 | 250 | - | 10 | 50 | 20 | 80 | 0 |
| A-75 | 250 | - | 0 | 90 | 30 | 90 | 30 |
| A-76 | 250 | - | 0 | 100 | 60 | 70 | 50 |
| A-77 | 250 | - | 0 | 20 | 10 | 0 | 0 |
| A-79 | 250 | - | 0 | 100 | 40 | 80 | 40 |
| A-80 | 250 | - | 0 | 70 | 30 | 40 | 0 |
| A-81 | 250 | - | 0 | 100 | 80 | 100 | 90 |
| A-82 | 250 | - | 20 | 90 | 80 | 100 | 90 |
| A-83 | 250 | - | 0 | 100 | 50 | 90 | 40 |
| A-87 | 250 | - | 0 | 0 | 0 | 0 | 0 |
| A-88 | 250 | - | 0 | 0 | 0 | 0 | 10 |
| A-89 | 250 | - | 0 | 50 | 0 | 0 | 0 |
| A-90 | 250 | - | 0 | 0 | 0 | 0 | 0 |
| A-92 | 250 | - | 0 | 60 | 10 | 50 | 0 |
| A-96 | 250 | - | 0 | 0 | 0 | 0 | 0 |
| A-97 | 250 | - | 0 | 60 | 0 | 50 | 0 |
| A-98 | 250 | - | 50 | 90 | 0 | 90 | 0 |
| A-99 | 250 | - | 20 | 100 | 80 | 100 | 50 |
| A-100 | 250 | - | 60 | 100 | 20 | 80 | 90 |
| A-101 | 250 | - | 0 | 100 | 70 | 100 | 100 |
| A-102 | 250 | - | 0 | 90 | 30 | 90 | 0 |
| A-103 | 250 | - | 0 | 0 | 0 | 0 | 0 |
| A-104 | 250 | - | 0 | 0 | 0 | 0 | 0 |
| A-105 | 250 | - | 0 | 0 | 0 | 0 | 0 |
| A-122 | 250 | - | 0 | 100 | 40 | 90 | 100 |
| A-123 | 250 | - | 0 | 100 | 50 | 70 | 80 |
| A-124 | 250 | - | 0 | 100 | 50 | 70 | 60 |
| A-125 | 250 | - | 0 | 100 | 70 | 90 | 80 |
| A-126 | 250 | - | 0 | 100 | 30 | 80 | 90 |
| A-127 | 250 | - | 0 | 90 | 30 | 50 | 70 |
| A-128 | 250 | - | 0 | 90 | 40 | 70 | 80 |
| Compound number | Ratio g/ha | SOLNI | AMARE | SETFA | ALOMY | ECHCG | AVEFA |
| A-129 | 250 | - | 0 | 90 | 20 | 40 | 30 |
| A-130 | 250 | - | 0 | 90 | 20 | 40 | 20 |
| A-132 | 250 | - | 0 | 0 | 0 | 0 | 0 |
| A-133 | 250 | - | 0 | 80 | 10 | 0 | 70 |
| A-135 | 250 | - | 0 | 100 | 80 | 100 | 100 |
| A-136 | 250 | - | 0 | 30 | 20 | 90 | 80 |
| A-137 | 250 | - | 0 | 100 | 70 | 100 | 90 |
| A-138 | 250 | - | 20 | 100 | 90 | 100 | 90 |
| A-139 | 250 | - | 0 | 70 | 0 | 30 | 0 |
| A-141 | 250 | - | 0 | 80 | 20 | 100 | 30 |
| A-142 | 250 | - | 0 | 100 | 60 | 70 | 70 |
| A-143 | 250 | - | 0 | 70 | 20 | 0 | 0 |
| A-144 | 250 | - | 30 | 100 | 100 | 90 | 80 |
| A-147 | 250 | - | 0 | 70 | 100 | 100 | 60 |
| A-149 | 250 | - | 0 | 90 | 60 | 100 | 30 |
| A-150 | 250 | - | 0 | 100 | 90 | 100 | 40 |
| A-151 | 250 | - | 0 | 100 | 100 | 100 | 100 |
