CN1784399A - 3-carbonylaminothiophenes and their use as fungicides - Google Patents

3-carbonylaminothiophenes and their use as fungicides Download PDF

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CN1784399A
CN1784399A CN 200480012218 CN200480012218A CN1784399A CN 1784399 A CN1784399 A CN 1784399A CN 200480012218 CN200480012218 CN 200480012218 CN 200480012218 A CN200480012218 A CN 200480012218A CN 1784399 A CN1784399 A CN 1784399A
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J·埃伦弗莱德
H·沃尔特
H·托布勒
C·兰伯斯
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Syngenta Participations AG
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Syngenta Participations AG
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Abstract

The invention also relates to novel compounds of formula (1) where Het is a 5- or 6-membered heterocyclic ring containing one to three heteroatoms, each independently selected from oxygen, nitrogen and sulphur, the ring being substituted by one to three groups R<4> ; R<1> is hydrogen, optionally substituted (C1-4)alkyl, formyl, optionally substituted (C1-4)alkylC(=0), optionally substituted (C1-4)alkylC(=0)0, optionally substituted (C1-4)alkoxy(C1-4)alkyl, optionally substituted allyl, optionally substittited propargyl or optionally substituted allenyl; each R<2> is, independently, halogen, optionally substituted (C1-4)alkyl, optionally substituted (C1-4)alkoxy or optionally substituted (C1-4)alkoxy(C1-4)alkyl; R<3> is either at position 2 or at position 4 of the thiophene ring and is an organie group containing three to thirteen carbon atoms and al least one silicon atom and, optionally, one to three heteroatoms, each independently selected from oxygen, nitrogen and sulphur, and is optionally substituted by one to four independently selected halogen atoms; each R<4> is, independently, halogen, C1-3 alkyl, C1-3 haloalkyl, C1-3alkoxy(C1-3)alkyl or cyano; r is 0, 1 or 2; and X is 0 or S; or an N-oxide thereof, to novel intermediates used in the preparation of these compounds, to agrochernical compositions which comprise at least one of the novel compounds as an active ingredient and to the use of the active ingredients or compositions in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.

Description

3-carbonylamino thiophene compound and as the purposes of mycocide
Novel thiophene-3-the acid amides that is replaced by siliceous substituting group on 2-that the present invention relates in thiphene ring or the 4-position, it has microbiocidal activity, especially fungicidal activity.The invention still further relates to the preparation method of these compounds, the new intermediate that relates to the preparation that is used for these compounds, relate at least a agricultural chemical composition that comprises in this novel cpd, relate to described preparation of compositions method and relate to activeconstituents or the purposes that plant is infected by phytopathogenic microorganism (preferred fungi) is controlled or prevented to composition in agricultural or gardening as activeconstituents.
Some thiophene-carboxamides that is replaced by siliceous substituting group has been disclosed among US5739338 and the WO97/19062.
The invention provides the compound of structural formula (I)
Wherein Het contains one to three heteroatomic 5-or 6-unit heterocycle, and this heteroatoms is selected from oxygen, nitrogen and sulphur independently of one another, and described ring is by one to three radicals R 4Replace; R 1Be hydrogen, the optional (C that replaces 1-4) alkyl, formyl radical, the optional (C that replaces 1-4) alkyl C (=O), the optional (C that replaces 1-4) alkyl C (=O) O, the optional (C that replaces 1-4) alkoxyl group (C 1-4) alkyl, the optional allyl group that replaces, optional propargyl that replaces or the optional propadiene base that replaces; Each R 2Be halogen independently, the optional (C that replaces 1-4) alkyl, the optional (C that replaces 1-4) alkoxyl group or the optional (C that replaces 1-4) alkoxyl group (C 1-4) alkyl;
R 3Be on 2 or 4 of thiphene ring and be to contain three to 13 carbon atoms and at least one Siliciumatom and one to three optional heteroatomic organic group, heteroatoms is selected from oxygen, nitrogen and sulphur independently of one another and is randomly replaced by one to four halogen atom of selecting independently; Each R 4Be halogen independently, C 1-3Alkyl, C 1-3Haloalkyl, C 1-3Alkoxyl group (C 1-3) alkyl or cyano group; R is 0,1 or 2;
With X be O or S; Or its N-oxide compound.
The invention provides the compound of structural formula (I) as defined above in yet another aspect, precondition is that the Het ring is not a 1,2,3-triazoles when X is O.
Halogen is a fluorine, chlorine, bromine or iodine, preferred fluorine, chlorine or bromine.
Each moieties is straight or branched and is for example methyl, ethyl, n-propyl, normal-butyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-or the tertiary butyl.
This alkenyl part, if suitable, can have (E)-or (Z)-configuration.
When existing, at moieties, allyl group; the optional substituting group of on propargyl and the propadiene base each is independently selected from halogen, hydroxyl, cyano group; carboxyl, methoxycarbonyl, ethoxy carbonyl; methoxyl group; oxyethyl group, methyl sulphonyl, ethylsulfonyl; difluoro-methoxy, trifluoromethoxy and trifluoromethyl thio-methoxy.
Preferred R 1Be hydrogen, propargyl, propadiene base, formyl radical, CH 3C (=O), C 2H 5C (=O) or CH 3OCH 2C (=0).
More preferably R 1Be hydrogen, propargyl, propadiene base, CH 3C (=O), C 2H 5C (=O) or CH 3OCH 2C (=O).
R most preferably 1Be hydrogen.
Preferably, each R 2Be independently selected from halogen, methyl, trifluoromethyl and trifluoromethoxy.
Preferably, Het is a pyrazolyl, pyrryl, thienyl, furyl, thiazolyl, isothiazolyl ， oxazolyl isoxazolyl, triazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, 5,6-dihydro pyranyl or 5,6-dihydro-1,4-oxathiin base (more preferably pyrazolyl, pyrryl, thienyl, furyl, thiazolyl oxazolyl, 1,2, the 3-triazolyl, pyridyl, pyrimidyl, pyridazinyl, 5,6-dihydro pyranyl or 5,6-dihydro-1,4-oxathiin base), separately can be by one to three radicals R 4Replace.
Preferred R 3Be to contain three to 13 carbon atoms and at least one Siliciumatom and one to three optional heteroatoms (to be selected from oxygen independently of one another, nitrogen and sulphur) aliphatics, saturated or undersaturated group, and randomly replaced by one to four halogen atom of selecting independently.
More preferably, R 3Be Y 1-Si (O mMe) (O nMe) (O pY 2), m wherein, n and p are 0 or 1 independently of one another; Y 1Be key or alkane 2 basis (alkylidene group), olefin 2 base (alkylene group) or alkynes two bases (alkynylene), each in them are branching or nonbranched and contain 1-6 carbon atom and randomly inserted by one or two Sauerstoffatom and randomly by one to three the halogen atom replacement of selection independently; And Y 2Be alkyl or alkenyl, each in them is a branching or nonbranched and contain 1-5 carbon atom and be selected from randomly that heteroatoms among O, S and the N inserts and optional by one to three the halogen atom replacement of selection independently.
Even more preferably, R 3Be SiMe 3, SiMe 2Et, SiMe 2CHMe 2, SiMe 2CH 2CHMe 2, SiMe 2CH 2CMe 3, SiMe 2OCHMe 2, SiMe 2OCH 2CHMe 2, CH 2SiMe 3, CH 2SiMe 2Et, CH 2SiMe 2CHMe 2, CH 2SiMe 2CH 2CHMe 2, CH 2SiMe 2OMe, CH 2SiMe 2OCHMe 2, CH 2SiMe 2OCH 2CHMe 2, CHMeSiMe 3, CHMeSiMe 2OMe, (CH 2) 2SiMe 3, (CH 2) 2SiMe 2Et, (CH 2) 2SiMe 2CHMe 2, (CH 2) 2SiMe 2CMe 3, (CH 2) 2SiMe 2CH 2CHMe 2, (CH 2) 2SiMe 2CH 2CH 2Me, (CH 2) 2SiMe 2CH 2CMe 3, (CH 2) 2SiMe 2OCHMe 2, (CH 2) 2SiMe 2OCH 2CHMe 2, CHMeCH 2SiMe 3, CHMeCH 2SiMe 2Et, CHMeCH 2SiMe 2CH 2CH 2Me, CHMeCH 2SiMe 2CHMe 2, CHMeCH 2SiMe 2CMe 3, CHMeCH 2SiMe 2CH 2CHMe 2, CFMeCH 2SiMe 3, CHMeCH 2CH 2SiMe 2OMe, CHMeCH 2SiMe 2OCHMe 2, CHMeCH 2SiMe 2OCH 2CHMe 2, CH 2CHMeSiMe 3, CH 2CHMeSiMe 2Et, CH 2CHMeSiMe 2CHMe 2, CHMeCHMeSiMe 3, CMe 2CH 2SiMe 3, (CH 2) 3SiMe 3, (CH 2) 3SiMe 2Et, (CH 2) 3SiMe 2CHMe 2, (CH 2) 3SiMe 2CH 2CHMe 2, (CH 2) 3SiMe 2OMe, (CH 2) 3SiMe 2OCHMe 2, (CH 2) 3SiMe 2OCH 2CHMe 2, CHMeCH 2CH 2SiMe 3, CHMeCH 2CH 2SiMe 2Et, CHMeCH 2CH 2SiMe 2CHMe 2, CHMeCH 2CH 2CH 2SiMe 2OMe, CHMeCH 2CH 2SiMe 2OCHMe 2, CMe=CHSiMe 3Or CH 2CH 2SiMe 2OMe.
