CN1829717A - Substituted pyrazolopyrimidines, methods for the production thereof, use of the same for controlling pathogenic fungi, and agents containing said compounds - Google Patents

Substituted pyrazolopyrimidines, methods for the production thereof, use of the same for controlling pathogenic fungi, and agents containing said compounds Download PDF

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CN1829717A
CN1829717A CN 200480015691 CN200480015691A CN1829717A CN 1829717 A CN1829717 A CN 1829717A CN 200480015691 CN200480015691 CN 200480015691 CN 200480015691 A CN200480015691 A CN 200480015691A CN 1829717 A CN1829717 A CN 1829717A
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alkyl
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methyl
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O·瓦格纳
T·格罗特
C·布莱特纳
M·格韦尔
W·格拉门奥斯
A·吉普瑟
B·米勒
J·莱茵海默
P·舍费尔
F·席韦克
A·施沃格勒尔
J·托尔莫艾布拉斯科
A·埃克斯
J·B·斯皮克曼
M·拉克
R·施蒂尔勒
M·舍勒尔
U·舍夫尔
S·施特拉特曼
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Abstract

The invention relates to substituted pyrazolopyrimidines of formula (I) wherein the substituents have the following designations: L represents halogen, alkyl, halogenalkyl, alkenyl, alkoxy, amino, NHR, NR2, cyano, S(=O)nA<1> or C(=O)A<2>, R representing alkyl or alkylcarbonyl, A<1> representing hydrogen, hydroxy, alkyl, alkylamino or dialkylamino, n representing 0, 1 or 2, and A<2> representing alkenyl, alkoxy, halogenalkoxy or one of the groups cited for A<1>; m represents 0 or 1 to 5; R<1> represents alkyl, halogenalkyl, cycloalkyl, halogencycloalkyl, alkenyl, alkadienyl, halogenalkenyl, cycloalkenyl, alkinyl, halogenalkinyl or cycloalkinyl, phenyl, naphthyl, or a five-membered to ten-membered saturated, partially unsaturated or aromatic heterocycle containing between one and four heteroatoms from the group O, N or S; and R<2> represents hydrogen or one of the groups cited for R<1>. Together with the nitrogen atom to which they are bonded, R<1> and R<2> can form a five-membered to six-membered ring that can be interrupted by an atom from the groups O, N and S, and R<1> and/or R<2> can also be substituted according to the description. Furthermore, in formula (I): X represents halogen, cyano, OH, alkyl, alkoxy or halogenalkoxy; Y represents a five-membered to ten-membered saturated, partially unsaturated or aromatic heterocycle according to the description, or a group X or another group according to the description; p represents 1 or 2, the groups Y being potentially different when p = 2; and p represents 0, when X is according to the description. The invention also relates to methods and intermediate products for producing said compounds, agents containing the same, and the use thereof for controlling phytopathogenic fungi.

Description

The pyrazolopyrimidine that replaces, its production method and purposes in the control harmful fungoid and the reagent that comprises described compound
The present invention relates to substituted pyrazolecarboxylic and the pyrimidine of formula I:
Figure A20048001569100081
Wherein substituting group is following defines:
L is halogen, C independently of each other 1-C 6Alkyl, C 2-C 6Alkenyl, C 1-C 6Haloalkyl, C 1-C 6Alkoxyl group, amino, NHR, NR 2, cyano group, S (=O) nA 1Or C (=O) A 2,
R is C 1-C 8Alkyl or C 1-C 8Alkyl-carbonyl;
A 1Be hydrogen, hydroxyl, C 1-C 8Alkyl, C 1-C 8Alkylamino or two (C 1-C 8Alkyl) amino;
N is 0,1 or 2;
A 2Be C 2-C 8Alkenyl, C 1-C 8Alkoxyl group, C 1-C 6Halogenated alkoxy or at A 1One of following group of being mentioned;
M is 0 or 1,2,3,4 or 5;
R 1Be C 1-C 8Alkyl, C 1-C 8Haloalkyl, C 3-C 6Cycloalkyl, C 3-C 6Halogenated cycloalkyl, C 2-C 8Alkenyl, C 4-C 10Alkadienyl, C 2-C 8Halogenated alkenyl, C 3-C 6Cycloalkenyl group, C 2-C 8Alkynyl, C 2-C 8Halo alkynyl or C 3-C 6Cycloalkynyl radical, phenyl, naphthyl or contain 1-4 and be selected from that the heteroatomic 5-10 unit of O, N and S is saturated, part is unsaturated or aromatic heterocycle;
R 2For hydrogen or at R 1One of following group of being mentioned;
R 1And R 2Can also form the atomic separation that can be selected from O, N and S and/or can have one or more halogen, C of being selected from the nitrogen-atoms that they connected 1-C 6Alkyl, C 1-C 6Haloalkyl and oxygen base-C 1-C 3The substituting group of alkylene oxide group or wherein nitrogen-atoms and adjacent carbons can be by C 1-C 45 or 6 yuan of rings that alkylidene chain connects;
R wherein 1And/or R 2Can be by 1-4 identical or different radicals R aReplace:
R aBe halogen, cyano group, nitro, hydroxyl, C 1-C 6Alkyl, C 1-C 6Haloalkyl, C 1-C 6Alkyl-carbonyl, C 3-C 6Cycloalkyl, C 1-C 6Alkoxyl group, C 1-C 6Halogenated alkoxy, C 1-C 6Carbalkoxy, C 1-C 6Alkylthio, C 1-C 6Alkylamino, two C 1-C 6Alkylamino, C 2-C 6Alkenyl, C 2-C 6Alkenyloxy, C 3-C 6Alkynyloxy group, C 3-C 6Cycloalkyl, phenyl, naphthyl, or contain 1-4 and be selected from that the heteroatomic 5-10 unit of O, N and S is saturated, part is unsaturated or aromatic heterocycle,
Wherein these aliphatic series, alicyclic or aromatic group itself can maybe can be had 1-3 radicals R by halo partially or completely b:
R bBe halogen, cyano group, nitro, hydroxyl, sulfydryl, amino, carboxyl, aminocarboxyl, thiocarbamoyl, alkyl, haloalkyl, alkenyl, alkenyloxy, alkynyloxy group, alkoxyl group, halogenated alkoxy, alkylthio, alkylamino, dialkyl amido, formyl radical, alkyl-carbonyl, alkyl sulphonyl, alkyl sulphinyl (alkylsulfoxyl), carbalkoxy, alkyl carbonyl oxy, alkyl amino-carbonyl, dialkyl amino carbonyl, the alkylamino thiocarbonyl group, the dialkyl amido thiocarbonyl group, wherein the alkyl in these groups contains 1-6 carbon atom and the alkenyl of mentioning or alkynyl and contains 2-8 carbon atom in these groups;
And/or 1-3 following groups:
Cycloalkyl, cycloalkyloxy, heterocyclic radical, heterocyclic oxy group, wherein the ring-type system contains 3-10 ring members; Aryl, aryloxy, arylthio, aryl-C 1-C 6Alkoxyl group, aryl-C 1-C 6Alkyl, heteroaryl, heteroaryloxy, heteroarylthio, wherein aryl preferably contains 6-10 ring members and heteroaryl contains 5 or 6 ring memberses, and wherein the ring-type system can or can be replaced by alkyl or haloalkyl by halo partially or completely;
X is halogen, cyano group, OH, C 1-C 4Alkyl, C 1-C 4Alkoxyl group or C 1-C 2Halogenated alkoxy,
Y contains 1-4 to be selected from that the heteroatomic 5-10 unit of O, N and S is saturated, part is unsaturated or aromatic heterocycle, or one of the group of under X, mentioning (this group can be by 1-4 identical or different radicals R aReplace), nitro, amino ,-CHO ,-NHCO-NH-C 1-C 6Alkyl ,-NHCO-O-C 1-C 6Alkyl ,-CO-NH 2
P is 1 or 2, and wherein as if p=2, then group Y can be different;
If radicals X is cyano group, C 1-C 4Alkyl, C 1-C 4Alkoxyl group or C 1-C 4Halogenated alkoxy, then p is 0.
In addition, the present invention relates to prepare the method and the intermediate of these compounds, the composition that comprises them and their purposes in control plant-pathogenic harmful fungoid.
Pyrazolopyrimidine is known by US 4 567 263, WO 96/35690 and US 5 817 663 with general fashion.WO 02/48151 discloses 6-phenylpyrazole and the pyrimidine that phenyl is wherein replaced by 1-4 group.EP-A 71 792 has described can be at 2 and/or 3 substituted 7-amino-pyrazols and pyrimidine.JP 2002-308878A and JP 2002-308879A disclose at 2 substituted pyrazole and pyrimidine.Knownly can be used to prevent and treat harmful fungoid at the compound described in these publications.
Yet the effect of known compound is also unsatisfactory in many cases.The purpose of this invention is to provide compound with improved activity and/or wideer activity profile.
We find that this purpose is realized by the defined compound of beginning.In addition, we have found to prepare the method and the intermediate of these compounds, the composition that comprises them and use Compound I methods for fighting harmful mushrooms.
Compound of the present invention with by EP-A 71 792 compound known, the compound described in the WO 02/48151 and be replacement among replacement, pyrazolopyrimidine skeleton 2 and/or 3 of 7-amino respectively by JP 2002-308878A and JP 2002-308879A compound known different and 5 in replacement.
Formula I compound and known compound compare harmful fungoid and have more high reactivity.
The compounds of this invention can obtain by different approaches.Usually, they are obtained under by WO 02/48151 known condition by the amino-pyrazol-derivatives II and the 2-phenylmalonic acid ester III that replace.In formula III, R is C 1-C 4Alkyl, especially methyl or ethyl.Some pyrazoles II are commercially available or can prepare under common known condition.The preparation of raw material II I is advantageously carried out under by EP-A 10 02 788 known conditions.
Make obtain in this way 5, the reaction of 7-dihydroxyl-6-phenylpyrazole and pyrimidines i V and halide reagent [HAL] obtains the 7-halo pyrazolopyrimidine of formula V.
In formula IV and V, the definition of variable is a halogen atom corresponding to formula I and " Hal ", preferred bromine or chlorine.
Preferred chlorination or bromide reagent such as phosphoryl bromide, phosphoryl chloride, thionyl chloride, thionyl bromide or sulfuryl chloride.This reaction can be carried out in the solvent existence or not.Temperature of reaction commonly used is 0-150 ℃, or preferred 80-125 ℃.
X is the pyrazolopyrimidine of the formula I of halogen to formula V compound by obtaining wherein with the reaction of formula VI amine.They are preferred themes of the present invention.The pyrazolopyrimidine that group Y is arranged particularly preferably in 3 bit strips.
Figure A20048001569100112
The reaction of V and amine VI is advantageously at 0-70 ℃, carries out under preferred 10-35 ℃, preferably carries out described solvent such as ethers, for example diox, ether or especially tetrahydrofuran (THF) in the presence of inert solvent; Halogenated hydrocarbon is as methylene dichloride; And aromatic hydrocarbons, as toluene [referring to WO 98/46608; WO 02/48151].