| A-152 | 250 | - | 0 | 100 | 70 | 100 | 90 |
| A-153 | 250 | - | 0 | 100 | 60 | 100 | 50 |
| A-154 | 250 | - | 0 | 90 | 50 | 100 | 20 |
| A-155 | 250 | - | 0 | 100 | 50 | 100 | 0 |
| B-2 | 1000 | 30 | 90 | 0 | 0 | 70 | 20 |
| B-4 | 1000 | 0 | 0 | 0 | 0 | 30 | 0 |
| B-6 | 1000 | 90 | 100 | 0 | 0 | 0 | 0 |
| B-7 | 1000 | 20 | 0 | 60 | 0 | 50 | 0 |
| B-9 | 250 | 0 | 0 | 0 | 0 | 0 | 0 |
| B-10 | 250 | 20 | 0 | 50 | 0 | 30 | 0 |
| B-12 | 250 | 0 | 0 | 50 | 0 | 30 | 0 |
| B-13 | 250 | 0 | 0 | 20 | 0 | 30 | 20 |
| B-18 | 250 | 0 | 0 | 20 | 40 | 0 | 0 |
| B-23 | 250 | 0 | 0 | 0 | 0 | 10 | 0 |
| B-25 | 250 | 0 | 0 | 0 | 0 | 0 | 0 |
| B-27 | 250 | 0 | 0 | 0 | 0 | 0 | 0 |
| B-28 | 250 | 0 | 0 | 0 | 0 | 0 | 0 |
| B-29 | 250 | 0 | 0 | 30 | 0 | 20 | 0 |
| B-30 | 250 | 0 | 0 | 0 | 0 | 0 | 0 |
| B-31 | 250 | 0 | 0 | 50 | 0 | 50 | 20 |
| Compound number | Ratio g/ha | SOLNI | AMARE | SETFA | ALOMY | ECHCG | AVEFA |
| C-4 | 250 | - | 0 | 0 | 0 | 0 | 0 |
| C-5 | 250 | - | 0 | 0 | 0 | 0 | 0 |
| C-6 | 250 | - | 0 | 0 | 0 | 0 | 0 |
| C-7 | 250 | - | 0 | 0 | 0 | 0 | 0 |
| C-8 | 250 | - | 0 | 0 | 0 | 0 | 0 |
| C-9 | 250 | - | 0 | 0 | 0 | 0 | 0 |
| C-10 | 250 | - | 0 | 0 | 20 | 40 | 20 |
| C-11 | 250 | - | 0 | 0 | 0 | 0 | 80 |
| C-12 | 250 | - | 0 | 90 | 0 | 20 | 90 |
| C-13 | 250 | - | 0 | 80 | 20 | 30 | 90 |
| D-7 | 1000 | 0 | 0 | 100 | 60 | 90 | 30 |
| D-8 | 1000 | 0 | 0 | 90 | 40 | 90 | 0 |
| D-9 | 1000 | 0 | 0 | 90 | 20 | 70 | 0 |
| D-10 | 1000 | 0 | 0 | 100 | 50 | 100 | 0 |
| D-11 | 1000 | 0 | 0 | 90 | 20 | 20 | 0 |
| D-12 | 1000 | 0 | 0 | 100 | 90 | 100 | 60 |
| D-13 | 1000 | 0 | 0 | 90 | 50 | 90 | 20 |
| D-14 | 1000 | 0 | 0 | 90 | 50 | 60 | 20 |
| D-15 | 1000 | 0 | 0 | 100 | 80 | 100 | 60 |
| D-16 | 1000 | 0 | 0 | 100 | 50 | 90 | 0 |
| D-17 | 1000 | 0 | 0 | 90 | 20 | 80 | 0 |
| D-18 | 1000 | 0 | 0 | 100 | 70 | 100 | 50 |
| D-19 | 1000 | 0 | 0 | 100 | 70 | 100 | 20 |
| D-20 | 1000 | 0 | 0 | 90 | 30 | 60 | 0 |
| D-21 | 1000 | 0 | 0 | 100 | 90 | 100 | 50 |
| D-22 | 250 | - | 0 | 100 | 60 | 100 | 50 |
| D-23 | 250 | - | 0 | 90 | 0 | 100 | 0 |
| D-24 | 250 | - | 20 | 90 | 0 | 100 | 0 |
| D-25 | 250 | - | 0 | 90 | 20 | 90 | 0 |
| D-28 | 250 | - | 0 | 80 | 30 | 20 | 40 |