Most preferably, R 3Be SiMe 3, SiMe 2Et, SiMe 2CHMe 2, SiMe 2CH 2CHMe 2, SiMe 2CH 2CMe 3, (CH 2) 2SiMe 3, (CH 2) 2SiMe 2Et, (CH 2) 2SiMe 2CHMe 2, (CH 2) 2SiMe 2CMe 3, (CH 2) 2SiMe 2CH 2CHMe 2, CHMeCH 2SiMe 3, CHMeCH 2SiMe 2Et, CH 2CHMeSiMe 3, CMe 2CH 2SiMe 3Or (CH 2) 3SiMe 3
At the Het ring nitrogen is unsubstituted or by R independently 4Replace.Work as R 4Its C preferably when being the substituting group on nitrogen-atoms 1-3Alkyl, C 1-3Haloalkyl or methoxyl group methylene radical; More preferably C 1-2Alkyl, CF 3, CF 2Cl, CHF 2, CH 2F or methoxyl group methylene radical; Even more preferably methyl, CHF 2Or methoxyl group methylene radical; More preferably methyl or methoxy methylene radical again; And most preferable.
In the Het ring, be not keyed to by CXNR 1Carbon atom on the atom that replaces is unsubstituted or by R independently 4Replace.Work as R 4Be not to be bonded in by CXNR 1During substituting group on the carbon atom on the atom that replaces, it is halogen preferably, C 1-3Alkyl, C 1-3Haloalkyl or methoxyl group methylene radical; More preferably chlorine, methoxyl group methylene radical, CH 3, CHF 2Or CF 3More preferably chlorine again, CH 3, CHF 2Or CF 3With in addition more preferably CH 3Or CF 3
In the Het ring, there is one or two to be keyed to by CXNR 1Carbon atom on the atom that replaces; These carbon atoms are unsubstituted or by R independently 4Replace.Work as R 4Be to be bonded in by CXNR 1During substituting group on the carbon atom on the atom that replaces, it is halogen preferably, C 1-3Alkyl or C 1-3Haloalkyl; More preferably chlorine, fluorine, bromine, C 1-2Alkyl, CF 3, CF 2Cl, CHF 2Or CH 2F; With in addition more preferably chlorine, fluorine, bromine, methyl, CF 3, CHF 2Or CH 2F.
More preferably, when only in Het ring, there being one to be bonded in by CXNR 1During carbon atom on the atom that replaces, this carbon atom is by R 4Replace.
More preferably, when in the Het ring, having two to be bonded in by CXNR 1During carbon atom on the atom that replaces, one of them carbon atom is by R 4Replace and another carbon atom is unsubstituted or by fluorine, chlorine or methyl substituted.
Most preferably, Het, R 4And CXNR 1Combination be 1-Me-3-R 4-4-CXNR 1Pyrazolyl, 1-Me-3-R 4-4-CXNR 1Pyrryl, 2-Me-3-R 4-4-CXNR 1Thiazolyl or 2-R 4-3-CXNR 1Pyridyl.
Preferred X is an oxygen.
Preferred r is 0.
When the compound of structural formula (I) was the N-oxide compound, then preferably, Het was by one to three radicals R 4The pyridyl that replaces.
In whole specification sheets, Me is used to represent methyl.Similarly, Et represents ethyl.
General formula (IIa) and thiophene (IIb)
Figure A20048001221800071
R wherein 3Be NH with A as defined above 2, NHCH (O), the optional (C that replaces 1-4) alkyl C (=O) NH, the optional (C that replaces 1-4) alkyl OC (=O) NH, halogen or N=C (C 6H 5) 2Can be used as the intermediate in the preparation of general formula (I) compound.
General formula (IIa) and compound (IIb), wherein R 3Be SiMe 2Et, SiMe 2CHMe 2, SiMe 2CH 2CHMe 2, SiMe 2CH 2CMe 3, CH=CHSiMe 3, (CH 2) 2SiMe 3, (CH 2) 2SiMe 2Et, (CH 2) 2SiMe 2CHMe 2, (CH 2) 2SiMe 2CMe 3, (CH 2) 2SiMe 2CH 2CHMe 2, CHMeCH 2SiMe 3, CHMeCH 2SiMe 2Et, CH 2CHMeSiMe 3, CMe 2CH 2SiMe 3Or (CH 2) 3SiMe 3[precondition is to work as R as defined above with A 3Be SiMe 3The time A be not halogen], be novel and preferably as the intermediate of the preparation usefulness of general formula (I) compound.R wherein 3Be SiMe 3With A be that the general formula (IIa) and the compound (IIb) of halogen is known already.
Therefore, the invention provides general formula (IIa) or compound (IIb), wherein R in yet another aspect 3Be SiMe 3, SiMe 2Et, SiMe 2CHMe 2, SiMe 2CH 2CHMe 2, SiMe 2CH 2CMe 3, CH=CHSiMe 3, (CH 2) 2SiMe 3, (CH 2) 2SiMe 2Et, (CH 2) 2SiMe 2CHMe 2, (CH 2) 2SiMe 2CMe 3, (CH 2) 2SiMe 2CH 2CHMe 2, CHMeCH 2SiMe 3, CHMeCH 2SiMe 2Et, CH 2CHMeSiMe 3, CMe 2CH 2SiMe 3, (CH 2) 3SiMe 3With A be NH 2, NHCH (O), the optional (C that replaces 1-4) alkyl C (=O) NH, the optional (C that replaces 1-4) alkyl OC (=O) NH, halogen or N=C (C 6H 5) 2Precondition is to work as R 3Be SiMe 3The time A be not halogen.
General formula (I) (IIa) can be used as different geometry or optically active isomer with the compound of (IIb) or exists with different tautomeric forms.The present invention has covered the mixture of all these type of isomer and tautomer and their various ratios and isotropic substance form such as deuterium for compound.
Table 1 illustrates particularly preferred compound of the present invention, wherein R to the compound in 28 below 5, R 6And R 7Be R defined above independently of one another 4Example.
When Table A is represented table 1 (when A is 1), during expression table 2 (when A is 2), expression table 3 (when A is 3) and expression table 4 (when A is 4).
Table A
Compound N o. R 1 R 3 R 5 R 6 R 7 X
A.1 H SiMe 3 H Me CF 3 O
A.2 H SiMe 3 H Me CF 2H O
A.3 H CH 2SiMe 3 H Me CF 3 O
A.4 H CH 2SiMe 3 H Me CF 3 S
A.5 H CH 2SiMe 3 H Me CF 2H O
A.6 Propargyl CH 2SiMe 3 H Me CF 3 O
A.7 H CHMeSiMe 3 H Me CF 3 O
A.8 H CHMeSiMe 3 H Me CF 2H O
A.9 H CHMeSiMe 3 H Me CF 3 S
A.10 Propargyl CHMeSiMe 3 H Me CF 3 O
A.11 The propadiene base CHMeSiMe 3 H Me CF 3 O
A.12 COMe CHMeSiMe 3 H Me CF 3 O
A.13 H CHMeSiMe 3 F Me Me O
A.14 H (CH 2) 2SiMe 3 H Me CF 3 O
A.15 H (CH 2) 2SiMe 3 H Me CF 3 S
A.16 H (CH 2) 2SiMe 3 H Me CF 2H O
A.17 Propargyl (CH 2) 2SiMe 3 H Me CF 3 O
A.18 H (CH 2) 2SiMe 3 F Me Me O
A.19 H (CH 2) 2SiMe 3 H CH 2OMe CF 3 O
A.20 H (CH 2) 2SiMe 3 H CH 2OMe CF 2H O
A.21 H CHMeCH 2SiMe 3 H Me CF 3 O
A.22 H CHMeCH 2SiMe 3 H Me CF 3 S
A.23 H CHMeCH 2SiMe 3 H CH 2OMe CF 3 O
A.24 H CHMeCH 2SiMe 3 H Me CF 2H O
A.25 H CHMeCH 2SiMe 3 H Me CF 2H S
A.26 Propargyl CHMeCH 2SiMe 3 H Me CF 3 O
A.27 The propadiene base CHMeCH 2SiMe 3 H Me CF 3 O
A.28 Propargyl CHMeCH 2SiMe 3 H Me CF 2H O