Preferred alkali, for example tertiary amine such as the triethylamine, or mineral alkali such as salt of wormwood of using; The amine of excessive formula IV can also be used as alkali.
The formula I compound that group Y is arranged at 3 bit strips is advantageously by 5, and 7-dihydroxyl pyrazolopyrimidine VII is by obtaining with the halide reagent reaction.The three halo pyrazolopyrimidines of the formula VIII that can obtain by this way are useful intermediates of preparation I compound.
In formula VII and VIII, the definition of variable is a halogen atom corresponding to formula I and " Hal ", preferred bromine or chlorine.Halogenation is similar to compound IV and carries out.
By with amine VI condensation, can obtain Compound I .A by compound VIII under these conditions.
They are particularly preferred theme of the present invention.Compound I .A also is the useful intermediates of other Compound I of preparation.
5 of formula II, 7-dihydroxyl pyrazolopyrimidine is known by WO 02/48151.The amine of some formula VI is known, can commercially maybe can prepare by currently known methods.
Be cyano group, C wherein at 5 X 1-C 6Alkoxyl group or C 1-C 2The Compound I of halogenated alkoxy (formula I.B) can advantageous manner by the feedstock production of approach as follows by formula I.A.
Figure A20048001569100122
Make Compound I (X=Hal) and compound M-X ' (formula IX) reaction, obtain Compound I .B.Depend on radicals X to be introduced ' implication, Compound I X is inorganic cyanide or alkoxide.This reaction is advantageously carried out in the presence of inert solvent.In formula IX, positively charged ion M is not too important; For the reason of reality, usually preferred ammonium, tetra-allkylammonium or basic metal or alkaline earth salt.Temperature of reaction is generally 0-120 ℃, preferred 10-40 ℃ [referring to J.Heterocycl.Chem. 12(1975), 861-863 page or leaf].
Suitable solvent comprises ethers such as diox, ether, preferred tetrahydrofuran (THF), halogenated hydrocarbon such as methylene dichloride and aromatic hydrocarbons such as toluene.
Wherein X is C 1-C 4Alkyl or C 1-C 4The Compound I of haloalkyl (formula I.C) can be the formula I compound of halogen by X wherein advantageously by following approach.
Wherein X " is C 1-C 4The formula I.C compound of alkyl can be by obtaining the 5-halo triazolo pyrimidine of formula IV.A and the organometallic reagent coupling of formula X.In an embodiment of this method, this is reflected at transition metal-catalyzed, as carrying out under Ni or the Pd catalysis.
Figure A20048001569100123
In formula X, X " is C 1-C 4Alkyl and M are the metal ion of Y valency, as B, Zn or Sn.This reaction for example is similar to following method and carries out: J.Chem.Soc.Perkin Trans.I, and 1187 (1994), the same, 1,2345 (1996); WO 99/41255; Aust.J.Chem., 43(1990), 733; J.Org.Chem., 43(1978), 358; J.Chem.Soc.Chem.Commun. (1979), 866; Tetrahedron Lett., 34(1993), 8267; It is the same, 33(1992), 413.
Wherein X is C 1-C 4Alkyl or C 1-C 4The formula I compound of haloalkyl (formula I.C) also can advantageously obtain by following route of synthesis:
5-alkyl-7-hydroxyl-6-phenylpyrazole and pyrimidine XII are obtained by the amino-pyrazol-derivatives II and the ketone ester XI that replace.In formula XI, R is C 1-C 4Alkyl, especially methyl or ethyl, and X " are C 1-C 4Alkyl.Wherein the X "=CH that use is easy to obtain 32-phenyl acetylacetic ester XIa, obtain 5-methyl-7-hydroxyl-6-phenylpyrazole and pyrimidine [referring to Chem.Pharm.Bull., 9 (1961), 801].Initial compounds XI advantageously prepares under by EP-A 10 02 788 known conditions.
Be similar to compound IV and make 5-alkyl-7-hydroxyl-6-phenylpyrazole and pyrimidine XII and halide reagent [HAL] reaction that obtains in this way, obtain the 7-halo pyrazolopyrimidine of formula XIII.
Figure A20048001569100132
The response class of XIII and amine VI is similar to the reaction of compound V and VI and carries out.
In addition, formula I.C compound can also be by the malonic ester preparation of Compound I .A and formula XIV.In formula XIV, X is hydrogen or C 1-C 3Alkyl and R are C 1-C 4Alkyl.These compounds are transformed accepted way of doing sth XV compound and decarboxylation, obtain Compound I .C[] referring to US 5 994 360.
Figure A20048001569100133
Malonic ester XIV is by the known [J.Am.Chem.Soc. of document 64(1942), 2714; J.Org.Chem. 39(1974), 2172; Helv.Chim.Acta 61(1978), 1565] or they can be according to the preparation of the document quoted.
Ester XV carries out under usual conditions with posthydrolysis; Depend on different structural units, the alkalescence of compounds X V or acidic hydrolysis may be favourable.Partially or completely decarboxylation becomes I.C even may carry out under esterolytic condition.
Figure A20048001569100141
Usually, decarboxylation is at 20-180 ℃, and in inert solvent, suitable words are carried out in the presence of acid under preferred 50-120 ℃ the temperature.
Wherein X is CN or C 1-C 4The formula I compound of alkoxyl group (formula I.D) can obtain by following route of synthesis:
By selective hydrolysis, be similar to Chem.Pharm.Bull.1961,9801 (triazolo pyrimidines) or J.Agric.Food Chem.41,12,1993,2411 (pyrimidines) make 5 of formula V, 7-dihalo pyrazolopyrimidine transforms 5-halo-7-hydroxypyrazoles and pyrimidine of accepted way of doing sth Va, or according to Khim.Geterotsikl.Soedin, RU, 21,3,1985,378 (pyrimidines) are that the solution in 10% the HCl Zai diox carries out with acid catalysis by working concentration.
Figure A20048001569100142
5-halo-7-hydroxypyrazoles and pyrimidine Va that the organometallic reagent of use formula IX will obtain in this way change into compounds X IIa.
Figure A20048001569100143
Wherein X ' is CN or C 1-C 4Alkoxyl group,
Halogenation XIIa then obtains formula XIIIa compound:
Figure A20048001569100144
And the amine of XIIIa and formula VI is reacted, and obtaining formula I.D. compound, this is similar to the preparation of Compound I .A.
Suitable acid is hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetate, tosic acid.Suitable solvent is a water, aliphatic hydrocarbon such as pentane, hexane, hexanaphthene and sherwood oil, aromatic hydrocarbons such as toluene, o-Xylol, m-xylene and p-Xylol, halogenated hydrocarbon such as methylene dichloride, chloroform and chlorobenzene, ethers such as ether, Di Iso Propyl Ether, t-butyl methyl ether diox, phenylmethylether and tetrahydrofuran (THF), nitrile such as acetonitrile and propionitrile, ketone such as acetone, methyl ethyl ketone, metacetone and tertiary butyl methyl ketone, alcohols such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, the propyl carbinol and the trimethyl carbinol, and methyl-sulphoxide, dimethyl formamide and N,N-DIMETHYLACETAMIDE; Preferred this is reflected in hydrochloric acid or the acetate and carries out especially.Can also use the mixture of above-mentioned solvent.
Reaction mixture is handled in a usual manner, for example by mixing, separate each with water mutually and suitable words chromatography purification crude product.Some intermediate and end product obtain with colourless or slight brown toughening oil, can will should oil purify or remove volatile constituent under decompression and the gentle temperature that raises.If intermediate and end product obtain with solid, then can also purify by recrystallization or dissolving (digestion).
If each Compound I can not obtain by above-mentioned approach, then they can prepare by other Compound I of deriving.
Each isomer obtains isomer mixture if synthesize, then do not require usually and separate, because can transform (for example under the effect of light, acid or alkali) mutually in the course of processing of using or in application in some cases.Such conversion can also take place after use, for example in the processing of plant, handling in the plant or in harmful fungoid to be prevented and treated.