| D-32 | 250 | - | 0 | 80 | 20 | 60 | 80 |
Active behind the seedling
| Compound number | Ratio g/ha | SOLNI | AMARE | SETFA | ALOMY | ECHCG | AVEFA |
| A-4 | 250 | - | 20 | 100 | 90 | 100 | 80 |
| A-15 | 1000 | 10 | 90 | 10 | 10 | 50 | 20 |
| A-16 | 1000 | 10 | 40 | 100 | 30 | 100 | 30 |
| A-20 | 1000 | 80 | 20 | 100 | 90 | 100 | 90 |
| A-21 | 1000 | 20 | 20 | 60 | 40 | 90 | 60 |
| A-22 | 1000 | 90 | 0 | 20 | 30 | 80 | 0 |
| A-24 | 1000 | 70 | 90 | 100 | 100 | 100 | 80 |
| A-25 | 1000 | 70 | 100 | 70 | 70 | 90 | 0 |
| A-26 | 1000 | 50 | 100 | 100 | 100 | 100 | 100 |
| A-27 | 1000 | 50 | 100 | 100 | 80 | 100 | 80 |
| A-29 | 1000 | 60 | 40 | 100 | 100 | 100 | 100 |
| A-30 | 1000 | 70 | 70 | 100 | 90 | 100 | 100 |
| A-31 | 1000 | 60 | 0 | 100 | 100 | 100 | 90 |
| A-37 | 1000 | 70 | 0 | 80 | 70 | 90 | 30 |
| A-54 | 1000 | 0 | 0 | 80 | 80 | 90 | 50 |
| A-56 | 1000 | 20 | 20 | 80 | 80 | 80 | 50 |
| A-58 | 1000 | 30 | 70 | 90 | 90 | 100 | 90 |
| A-59 | 250 | - | 0 | 90 | 30 | 100 | 50 |
| A-60 | 250 | - | 60 | 80 | 20 | 80 | 0 |
| A-62 | 250 | - | 0 | 100 | 70 | 100 | 70 |
| A-63 | 250 | - | 0 | 100 | 90 | 100 | 60 |
| A-64 | 250 | - | 20 | 90 | 20 | 100 | 0 |
| A-65 | 250 | - | 10 | 70 | 20 | 90 | 0 |
| A-66 | 250 | - | 10 | 100 | 20 | 100 | 30 |
| A-67 | 250 | - | 100 | 30 | 80 | 100 | 80 |
| A-69 | 250 | - | 90 | 100 | 70 | 100 | 90 |
| A-71 | 250 | - | 100 | 100 | 30 | 100 | 30 |
| A-72 | 250 | - | 60 | 80 | 20 | 80 | 0 |
| A-73 | 250 | - | 0 | 90 | 20 | 90 | 0 |
| A-74 | 250 | - | 70 | 90 | 0 | 90 | 0 |
| A-75 | 250 | - | 0 | 100 | 90 | 100 | 90 |
| A-76 | 250 | - | 0 | 100 | 90 | 100 | 70 |
| A-77 | 250 | - | 0 | 90 | 70 | 100 | 60 |
| Compound number | Ratio g/ha | SOLNI | AMARE | SETFA | ALOMY | ECHCG | AVEFA |
| A-79 | 250 | - | 0 | 100 | 80 | 100 | 50 |
| A-80 | 250 | - | 0 | 90 | 30 | 100 | 0 |
| A-81 | 250 | - | 0 | 100 | 100 | 100 | 100 |
| A-82 | 250 | - | 0 | 100 | 100 | 100 | 100 |
| A-83 | 250 | - | 0 | 100 | 80 | 100 | 80 |
| A-87 | 250 | - | 0 | 80 | 10 | 80 | 0 |
| A-88 | 250 | - | 0 | 90 | 50 | 90 | 10 |
| A-89 | 250 | - | 0 | 80 | 80 | 90 | 50 |
| A-90 | 250 | - | 0 | 90 | 40 | 90 | 20 |
| A-92 | 250 | - | 0 | 90 | 50 | 100 | 0 |