A.29 The propadiene base CHMeCH 2SiMe 3 H Me CF 2H O
A.30 H CHMeCH 2SiMe 3 F Me Me O
A.31 COMe CHMeCH 2SiMe 3 H Me CF 3 O
A.32 H (CH 2) 3SiMe 3 H Me CF 2H O
A.33 H CH 2Si(Me 2)Et H Me CF 3 O
A.34 H CH 2Si(Me 2)Et H Me CF 2H O
A.35 H CH 2Si(Me 2)CHMe 2 H Me CF 3 O
A.36 H CH 2Si(Me 2)CHMe 2 H Me CF 2H O
A.37 H CH 2Si(Me 2)OMe H Me CF 3 O
A.38 H CH 2Si(Me 2)OMe H Me CF 2H O
A.39 H CH 2CH 2Si(Me 2)OMe H Me CF 3 O
A.40 H CHMeSi(Me 2)OMe H Me CF 3 O
A.41 H CHMeSi(Me 2)OMe H Me CF 2H O
A.42 H CH 2CH 2Si(Me 2)OMe H Me CF 2H O
A.43 H C(Me)＝CHSiMe 3 H Me CF 3 O
A.44 H SiMe 3 H Me CH 2F O
A.45 H (CH 2) 2SiMe 3 H Me CH 2F O
A.46 H CH 2CHMeSiMe 3 H Me CH 2F O
A.47 H CH 2CHMeSiMe 3 H Me CF 3 O
A.48 H CH 2CHMeSiMe 3 H Me CF 2H O
A.49 H CHMeCH 2SiMe 3 H Me CH 2F O
A.50 H CMe 2CH 2SiMe 3 H Me CF 3 O
A.51 H CMe 2CH 2SiMe 3 H Me CF 2H O
A.52 H CHMeCHMeSiMe 3 H Me CF 2H O
A.53 H CHMeCHMeSiMe 3 H Me CF 3 O
A.54 H CH 2CMe 2SiMe 3 H Me CF 3 O
A.55 H CH 2CMe 2SiMe 3 H Me CF 2H O
A.56 H CHMe(CH 2) 2SiMe 3 H Me CF 2H O
A.57 H CHMe(CH 2) 2SiMe 3 H Me CF 3 O
A.58 H (CH 2) 2Si(Me 2)(CH 2) 2Me H Me CF 2H O
A.59 H (CH 2) 2Si(Me 2)(CH 2) 2Me H Me CF 3 O
A.60 H CHMeCH 2Si(Me 2)CMe 3 H Me CF 3 O
A.61 H C(＝CH 2)CH 2Si(Me 2)CMe 3 H Me CF 3 O
A.62 H C(＝CH 2)CH 2Si(Me 2)CH 2Me H Me CF 3 O
A.63 H (CH 2) 2Si(Me 2)CH 2Me H Me CF 3 O
A.64 H CHMeCH 2Si(Me 2)CH 2Me H Me CF 3 O
A.65 H (CH 2) 2Si(Me 2)CHMe 2 H Me CF 3 O
A.66 H CHMeCH 2Si(Me 2)CHMe 2 H Me CF 3 O
A.67 H CHMeCH 2Si(Me 2)CH 2CHMe 2 H Me CF 3 O
A.68 H Si(Me 2)CH 2Me H Me CF 2H O
A.69 H Si(Me 2)CH 2Me H Me CF 3 O
A.70 H Si(Me 2)CHMe 2 H Me CF 3 O
A.71 H Si(Me 2)CHMe 2 H Me CF 2H O
A.72 H Si(Me 2)CH 2CHMe 2 H Me CF 2H O
A.73 H Si(Me 2)CH 2CHMe 2 H Me CF 3 O
A.74 H C：CCH 2SiMe 3 H Me CF 3 O
A.75 Propargyl (CH 2) 2SiMe 3 H Me CF 2H O
A.76 The propadiene base (CH 2) 2SiMe 3 H Me CF 2H O
A.77 The propadiene base (CH 2) 2SiMe 3 H Me CF 3 O
A.78 H (CH 2) 2SiMe 3 H Me CF 2Cl O
A.79 H (CH 2) 3SiMe 3 H Me CF 3 O
A.80 H (CH 2) 2SiMe 3 Br Me CF 3 O
A.81 H (CH 2) 2SiMe 3 Cl Me CF 3 O
A.82 H (CH 2) 2SiMe 3 H Me Me O
A.83 H C:CSiMe 3 H Me CF 3 O
A.84 H C:CSiMe 3 H Me CF 2H O
A.85 CHO (CH 2) 2SiMe 3 H Me CF 2H O
A.86 CHO (CH 2) 2SiMe 3 H Me CF 3 O
Table 1 provides 86 kinds of compounds, wherein R of general formula (Ia) 1, R 3, R 5, R 6, R 7With X such as at table 1 definition.
Figure A20048001221800111
Table 2 provides 86 kinds of compounds, wherein R of general formula (Ib) 1, R 3, R 5, R 6, R 7With X such as at table 2 definition.
Figure A20048001221800112
Table 3 provides 86 kinds of compounds, wherein R of general formula (Ic) 1, R 3, R 5, R 6, R 7With X such as at table 3 definition.
Figure A20048001221800113
Table 4 provides 86 kinds of compounds, wherein R of general formula (Id) 1, R 3, R 5, R 6, R 7With X such as at table 4 definition.
Figure A20048001221800114
Table B represents table 5 (when B is 5), expression table 6 (when B is 6), expression table 7 (when B is 7) and expression table 8 (when B is 8).
Table B
Compound N o. R 1 R 3 R 5 R 6 X
B.1 H SiMe 3 Me CF 3 O
B.2 H SiMe 3 Me CF 2H O
B.3 H CH 2SiMe 3 Me CF 3 O
B.4 H CH 2SiMe 3 Me CF 3 S
B.5 H CH 2SiMe 3 Me CF 2H O
B.6 Propargyl CH 2SiMe 3 Me CF 3 O
B.7 H CHMeSiMe 3 Me CF 3 O
B.8 H CHMeSiMe 3 Me CF 2H O
B.9 H CHMeSiMe 3 Me CF 3 S
B.10 Propargyl CHMeSiMe 3 Me CF 3 O
B.11 The propadiene base CHMeSiMe 3 Me CF 3 O
B.12 COMe CHMeSiMe 3 Me CF 3 O
B.13 H CHMeSiMe 3 Me Me O
B.14 H (CH 2) 2SiMe 3 Me CF 3 O
B.15 H (CH 2) 2SiMe 3 Me CF 3 S
B.16 H (CH 2) 2SiMe 3 Me CF 2H O
B.17 Propargyl (CH 2) 2SiMe 3 Me CF 3 O
B.18 H (CH 2) 2SiMe 3 Me Me O
B.19 H (CH 2) 2SiMe 3 CF 3 CF 3 O
B.20 H CHMeCH 2SiMe 3 Me CF 3 O
B.21 H CHMeCH 2SiMe 3 Me CF 3 S
B.22 H CHMeCH 2SiMe 3 Me CF 2H O
B.23 H CHMeCH 2SiMe 3 Me CF 2H S
B.24 Propargyl CHMeCH 2SiMe 3 Me CF 3 O
B.25 Propargyl CHMeCH 2SiMe 3 Me CF 2H O
B.26 H CHMeCH 2SiMe 3 Me Me O
B.27 H CHMeCH 2SiMe 3 CF 3 CF 3 O
B.28 COMe CHMeCH 2SiMe 3 Me CF 3 O
B.29 H (CH 2) 3SiMe 3 Me CF 3 O
B.30 H (CH 2) 3SiMe 3 Me CF 2H O
B.31 H CH 2Si(Me 2)Et Me CF 3 O
B.32 H CH 2Si(Me 2)Et Me CF 2H O
B.33 H CH 2Si(Me 2)CHMe 2 Me CF 3 O
B.34 H CH 2Si(Me 2)CHMe 2 Me CF 2H O
B.35 H CH 2CHMeSiMe 3 Me CF 3 O
B.36 H CH 2CHMeSiMe 3 Me CF 2H O
B.37 H CMe 2CH 2SiMe 3 Me CF 3 O
B.38 H CMe 2CH 2SiMe 3 Me CF 2H O
B.39 H CHMeCHMeSiMe 3 Me CF 2H O
B.40 H CHMeCHMeSiMe 3 Me CF 3 O
B.41 H CH 2CMe 2SiMe 3 Me CF 3 O
B.42 H CH 2CMe 2SiMe 3 Me CF 2H O
B.43 H CHMe(CH 2) 2SiMe 3 Me CF 2H O
B.44 H CHMe(CH 2) 2SiMe 3 Me CF 3 O
B.45 H (CH 2) 2SiMe 3 CH 2OMe CH 2Me O
B.46 H (CH 2) 2SiMe 3 CH 2OCH 2Me CH 2Me O
B.47 H SiMe 2CH 2CHMe 2 Me CF 3 O
Table 5 provides 47 kinds of compounds, wherein R of general formula (Ie) 1, R 3, R 5, R 6With X such as at table 5 definition.
Figure A20048001221800131
Table 6 provides 47 kinds of compounds, wherein R of general formula (If) 1, R 3, R 5, R 6With X such as at table 6 definition.
Figure A20048001221800132
Table 7 provides 47 kinds of compounds, wherein R of general formula (Ig) 1, R 3, R 5, R 6With X such as at table 7 definition.
Table 8 provides 47 kinds of compounds, wherein R of general formula (Ih) 1, R 3, R 5, R 6With X such as at table 8 definition.
Figure A20048001221800134
Table BB represents table 9 (when BB is 9) and expression table 10 (when BB is 10).
Table BB
Compound N o. R 1 R 3 R 5 R 6 X
BB.1 H CH 2SiMe 3 Me CF 3 S
BB.2 H CHMeSiMe 3 Me CF 3 S
BB.3 H (CH 2) 2SiMe 3 Me CF 3 S
BB.4 H CHMeCH 2SiMe 3 Me CF 3 S
BB.5 H CHMeCH 2SiMe 3 Me CF 2H S
Table 9 provides 5 kinds of compounds, wherein R of general formula (Ii) 1, R 3, R 5, R 6With X such as at table 9 definition.
Figure A20048001221800141
Table 10 provides 5 kinds of compounds, wherein R of general formula (Ij) 1, R 3, R 5, R 6With X such as at table 10 definition.
Figure A20048001221800142
Table C represents table 11 (when C is 11), expression table 12 (when C is 12), expression table 13 (when C is 13) and expression table 14 (when C is 14).