In following formula, in the definition of the symbol of giving, use the following substituent collectivity term of representative usually:
Halogen: fluorine, chlorine, bromine and iodine;
Alkyl: have 1-4,6,8 or 10 saturated straight chain or the branched hydrocarbyl radical that carbon is former, for example C 1-C 6Alkyl, as methyl, ethyl, propyl group, the 1-methylethyl, butyl, the 1-methyl-propyl, the 2-methyl-propyl, 1, the 1-dimethyl ethyl, amyl group, the 1-methyl butyl, the 2-methyl butyl, the 3-methyl butyl, 2, the 2-dimethyl propyl, the 1-ethyl propyl, hexyl, 1, the 1-dimethyl propyl, 1, the 2-dimethyl propyl, the 1-methyl amyl, the 2-methyl amyl, the 3-methyl amyl, the 4-methyl amyl, 1, the 1-dimethylbutyl, 1, the 2-dimethylbutyl, 1, the 3-dimethylbutyl, 2, the 2-dimethylbutyl, 2, the 3-dimethylbutyl, 3, the 3-dimethylbutyl, the 1-ethyl-butyl, the 2-ethyl-butyl, 1,1,2-trimethylammonium propyl group, 1,2,2-trimethylammonium propyl group, 1-ethyl-1-methyl-propyl and 1-ethyl-2-methyl-propyl;
Haloalkyl: have the straight chain or the branched-alkyl (as mentioned above) of 1-2,4 or 6 carbon atoms, wherein some or all hydrogen atoms can be replaced by above-mentioned halogen atom in these groups; Especially C 1-C 2Haloalkyl, as chloromethyl, brooethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl, trifluoromethyl, chlorine methyl fluoride, dichloro one methyl fluoride, a chlorodifluoramethyl-, 1-chloroethyl, 1-bromotrifluoromethane, 1-fluoro ethyl, 2-fluoro ethyl, 2,2-two fluoro ethyls, 2,2,2-trifluoroethyl, 2-chloro-2-fluoro ethyl, 2-chloro-2,2-two fluoro ethyls, 2,2-two chloro-2-fluoro ethyls, 2,2,2-three chloroethyls, pentafluoroethyl group or 1,1,1-trifluoropropyl-2-base;
Alkenyl: have the unsaturated straight chain or the branched hydrocarbyl radical of 2-4,6,8 or 10 carbon atoms and 1 or 2 two key at an arbitrary position, for example C 2-C 6Alkenyl, as vinyl, the 1-propenyl, the 2-propenyl, the 1-methyl ethylene, the 1-butylene base, crotyl, the 3-butenyl, 1-methyl isophthalic acid-propenyl, 2-methyl isophthalic acid-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, the 1-pentenyl, pentenyl, the 3-pentenyl, the 4-pentenyl, 1-methyl isophthalic acid-butenyl, the 2-methyl-1-butene thiazolinyl, the 3-methyl-1-butene base, 1-methyl-2-butene base, 2-methyl-2-butene base, 3-methyl-2-butene base, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, the 1-hexenyl, the 2-hexenyl, the 3-hexenyl, the 4-hexenyl, the 5-hexenyl, 1-methyl-1-pentene thiazolinyl, 2-methyl-1-pentene thiazolinyl, 3-methyl-1-pentene thiazolinyl, the 4-methyl-1-pentene base, 1-methyl-pentenyl, 2-methyl-pentenyl, 3-methyl-pentenyl, 4-methyl-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-crotyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butylene base, 1,2-dimethyl-crotyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butylene base, 1,3-dimethyl-crotyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butylene base, 2,3-dimethyl-crotyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butylene base, 3,3-dimethyl-crotyl, 1-ethyl-1-butylene base, 1-ethyl-crotyl, 1-ethyl-3-butenyl, 2-ethyl-1-butylene base, 2-ethyl-crotyl, 2-ethyl-3-butenyl, 1,1,2-trimethylammonium-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl isophthalic acid-propenyl and 1-ethyl-2-methyl-2-propenyl;
Halogenated alkenyl: unsaturated straight chain or branched hydrocarbyl radical (as mentioned above) with 2-10 carbon atom and 1 or 2 two key at an arbitrary position, wherein some or all hydrogen atoms can be replaced by above-mentioned halogen atom in these groups, are especially replaced by fluorine, chlorine and bromo;
Alkynyl: have the straight chain or the branched hydrocarbyl radical of 2-4,6,8 or 10 carbon atoms and 1 or 2 three key at an arbitrary position, for example C 2-C 6Alkynyl, as ethynyl, the 1-proyl, 2-propynyl, the ethyl acetylene base, the 2-butyne base, the 3-butynyl, 1-methyl-2-propynyl, the 1-pentynyl, the valerylene base, the 3-pentynyl, the 4-pentynyl, 1-methyl-2-butyne base, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl isophthalic acid-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexin base, 2-hexin base, 3-hexin base, 4-hexin base, 5-hexin base, 1-methyl-valerylene base, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentene alkynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentene alkynyl, 4-methyl-valerylene base, 1,1-dimethyl-2-butyne base, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-ethyl acetylene base, 1-ethyl-2-butyne base, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl;
Cycloalkyl: monocycle or dicyclo saturated hydrocarbyl, for example C with 3-6 or 8 carbocyclic ring members 3-C 8Cycloalkyl is as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl and ring octyl group; Contain 1-4 and be selected from that the heteroatomic 5-10 unit of O, N and S is saturated, part is unsaturated or aromatic heterocycle:
-contain 5 or 6 yuan of part unsaturated heterocycle bases of 1-3 nitrogen-atoms and/or 1 oxygen or sulphur atom or 1 or 2 oxygen and/or sulphur atom, for example 3,6-dihydro-2H-pyridine-1-base and 2,5-pyrrolin-1-base;
-contain 5 or 6 yuan of saturated heterocyclyls of 1-3 nitrogen-atoms and/or 1 oxygen or sulphur atom or 1 or 2 oxygen and/or sulphur atom, 2-tetrahydrofuran base for example, the 3-tetrahydrofuran base, the 2-tetrahydro-thienyl, the 3-tetrahydro-thienyl, the 2-pyrrolidyl, the 3-pyrrolidyl, the 3-isoxazole alkyl, the 4-isoxazole alkyl, the 5-isoxazole alkyl, 3-isothiazole alkyl, 4-isothiazole alkyl, 5-isothiazole alkyl, the 3-pyrazolidyl, the 4-pyrazolidyl, the 5-pyrazolidyl, the 2-oxazolidinyl, the 4-oxazolidinyl, the 5-oxazolidinyl, the 2-thiazolidyl, the 4-thiazolidyl, the 5-thiazolidyl, the 2-imidazolidyl, the 4-imidazolidyl, 2-pyrroline-2-base, 2-pyrroline-3-base, 3-pyrroline-2-base, 3-pyrroline-3-base, the 2-piperidyl, the 3-piperidyl, the 4-piperidyl, 1,3-diox-5-base, the 2-THP trtrahydropyranyl, the 4-THP trtrahydropyranyl, the 2-tetrahydro-thienyl, 3-hexahydro-pyridazine base, 4-hexahydro-pyridazine base, 2-hexahydropyrimidine base, 4-hexahydropyrimidine base, 5-hexahydropyrimidine base and 2-piperazinyl;
-contain 5 yuan of heterocyclic radicals of 1-4 nitrogen-atoms or 1-3 nitrogen-atoms and 1 sulphur or Sauerstoffatom: except carbon atom, can also contain 1-4 nitrogen-atoms or 1-3 nitrogen-atoms and 1 sulphur or Sauerstoffatom 5 yuan of heteroaryls as ring members, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrryl, 3-pyrryl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl and 1,3,4-triazole-2-base;
-contain 6 yuan of heteroaryls of 1-3 or 1-4 nitrogen-atoms: except carbon atom, also can contain the 6 yuan heteroaryls of individual or 1-4 the nitrogen-atoms of 1-3, for example 2-pyridyl, 3-pyridyl, 4-pyridyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidyl, 4-pyrimidyl, 5-pyrimidyl and 2-pyrazinyl as ring members.
Alkylidene group: a 3-5 CH 2The divalence of group is branched chain not, for example CH 2, CH 2CH 2, CH 2CH 2CH 2, CH 2CH 2CH 2CH 2And CH 2CH 2CH 2CH 2CH 2
Oxyalkylene: a 2-4 CH 2The divalence of group is branched chain not, and wherein a radical valence key links to each other with skeleton via Sauerstoffatom, for example OCH 2CH 2, OCH 2CH 2CH 2And OCH 2CH 2CH 2CH 2
Oxygen alkylene oxide group: a 1-3 CH 2The divalence of group is branched chain not, and wherein two radical valence keys all link to each other with skeleton via Sauerstoffatom, for example OCH 2O, OCH 2CH 2O and OCH 2CH 2CH 2O.
Scope of the present invention comprises (R) of the formula I compound with chiral centre-and (S)-isomer and racemic modification.
For variable, the particularly preferred embodiment of intermediate is corresponding to those group L of formula I m, R 1, R 2, X and Y p
Consider the practical use of the pyrazolopyrimidine of formula I, the following meanings of special preferred substituents, independent in each case or combination:
Preferred R wherein 1Be C 1-C 4Alkyl, C 2-C 6Alkenyl or C 1-C 8The Compound I of haloalkyl.
Especially preferred R wherein 1For in the alkenyl of alpha-carbon atom place branching or the Compound I of alkynyl.In these cases, radicals R 1Corresponding to group A:
Wherein # is the key with nitrogen-atoms, and
R 11Be C 1-C 3Alkyl or C 1-C 3Haloalkyl;
R 12Be hydrogen, C 1-C 3Alkyl or C 1-C 3Haloalkyl;
R 13Be C 2-C 10Alkenyl or C 2-C 8Alkynyl, wherein R 13Can not be substituted or by halo partially or completely and/or can have 1-3 radicals R a
Equally preferred R wherein 1For containing 1 or 2 heteroatoms that is selected from N, O and S and can be saturated or the Compound I of aromatic heterocycle by 5 or 6 yuan that 1 or 2 alkyl or haloalkyl replace.
Preferred R wherein 1Compound I for group B:
Wherein
Z 1Be hydrogen, fluorine or C 1-C 6-fluoro-alkyl,
Z 2Be hydrogen or fluorine, or
Z 1And Z 2Form two keys together;
Q is 0 or 1; With
R 3Be hydrogen or methyl.
In addition, preferred R wherein 1For can be by C 1-C 4The C that alkyl replaces 3-C 6The Compound I of cycloalkyl.
Especially preferred R wherein 2Compound I for hydrogen.
Equally preferred R wherein 2Compound I for methyl or ethyl.
If R 1And/or R 2Comprise haloalkyl or halogenated alkenyl, then to preferred (the S)-isomer of these groups with chiral centre.At R 1Or R 2In have under the not halogen-containing alkyl or alkenyl situation of chiral centre the isomer of preferred (R)-configuration.
In addition, be preferably as follows Compound I: R wherein 1And R 2Form saturated or unsaturated 5 or 6 yuan of rings with the nitrogen-atoms that they connected, this ring can be selected from the atomic separation of O, N and S and/or can be had one or more halogen, C of being selected from 1-C 6Alkyl, C 1-C 6Haloalkyl and oxygen-C 1-C 3The substituting group of alkylene oxide group or wherein two adjacent ring members can be by C 1-C 4Alkylidene chain connects.
Be preferably as follows Compound I especially: R wherein 1And R 2Form piperidyl, morpholinyl or sulfo-beautiful jade basic ring with the nitrogen-atoms that they connected, especially be not substituted or by 1-3 halogen, C 1-C 4Alkyl or C 1-C 4Haloalkyl replaces, especially by the methyl substituted piperidines basic ring of 4-.
The also preferred theme of the present invention is following Compound I: R wherein 1And R 2Form with the nitrogen-atoms that they connected and not to be substituted or by 1 or 2 halogen, C 1-C 4Alkyl or C 1-C 4Haloalkyl replaces, especially by 3, and 5-dimethyl or 3, the pyrazoles ring that 5-two (trifluoromethyl) replaces.
Preferred wherein at least one group L is positioned at the adjacent Compound I with triazolo pyrimidine skeleton tie point; Especially wherein n is those compounds of 1,2 or 3.
Preferred L wherein mBe halogen, methyl, ethyl, C 1Haloalkyl, methoxyl group or-C (=O)-A 2Compound I, A wherein 2Be hydrogen, hydroxyl, C 1-C 4Alkoxyl group, C 1-C 4Halogenated alkoxy, C 1-C 2Alkylamino or two C 1-C 2Alkylamino.
In addition, especially preferably wherein by L mThe phenyl that replaces is the Compound I of group C:
Figure A20048001569100201
Wherein # is the tie point with the pyrazolopyrimidine skeleton, and
L 1Be fluorine, chlorine, CH 3Or CF 3
L 2, L 4Be hydrogen or fluorine independently of each other;
L 3Be hydrogen, fluorine, chlorine, cyano group, CH 3Or COOCH 3With
L 5Be hydrogen, fluorine or CH 3
Preferably wherein X is halogen, CN, OH, C 1-C 4Alkyl or C 1-C 4The Compound I of alkoxyl group.
Further preferably wherein X be halogen, CN or C 1-C 4The Compound I of alkyl.
Especially preferably wherein X is halogen or C 1-C 4Alkyl, as chlorine or methyl, the Compound I of halogen such as chlorine especially.
In addition, preferably wherein Y is halogen, especially fluorine or chlorine, or the Compound I of alkyl, especially methyl.In particularly preferred embodiment of the present invention, radicals X is that chlorine atom and Y are fluorine, chlorine or methyl.
In addition, the also preferred wherein Compound I of index p=1.