| A-96 | 250 | - | 0 | 90 | 50 | 100 | 30 |
| A-97 | 250 | - | 0 | 70 | 40 | 90 | 30 |
| A-98 | 250 | - | 30 | 100 | 50 | 100 | 70 |
| A-99 | 250 | - | 0 | 100 | 90 | 100 | 90 |
| A-100 | 250 | - | 0 | 100 | 90 | 100 | 90 |
| A-101 | 250 | - | 0 | 100 | 100 | 100 | 100 |
| A-102 | 250 | - | 0 | 30 | 20 | 70 | 0 |
| A-103 | 250 | - | 0 | 100 | 10 | 100 | 0 |
| A-122 | 250 | - | 40 | 100 | 80 | 100 | 50 |
| A-123 | 250 | - | 0 | 100 | 90 | 100 | 70 |
| A-124 | 250 | - | 20 | 100 | 80 | 100 | 90 |
| A-125 | 250 | - | 0 | 100 | 100 | 100 | 90 |
| A-126 | 250 | - | 0 | 100 | 70 | 100 | 90 |
| A-127 | 250 | - | 0 | 100 | 80 | 100 | 40 |
| A-128 | 250 | - | 0 | 100 | 80 | 100 | 90 |
| A-129 | 250 | - | 0 | 80 | 70 | 90 | 80 |
| A-130 | 250 | - | 0 | 100 | 40 | 100 | 40 |
| A-132 | 250 | - | 0 | 90 | 20 | 70 | 30 |
| A-133 | 250 | - | 70 | 100 | 20 | 100 | 80 |
| A-135 | 250 | - | 0 | 100 | 100 | 100 | 100 |
| A-136 | 250 | - | 0 | 70 | 80 | 100 | 100 |
| A-137 | 250 | - | 30 | 100 | 90 | 100 | 90 |
| A-138 | 250 | - | 60 | 100 | 100 | 100 | 100 |
| A-139 | 250 | - | 50 | 80 | 30 | 100 | 50 |
| A-141 | 250 | - | 0 | 80 | 50 | 100 | 50 |
| A-142 | 250 | - | 0 | 80 | 100 | 100 | 80 |
| Compound number | Ratio g/ha | SOLNI | AMARE | SETFA | ALOMY | ECHCG | AVEFA |
| A-143 | 250 | - | 0 | 90 | 90 | 100 | 80 |
| A-144 | 250 | - | 40 | 100 | 100 | 100 | 100 |
| A-147 | 250 | - | 0 | 70 | 100 | 100 | 90 |
| A-149 | 250 | - | 20 | 100 | 90 | 100 | 70 |
| A-150 | 250 | - | 0 | 100 | 90 | 100 | 80 |
| A-151 | 250 | - | 0 | 100 | 100 | 100 | 100 |
| A-152 | 250 | - | 0 | 100 | 100 | 100 | 100 |
| A-153 | 250 | - | 30 | 100 | 100 | 100 | 100 |
| A-154 | 250 | - | 0 | 100 | 100 | 100 | 70 |
| A-155 | 250 | - | 40 | 100 | 100 | 100 | 90 |
| B-2 | 1000 | 40 | 70 | 20 | 0 | 80 | 0 |
| B-4 | 1000 | 40 | 70 | 90 | 80 | 90 | 30 |
| B-6 | 1000 | 0 | 0 | 30 | 20 | 50 | 0 |
| B-7 | 1000 | 70 | 70 | 70 | 20 | 60 | 20 |
| B-9 | 250 | 20 | 40 | 70 | 40 | 80 | 0 |
| B-10 | 250 | 0 | 40 | 80 | 40 | 90 | 20 |
| B-12 | 250 | 0 | 30 | 90 | 60 | 100 | 0 |
| B-13 | 250 | 0 | 20 | 90 | 0 | 80 | 30 |
| B-18 | 250 | 0 | 0 | 70 | 10 | 60 | 0 |
| B-23 | 250 | 0 | 0 | 70 | 30 | 60 | 0 |