Table C
Compound N o. R 1 R 3 R 5 R 6 R 7 X
C.1 H SiMe 3 Me Me H O
C.2 H SiMe 3 Me Me H O
C.3 H CH 2SiMe 3 Me Me Me O
C.4 H CH 2SiMe 3 Me Me CF 3 O
C.5 H CH 2SiMe 3 Me Me H O
C.6 Propargyl CH 2SiMe 3 Me Me CF 3 O
C.7 H CHMeSiMe 3 Me Me CF 3 O
C.8 H CHMeSiMe 3 Me Me Me O
C.9 H CHMeSiMe 3 Me Me Me S
C.10 Propargyl CHMeSiMe 3 Me Me Me O
C.11 The propadiene base CHMeSiMe 3 Me Me Me O
C.12 COMe CHMeSiMe 3 Me Me Me O
C.13 H CHMeSiMe 3 Me Me Me O
C.14 H (CH 2) 2SiMe 3 Me Me CF 3 O
C.15 H (CH 2) 2SiMe 3 H H CF 3 O
C.16 H (CH 2) 2SiMe 3 H H CF 3 S
C.17 Propargyl (CH 2) 2SiMe 3 H H CF 3 O
C.18 H (CH 2) 2SiMe 3 Me Me H O
C.19 H CHMeCH 2SiMe 3 H H CF 3 O
C.20 H CHMeCH 2SiMe 3 H H CF 3 S
C.21 H CHMeCH 2SiMe 3 Me Me Me O
C.22 H CHMeCH 2SiMe 3 H Me CF 3 O
C.23 H CHMeCH 2SiMe 3 Me Me H O
C.24 COMe CHMeCH 2SiMe 3 Me Me H O
C.25 Propargyl CHMeCH 2SiMe 3 Me Me H O
C.26 The propadiene base CHMeCH 2SiMe 3 Me Me H O
C.27 Propargyl CHMeCH 2SiMe 3 Me Me Me O
C.28 The propadiene base CHMeCH 2SiMe 3 Me Me Me O
C.29 COMe CHMeCH 2SiMe 3 Me Me Me O
C.30 COEt CHMeCH 2SiMe 3 Me Me Me O
C.31 H CH 2CHMeSiMe 3 H H CF 3 O
C.32 H CH 2CHMeSiMe 3 H H CF 3 S
C.33 H CH 2CHMeSiMe 3 Me Me Me O
C.34 H CH 2CHMeSiMe 3 H Me CF 3 O
C.35 H CH 2CHMeSiMe 3 Me Me H O
Table 11 provides 35 kinds of compounds, wherein R of general formula (Ik) 1, R 3, R 5, R 6, R 7With X such as at table 11 definition.
Table 12 provides 35 kinds of compounds, wherein R of general formula (Il) 1, R 3, R 5, R 6, R 7With X such as at table 12 definition.
Figure A20048001221800162
Table 13 provides 35 kinds of compounds, wherein R of general formula (Im) 1, R 3, R 5, R 6, R 7With X such as at table 13 definition.
Figure A20048001221800163
Table 14 provides 35 kinds of compounds, wherein R of general formula (In) 1, R 3, R 5, R 6, R 7With X such as at table 14 definition.
Table D represents table 15 (when D is 15), expression table 16 (when D is 16), expression table 17 (when D is 17) and expression table 18 (when D is 18).
Table D
Compound N o. R 1 R 3 R 5 X
D.1 H SiMe 3 Me O
D.2 H SiMe 3 CF 3 O
D.3 H CH 2SiMe 3 Me O
D.4 H CH 2SiMe 3 CF 3 S
D.5 COMe CH 2SiMe 3 Me O
D.6 Propargyl CH 2SiMe 3 Me O
D.7 H CHMeSiMe 3 Me O
D.8 H CHMeSiMe 3 CF 3 O
D.9 H CHMeSiMe 3 CF 3 S
D.10 Propargyl CHMeSiMe 3 Me O
D.11 The propadiene base CHMeSiMe 3 Me O
D.12 COMe CHMeSiMe 3 Me O
D.13 Propargyl CHMeSiMe 3 CF 3 O
D.14 H (CH 2) 2SiMe 3 Me O
D.15 H (CH 2) 2SiMe 3 CF 3 O
D.16 H (CH 2) 2SiMe 3 CF 3 S
D.17 Propargyl (CH 2) 2SiMe 3 Me O
D.18 COMe (CH 2) 2SiMe 3 Me O
D.19 H CHMeCH 2SiMe 3 Me O
D.20 H CHMeCH 2SiMe 3 CF 3 O
D.21 H CHMeCH 2SiMe 3 CF 3 S
D.22 Propargyl CHMeCH 2SiMe 3 Me O
D.23 The propadiene base CHMeCH 2SiMe 3 Me O
D.24 COMe CHMeCH 2SiMe 3 Me O
D.25 Propargyl CHMeCH 2SiMe 3 CF 3 O
D.26 The propadiene base CHMeCH 2SiMe 3 CF 3 O
D.27 COMe CHMeCH 2SiMe 3 CF 3 O
D.28 The propadiene base CHMeCH 2SiMe 3 Me O
D.29 H (CH 2) 3SiMe 3 Me O
D.30 H (CH 2) 3SiMe 3 CF 3 O
D.31 H CH 2CHMeSiMe 3 Me O
D.32 H CH 2CHMeSiMe 3 CF 3 O
Table 15 provides 32 kinds of compounds, wherein R of general formula (Io) 1, R 3, R 5With X such as at table 15 definition.
Table 16 provides 32 kinds of compounds, wherein R of general formula (Ip) 1, R 3, R 5With X such as at table 16 definition.
Figure A20048001221800181
Table 17 provides 32 kinds of compounds, wherein R of general formula (Iq) 1, R 3, R 5With X such as at table 17 definition.
Figure A20048001221800182
Table 18 provides 32 kinds of compounds, wherein R of general formula (Ir) 1, R 3, R 5With X such as at table 18 definition.
Table E represents table 19 (when E is 19), expression table 20 (when E is 20), expression table 21 (when E is 21), expression table 22 (when E is 22), expression table 23 (when E is 23) and expression table 24 (when E is 24).
Table E
Compound N o. R 1 R 3 R 3 X
E.1 H SiMe 3 Cl O
E.2 H SiMe 3 CF 3 O
E.3 H CH 2SiMe 3 Cl O
E.4 H CH 2SiMe 3 Br O
E.5 H CH 2SiMe 3 CF 3 O
E.6 Propargyl CH 2SiMe 3 Cl O
E.7 H CHMeSiMe 3 Cl O
E.8 H CHMeSiMe 3 Br O
E.9 H CHMeSiMe 3 CF 3 O
E.10 Propargyl CHMeSiMe 3 Cl O
E.11 The propadiene base CHMeSiMe 3 Cl O
E.12 COMe CHMeSiMe 3 Cl O
E.13 H CHMeSiMe 3 Cl S
E.14 H (CH 2) 2SiMe 3 Cl O
E.15 H (CH 2) 2SiMe 3 Br O
E.16 H (CH 2) 2SiMe 3 CF 3 O
E.17 Propargyl (CH 2) 2SiMe 3 Cl O
E.18 COMe (CH 2) 2SiMe 3 Cl O
E.19 H CHMeCH 2SiMe 3 Cl O
E.20 H CHMeCH 2SiMe 3 Cl S
E.21 H CHMeCH 2SiMe 3 Br O
E.22 H CHMeCH 2SiMe 3 CF 3 O
E.23 Propargyl CHMeCH 2SiMe 3 Cl O
E.24 The propadiene base CHMeCH 2SiMe 3 Cl O
E.25 COMe CHMeCH 2SiMe 3 Cl O
E.26 Propargyl CHMeCH 2SiMe 3 Br O
E.27 The propadiene base CHMeCH 2SiMe 3 Br O
E.28 COMe CHMeCH 2SiMe 3 Br O
E.29 COCH 2OMe CHMeCH 2SiMe 3 Cl O
E.30 COCH 2OMe CHMeCH 2SiMe 3 CF 3 O
E.31 H (CH 2) 3SiMe 3 Cl O
E.32 H (CH 2) 3SiMe 3 Br O
E.33 H (CH 2) 3SiMe 3 CF 3 O
E.34 H CH 2CHMeSiMe 3 CF 3 O
E.35 H CH 2CHMeSiMe 3 Cl O
E.36 H CH 2CHMeSiMe 3 Br O
E.37 H SiMe 2CH 2Me CF 3 O
E.38 H SiMe 2CH 2Me Cl O
E.39 H SiMe 2CH 2Me Br O
E.40 H SiMe 2CHMe 2 CF 3 O
E.41 H SiMe 2CHMe 2 Cl O
E.42 H SiMe 2CHMe 2 Br O
E.43 H SiMe 2CH 2CH 2Me CF 3 O
E.44 H SiMe 2CH 2CH 2Me Cl O
E.45 H SiMe 2CH 2CH 2Me Br O
Table 19 provides 45 kinds of compounds, wherein R of general formula (Is) 1, R 3, R 5With X such as at table 19 definition.
Table 20 provides 45 kinds of compounds, wherein R of general formula (It) 1, R 3, R 5With X such as at table 20 definition.
Figure A20048001221800202
Table 21 provides 45 kinds of compounds, wherein R of general formula (Iu) 1, R 3, R 5With X such as at table 21 definition.
Table 22 provides 45 kinds of compounds, wherein R of general formula (Iv) 1, R 3, R 5With X such as at table 22 definition.
Figure A20048001221800204
Table 23 provides 45 kinds of compounds, wherein R of general formula (Iw) 1, R 3, R 5With X such as at table 23 definition.
Table 24 provides 45 kinds of compounds, wherein R of general formula (Ix) 1, R 3, R 5With X such as at table 24 definition.
Table 25 provides 10 kinds of compounds, wherein R of general formula (Iy) 7(R 2) rSuch as at table 25 definition.
Figure A20048001221800212
Table 25
Compound N o R 7 (R 2) r
25.1 CF 3 2-Cl
25.2 CF 3 5-Cl
25.3 CF 3 2-Br
25.4 CF 3 5-Br
25.5 CF 2H 2-Cl
25.6 CF 2H 5-Cl
25.7 CF 2H 2-Br
25.8 CF 2H 5-Br
25.9 CF 3 2-Cl.5-Cl
25.10 CF 2H 2-Cl.5-Cl
Table 26 provides 10 kinds of compounds, wherein R of general formula (Iz) 7(R 2) rSuch as at table 26 definition.