In addition, also preferred wherein Y is positioned at the Compound I of 3 (formula is I.1) of pyrimidine skeleton:
Figure A20048001569100211
In another preferred embodiment of the present invention, group Y is positioned at 2 (formula is I.2) of pyrimidine skeleton:
Figure A20048001569100212
Formula I.A compound is a preferred especially theme of the present invention:
Figure A20048001569100213
Especially consider that it uses, and preferably is compiled in the Compound I in the following table.In addition, to the group mentioned of substituting group in these tables this as described substituent particularly preferred embodiment, irrelevant with the combination of mentioning them.
Table 1
Wherein X and Y are chlorine, L mBe 2-fluoro-6-chlorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 2
Wherein X and Y are chlorine, L mBe 2,6-difluoro and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 3
Wherein X and Y are chlorine, L mBe 2,6-dichloro and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 4
Wherein X and Y are chlorine, L mBe 2-fluoro-6-methyl and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 5
Wherein X and Y are chlorine, L mBe 2,4,6-trifluoro and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 6
Wherein X and Y are chlorine, L mBe 2,6-two fluoro-4-methoxyl group and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 7
Wherein X and Y are chlorine, L mBe five fluorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 8
Wherein X and Y are chlorine, L mBe 2-methyl-4-fluorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 9
Wherein X and Y are chlorine, L mBe 2-trifluoromethyl and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 10
Wherein X and Y are chlorine, L mBe 2-methoxyl group-6-fluorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 11
Wherein X and Y are chlorine, L mBe 2-chlorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 12
Wherein X and Y are chlorine, L mBe 2-fluorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 13
Wherein X and Y are chlorine, L mBe 2,4-difluoro and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 14
Wherein X and Y are chlorine, L mBe 2-fluoro-4-chlorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 15
Wherein X and Y are chlorine, L mBe 2-chloro-4-fluorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 16
Wherein X and Y are chlorine, L mBe 2,3-difluoro and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 17
Wherein X and Y are chlorine, L mBe 2,5-difluoro and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 18
Wherein X and Y are chlorine, L mBe 2,3,4-trifluoro and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 19
Wherein X and Y are chlorine, L mBe 2-methyl and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 20
Wherein X and Y are chlorine, L mBe 2,4-dimethyl and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 21
Wherein X and Y are chlorine, L mBe 2-methyl-4-chlorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 22
Wherein X and Y are chlorine, L mBe 2-fluoro-4-methyl and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 23
Wherein X and Y are chlorine, L mBe 2,6-dimethyl and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 24
Wherein X and Y are chlorine, L mBe 2,4,6-trimethylammonium and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 25
Wherein X and Y are chlorine, L mBe 2,6-two fluoro-4-cyano group and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 26
Wherein X and Y are chlorine, L mBe 2,6-two fluoro-4-methyl and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 27
Wherein X and Y are chlorine, L mBe 2,6-two fluoro-4-methoxycarbonyl and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 28
Wherein X and Y are chlorine, L mBe 2-trifluoromethyl-4-fluorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 29
Wherein X and Y are chlorine, L mBe 2-trifluoromethyl-5-fluorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 30
Wherein X and Y are chlorine, L mBe 2-trifluoromethyl-5-chlorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.1
Table 31
Wherein X is a chlorine, and Y is a methyl, L mBe 2-fluoro-6-chlorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 32
Wherein X is a chlorine, and Y is a methyl, L mBe 2,6-difluoro and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 33
Wherein X is a chlorine, and Y is a methyl, L mBe 2,6-dichloro and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 34
Wherein X is a chlorine, and Y is a methyl, L mBe 2-fluoro-6-methyl and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 35
Wherein X is a chlorine, and Y is a methyl, L mBe 2,4,6-trifluoro and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 36
Wherein X is a chlorine, and Y is a methyl, L mBe 2,6-two fluoro-4-methoxyl group and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 37
Wherein X is a chlorine, and Y is a methyl, L mBe five fluorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 38
Wherein X is a chlorine, and Y is a methyl, L mBe 2-methyl-4-fluorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 39
Wherein X is a chlorine, and Y is a methyl, L mBe 2-trifluoromethyl and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 40
Wherein X is a chlorine, and Y is a methyl, L mBe 2-methoxyl group-6-fluorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 41
Wherein X is a chlorine, and Y is a methyl, L mBe 2-chlorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 42
Wherein X is a chlorine, and Y is a methyl, L mBe 2-fluorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 43
Wherein X is a chlorine, and Y is a methyl, L mBe 2,4-difluoro and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 44
Wherein X is a chlorine, and Y is a methyl, L mBe 2-fluoro-4-chlorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 45
Wherein X is a chlorine, and Y is a methyl, L mBe 2-chloro-4-fluorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 46
Wherein X is a chlorine, and Y is a methyl, L mBe 2,3-difluoro and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 47
Wherein X is a chlorine, and Y is a methyl, L mBe 2,5-difluoro and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 48
Wherein X is a chlorine, and Y is a methyl, L mBe 2,3,4-trifluoro and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 49
Wherein X is a chlorine, and Y is a methyl, L mBe 2-methyl and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 50
Wherein X is a chlorine, and Y is a methyl, L mBe 2,4-dimethyl and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 51
Wherein X is a chlorine, and Y is a methyl, L mBe 2-methyl-4-chlorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 52
Wherein X is a chlorine, and Y is a methyl, L mBe 2-fluoro-4-methyl and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 53
Wherein X is a chlorine, and Y is a methyl, L mBe 2,6-dimethyl and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 54
Wherein X is a chlorine, and Y is a methyl, L mBe 2,4,6-trimethylammonium and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 55
Wherein X is a chlorine, and Y is a methyl, L mBe 2,6-two fluoro-4-cyano group and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 56
Wherein X is a chlorine, and Y is a methyl, L mBe 2,6-two fluoro-4-methyl and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 57
Wherein X is a chlorine, and Y is a methyl, L mBe 2,6-two fluoro-4-methoxycarbonyl and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 58
Wherein X is a chlorine, and Y is a methyl, L mBe 2-trifluoromethyl-4-fluorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 59
Wherein X is a chlorine, and Y is a methyl, L mBe 2-trifluoromethyl-5-fluorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 60
Wherein X is a chlorine, and Y is a methyl, L mBe 2-trifluoromethyl-5-chlorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.2
Table 61
Wherein X is a methyl, and Y is a hydrogen, L mBe 2-fluoro-6-chlorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 62
Wherein X is a methyl, and Y is a hydrogen, L mBe 2,6-difluoro and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 63
Wherein X is a methyl, and Y is a hydrogen, L mBe 2,6-dichloro and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 64
Wherein X is a methyl, and Y is a hydrogen, L mBe 2-fluoro-6-methyl and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 65
Wherein X is a methyl, and Y is a hydrogen, L mBe 2,4,6-trifluoro and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 66
Wherein X is a methyl, and Y is a hydrogen, L mBe 2,6-two fluoro-4-methoxyl group and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 67
Wherein X is a methyl, and Y is a hydrogen, L mBe five fluorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 68
Wherein X is a methyl, and Y is a hydrogen, L mBe 2-methyl-4-fluorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 69
Wherein X is a methyl, and Y is a hydrogen, L mBe 2-trifluoromethyl and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 70
Wherein X is a methyl, and Y is a hydrogen, L mBe 2-methoxyl group-6-fluorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 71
Wherein X is a methyl, and Y is a hydrogen, L mBe 2-chlorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 72
Wherein X is a methyl, and Y is a hydrogen, L mBe 2-fluorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 73
Wherein X is a methyl, and Y is a hydrogen, L mBe 2,4-difluoro and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 74
Wherein X is a methyl, and Y is a hydrogen, L mBe 2-fluoro-4-chlorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 75
Wherein X is a methyl, and Y is a hydrogen, L mBe 2-chloro-4-fluorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 76
Wherein X is a methyl, and Y is a hydrogen, L mBe 2,3-difluoro and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 77
Wherein X is a methyl, and Y is a hydrogen, L mBe 2,5-difluoro and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 78
Wherein X is a methyl, and Y is a hydrogen, L mBe 2,3,4-trifluoro and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 79