| B-25 | 250 | 0 | 0 | 20 | 20 | 70 | 0 |
| B-27 | 250 | 0 | 0 | 60 | 70 | 80 | 0 |
| B-28 | 250 | 0 | 0 | 70 | 0 | 70 | 0 |
| B-29 | 250 | 30 | 20 | 80 | 30 | 100 | 0 |
| B-30 | 250 | 10 | 0 | 70 | 20 | 70 | 0 |
| B-31 | 250 | 0 | 0 | 90 | 10 | 90 | 0 |
| C-4 | 250 | - | 20 | 70 | 60 | 70 | 30 |
| C-5 | 250 | - | 0 | 90 | 70 | 100 | 70 |
| C-6 | 250 | - | 40 | 30 | 20 | 60 | 0 |
| C-7 | 250 | - | 0 | 30 | 20 | 60 | 0 |
| C-8 | 250 | - | 0 | 40 | 20 | 60 | 0 |
| C-9 | 250 | - | 0 | 10 | 50 | 70 | 40 |
| C-10 | 250 | - | 0 | 20 | 20 | 70 | 50 |
| C-11 | 250 | - | 20 | 30 | 70 | 80 | 60 |
| C-12 | 250 | - | 0 | 90 | 80 | 90 | 90 |
| C-13 | 250 | - | 20 | 100 | 80 | 100 | 90 |
| Compound number | Ratio g/ha | SOLNI | AMARE | SETFA | ALOMY | ECHCG | AVEFA |
| D-7 | 1000 | 0 | 0 | 100 | 90 | 100 | 70 |
| D-8 | 1000 | 0 | 0 | 100 | 60 | 100 | 10 |
| D-9 | 1000 | 0 | 0 | 90 | 30 | 100 | 0 |
| D-10 | 1000 | 0 | 20 | 100 | 90 | 100 | 20 |
| D-11 | 1000 | 0 | 0 | 90 | 40 | 100 | 0 |
| D-12 | 1000 | 0 | 0 | 100 | 90 | 100 | 90 |
| D-13 | 1000 | 0 | 0 | 100 | 60 | 100 | 0 |
| D-14 | 1000 | 0 | 0 | 100 | 20 | 100 | 10 |
| D-15 | 1000 | 0 | 0 | 100 | 80 | 100 | 60 |
| D-16 | 1000 | 0 | 0 | 100 | 90 | 100 | 20 |
| D-17 | 1000 | 0 | 10 | 100 | 60 | 100 | 20 |
| D-18 | 1000 | 0 | 20 | 100 | 100 | 100 | 90 |
| D-19 | 1000 | 0 | 0 | 100 | 90 | 100 | 80 |
| D-20 | 1000 | 0 | 20 | 100 | 100 | 100 | 90 |
| D-21 | 1000 | 30 | 10 | 100 | 100 | 100 | 90 |
| D-22 | 250 | - | 0 | 100 | 90 | 100 | 100 |
| D-23 | 250 | - | 0 | 90 | 0 | 100 | 0 |
| D-24 | 250 | - | 0 | 100 | 0 | 100 | 20 |
| D-25 | 250 | - | 0 | 90 | 0 | 90 | 20 |
| D-28 | 250 | - | 0 | 80 | 80 | 90 | 50 |
| D-32 | 250 | - | 0 | 80 | 50 | 90 | 70 |
Claims (21)
1. formula I compound
Wherein
R
1Be the propyl group of fluorine, chlorine, bromine, methyl, ethyl, straight chain isomeric forms, propyl group, cyclopropyl, vinyl, methoxyl group, oxyethyl group, the propoxy-of straight chain isomeric forms or the propoxy-of branched isomer form of branched isomer form;
R
2Be phenyl, pyrazolyl, imidazolyl or pyridyl, wherein these rings are unsubstituted or by halogen, C
1-C
4Alkyl, C
1-C
4Haloalkyl, C
2-C
4Thiazolinyl, C
2-C