Figure A20048001221800221
Table 26
Compound N o R 7 (R 2) r
26.1 CF 3 4-Cl
26.2 CF 3 5-Cl
26.3 CF 3 4-Br
26.4 CF 3 5-Br
26.5 CF 3 4-Cl，5-Cl
26.6 CF 2H 4-Cl
26.7 CF 2H 5-Cl
26.8 CF 2H 4-Br
26.9 CF 2H 5-Br
26.10 CF 2H 4-Cl，5-Cl
Table G represents table 27 (when G is 27) and expression table 28 (when G is 28).
Table G
Compound N o R 3 A
G.1 (CH 2) 2SiMe 3 NH 2
G.2 (CH 2) 2SiMe 3 NHCHO
G.3 (CH 2) 2SiMe 3 NHCOOC(CH 3) 3
G.4 (CH 2) 2SiMe 3 Br
G.5 (CH 2) 2SiMe 3 N＝C(C 6H 5) 2
G.6 (CH 2) 2SiMe 3 NHCOC(CH 3) 3
G.7 CHMeCH 2SiMe 3 NH 2
G.8 CHMeCH 2SiMe 3 NHCHO
G.9 CHMeCH 2SiMe 2 NHCOOC(CH 3) 3
G.10 CHMeCH 2SiMe 3 Br
G.11 CHMeCH 2SiMe 3 N＝C(C 6H 5) 2
G.12 CHMeCH 2SiMe 3 NHCOC(CH 3) 3
G.13 SiMe 3 NHCHO
G.14 SiMe 2CH 2CHMe 2 NHCHO
Table 27 provides 14 kinds of compounds, wherein R of general formula (IIa) 3With A such as at table 27 definition.
Table 28 provides 14 kinds of compounds, wherein R of general formula (IIb) 3With A such as at table 28 definition.
Figure A20048001221800232
In whole specification sheets, temperature is to provide with centigradetemperature; " NMR " refers to NMR (Nuclear Magnetic Resonance) spectrum; MS represents mass spectrum; " % " is wt%, unless corresponding concentration is with other unit representation.
Following abbreviation is used in whole specification sheets:
M.p.=fusing point b.p.=boiling point
The unimodal br=broad peak of s=
The bimodal dd=double doublet of d=
T=triplet q=quartet
M=multiplet ppm=1,000,000/
The two quartet sext=sextets of qd=
Table 29 has shown the selected fusing point of the compound of table 1 to 28, and selected NMR data all use CDCl 3As solvent (except as otherwise noted; If there is the mixture of solvent, then this is expressed as, for example, and (CDCl 3/ d 6-DMSO)) and characteristic properties spectrum signal (not attempting to enumerate whole characterization datas in all cases).
Table 29
Compound N o 1H-NMR data: (quantity of ppm/ multiplicity/Hs) or mass signal m.p./ (℃)
1.14 140-142
1.16 145-147
2.1 121-124
2.2 85-88
2.14 109-111
2.16 140-142
2.72 57-59
2.73 70-71
2.75 80-83
2.76 74-76
2.84 130-133
2.85 (M ++Cl)：420
6.1 88-92
6.14 74-77
6.47 (M ++H)：407
20.1 0.4(s，9)；7.45(m，1)；7.6(d，1)；7.8(d，1)；8.2 (br，1)；8.25(m，1)；8.6(m，1).
20.14 106-110
27.2 (M +-1)：226
27.4 0.0(s，9)；0.8(m，2)；2.6(m，2)；6.9(d，1)；7.2(d，1) 126-128
28.1 0.05(s，9)；0.85(m，2)；2.6(m，2)；3.3(br.s，2)； 6.6(d，1)；6.9(d，1)
28.2 52-53
28.3 0.0(s，9)；0.9(m，2)；1.4(s，9)；2.6(m，2)；6.0(br.s，1)； 7.0(m，2)
Can prepare according to following reaction mechanism according to compound of the present invention, wherein, except as otherwise noted, the definition of each variable is identical with the definition of above compound for general formula (I).
Other method that the compound of many preparation general formulas (I) is arranged.
Method A
The compound of general formula (I) can [wherein A be NH by general formula (IIa) or compound (IIb) 2, NHCH (O), the optional (C that replaces 1-4) alkyl C (=O) NH or the optional (C that replaces 1-4) alkyl OC (and=O) NH] with general formula Het-C (=O) compound of OR ' [wherein R ' is C 1-5Alkyl] in the presence of highly basic [for example NaH or hexamethyldisilazane sodium], in dry polar solvent [preferred THF] and under the temperature between the boiling point of-10 ℃ and solvent [preferably at ambient temperature] react and prepare.People's such as J.Wang [Synlett 2001,1485] article provides similar preparation method's details.When A is NHCH (O), choose (the C that replaces wantonly 1-4) alkyl C (=O) NH or the optional (C that replaces 1-4) alkyl OC (=O) during NH; R wherein 1When the compound that is the general formula (I) of H is needed, then must carry out according to the hydrolysis of following method E.
Method B
The compound of general formula (I) can be by general formula (IIa) or (IIb) [wherein A with above in method A definition identical] compound and general formula Het-C (=O) R " [wherein R " be OH or leavings group, as Cl, Br, F or OC (=O) C 1-4Alkyl] compound react in [preferably at ambient temperature] in the inert organic solvents [as ethyl acetate, methylene dichloride, diox, THF or DMF] and under the temperature between the boiling point at-10 ℃ and solvent and prepare.If R " be OH, then reaction is to carry out under activator [for example BOP-Cl] and two normal alkali [as tertiary amine, inorganic carbonate or supercarbonate] existence.Additionally, if R " be leavings group, then reaction is at least one normal alkali [pyridine for example, tertiary amine, inorganic carbonate or supercarbonate; When A is NHCH (O), choose (the C that replaces wantonly 1-4) alkyl C (=O) NH or the optional (C that replaces 1-4) alkyl OC (=O) during NH, can use stronger alkali, as NaH or hexamethyldisilazane sodium] carry out under existing.If R wherein 1The compound that is the general formula (I) of H is needed, then must carry out according to the hydrolysis of method E.
Method C
The compound of general formula (I) [R wherein 1As defined above but be not hydrogen] can pass through the compound [R wherein of general formula (I) 1Be hydrogen] and general formula R 1-L 1[R wherein 1As defined above but be not hydrogen; And L 1Be leavings group, as Cl, Br, I, sulphonate (for example methanesulfonates or tosylate) or OC (O) C 1-4Alkyl] compound at solvent [as halogenated solvent (for example methylene dichloride), ether, ethyl acetate, DMF or even water (as biphase mixture, choose wantonly at phase-transfer catalyst such as tetrabutylammonium hydrosulfate)] in and at alkali [as tertiary amine, alkaline carbonate, alkali metal hydrocarbonate, alkali metal hydroxide or NaH; Yet work as L 1Be O (CO) C 1-4During alkyl then under the situation that does not have alkali to exist simply heating be possible] in the presence of react and prepare.
Method D
The compound of general formula (I) can be by general formula (IIa) or (IIb) compound of [wherein A is a halogen, preferred bromine or iodine] and general formula Het-C (=O) NH 2Compound exist at elevated temperatures, preferably under reflux state, to react down at Cu (I) compound and aprotonic solvent [as cyclic ethers, for example diox] and prepare.Preferably, CuI is with the amount with respect to the 2%-100%mol/mol of general formula (IIb) compound, forming as part with 1 of material, the 2-diamines is (as 1,2-diamino-cyclohexane or quadrol) and at least one normal alkali (as alkaline carbonate or alkali metal phosphate) existence is down, uses.People's such as A.Klapars article, J.Am.Chem.Soc.123,7727 (2001) provide similar preparation method's details.
Method E
The compound of general formula (I) [R wherein 1Be H] can be by acid or basic hydrolysis method by the compound of general formula (I) [R wherein 1As defined above, but be not H] preparation.For this purpose, this compound is with aqueous acid or alkali, HCl for example, HBr or organic hydroxide [as sodium-, potassium-, calcium-or barium-oxyhydroxide] in suitable solvent, under the temperature of envrionment temperature or rising, handle, this solvent preferably can be miscible with water [for example THF diox, lower alcohol or water itself].
Method F
The compound of general formula (I) [R wherein 1Be H] can be by A be changed into NH 2, the method for describing according to people Tetrahedron Letters such as J.Ahman 38,6363 (1997) for example, and carry out according to method A or method B, preferably there are not the segregation or the purification of intermediate, [wherein A is N=C (C from general formula (IIa) or (IIb) 6H 5) 2] compound.
General formula (IIa) and some compounds (IIb) are early known; General formula (IIa) or novel cpd (IIb) can prepare with following synthesis strategy as described below according to being presented in the following reaction mechanism:
Figure A20048001221800261
Step 1: from carry precursor substituting group PS[it be the protection or the free amido functional group, can in the synthetic last stages, change into NH 2A kind of substituting group, or belong to the precursor group of A defined above] and optional substituting group T[it can change into " Si ", siliceous substituting group, it or R as defined above 3Or R 3Precursor] the appropriate precursors of general formula (III) initial, suitable contain that Si-functional group (" Si ") is introduced in the ortho position and the compound that obtains general formula (IV).
Step 2: if necessary, " Si " group of being introduced is further adjusted, and forms required substituent R in the compound of logical formula V 3
Step 3: precursor is substituent to be gone protection (if necessary) or transforms to obtain substituent A, thereby has obtained general formula (IIa) or compound (IIb).
Step 2 and 3 also can reverse the right order and carry out.
NH 2The example of the protecting group of functional group is a formyl radical, acyl group, halogen acyl group, trialkylsilkl, (replacement) benzyl and alkoxy carbonyl.The more roundup content that can be used for the protection of aromatics among the present invention and heteroaromatic amine and de-protected method can be at T.W.Green andP.G.M.Wuts, and p.503-614 the Protective Groups in Organic Synthesis third edition finds in (Wiley 1999).