Wherein X is a methyl, and Y is a hydrogen, L mBe 2-methyl and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 80
Wherein X is a methyl, and Y is a hydrogen, L mBe 2,4-dimethyl and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 81
Wherein X is a methyl, and Y is a hydrogen, L mBe 2-methyl-4-chlorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 82
Wherein X is a methyl, and Y is a hydrogen, L mBe 2-fluoro-4-methyl and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 83
Wherein X is a methyl, and Y is a hydrogen, L mBe 2,6-dimethyl and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 84
Wherein X is a methyl, and Y is a hydrogen, L mBe 2,4,6-trimethylammonium and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 85
Wherein X is a methyl, and Y is a hydrogen, L mBe 2,6-two fluoro-4-cyano group and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 86
Wherein X is a methyl, and Y is a hydrogen, L m2,6-two fluoro-4-methyl and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 87
Wherein X is a methyl, and Y is a hydrogen, L mBe 2,6-two fluoro-4-methoxycarbonyl and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 88
Wherein X is a methyl, and Y is a hydrogen, L mBe 2-trifluoromethyl-4-fluorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 89
Wherein X is a methyl, and Y is a hydrogen, L mBe 2-trifluoromethyl-5-fluorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table 90
Wherein X is a methyl, and Y is a hydrogen, L mBe 2-trifluoromethyl-5-chlorine and R 1And R 2Combination for each compound corresponding to the formula of the delegation of Table A compound I.3
Table A
Numbering R 1 R 2
A-1 CH 3 H
A-2 CH 3 CH 3
A-3 CH 2CH 3 H
A-4 CH 2CH 3 CH 3
A-5 CH 2CH 3 CH 2CH 3
A-6 CH 2CF 3 H
A-7 CH 2CF 3 CH 3
A-8 CH 2CF 3 CH 2CH 3
A-9 CH 2CCl 3 H
A-10 CH 2CCl 3 CH 3
A-11 CH 2CCl 3 CH 2CH 3
A-12 CH 2CH 2CH 3 H
A-13 CH 2CH 2CH 3 CH 3
A-14 CH 2CH 2CH 3 CH 2CH 3
A-15 CH 2CH 2CH 3 CH 2CH 2CH 3
A-16 CH(CH 3) 2 H
A-17 CH(CH 3) 2 CH 3
A-18 CH(CH 3) 2 CH 2CH 3
A-19 CH 2CH 2CH 2CH 3 H
A-20 CH 2CH 2CH 2CH 3 CH 3
A-21 CH 2CH 2CH 2CH 3 CH 2CH 3
A-22 CH 2CH 2CH 2CH 3 CH 2CH 2CH 3
A-23 CH 2CH 2CH 2CH 3 CH 2CH 2CH 2CH 3
A-24 (±)CH(CH 3)-CH 2CH 3 H
A-25 (±)CH(CH 3)-CH 2CH 3 CH 3
A-26 (±)CH(CH 3)-CH 2CH 3 CH 2CH 3
A-27 (S)CH(CH 3)-CH 2CH 3 H
A-28 (S)CH(CH 3)-CH 2CH 3 CH 3
A-29 (S)CH(CH 3)-CH 2CH 3 CH 2CH 3
A-30 (R)CH(CH 3)-CH 2CH 3 H
A-31 (R)CH(CH 3)-CH 2CH 3 CH 3
A-32 (R)CH(CH 3)-CH 2CH 3 CH 2CH 3
Numbering R 1 R 2
A-33 (±)CH(CH 3)-CH(CH 3) 2 H
A-34 (±)CH(CH 3)-CH(CH 3) 2 CH 3
A-35 (±)CH(CH 3)-CH(CH 3) 2 CH 2CH 3
A-36 (S)CH(CH 3)-CH(CH 3) 2 H
A-37 (S)CH(CH 3)-CH(CH 3) 2 CH 3
A-38 (S)CH(CH 3)-CH(CH 3) 2 CH 2CH 3
A-39 (R)CH(CH 3)-CH(CH 3) 2 H
A-40 (R)CH(CH 3)-CH(CH 3) 2 CH 3
A-41 (R)CH(CH 3)-CH(CH 3) 2 CH 2CH 3
A-42 (±)CH(CH 3)-C(CH 3) 3 H
A-43 (±)CH(CH 3)-C(CH 3) 3 CH 3
A-44 (±)CH(CH 3)-C(CH 3) 3 CH 2CH 3
A-45 (S)CH(CH 3)-C(CH 3) 3 H
A-46 (S)CH(CH 3)-C(CH 3) 3 CH 3
A-47 (S)CH(CH 3)-C(CH 3) 3 CH 2CH 3
A-48 (R)CH(CH 3)-C(CH 3) 3 H
A-49 (R)CH(CH 3)-C(CH 3) 3 CH 3
A-50 (R)CH(CH 3)-C(CH 3) 3 CH 2CH 3
A-51 (±)CH(CH 3)-CF 3 H
A-52 (±)CH(CH 3)-CF 3 CH 3
A-53 (±)CH(CH 3)-CF 3 CH 2CH 3
A-54 (S)CH(CH 3)-CF 3 H
A-55 (S)CH(CH 3)-CF 3 CH 3
A-56 (S)CH(CH 3)-CF 3 CH 2CH 3
A-57 (R)CH(CH 3)-CF 3 H
A-58 (R)CH(CH 3)-CF 3 CH 3
A-59 (R)CH(CH 3)-CF 3 CH 2CH 3
A-60 (±)CH(CH 3)-CCl 3 H
A-61 (±)CH(CH 3)-CCl 3 CH 3
A-62 (±)CH(CH 3)-CCl 3 CH 2CH 3
A-63 (S)CH(CH 3)-CCl 3 H
A-64 (S)CH(CH 3)-CCl 3 CH 3
A-65 (S)CH(CH 3)-CCl 3 CH 2CH 3
Numbering R 1 R 2
A-66 (R)CH(CH 3)-CCl 3 H
A-67 (R)CH(CH 3)-CCl 3 CH 3
A-68 (R)CH(CH 3)-CCl 3 CH 2CH 3
A-69 CH 2CF 2CF 3 H
A-70 CH 2CF 2CF 3 CH 3
A-71 CH 2CF 2CF 3 CH 2CH 3
A-72 CH 2(CF 2) 2CF 3 H
A-73 CH 2(CF 2) 2CF 3 CH 3
A-74 CH 2(CF 2) 2CF 3 CH 2CH 3
A-75 CH 2C(CH 3)＝CH 2 H
A-76 CH 2C(CH 3)＝CH 2 CH 3
A-77 CH 2C(CH 3)＝CH 2 CH 2CH 3
A-78 CH 2CH＝CH 2 H
A-79 CH 2CH＝CH 2 CH 3
A-80 CH 2CH＝CH 2 CH 2CH 3
A-81 CH(CH 3)CH＝CH 2 H
A-82 CH(CH 3)CH＝CH 2 CH 3
A-83 CH(CH 3)CH＝CH 2 CH 2CH 3
A-84 CH(CH 3)C(CH 3)＝CH 2 H
A-85 CH(CH 3)C(CH 3)＝CH 2 CH 3
A-86 CH(CH 3)C(CH 3)＝CH 2 CH 2CH 3
A-87 CH 2-C≡CH H
A-88 CH 2-C≡CH CH 3
A-89 CH 2-C≡CH CH 2CH 3
A-90 Cyclopentyl H
A-91 Cyclopentyl CH 3
A-92 Cyclopentyl CH 2CH 3
A-93 Cyclohexyl H
A-94 Cyclohexyl CH 3
A-95 Cyclohexyl CH 2CH 3
A-96 CH 2-C 6H 5 H
A-97 CH 2-C 6H 5 CH 3
A-98 CH 2-C 6H 5 CH 2CH 3
Numbering R 1 R 2
A-99 -(CH 2) 2CH＝CHCH 2-
A-100 -(CH 2) 2C(CH 3)＝CHCH 2-
A-101 -(CH 2) 2CH(CH 3)(CH 2) 2-
A-102 -(CH 2) 3CHFCH 2-
A-103 -(CH 2) 2CHF(CH 2) 2-
A-104 -CH 2CHF(CH 2) 3-
A-105 -(CH 2) 2CH(CF 3)(CH 2) 2-
A-106 -(CH 2) 2O(CH 2) 2-
A-107 -(CH 2) 2S(CH 2) 2-
A-108 -(CH 2) 5-
A-109 -(CH 2) 4-
A-110 -CH 2CH＝CHCH 2-
A-111 -CH(CH 3)(CH 2) 3-
A-112 -CH 2CH(CH 3)(CH 2) 2-
A-113 -CH(CH 3)-(CH 2) 2-CH(CH 3)-
A-114 -CH(CH 3)-(CH 2) 4-
A-115 -CH 2-CH(CH 3)-(CH 2) 3-
A-116 -(CH 2)-CH(CH 3)-CH 2-CH(CH 3)-CH 2-
A-117 -CH(CH 2CH 3)-(CH 2) 4-
A-118 -(CH 2) 2-CHOH-(CH 2) 2-
A-119 -(CH 2)-CH＝CH-(CH 2) 2-
A-120 -(CH 2) 6-
A-121 -CH(CH 3)-(CH 2) 5-
A-122 -(CH 2) 2-N(CH 3)-(CH 2) 2-
A-123 -N＝CH-CH＝CH-
A-124 -N＝C(CH 3)-CH＝C(CH 3)-
A-125 -N＝C(CF 3)-CH＝C(CF 3)-
Compound I is suitable for as mycocide.They are characterised in that the plant pathogenic fungi to wide region has remarkable effectiveness, and described fungi especially is selected from Ascomycetes (Ascomycetes), deuteromycetes (Deuteromycetes), Oomycete (Oomycetes) and Basidiomycetes (Basidiomycetes) fungi.Inhale in them some effectively and can be used as the blade face and soil effect mycocide is used for plant protection.
They are even more important to a large amount of fungies of control in the seed of various cultivated plants such as wheat, rye, barley, oat, rice, corn, dogstail, banana, cotton, soybean, coffee, sugarcane, grape vine, fruit and ornamental plant and vegetables such as cucumber, beans, tomato, potato and cucurbitaceous plant and these plants.
They are particularly suited for preventing and treating the following plants disease:
Chain lattice spore (Alternaria) on vegetables and the fruit belongs to,
Flat navel in cereal class, rice and the lawn wriggles that spore (Bipolaris) belongs to and interior navel is wriggled spore (Drechslera) genus,
Standing grain powdery mildew in the cereal class (Blumeria graminis) (Powdery Mildew),
Botrytis cinerea on strawberry, vegetables, ornamental plant and the grape vine (Botrytis cinerea) (gray mold),
Two spore powdery mildews (Erysiphe cichoracearum) on the cucurbitaceous plant and monofilament shell (Sphaerotheca fuliginea),
Fusarium on each kind of plant (Fusarium) belongs to and wheel branch spore (Verticillium) belongs to,
Length on the cereal class spore (Helminthosporium) of wriggling belongs to,
Ball chamber bacterium (Mycosphaerella) on cereal class, banana and the peanut belongs to,
Phytophthora infestans on potato and the tomato (Phytophthora infestans),
Grape on the grape vine is given birth to single shaft mould (Plasmopara viticola),
Apple mildew bacterium on the apple (Podosphaera leucotricha),
Basal stem rot bacterium on wheat and the barley (Pseudocercosporella herpotrichoides),
False downy mildew (Pseudoperonospora) on hops and the cucumber belongs to,
Handle rest fungus (Puccinia) on the cereal class belongs to,
Pyricularia oryzae on the rice (Pyricularia oryzae),
Rhizoctonia on cotton, rice and the lawn (Rhizoctonia) belongs to,
Wheat septoria on the wheat (Septoria tritici) and the many spores of clever withered shell (Stagonosporanodorum),
Grape snag shell (Uncinula necator) on the grape vine,
Ustilago on cereal class and the sugarcane (Ustilago) belongs to, and
Black star bacterium (Venturia) on apple and the pears belongs to (black spot).
Compound I also is suitable for preventing and treating harmful fungoid such as Paecilomyces varioti (Paecilomyces variotii) product with protecting materials (as timber, paper, lacquer dispersion, fiber or fabric) and protection storage.
Compound I needs maybe to prevent that by handling fungi with the active compound of fungicidal significant quantity plant, seed, material or the soil of fungal attack from using.Use and before material, plant or seed are by fungal infection and afterwards, to carry out.
Fungicide composition comprises 0.1-95 weight % usually, the active compound of preferred 0.5-90 weight %.
When being used for plant protection, amount of application depends on that the kind of required effect is 0.01-2.0kg active compound/hectare.
Handling kind of a period of the day from 11 p.m. to 1 a.m, the active compound amount that every kg seed needs usually is 0.001-0.1g, preferred 0.01-0.05g.
When being used for protecting materials or storage product, the amount of application of active compound depends on type and the required effect of using the zone.Usually the amount of using in protecting materials for example is 0.001g-2kg, preferred 0.005g-1kg active compound/m 3Handle material.
Compound I can be changed into conventional preparaton, for example solution, emulsion, suspension, pulvis, powder, paste and particle.Administration form depends on specific purpose; All should guarantee the meticulous and distribution equably of The compounds of this invention in each case.
Preparaton prepares in a known way, for example prepares by active compound is mixed with solvent and/or carrier, and the words that need are used emulsifying agent and dispersion agent.Suitable solvent/auxiliary agent mainly is:
-water, aromatic solvent (as Solvesso product, dimethylbenzene), paraffin (as mineral oil fractions), alcohols (as methyl alcohol, butanols, amylalcohol, benzylalcohol), ketone (as pimelinketone, gamma-butyrolactone), pyrrolidone (NMP, NOP), acetic ester (glycol diacetate), glycol, lipid acid diformamide, lipid acid and fatty acid ester.Can also use solvent mixture in principle.
-carrier such as ground natural mineral (as kaolin, clay, talcum, chalk) and ground synthetic mineral (as silica, the silicate of high dispersing); Emulsifying agent such as nonionic and anionic emulsifier (as polyoxyethylene aliphatic alcohol ether, alkylsulfonate and arylsulphonate) and dispersion agent such as lignin sulfite waste lye and methylcellulose gum.