4Haloalkenyl group, C
2-C
4Alkynyl, C
1-C
4Alkoxyl group, C
1-C
4Halogenated alkoxy, C
1-C
4Alkylthio, C
1-C
4Alkyl sulphinyl, C
1-C
4Alkyl sulphonyl, C
1-C
4Halogenated alkylthio, C
1-C
4Haloalkyl sulfinyl, C
1-C
4Halogenated alkyl sulfonyl, nitro or cyanic acid replace;
R is 0,1 or 2;
R
3If r is 1, be halogen or C
1-C
6Alkyl; Or said substituent R
3If r is 2, be halogen or C independently of one another
1-C
6Alkyl;
R
4, R
5, R
6And R
7Be hydrogen, C independently of one another
1-C
4Alkyl or C
1-C
4Alkoxy C
1-C
4Alkyl; Perhaps
R
4With R
5, or R
6With R
7Form the saturated ring of 5-7 unit together, wherein methylene radical is randomly replaced by oxygen or sulphur atom; Perhaps
R
4With R
7Form together without replacement or by substituted 5-7 saturated or undersaturated ring: the C of unit of following radicals
1-or C
2Alkyl or C
1-C
2Alkoxy C
1-C
2Alkyl; With
Y is O, C=O or S (O)
mCondition is when Y is C=O, works as R
4Or R
5R when being hydrogen
6And R
7Not hydrogen, and work as R
6Or R
7R when being hydrogen
4And R
5Not hydrogen;
M is 0 or 1 or 2; And
G is the acceptable positively charged ion or the group of hiding on hydrogen, the agricultural;
And wherein, when G be that G representes C (X when hiding group
a)-R
aOr C (X
b)-X
c-R
b, X wherein
a, X
bAnd X
cBe oxygen, R
aBe C
1-C
6Alkyl, C
2-C
6Thiazolinyl, C
2-C
6Alkynyl, C
3-C
6Naphthenic base or C
1-C
4Alkoxy C
1-C
4Alkyl and R
bBe C
1-C
6Alkyl, C
3-C
6Thiazolinyl, C
3-C
6Alkynyl, C
3-C
6Naphthenic base or C
1-C
4Alkoxy C
1-C
4Alkyl;
And wherein, work as R
2Be not replace or substituted pyrazolyl, do not replace or substituted imidazolyl or do not replace or during substituted pyridyl, said formula (I) compound randomly is the salt of this formula (I) compound.
2. according to the compound of claim 1, R wherein
1Be the propyl group of fluorine, chlorine, bromine, methyl, ethyl, straight chain isomeric forms, the propyl group or the vinyl of branched isomer form.
3. according to the compound of claim 1, R wherein
2Be phenyl or pyridyl; Perhaps by halogen, nitro, cyanic acid, C
1-C
2Alkyl, C
1-C
2Haloalkyl, C
1-C
2Alkoxyl group or C
1-C
2Substituted phenyl of halogenated alkoxy or pyridyl.