The example of precursor substituting group PS is that [both can be converted to NH by reduction or hydrogenation for nitro and azido- 2]; [they can experience to reset and form isocyanic ester for carboxyl and carboxyl deriveding group; for example by Curtius-, Schmidt-or Hofmann-degraded] and halogen and triflate [it is via reacting the NH that the catalytic amination reaction of known palladium is converted to protected or unprotected form with title " Buchwald Hartwig " at present 2, referring to people such as people Tetrahedron Letters 38,6363 (1997) such as for example J.Ahman and X.Huang, Org.Lett.3,3417 (2001) and the reference wherein quoted of ginseng].
NH 2The substituent more comprehensive explanation of useful precursor can be in Rodd ' s Chemistryof Carbon Compounds IIIB and it the volume of augmenting (Elsevier 1974,1981 and 1995) in and at Compendium of Organic Synthetic Methods, 1-9 rolls up in the 7th chapter (Wiley 1971-2000) and finds.
(in the step 1), many synthetic methods are spendable to be incorporated into the thienyl derivative for the functional group that contains Si.Technology people unit in this area will be understood that, according to for step 1 method selected, can use different group T.The substituent example of useful T is halogen (as Cl, Br and I), sulphonate (as triflate, tosylate and methanesulfonates), phosphoric acid ester, C 1-4Alkyl, C 2-4Alkenyl and C 2-4Alkynyl.
The modification that contains functional group's (step 2) of Si is known in the literature.Nearest summary can be at The Chemistry of Organosilicon Compounds, the 1-3 volume, S.Patay, Z.Rappaport and Y.Apeloig compile, Wiley, in 1989,1998,2001 and at Houben-Weyl Science of Synthesis, Organometallics, 4 volumes, I.Fleming compiles, and finds among the G.Thieme 2002.
The example of the modification especially relevant with the present invention is that the hydrogenation of two keys in containing the group of Si or three key (or both) or reduction are (referring to the following examples 3, step B) and the functional group's derivatize on Siliciumatom (for example halogen changes into alkyl or alkoxyl group).
Illustrated that the document example for employed with therefore especially relevant with the preparation of general formula (IIa) and compound (IIb) certain methods of the suitable modification of step 1 in above reaction mechanism comprises Tetrahedron57,5339 (2001); Tetrahedron 56,2985 (2000); Tetrahedron 46,2632 and 2632 (1990); WO94/12505; J.Org.Chem.64,2471 (1999); J.Org.Chem.55,2993 (1990); J.Org.Chem.51,5286 (1986); US4777262; Zh.Obschei Khimi, 52,2767 (1982); ChemicaScripta 18,192 (1981); J.Med.Chem.45,3022 (2002); People such as A.R.M.Allison, Tetrahedron Letters 35,4425 (1994); Tetrahedron Letters 25,81 and 83 (1984); Tetrahedron Letters 30,3735 (1989); Chemistry Letters 2001,386; Chemistry Letters 1990,2175 and the reference of wherein quoting.
Present amazing discovery, the novel cpd of general formula (I) in fact have the opposing of unusual ideal protective plant by fungi and by the activity profile of bacterium and viral caused disease.
The compound of general formula (I) can be used as the activeconstituents of controlling plant insect in agricultural sector and association area.Novel cpd outstanding behaviours excellent active under low rate of application can finely be tolerated by plant and be safe to environment.They have very useful treatment, prevention with systematic performance and be used to protect a lot of cultivated plants.The compound of general formula (I) can be used for suppressing or the various piece of the plant of destroying or plant in the Different Crop that belongs to useful plant on (fruit; flower; leaf; stem; stem tuber; root) goes up the insect that exists, go back those parts of the later growth of protective plant simultaneously and avoid for example infringement of phytopathogenic microorganism.
Also the compound of general formula (I) might be used for plant propagation material as seed dressing, especially seed (fruit, stem tuber, grain) and the transplant processing of (for example paddy rice) of plant, be used for the phytopathogenic fungi that prevents fungal infection and opposing to exist at soil.
In addition, can be in association area according to compound of the present invention, for example in the Industrial materials protection of (comprising the Industrial products that timber is relevant with timber), in Food storage, in hygiene control or the like, be used to control fungi.
The compound of general formula (I) is effective for the phytopathogenic fungi of following type for example: (for example grape grape spore belongs to deuteromycetes, Pyricularia, Helminthosporium, fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (for example Rhizoctonia, hunchbacked spore Rust, Puccinia).In addition, they also have activity for Ascomycetes kind (chain sclerotinia sclerotiorum belongs to, Uncinula for for example Venturia and Erysiphe, Podosphaera) and oomycetes (Oomycetes) class (for example phytophthora, pythium, Plasmopara).Observed outstanding inhibition activity for Powdery Mildew (Erysiphe).In addition, the novel cpd of general formula I for phytopathogenic bacterium and virus (for example for Xanthomonas, Pseudomonas, separate the starch Erwinia and for tobacco mosaic virus (TMV)) be effective.
Within the scope of the present invention, the target farm crop that need protection typically comprise following plants: cereal (wheat, barley, rye, oat, rice, corn, Chinese sorghum and relevant kind); Beet (sugar beet and fodder beet); The operatic circle, drupe and mushy fruit (apple, pears, plum, peach, apricot, cherry, strawberry, raspberry and strawberry); Bean (soya bean, root of Szemao crotalaria, pea, soybean); Oilseed plant (rape, mustard, opium poppy, olive, Sunflower Receptacle, coconut, castor-oil plant, cocoa beans, peanut); Mellon plant (pumpkin, cucumber, muskmelon); Textile fiber plant (cotton, flax, hemp fibre, jute); Citrus fruits (orange tree, lemon, grapefruit, mandarin orange); Vegetables (spinach, lettuce, asparagus, Caulis et Folium Brassicae capitatae, Radix Dauci Sativae, onion, tomato, potato, capsicum); Lauraceae (avocado, Chinese cassia tree, camphor) or plant such as tobacco, nuts, coffee, eggplant, sugarcane, tea, pepper, grape, hops, banana and natural rubber plant, and ornamental plant.
The compound of general formula (I) use with unmodified form or, preferred, the auxiliary agent in being generally used for the preparaton field uses.For this purpose, they can be formulated into emulsifiable concentrate easily in known manner, the paste that can apply, directly sprayable or dilutable solution, dilute emulsion, wettable powder, soluble powder, dust, granula, and encapsulation agent are for example in polymkeric substance.As the type of composition, application process, as spraying, atomizing, dust formation disseminates, and applies or pours, and target of Shi Yonging and fashion trend are selected on the estimation.Composition can also contain other auxiliary agent such as stablizer, antifoams, and viscosity modifier, binding agent or tackifier and fertilizer, micro-nutrients is to body or in order to obtain other auxiliary agent of special-effect.
Suitable carriers and auxiliary agent can be solid or liquid and be the material that can be used in the formulation art, for example natural or regenerated mineral substance, solvent, dispersion agent, wetting agent, tackifier, thickening material, binding agent or fertilizer.Examples of such carriers for example is described among the WO97/33890.
The compound of general formula (I) use with the form of composition usually and with other compound simultaneously or successively be applied on the pending cropping region or plant.These other compounds can be that for example, fertilizer or micro-nutrients are given body or influenced other preparation of plant-growth.They also can be selective herbicide and sterilant, mycocide, sterilant, nematocides, the mixture of invertebrate poison or several these class preparations, the carrier of other in being generally used for formulation art, tensio-active agent or use the promoted type auxiliary agent and use if necessary.
General formula (I) compound can mix with other mycocide, some the time can cause unexpected synergistic activity.Particularly preferred mixing component is an azole, as penta ring azoles, BAY14120, Bitertanol, bromuconazole, cyproconazole Difenoconazole, alkene azoles alcohol, fluorine ring azoles, RH-7592, fluquinconazole, fluzilazol, flutriafol, own azoles alcohol presses down mould azoles, the acid amides azoles, plant the bacterium azoles, metconazole, nitrile bacterium azoles, pefurazoate, Topaze, pyrifenox, prochloraz, Wocosin 50TK, simeconazoles, tebuconazole, fluorine ether azoles, triazolone, triadimenol, fluorine bacterium azoles, triticonazole; Pyrimidyl carbinole is as the phonetic alcohol of three ring benzene, fenarimol, nuarimol; 2-amino-pyrimidine, as bupirimate, dimethirimol, the phonetic phenol of second; Morpholine, such as dodemorph, fenpropidin, fenpropimorph, tridemorph, anilino-pyrimidine, such as cyprodinil, mepanipyrim, phonetic mould amine; Pyroles, as fenpiclonil, fludioxonil; Phenylamide, as M 9834, furalaxyl, metaxanin, R-metaxanin, the spirit of fenfuram ， Evil frost; Benzimidazoles, as F-1991, derosal, two ethoxy imidazoles become, fuberidazole, thiabendazole; The dicarboximide class, as chlozolinate, dichlozolin, RP-26019, myclozolin, procymidone, Vinclozoline; Carboxyl acylamide, as carboxin, first furan anilide, fultolanil, mebenil, oxycarboxin, thifluzamide; Dodine, fixed as seed-grain, dodine, biguanide spicy acid salt; Strobilurines, as Azoxystrobin, kresoxim-methyl, SSF 126, SSF-129, oxime bacterium ester, picoxystrobin, BAS500F (proposal name pyraclostrobin), BAS520; Dithiocarbamate, as Karbam Black, zinc manganese ethylenebisdithiocarbamate, maneb, Carbatene, zinc 1,2-propylene bisdithiocarbamate, thiram, zineb, ziram; N-monochloromethyl sulfo-tetrahydric phthalimide class, as Difolatan, Vancide 89, dichlofluanid, fluoromide, Phaltan, Tolylfluanid; The Cu-compound, as Bordeaux mixture, copper hydroxide, Cupravit, copper sulfate, copper sandoz, mancopper, oxinecopper; Nitrophenol derivative, as dinitrocrotonate, a nitre phthalein isopropyl ester; Organic radical-p-derivative, as Hinosan, iprobenphos, isoprothiolane, the sick phosphorus of rice, the phonetic phosphorus of pyrrole, tolclofosmethyl; Various other materials are as Acibenzolar-S-methyl, anilazine, benthiavalicarb, miewensu-S, mite is gone out suddenly, chloroneb, m-tetrachlorophthalodinitrile, cyflufenamid, frost urea cyanogen, dichlone, diclomezine, dicloran, the mould prestige of second, dimethomorph, SYP-LI90 (proposal name: flumorph), the Delan, Guardian, etridiazole ， oxazole bacterium ketone, fenamidone, zarilamid, fentin hydroxide, ferimzone, fluazinam, flusulfamide, fenhexamid, ethyl phosphine-Lv ， hymexazos, iprovalicarb, IKF-916 (cyazofamid), kasugamycin, methasulfocarb, metrafenone, nicobifen, pencycuron, phthalide, Polyoxin, allyl isothiazole, propionic acid amide, pyroquilon, benzene oxygen quinoline, quintozene, Sulfur, azoles bacterium piperazine, tricyclazole, triforine, validamycin, zoxamide (RH7281).