Suitable tensio-active agent is a lignosulfonic acid, naphthene sulfonic acid, sulfocarbolic acid, the an alkali metal salt of dibutyl naphthene sulfonic acid, alkaline earth salt and ammonium salt, alkylaryl sulphonate, alkyl-sulphate, alkylsulfonate, aliphatic alcohol sulfate, lipid acid and sulphated fatty alcohol glycol ether, the condensation product that also has sulfonated naphthalene and naphthalene derivatives and formaldehyde in addition, the condensation product of naphthalene or naphthene sulfonic acid and phenol and formaldehyde, polyoxyethylene octylphenol ether, the ethoxylation isooctylphenol, octyl phenol and nonyl phenol, alkyl phenol polyoxyethylene glycol ether, tributyl phenyl polyglycol ether, three stearyl phenyl polyglycol ethers, alkyl aryl polyether alcohol, pure and mild Fatty Alcohol(C12-C14 and C12-C18)/ethylene oxide condensation product, ethoxylated castor oil, Voranol EP 2001, ethoxylation polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol ester, lignin sulfite waste lye and methylcellulose gum.
The material that is suitable for preparing direct sprayable solution, emulsion, paste or oil dispersion is that mid-boiling point arrives high boiling mineral oil fractions such as kerosene or diesel oil, the oil that also has coal tar and plant or animal-origin in addition, aliphatic series, ring-type and aromatic hydrocarbon such as toluene, dimethylbenzene, paraffin, tetraline, alkylated naphthalene or derivatives thereof, methyl alcohol, ethanol, propyl alcohol, butanols, hexalin, pimelinketone, isophorone, intensive polar solvent such as methyl-sulphoxide, N-Methyl pyrrolidone and water.
Powder, but broadcasting sowing can be by with active substance with solid carrier mixes or grind together and prepare with material and dusting product.
Particle (as coating particle, impregnated granules and homogeneous particle) can prepare by active compound and solid carrier are adhered to.The solid carrier example is that ore deposit soil is as silica gel, silicate, talcum, kaolin, activated clay (Attaclay), Wingdale, lime, chalk, terra miraculosa, loess, clay, rhombspar, diatomite, calcium sulfate, sal epsom, magnesium oxide, the ground synthetic mineral, fertilizer such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, the product of plant origin such as flour, tree bark powder, wood powder and nutshell powder, cellulose powder and other solid carrier.
Preparaton comprises 0.01-95 weight % usually, the active compound of preferred 0.1-90 weight %.This active compound is with 90%-100%, and the purity (according to NMR spectrum) of preferred 95%-100% is used.
Under classify the preparaton example as:
1. the product of dilute with water
A) water-soluble concentrate (SL)
With 10 weight part The compounds of this invention in the water-soluble or water-soluble solvent.Perhaps, add wetting agent or other auxiliary agent.Active compound is through water dilution dissolving.
B) dispersed enriched material (DC)
Be dissolved in 20 weight part The compounds of this invention in the pimelinketone and add dispersion agent such as Polyvinylpyrolidone (PVP).Dilute with water obtains dispersion.
C) missible oil (EC)
Be dissolved in 15 weight part The compounds of this invention in the dimethylbenzene and add calcium dodecylbenzene sulphonate and castor oil ethoxylate (being 5%) under each situation.Dilute with water obtains emulsion.
D) emulsion (EW, EO)
Be dissolved in 40 weight part The compounds of this invention in the dimethylbenzene and add calcium dodecylbenzene sulphonate and castor oil ethoxylate (being 5%) under each situation.Introduce this mixture in water and make equal phase emulsion by emulsor (Ultraturax).Dilute with water obtains emulsion.
E) suspension (SC, OD)
In the ball mill that stirs, 20 weight part The compounds of this invention are pulverized and adding dispersion agent, wetting agent and water or organic solvent, obtain active compound suspension in small, broken bits.Dilute with water obtains stable active compound suspension.
F) water-dispersible granule and water-soluble granular (WG, SG)
With the grinding in small, broken bits of 50 weight part The compounds of this invention and adding dispersion agent and wetting agent, be made into water dispersible or water-soluble granular by full scale plant (as forcing machine, spray tower, fluidized-bed).Dilute with water obtains stable active compound dispersion or solution.
G) water dispersible pow-ders and water-soluble powder (WP, SP)
With 75 weight part The compounds of this invention in the rotor-stator grinding machine for grinding and add dispersion agent, wetting agent and silica gel.Dilute with water obtains stable active compound dispersion or solution.
2. the product of using without dilution
H) but dusting powder (DP)
With the grinding in small, broken bits of 5 weight part The compounds of this invention and with 95% kaolin thorough mixing in small, broken bits.But this obtains the dusting product.
I) particle (GR, FG, GG, MG)
With the grinding in small, broken bits of 0.5 weight part The compounds of this invention and in conjunction with 95.5% carrier.Current methods be extrude, spraying drying or bed process.The particle that this obtains using without dilution.
J) ULV solution (UL)
10 weight part The compounds of this invention are dissolved in organic solvent such as the dimethylbenzene.The product that this obtains using without dilution.
Active compound can be directly, with its preparaton form or type of service prepared therefrom (but as directly spray solution, powder, suspension or dispersion, emulsion, oil dispersion, paste dusting product, broadcast sowing), by spraying, atomizing, dusting, broadcast sowing or water and use with material or particle form.Type of service depends on the purpose that is intended to fully; Be intended to always guarantee in all cases that the best of active compound of the present invention may distribute.
Moisture type of service can be prepared by emulsion concentrates, paste or wettable powder (sprayable powder, oil dispersion) by adding entry.Be preparation emulsion, paste or oil dispersion, can be with this material directly or be dissolved in back homogenizing in water in oil or the solvent by wetting agent, tackifier, dispersion agent or emulsifying agent.If perhaps, can prepare by active substance, wetting agent, tackifier, dispersion agent or emulsifying agent with suitable, enriched material and this enriched material that solvent or oil are formed are suitable for dilute with water.
Promptly can in relative broad range, change with the activity compound concentration in the preparation.Be generally 0.0001-10%, preferred 0.01-1%.
Active compound also can successfully be used for ultra-low volume method (ULV), wherein can use to comprise the preparaton that surpasses 95 weight % active compounds, or even use the active compound that does not contain additive.
Various types of oil, wetting agent, auxiliary, weedicide, mycocide, other agricultural chemicals or sterilant all can add in the active compound, need, and just add (bucket mixes) before the next-door neighbour uses.These reagent can with reagent of the present invention with 1: 10-10: 1 weight ratio is mixed.
In the administration form as mycocide, the present composition also can exist with other active compound, for example exists with weedicide, sterilant, growth regulator, mycocide or fertilizer.When the Compound I that will use as mycocide or the composition that comprises them mix with other mycocide, obtain the Fungicidally active spectrum of widening in many cases.
The following mycocide that The compounds of this invention can be united use with it is used for setting forth possible combination, but does not impose any restriction:
Acyl group L-Ala class, as M 9834 (benalaxyl), metaxanin (metalaxyl), fenfuram (ofurace) Huo Evil frost spirit (oxadixyl),
Sulfonamide derivatives, as aldimorph, dodine (dodine), dodemorfe (dodemorph), fenpropimorph (fenpropimorph), fenpropidin (fenpropidin), Guanoctine (guazatine), biguanide spicy acid salt (iminoctadine), luxuriant amine of Luo Evil (spiroxamine) or tridemorph (tridemorph)
Anilino-pyrimidine, as pyrimethanil (pyrimethanil), mepanipyrim (mepanipyrim) or cyprodinyl,
Antibiotic, as cycloheximide (cycloheximide), grisovin (griseofulvin), spring thunder element (kasugamycin), myprozine (natamycin), Polyoxin (polyoxin) or Streptomycin sulphate (streptomycin),
Azole, as Bitertanol (bitertanol), bromuconazole (bromoconazole), cyproconazole (cyproconazole) Difenoconazole (difenoconazole), alkene azoles alcohol (dinitroconazole), oxole bacterium (epoxiconazole), RH-7592 (fenbuconazole), Fluquinconazole (fluquinconazole), fluzilazol (flusilazole), own azoles alcohol (hexaconazole), IMAZALIL (imazalil), encircle penta azoles bacterium (meteonazole), nitrile bacterium azoles (myclobutanil), Topaze (penconazole), Wocosin 50TK (propiconazole), Prochloraz (prochloraz), prothioconazole, tebuconazole (tebuconazole), triazolone (triadimefon), Triabimeno I (triadimenol), fluorine bacterium azoles (triflumizole) or triticonazole (triticonazole)
The dicarboximide class, as different third fixed (iprodione), myclozolin (myclozolin), sterilization profit (procymidone) or the vinclozolin (vinclozolin),
Dithiocarbamate(s), as Karbam Black (ferbam), Parzate (nabam), maneb (maneb), zinc manganese ethylenebisdithiocarbamate (mancozeb), one-tenth hundred mu of (metam), Carbatene (metiram), propineb (propineb), polycarbamate (polycarbamate), thiram (thiram), ziram (ziram) or zineb (zineb)
Heterogeneous ring compound, as anilazine (anilazine), F-1991 (benomyl), boscalid amine (boscalid), derosal (carbendazim), carboxin (carboxin), oxycarboxin (oxycarboxin), cyanogen frost azoles (cyazofamid), dazomet (dazomet), Delan (dithianon) azolactone bacterium (famoxadone), fenamidone (fenamidone), fenarimol (fenarimol), fuberidazole (fuberidazole), fultolanil (flutolanil), furan pyrazoles spirit (furametpyr), isoprothiolane (isoprothiolane), third oxygen goes out and embroiders amine (mepronil), nuarimol (nuarimol), thiabendazole (probenazole), proquinazid, pyrifenox (pyrifenox), pyroquilon (pyroquilon), quinoxyfen (quinoxyfen), silicon metsulfovax (silthiofam), Apl-Luster (thiabendazole), thifluzamide (thifluzamide), thiophanate methyl (thiophanate-methyl), tiadinil, tricyclazole (tricyclazole) or triforine (triforine)
The copper fungicide agent, as Bordeaux mixture (Bordeaux mixture), neutralized verdigris, Cupravit or Basic Chrome Sulphate,
Nitrophenyl derivative, as Niagara 9044 (binapacryl), dinocap (dinocap), dinobuton (dinobuton) or different third disappear (nitrothal-isopropyl),
The phenylpyrrole class, as fenpiclonil (fenpiclonil) Huo Fu Evil bacterium (fludioxonil),
Sulphur,
Other mycocide, as thiadiazoles element (acibenzolar-S-methyl), benzene metsulfovax (benthiavalicarb), carpropamide (carpropamid), m-tetrachlorophthalodinitrile (chlorothalonil), cyflufenamid, cymoxanil (cymoxanil), dazomet (dazomet), diclomezine (diclomezine), two chlorine zarilamids (diclocymet), the mould prestige of second (diethofencarb), Hinosan (edifenphos), Guardian (ethaboxam), fenhexamid (fenhexamid), fentinacetate (fentin acetate), zarilamid (fenoxanil), ferimzone (ferimzone), fluazinam (fluazinam), fosetyl (fosetyl), fosetyl (fosetyl-aluminum), iprovalicarb (iprovalicarb), Perchlorobenzene (hexachlorobenzene), metrafenone, pencycuron (pencycuron), hundred dimension spirits (propamocarb), phthalide (phthalide), tolclofosmethyl (tolclofos-methyl), quintozene (quintozene) or zoxamide (zoxamide)
The strobilurins class, as nitrile Azoxystrobin (azoxystrobin), dimoxystrobin, fluoxastrobin (fluoxastrobin), imines bacterium (kresoxim-methyl), fork phenalgin acid amides (metominostrobin), orysastrobin, ZEN 90160 (picoxystrobin), Strobilurin (pyraclostrobin) or oxime bacterium ester (trifloxystrobin)
The sulfenic acid derivative, as Difolatan (captafol) but bacterium pellet (captan), Pecudin (dichlofluanid), Phaltan (folpet) or tolylfluanid (tolylfluanid),
Cinnamide and similar compound are as dimethomorph (dimethomorph), fluorine biphenyl bacterium (flumetover) or flumorph (flumorph).