4. according to the compound of claim 1, R wherein
3Be hydrogen, its expression r is 0.
5. according to the compound of claim 1, R wherein
4, R
5, R
6And R
7Be hydrogen, C independently of one another
1-C
4Alkyl or C
1-C
4Alkoxy C
1-C
4Alkyl.
6. according to the compound of claim 5, R wherein
4, R
5, R
6And R
7Be hydrogen, C independently of one another
1-C
2Alkyl or C
1-C
2Alkoxy-C
1-C
2Alkyl.
7. according to the compound of claim 1, wherein Y is O, S or C-O.
8. according to the compound of claim 1, wherein G is the group of hiding, and it is C (X
a)-R
a, C (X
b)-X
c-R
b, X wherein
a, X
bAnd X
cBe oxygen, R
aBe C
1-C
6Alkyl, C
2-C
6Thiazolinyl, C
2-C
6Alkynyl, C
3-C
6Naphthenic base or C
1-C
4Alkoxy C
1-C
4Alkyl and R
bBe C
1-C
6Alkyl, C
3-C
6Thiazolinyl, C
3-C
6Alkynyl, C
3-C
6Naphthenic base or C
1-C
4Alkoxy C
1-C
4Alkyl.
9. according to the compound of claim 1, wherein G is that hydrogen or conduct agricultural go up acceptable cationic basic metal or alkaline earth metal cation.
10. according to the compound of claim 9, wherein G is a hydrogen.
11. according to the compound of claim 1, wherein
R
1Be the propyl group of methyl, ethyl, straight chain isomeric forms or the propyl group of branched isomer form,
R
2It is phenyl or by halogen or C
1-C
2The substituted phenyl of alkyl,
R
3Be hydrogen, its expression r is 0,
R
4, R
5, R
6And R
7Be C independently of one another
1-C
2Alkyl,
Y is O, and
G is a hydrogen.
G is the method for the formula according to claim 1 (I) compound of hydrogen 12. prepare wherein, and it comprises formula (J) compound,
Formula (J)
R wherein
4, R
5, R
6, R
7Have the implication of giving them in the claim 1 with Y, plumbous with formula (K) aryl nitrilotriacetic
Formula (K)
R wherein
1, R
2, R
3With
rHas the implication of giving them in the claim 1, reaction in the presence of containing n-donor ligand.
G is the method for the formula according to claim 1 (I) compound of hydrogen 13. prepare wherein, and it is included in rearrangement formula (Q) compound under the situation that there is down and exists catalyzer in alkali
Formula (Q) formula (I)
R wherein
1, R
2, R
3, R
4, R
5, R
6, R
7, Y and r have the implication of giving them in the claim 1.
Exist down 14. preparation, wherein is included in suitable palladium catalyst, part and alkali according to the method for formula (I) compound of claim 1, and in The suitable solvent with formula (H) compound
Formula (H),
R wherein
1, R
3, R
4, R
5, R
6, R
7, to have the implication and the Hal that give them in the claim 1 be chlorine, bromine, iodine or trifluoro-methanesulfonyl oxy for Y and r, with formula R
2B (OH)
2Aryl or heteroaryl boric acid or its salt or ester reaction, wherein R
2Has the implication of giving it in the claim 1.
Exist down 15. preparation, wherein is included in suitable palladium catalyst, part and alkali according to the method for formula (I) compound of claim 1, and in The suitable solvent with formula (X) aryl boric acid or its salt or ester
R wherein
1, R
3, R
4, R
5, R
6, R
7, Y and r have the implication of giving them in the claim 1, with formula R
2The reaction of-Hal compound, wherein R
2Have the implication of giving it in the claim 1, and Hal is chlorine, bromine, iodine or trifluoro-methanesulfonyl oxy.