Use the compound of general formula (I), or the preferred method of using the agricultural chemical composition that contains at least a this compound is a foliage applying.Frequency of using and amount of application will depend on the hazard level of the infringement that corresponding pathogenic agent causes.Yet the compound of general formula I also can be by soaking the growth place of plant with liquid preparation, or by for example using this compound to soil (soil application) with particle shape with solid form, infiltrate this plant (systemic action) through soil by root.In rice crop, these granulas can be applied in the rice field of irrigation water.The compound of general formula I also can enough mycocide liquid preparation dipping seed stem tuber or with solid-state preparaton coating they are applied to seed (coating).
Preparation [compound compositions that promptly contains general formula (I)] and, if desired, solid or liquid adjuvants, be in known manner, typically by for example solvent, solid carrier and optional surface active cpd (tensio-active agent) thoroughly mix and/or grind and prepare with compound and filler.
This agrochemical formulation contains 0.1 to 99% (weight) usually, the compound of the general formula I of preferred 0.1 to 95% (weight), 99.9 to 1% (weight), the solid of preferred 99.8 to 5% (weight) or liquid adjuvants, and 0 to 25wt%, preferred 0.1 to 25wt% tensio-active agent.
The ideal amount of application is the activeconstituents of 5g-2kg (a.i.)/per hectare (ha) normally, preferred 10g-1kg a.i./ha, most preferably 20g-600g a.i./ha.When the seed wetting agent, suitable dosage is the seed of the active substance of 10mg-1g/every kilogram.
Though preferably commerical prod is mixed with enriched material, the final user uses the preparaton of dilution usually.
Following non-restrictive example is used for illustrating in more detail foregoing invention.
Embodiment 1
Present embodiment illustrates the preparation of compound N o27.2 and 1.14.
Steps A
With 4-bromo-3-thiophene carboxylic acid (according to J.Heterocyclic Chem.1999,36,761 make) (2g), triethylamine (1.5g) and acetone (15ml) is cooled to-10 ℃, adds Vinyl chloroformate (1.15g) under this temperature.Reaction mixture at room temperature stirred 2 hours, was cooled to 0 ℃ and also lentamente the sodiumazide (0.97g) in water-soluble (5ml) was added.After at room temperature 2 hours, mixture filters, and evaporates acetone, and residue dilutes with methylene dichloride, washes with water, dried over sodium sulfate.Evaporating solvent obtains the linen powder of 1.7g, and it is directly used in next step.
Step B:4-bromo-3-thiophene-methane amide
(30ml) is heated to backflow with formic acid, and the product that will be dissolved in the steps A in the formic acid (10ml) then drips into.Mixture heating up 30 minutes, up to gas select stop till.Vacuum is removed formic acid removal, then this residue is washed with the ethyl acetate dilution with saturated sodium bicarbonate solution.In the drying of solvent with after removing, product separates (hexane: ethyl acetate 2: 1), obtain the product (m.p.108-110 ℃) of 1.1g at the enterprising circumstances in which people get things ready for a trip layer of silica gel.
Step C:4-(trimethyl silyl) ethynyl-3-thenoyl amine
Product (1g), tributyl stannyl (trimethyl silyl) acetylene (2.16g) and (four) triphenylphosphine palladium (0.28g) of step B are joined in the degassed toluene (20ml), and mixture heated 16 hours in nitrogen atmosphere under reflux state.After cooling, except that desolvating and this residue being separated (hexane: ethyl acetate 3: 1) at the enterprising circumstances in which people get things ready for a trip layer of silica gel.From hexane, after the crystallization, obtained 4-(trimethyl silyl) ethynyl-3-thenoyl amine (m.p.90-94 ℃) of 0.3g continuously at three times.
Step D: compound N o27.2
The product that obtains from step C (0.3g) is gone up hydrogenation at Pd/ charcoal (10%) in THF, till the hydrogen absorption stops.Evaporating solvent obtains compound N o27.2 (0.28g).
Step e: compound N o1.14
Sodium hydride (0.06g) is dispersed among the THF (10ml), and mixture cools off with ice bath.The compound N o27.2 (0.14g) that will be dissolved among the THF (5ml) adds, and gained suspension stirred 30 minutes down at 0-5 ℃.Under this temperature, add N-methyl-3-trifluoromethyl-4-chloroformyl-pyrazoles (0.2g), reaction mixture at room temperature stirs and spends the night.Reaction mixture is poured in the water product ethyl acetate extraction.Organic phase washes with water, and is dry on sodium sulfate, evaporating solvent.This residue is handled in methyl alcohol with excessive sodium methylate, and then, after at room temperature 15 minutes, mixture is with the HCl acidifying and use ethyl acetate extraction.With saturated sodium bicarbonate washing, dried over sodium sulfate and remove desolvate after, this residue separates at the enterprising circumstances in which people get things ready for a trip layer of silica gel that (hexane: recrystallization ethyl acetate 1: 1) and from hexane obtains compound N o1.14 (0.072g).
Embodiment 2
Present embodiment illustrates compound N o28.2,2.85 and 2.16 preparation.
Steps A: 2-iodo-3-formamido group thiophene
3-formamido group-thiophene (21g), N-iodine succinimide (37.2g) and tetrachloromethane (200ml) were refluxed 3 hours together.Reaction mixture is cooled to 0-5 ℃, filters then.Solids is dissolved in the ethyl acetate, with sodium hydroxide (10% solution) washing three times, with salt water washing and dry on sodium sulfate.Evaporating solvent with residue is separated in the enterprising circumstances in which people get things ready for a trip of silica gel spectrum (hexane: ethyl acetate 2: 1) can obtain the product (m.p.100-107 ℃) of 37.8g, it is directly used among the step B.
Step B:2-(trimethyl silyl ethynyl)-3-formamido group-thiophene.
The product (37.8g) of steps A is dissolved in the mixture of DMF (500ml) and triethylamine (150ml).In nitrogen atmosphere, add two (triphenylphosphinyl) palladiums (5.2g) of CuI (1.4g) and dichloro, after 15 minutes, drip ethynyl three silicomethanes (22g).After 6 hours, solvent removed in vacuo, residue separates (hexane: ethyl acetate 2: 1) obtain 2-(trimethyl silyl ethynyl)-3-formamido group-thiophene (31.78g) (m.p.87-93 ℃) at the enterprising circumstances in which people get things ready for a trip layer of silica gel.
Step C: compound N o28.2
Product (31.78g) hydrogenation on Pd (30g)/charcoal in THF with step B according to carrying out for the described method of compound N o27.2, obtains compound N o28.2 (26.3g) in the step D of embodiment 1.
Step D: compound N o2.85 and 2.16
Compound 28.2 (23.4g) with sodium hydride (7.4g) and N-methyl-chloroformyl pyrazoles of 3-difluoromethyl-4-(30g), according in method described in the step e of embodiment 1, is handled and formed reaction mixture.
In order to prepare compound N o2.85,1/10th of reaction mixture is poured in the water, and uses ethyl acetate extraction.Organic phase washes with water, dried over sodium sulfate, evaporating solvent.Residue separates (hexane: ethyl acetate 1: 1), obtain compound N o2.85 by removing to desolvate at the enterprising circumstances in which people get things ready for a trip layer of silica gel; Output: 0.6g.
In order to prepare compound N o2.16, reaction mixture is handled and is stirred and spend the night with sodium hydroxide (the 10%w/w aqueous solution of 100ml).Reaction mixture dilutes with saturated ammonium chloride solution, uses ethyl acetate extraction, dried over sodium sulfate and under reduced pressure remove and desolvate.This residue hexane: toluene (3: 1) recrystallization obtains compound N o2.16 (27.7g).
Embodiment 3
Present embodiment illustrates the preparation of compound N o6.1.
Steps A
Under-70 ℃, the 3-formamido group thiophene (Bull.Soc.Chim.Fr.1976,151) that will be dissolved among the anhydrous THF (20ml) (2g) is added drop-wise in the solution of freshly prepd diisopropylamino lithium (0.035mol) in THF (35ml).Solution rises to-20 ℃ and stir 30 minutes, and then is cooled to-70 ℃, adds trimethylchlorosilane (5ml).After stirring other 1 hour under this temperature, mixture rises to room temperature lentamente and stirred 4 hours.Use the saturated ammonium chloride solution cancellation, use ethyl acetate extraction, dried over sodium sulfate is except that desolvating and separating (hexane: ethyl acetate 2: 1) can obtain 2-trimethyl silyl-3-formamido group thiophene (1.2g) (m.p.74-76 ℃) in the enterprising circumstances in which people get things ready for a trip spectrum of silica gel.