Synthetic embodiment
Use the program described in the following synthetic embodiment to prepare other compounds by the appropriate change initial compounds.The compound that so obtains is in physical data is listed in the table below.
Embodiment 1:2-methyl-6-(2,4, the 6-trifluorophenyl) pyrazolos [1,5-a] pyrimidine-5,7-glycol [I-1]
The mixture of 3g (10.3mmol) 2-(2,4, the 6-trifluorophenyl) diethyl malonate, 1g (10.3mmol) 3-amino-5-methylpyrazole and 2.11g (11.4mmol) Tributylamine was stirred 5 hours down at 140 ℃, remove the ethanol of formation by distillation.Be cooled to after 20-25 ℃, adding the NaOH solution of about 10% concentration.With this mixture with methyl tertiary butyl ether (MTBE) extraction and with rare HCl solution acidifying water.Leach and the sedimentary crystal of dry gained.Obtain the 3g fusing point and be 304 ℃ title compound.
Embodiment 2:3,5,7-three chloro-6-(2,4, the 6-trifluorophenyl) pyrazolo [1,5-a] pyrimidine [II-1]
With 3.0g (10.7mmol) 6-(2,4, the 6-trifluorophenyl) pyrazolo [1,5-a] pyrimidine-5,7-glycol (referring to WO 02/48151), 2.22g (10.7mmol) phosphorus pentachloride and 9.72g (42.6mmol) benzyltriethylammoinium chloride refluxed 20 hours in the solution of 40ml phosphoryl chloride and 35ml acetonitrile.After the cooling, from reaction mixture, remove volatile constituent and resistates is dissolved in the methylene dichloride.To neutralize in this solution impouring frozen water and with sodium carbonate solution.After being separated, wash organic phase and dry with water, remove then and desolvate.Resistates obtains the 0.5g fusing point and is 128 ℃ title compound behind chromatography on the silica gel (cyclohexane/ethyl acetate mixture).
Embodiment 3:3,5-two chloro-7-(4-methyl piperidine-1-yl)-6-(2,4, the 6-trifluorophenyl) pyrazolo [1,5-a] pyrimidine [III-1]
With 0.1g (0.284mmol) 3,5,7-three chloro-6-(2,4, the 6-trifluorophenyl) pyrazolo [1,5-a] pyrimidine (embodiment 2), 0.03g (0.284mmol) 4-methyl piperidine and the solution of 0.03g triethylamine in the 1ml methylene dichloride were 20-25 ℃ of following stir about 4 hours.Add entry and separate each phase, use rare HCl solution and water washing organic phase and dry then, remove then and desolvate.It is 138 ℃ title compound that resistates obtains the 0.102g fusing point.
Embodiment 4:5-methyl-7-(4-methyl piperidine-1-yl)-6-(2,4, the 6-trifluorophenyl) pyrazolos [1,5-a] pyrimidine
Step a:5-methyl-6-(2,4, the 6-trifluorophenyl) pyrazolos [1,5-a] pyrimidin-7-ol
Figure A20048001569100421
The mixture of 2g (0.0081mol) 3-oxo-2-(2,4, the 6-trifluorophenyl) methyl-butyrate, 0.68g (0.0081mol) 3-amino-pyrazol and 1.66g (0.0089mol) Tributylamine was stirred 4 hours down at 160 ℃, steam and remove the methyl alcohol that forms.After cooling, adding concentration is 10% sodium hydroxide solution.Also use dilute hydrochloric acid acidifying water with methyl tertiary butyl ether extraction mixture.Leach crystal and drying by aqueous phase precipitation.Obtain the 1.9g isomer mixture, wherein 15% is that title compound and 85% is 7-methyl-6-(2,4, the 6-trifluorophenyl) pyrazolo [1,5-a] pyrimidine-5-alcohol.Under not purifying, isomer mixture is further reacted.
Step b:7-chloro-5-methyl-6-(2,4, the 6-trifluorophenyl) pyrazolos [1,5-a] pyrimidine
Figure A20048001569100431
The isomer mixture that under refluxing, obtains above with 2.8g (0.01mol) reflux 6 hours in the 10ml phosphoryl chloride.After cooling, in the careful impouring frozen water, use sodium carbonate solution to be adjusted to pH 7-8, the dry then organic phase that merges reaction mixture also with ethyl acetate extraction twice.Concentrate and obtain the 2.6g isomer mixture, it contains 15% title compound of having an appointment.
(hexanaphthene: ethyl acetate mixture) obtain the 400mg isomer mixture, it contains 80% title compound of having an appointment to chromatography on silica gel.
Step c:5-methyl-7-(4-methyl piperidine-1-yl)-6-(2,4, the 6-trifluorophenyl) pyrazolos [1,5-a] pyrimidine:
Isomer mixture (0.0013mol) and 0.25g (0.0025mol) 4-methyl piperidine that 0.4g is obtained above stirred 4 hours down and at room temperature stirred 12 hours at 40 ℃.Reaction mixture is dissolved in the ethyl acetate, is 5% hydrochloric acid washed twice with concentration, washes with water then, dry and concentrate.With the resistates chromatography, obtain the 0.176g isomer mixture, it contains 80% title compound of having an appointment.
Table I-Shi IV intermediate
Numbering Y p L m Physical data (fusing point [℃])
I-1 2-CH 3 2，4，6-F 3 304
I-2 2，3-(CH 3) 2 2，4，6-F 3 375 (decomposition)
I-3 3-CN 2，4，6-F 3 241
Table II-Shi V intermediate
Numbering Y p Hal L m Physical data (fusing point [℃])
II-1 3-Cl Cl 2，4，6-F 3 128
II-2 2-CH 3-3-Cl Cl 2，4，6-F 3 194
II-3 2-CH 3 Cl 2，4，6-F 3 Oil
II-4 2，3CH 3 Cl 2，4，6-F 3 Oil
Table III-Shi I compound
Numbering Y p R 1 R 2 X L m Physical data (fusing point [℃])
III-1 3-Cl -(CH 2) 2CH(CH 3)(CH 2) 2- Cl 2，4，6-F 3 138
III-2 2-CH 3-3-Cl -(CH 2) 2CH(CH 3)(CH 2) 2- Cl 2，4，6-F 3 135
III-3 2-CH 3 -(CH 2) 2CH(CH 3)(CH 2) 2- Cl 2，4，6-F 3 185
III-4 2-CH 3 -CH(CH 3)(CH 2) 3- Cl 2，4，6-F 3 163
III-5 2-CH 3-3-Cl -CH(CH 3)(CH 2) 3- Cl 2，4，6-F 3 152
III-6 3-Cl -CH(CH 3)(CH 2) 3- Cl 2，4，6-F 3 69 (decomposition)
III-7 2，3-CH 3 -(CH 2) 2CH(CH 3)(CH 2) 2- Cl 2，4，6-F 3 Oil
III-8 3-CN -(CH 2) 2CH(CH 3)(CH 2) 2- Cl 2，4，6-F 3 8.08 *
III-9 isomer A 3-CN (CH 3) 2CHCH(CH 3)- H Cl 2，4，6-F 3 8.23 *
III-10 isomer B 3-CN (CH 3) 2CHCH(CH 3)- H Cl 2，4，6-F 3 8.24 *
III-11 isomer A 3-CN (CH 3) 3CH(CH 3)- H Cl 2，4，6-F 3 8.24 *
III-12 isomer B 3-CN (CH 3) 3CH(CH 3)- H Cl 2，4，6-F 3 8.23 *
III-13 3-CN CH 3CH 2- CH 3CH 2- Cl 2，4，6-F 3 8.31 *
III-14 3-CN CH 2C(CH 3)CH 2- CH 3CH 2 Cl 2，4，6-F 3 8.35 *
III-15 3-CN (CH 3) 2CH- H Cl 2，4，6-F 3 146
III-16 3-CN CH 3CH 2CH(CH 3)- H Cl 2，4，6-F 3 119
III-17 3-CH 3 -(CH 2) 2CH(CH 3)(CH 2) 2- Cl 2，4，6-F 3 153
III-18 3-CH 3 -(CH 2) 2CH(CH 3)(CH 2) 2- OH 2，4，6-F 3 234
III-19 3-Cl -(CH 2) 2CH(CH 3)(CH 2) 2- CN 2，4，6-F 3 7.9 *
III-20 3-Cl -(CH 2) 2CH(CH 3)(CH 2) 2- OCH 3 2，4，6-F 3 8.13 *
III-21 3-CN -(CH 2) 2CH(CH 3)(CH 2) 2- OCH 3 2，4，6-F 3 8.62 *
III-22 3-CN -(CH 2) 2CH(CH 3)(CH 2) 2- CN 2，4，6-F 3 150
III-23 3-CN -(CH 2) 2CH(CH 3)(CH 2) 2- CH 3 2，4，6-F 3 8.27 *
* 1H-NMR(CDCl 3)：1H(H-2)
Effect embodiment to harmful fungoid
Fungicidal action by following experiment confirm formula I compound:
Active compound is prepared into the liquid storage that in acetone or DMSO, contains 0.25 weight % active compound separately.The emulsifying agent Uniperol that in this solution, adds 1 weight % EL (wetting agent with emulsification and dissemination is based on ethoxylated alkylphenol), and this solution with water is diluted to desired concn.
Application Example 1-is to the activity of the gray mold that caused on Folium Capsici by Botrytis cinerea (Botrytis cinerea), and protectiveness is used
Cultivar is sprayed to drip point with activity compound concentration aq suspension as described below for the capsicum rice shoot of " Neusiedler Ideal Elite " after the 4-5 sheet leaf that reaches full growth out.The plant that to handle in second day is with the spore suspension inoculation of Botrytis cinerea, and this suspension contains 1.7 * 10 in concentration is 2% biological malt water solution 6Individual spore/ml.Then test plant is placed the climatic regulation chamber of 22-24 ℃ and high atmospheric moisture.Can the % naked eyes after 5 days measure the fungal infection degree on the leaf.