16. preparation is according to the method for formula (I) compound of claim 1, G is C (X in said formula (I) compound
a)-R
aOr C (X
b)-X
c-R
b, X wherein
a, X
bAnd X
cBe oxygen, R
aBe C
1-C
6Alkyl, C
2-C
6Thiazolinyl, C
2-C
6Alkynyl, C
3-C
6Naphthenic base or C
1-C
4Alkoxy C
1-C
4Alkyl and R
bBe C
1-C
6Alkyl, C
3-C
6Thiazolinyl, C
3-C
6Alkynyl, C
3-C
6Naphthenic base or C
1-C
4Alkoxy C
1-C
4Alkyl, it is included in the existence of at least 1 equivalent alkali or does not exist down handles formula (A) compound with acylating reagent
Formula (A).
17. control gramineous grass and method for weed in the crop of useful plant, each defined formula (I) compound of claim 1-11 that it comprises herbicidally effective amount perhaps comprises this compound compositions and is applied to plant or its place.
18. herbicidal composition, it also comprises each defined formula I compound of claim 1-11 of herbicidally effective amount except comprising formulation auxiliary agents.
19. according to the herbicidal composition of claim 18, it also comprises other weedicide as mixed thing except comprising formula I compound.
20. according to the herbicidal composition of claim 18, it also comprises safener except comprising formula I compound.
21. according to the herbicidal composition of claim 18, it also comprises other weedicide as mixed thing and safener except comprising formula I compound.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0624961A GB0624961D0 (en) | 2006-12-14 | 2006-12-14 | Novel herbicides |
| GB0624961.9 | 2006-12-14 | ||
| GB0705044A GB0705044D0 (en) | 2007-03-15 | 2007-03-15 | Novel herbicides |
| GB0705044.6 | 2007-03-15 | ||
| PCT/EP2007/010848 WO2008071405A1 (en) | 2006-12-14 | 2007-12-12 | 4-phenyl-pyrane-3,5-diones, 4-phenyl-thiopyrane-3,5-diones and cyclohexanetriones as novel herbicides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101605771A CN101605771A (en) | 2009-12-16 |
| CN101605771B true CN101605771B (en) | 2012-09-05 |
Family
ID=37712134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800511842A Expired - Fee Related CN101605771B (en) | 2006-12-14 | 2007-12-12 | 4-phenyl-pyrane-3,5-diones, 4-phenyl-thiopyrane-3,5-diones and cyclohexanetriones as novel herbicides |
Country Status (4)
| Country | Link |
|---|---|
| CN (1) | CN101605771B (en) |
| GB (1) | GB0624961D0 (en) |
| UA (1) | UA98316C2 (en) |
| ZA (1) | ZA200904116B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102711465A (en) * | 2009-12-17 | 2012-10-03 | 辛根塔有限公司 | Herbicidal composition comprising a pyrandione herbicide and a co-herbicide |
| CA2889200A1 (en) | 2012-11-28 | 2014-06-05 | Sumitomo Chemical Company, Limited | Dihydropyrone compounds and herbicides comprising the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1481970A1 (en) * | 1999-09-07 | 2004-12-01 | Syngenta Participations AG | Novel herbicides |
-
2006
- 2006-12-14 GB GB0624961A patent/GB0624961D0/en not_active Ceased
-
2007
- 2007-12-12 UA UAA200907136A patent/UA98316C2/en unknown
- 2007-12-12 CN CN2007800511842A patent/CN101605771B/en not_active Expired - Fee Related
-
2009
- 2009-06-11 ZA ZA200904116A patent/ZA200904116B/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1481970A1 (en) * | 1999-09-07 | 2004-12-01 | Syngenta Participations AG | Novel herbicides |
| US20050164883A1 (en) * | 1999-09-07 | 2005-07-28 | Thomas Maetzke | Novel herbicides |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101605771A (en) | 2009-12-16 |
| GB0624961D0 (en) | 2007-01-24 |
| UA98316C2 (en) | 2012-05-10 |
| ZA200904116B (en) | 2010-03-31 |
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