Step B: compound N o6.1
By use from above-mentioned intermediate (0.4g), sodium hydride (0.13g), the 2-methyl-4-trifluoromethyl-5-of steps A chloroformyl-thiazole (0.69g) and sodium hydroxide solution (the 2mol solution of 1.5ml), carry out the preparation of compound N o6.1 according to the step D of embodiment 2.Chromatographic separation on silica gel (hexane: ethyl acetate 4: 1) obtain compound N o6.1 (0.29g).
The example of formulations of general formula (I) compound
The preparation of preparation compound of Formula I such as the method for missible oil, solution, granula, pulvis and wettable powder are described among the WO97/33890.
Biological Examples: fungicidal action
Embodiment B-1: for Puccinia recondita (Puccinia recondita)/wheat ( Brown mould on the wheat) activity
1 the length of time in week wheat plant cv.Arina handle in the spray chamber with the test compound of preparing (0.02% activeconstituents).After using one day, wheat plant is by the spore suspension (1 * 10 of spraying on test plant 5Uredospore/ml) inoculate.After 2 days incubation periods under 20 ℃ and the 95%r.h., plant kept 8 days under 20 ℃ and 60%r.h in the greenhouse.Estimated later sickness rate at postvaccinal 10 days.
Each of dying in the usefulness compound 1.14,1.16,2.1,2.2,2.14,2.16,2.75,2.76,2.84,2.85 and 6.01 all almost entirely prevents to infect (0-5% infringement).
Embodiment B-2: for apple mildew handle coccus (Podosphaera leucotricha) The effect of (Powdery Mildew on the apple)
5 the length of time in week apple seedling cv.McIntosh handle in the spray chamber with the test compound of preparing (0.002% activeconstituents).After using one day, the plant that the apple plant has infectd apple mildew by shake on test plant inoculates.Under 22 ℃ and 60%r.h., under the illumination program of 14/10 hour (illumination/dark), after 12 days the incubation period, estimate sickness rate.
Compound 2.14 and 2.16 respectively demonstrates intensive effect (＜20% infects).
Embodiment B-3: for venturia inaequalis (Venluria inaequalis) (on the apple Scar) effect
4 the length of time in week apple sapling cv.McIntosh handle in the spray chamber with the test compound of preparing (0.02% activeconstituents).After using one day, the apple plant is by the spore suspension (4 * 10 of spraying on test plant 5Conidium/ml) inoculate.After 4 days incubation periods under 21 ℃ and the 95%r.h., plant was placed 4 days under 21 ℃ and 60%r.h in the greenhouse.Under 21 ℃ and 95%r.h., estimated sickness rate after the incubation period in other 4 days.
Compound 2.14 and 2.16 respectively demonstrates intensive effect (＜20% infects).
Embodiment B-4: for Powdery Mildew (Erysiphe graminis)/barley (on barley Powdery mildew) effect
1 the length of time in week barley strain cv.Express handle in the spray chamber with the test compound of preparing (0.02% activeconstituents).After using one day, the plant that barley strain has been infectd Powdery Mildew by shake on test plant inoculates.After 6 days the incubation period under 20 ℃/18 ℃ (daytime/night) and 60% relative humidity in the greenhouse, estimate sickness rate.
Compound 1.14,1.16,2.14,2.16,2.75,2.76 and 2.85 demonstrate intensive effect (＜20% infects) separately.
Embodiment B-5: for tomato Botrytis cinerea (Botrytis cinerea) (on tomato Grape grape spore belong to) effect
4 the length of time in week tomato plant cv.Roter Gnom handle in the spray chamber with the test compound of preparing (0.02% activeconstituents).Using two days later, tomato plant is by the spore suspension (1 * 10 of spraying on the test plant 5Conidium/ml) inoculate.In the growth room, under 20 ℃ and 95% relative humidity, after 4 days the incubation period, estimate sickness rate.
Compound 1.14,1.16,2.14,2.16,2.75,2.76 and 2.85 demonstrate intensive effect (＜20% sickness rate) separately.
Embodiment B-6 for the withered septoria musiva of wheat grain husk (Septoria nodorum) (at wheat On spot blight) activity
1 the length of time in week wheat plant cv.Arina handle in the spray chamber with the test compound of preparing (0.02% activeconstituents).After using one day, wheat plant is by the spore suspension (5 * 10 of spraying on test plant 5Conidium/ml) inoculate.After 1 day incubation period under 20 ℃ and the 95%r.h., plant was placed 10 days under 20 ℃ and 60%r.h in the greenhouse.Estimated later sickness rate at postvaccinal 11 days.
Compound 1.14,1.16,2.14,2.16,2.75,2.76 and 2.85 demonstrate good activity (＜60% sickness rate) separately in this test.

Claims (10)

1. the compound of general formula (I):
Wherein Het contains one to three heteroatomic 5-or 6-unit heterocycle, and this heteroatoms is selected from oxygen, nitrogen and sulphur independently of one another, and described ring is by one to three radicals R 4Replace; R 1Be hydrogen, the optional (C that replaces 1-4) alkyl, formyl radical, the optional (C that replaces 1-4) alkyl C (=O), the optional (C that replaces 1-4) alkyl C (=O) O, the optional (C that replaces 1-4) alkoxyl group (C 1-4) alkyl, the optional allyl group that replaces, optional propargyl that replaces or the optional propadiene base that replaces; Each R 2Be halogen independently, the optional (C that replaces 1-4) alkyl, the optional (C that replaces 1-4) alkoxyl group or the optional (C that replaces 1-4) alkoxyl group (C 1-4) alkyl; R 3Be on 2 or 4 of thiphene ring and be to contain three to 13 carbon atoms and at least one Siliciumatom and one to three optional heteroatomic organic group, heteroatoms is selected from oxygen, nitrogen and sulphur independently of one another and is randomly replaced by one to four halogen atom of selecting independently; Each R 4Be halogen independently, C 1-3Alkyl, C 1-3Haloalkyl, C 1-3Alkoxyl group (C 1-3) alkyl or cyano group; R is 0,1 or 2; With X be O or S; Or its N-oxide compound.
2. the compound of the defined general formula of claim 1 (I), precondition are that the Het ring is not a 1,2,3-triazoles when X is O.
3. the compound of defined general formula (I), wherein R in the claim 1 or 2 1Be hydrogen, propargyl, propadiene base, formyl radical, CH 3C (=O), C 2H 5C (=O) or CH 3OCH 2C (=O).
4. the compound of defined general formula (I), wherein each R in the claim 1,2 or 3 2Be independently selected from halogen, methyl, trifluoromethyl and trifluoromethoxy.
5. claim 1, the compound of defined general formula (I) in 2,3 or 4, wherein Het is a pyrazolyl, pyrryl, thienyl, furyl, thiazolyl, isothiazolyl ， oxazolyl ， isoxazolyl, triazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, 5,6-dihydro pyranyl or 5,6-dihydro-1,4-oxathiin base separately can be by one to three radicals R 4Replace.
6. defined general formula (I) compound, wherein R in the claim 1,2,3,4 or 5 3Be to contain three to 13 carbon atoms and at least one Siliciumatom and optional one to three heteroatomic aliphatics, saturated or undersaturated group, it is randomly replaced by one to four halogen atom of selecting independently, and described heteroatoms is selected from oxygen, nitrogen and sulphur independently of one another.
7. claim 1, the compound of defined general formula (I) in 2,3,4,5 or 6, wherein X is an oxygen.
8. general formula (IIa) or compound (IIb)
Figure A2004800122180003C1
R wherein 3Be SiMe 2Et, SiMe 2CHMe 2, SiMe 2CH 2CHMe 2, SiMe 2CH 2CMe 3, CH=CHSiMe 3, (CH 2) 2SiMe 3, (CH 2) 2SiMe 2Et, (CH 2) 2SiMe 2CHMe 2, (CH 2) 2SiMe 2CMe 3, (CH 2) 2SiMe 2CH 2CHMe 2, CHMeCH 2SiMe 3, CHMeCH 2SiMe 2Et, CH 2CHMeSiMe 3, CMe 2CH 2SiMe 3, (CH 2) 3SiMe 3With A be NH 2, NHCH (O), the optional (C that replaces 1-4) alkyl C (=O) NH, the optional (C that replaces 1-4) alkyl OC (=O) NH, halogen or N=C (C 6H 5) 2Precondition is to work as R 3Be SiMe 3The time A be not halogen.
9. controlling microbial and prevent plant by its invasion and attack and the composition that infects, wherein activeconstituents is the compound according to the desired general formula of claim (I) with suitable carrier.
Control or prevent cultivated plant by the method for phytopathogenic microbial infection, comprise and will be applied to various piece of plant, plant or their growth place according to the compound of the desired general formula of claim 1 (I) or according to the desired composition of claim 9.
CN 200480012218 2003-05-07 2004-04-21 3-carbonylaminothiophenes and their use as fungicides Pending CN1784399A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102203086A (en) * 2008-09-03 2011-09-28 拜尔农作物科学股份公司 Thienylamino pyrimidines for use as fungicides
CN109374806A (en) * 2018-11-07 2019-02-22 南京明捷生物医药检测有限公司 A kind of method of 3- aminothiophene content in measurement bulk pharmaceutical chemicals

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102203086A (en) * 2008-09-03 2011-09-28 拜尔农作物科学股份公司 Thienylamino pyrimidines for use as fungicides
CN109374806A (en) * 2018-11-07 2019-02-22 南京明捷生物医药检测有限公司 A kind of method of 3- aminothiophene content in measurement bulk pharmaceutical chemicals

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