In this test, use the active compound III-1 of 250ppm Table III or the plant of III-6 to demonstrate 7% infect at the most, and the plant 90% of being untreated is infected.
Application Example 2-is to the activity of the mildew that caused on Folium Cucumidis sativi by monofilament shell (Sphaerotheca fuliginea), and protectiveness is used
Cultivar is sprayed to drip point in the cotyledon stage with activity compound concentration aq suspension as described below for the leaf of the potted plant cucumber rice shoot of " Chinese snake ".Behind dry 20 hours of the spray-painting, with the moisture spore suspension inoculation plant of cucumber mildew (being the monofilament shell).Then with plant temperature be 20-24 ℃ and relatively atmospheric moisture be cultivation 7 days in the greenhouse of 60-80%.The % that infects with the cotyledon area measures the mildew development degree then.
In this test, the active compound III-1 of use 250ppm Table III or the plant of III-6 do not demonstrate infects, and the plant 90% of being untreated is infected.

Claims (16)

1. the substituted pyrazolecarboxylic of formula I and pyrimidine:
Figure A2004800156910002C1
Wherein substituting group is following defines:
L is halogen, C independently of each other 1-C 6Alkyl, C 2-C 6Alkenyl, C 1-C 6Haloalkyl, C 1-C 6Alkoxyl group, amino, NHR, NR 2, cyano group, S (=O) nA 1Or C (=O) A 2,
R is C 1-C 8Alkyl or C 1-C 8Alkyl-carbonyl;
A 1Be hydrogen, hydroxyl, C 1-C 8Alkyl, C 1-C 8Alkylamino or two (C 1-C 8Alkyl) amino;
N is 0,1 or 2;
A 2Be C 2-C 8Alkenyl, C 1-C 8Alkoxyl group, C 1-C 6Halogenated alkoxy or at A 1One of following group of being mentioned;
M is 0 or 1,2,3,4 or 5;
R 1Be C 1-C 8Alkyl, C 1-C 8Haloalkyl, C 3-C 6Cycloalkyl, C 3-C 6Halogenated cycloalkyl, C 2-C 8Alkenyl, C 4-C 10Alkadienyl, C 2-C 8Halogenated alkenyl, C 3-C 6Cycloalkenyl group, C 2-C 8Alkynyl, C 2-C 8Halo alkynyl or C 3-C 6Cycloalkynyl radical, phenyl, naphthyl or contain 1-4 and be selected from that the heteroatomic 5-10 unit of O, N and S is saturated, part is unsaturated or aromatic heterocycle;
R 2For hydrogen or at R 1One of following group of being mentioned;
R 1And R 2Can also form the atomic separation that can be selected from O, N and S and/or can have one or more halogen, C of being selected from the nitrogen-atoms that they connected 1-C 6Alkyl, C 1-C 6Haloalkyl and oxygen base-C 1-C 3The substituting group of alkylene oxide group or wherein nitrogen-atoms and adjacent carbons can be by C 1-C 45 or 6 yuan of rings that alkylidene chain connects;
R wherein 1And/or R 2Can be by 1-4 identical or different radicals R aReplace:
R aBe halogen, cyano group, nitro, hydroxyl, C 1-C 6Alkyl, C 1-C 6Haloalkyl, C 1-C 6Alkyl-carbonyl, C 3-C 6Cycloalkyl, C 1-C 6Alkoxyl group, C 1-C 6Halogenated alkoxy, C 1-C 6Carbalkoxy, C 1-C 6Alkylthio, C 1-C 6Alkylamino, two C 1-C 6Alkylamino, C 2-C 6Alkenyl, C 2-C 6Alkenyloxy, C 3-C 6Alkynyloxy group, C 3-C 6Cycloalkyl, phenyl, naphthyl, or contain 1-4 and be selected from that the heteroatomic 5-10 unit of O, N and S is saturated, part is unsaturated or aromatic heterocycle,
Wherein these aliphatic series, alicyclic or aromatic group itself can maybe can be had 1-3 radicals R by halo partially or completely b:
R bBe halogen, cyano group, nitro, hydroxyl, sulfydryl, amino, carboxyl, aminocarboxyl, thiocarbamoyl, alkyl, haloalkyl, alkenyl, alkenyloxy, alkynyloxy group, alkoxyl group, halogenated alkoxy, alkylthio, alkylamino, dialkyl amido, formyl radical, alkyl-carbonyl, alkyl sulphonyl, alkyl sulphinyl, carbalkoxy, alkyl carbonyl oxy, alkyl amino-carbonyl, dialkyl amino carbonyl, the alkylamino thiocarbonyl group, the dialkyl amido thiocarbonyl group, wherein the alkyl in these groups contains 1-6 carbon atom and the alkenyl of mentioning or alkynyl and contains 2-8 carbon atom in these groups;
And/or 1-3 following groups:
Cycloalkyl, cycloalkyloxy, heterocyclic radical, heterocyclic oxy group, wherein the ring-type system contains 3-10 ring members; Aryl, aryloxy, arylthio, aryl-C 1-C 6Alkoxyl group, aryl-C 1-C 6Alkyl, heteroaryl, heteroaryloxy, heteroarylthio, wherein aryl preferably contains 6-10 ring members and heteroaryl contains 5 or 6 ring memberses, and wherein the ring-type system can or can be replaced by alkyl or haloalkyl by halo partially or completely;
X is halogen, cyano group, OH, C 1-C 4Alkyl, C 1-C 4Alkoxyl group or C 1-C 2Halogenated alkoxy, Y are to contain 1-4 to be selected from that the heteroatomic 5-10 unit of O, N and S is saturated, part is unsaturated or aromatic heterocycle, or one of the group of under X, mentioning (this group can be by 1-4 identical or different radicals R aReplace), nitro, amino ,-CHO ,-NHCO-NH-C 1-C 6Alkyl ,-NHCO-O-C 1-C 6Alkyl ,-CO-NH 2
P is 1 or 2, and wherein as if p=2, then group Y can be different;
If radicals X is cyano group, C 1-C 4Alkyl, C 1-C 4Alkoxyl group or C 1-C 4Halogenated alkoxy, then p is 0.
2. according to the formula I compound of claim 1, wherein X is halogen, CN, OH, C 1-C 4Alkyl or C 1-C 4Alkoxyl group.
3. according to the formula I compound of claim 1, wherein X is halogen, CN or C 1-C 4Alkyl.
4. according to the formula I compound of claim 1, wherein X is halogen or C 1-C 4Alkyl.
5. according to the formula I compound of claim 1, wherein X is a halogen.
6. according to each formula I compound among the claim 1-5, wherein R 1And R 2The following definition:
R 1Be C 1-C 6Alkyl, C 1-C 8Haloalkyl, C 3-C 6Cycloalkyl, C 3-C 6Halogenated cycloalkyl, C 2-C 8Alkenyl, C 2-C 8Halogenated alkenyl, C 2-C 8Alkynyl; With
R 2Be hydrogen or C 1-C 4Alkyl; Or
R 1And R 2Can also form with the nitrogen-atoms that they connected and to have 1 or 2 and be selected from halogen, C 1-C 6Alkyl and C 1-C 6Substituent 5 or 6 yuan of saturated or unsaturated rings of haloalkyl.
7. according to each formula I compound among the claim 1-6, wherein by L mThe phenyl that replaces is group C:
Figure A2004800156910004C1
Wherein # is the tie point with the triazolo pyrimidine skeleton, and
L 1Be fluorine, chlorine, CH 3Or CF 3
L 2, L 4Be hydrogen or fluorine independently of each other;
L 3Be hydrogen, fluorine, chlorine, cyano group, CH 3, OCH 3Or COOCH 3With
L 5Be hydrogen, fluorine or CH 3
8. preparation is the method for the formula I compound of halogen according to the wherein X of claim 1, wherein makes wherein Y pAs replacement 3-amino-pyrazol-derivatives according to the defined formula II of formula I of claim 1:
Figure A2004800156910004C2
React with 2-phenylmalonic acid ester III:
Figure A2004800156910004C3
Obtain dihydroxyl pyrazolopyrimidine IV,
The IV halogenation is obtained halo pyrazolopyrimidine V:
Figure A2004800156910005C2
And the amine of V and formula VI is reacted:
Figure A2004800156910005C3
9. preparation is the method that halogen and Y are positioned at 3 formula I compound of pyrazolopyrimidine skeleton according to the wherein radicals X and the Y of claim 1, wherein halogenation formula VII compound:
Figure A2004800156910005C4
Wherein variable defines suc as formula I and Hal is a halogen atom, obtains the three halo pyrazolopyrimidines of formula VIII:
And make VIII and amine reaction according to the formula VI of claim 5, obtain formula I.A compound:
Figure A2004800156910005C6
10. preparation is cyano group, C according to the wherein X of claim 1 1-C 6Alkoxyl group or C 1-C 2The method of the formula I compound of halogenated alkoxy, wherein making wherein, X is halo pyrazolopyrimidine and the reaction of formula IX compound of the formula I of halogen:
M-X′ IX
Wherein X ' is cyano group, C 1-C 6Alkoxyl group or C 1-C 2Halogenated alkoxy and M are ammonium, tetra-allkylammonium or basic metal or alkaline earth metal cation, obtain formula I.B compound:
Figure A2004800156910006C1
11. preparation is C according to the wherein X of claim 1 1-C 4The method of the formula I compound of alkyl, wherein making X wherein is that the halo pyrazolopyrimidine of formula I of halogen and the compound of formula X react in inert solvent or thinner down transition metal-catalyzed:
M y(X″) y X
Wherein X " is C 1-C 4Alkyl and M are the metal ion of Y valency, especially B, Zn or Sn, obtain formula I.C compound:
Wherein X " is C 1-C 4Alkyl.
12. preparation is C according to the wherein X of claim 1 1-C 4The method of the formula I compound of alkyl wherein makes the ketone ester reaction according to replacement 3-amino-pyrazol and the formula XI of the formula II of claim 5:
Figure A2004800156910006C3
Wherein R is C 1-C 4Alkyl and X " are C 1-C 4Alkyl obtains hydroxypyrazoles and the pyrimidine of formula XII:
Figure A2004800156910006C4
And, obtain the compound of formula XIII with the XII halogenation:
Figure A2004800156910006C5
And make XIII and amine reaction according to the formula VI of claim 5, obtaining wherein, X is C 1-C 4The formula I compound of alkyl.
13. preparation is CN or C according to the wherein X of claim 1 1-C 4The method of the formula I compound of alkoxyl group wherein uses the aqueous sodium hydroxide solution partial hydrolysis according to 5 of the formula V of claim 5, and 7-dihalo pyrazolopyrimidine obtains 5-halo-7-hydroxypyrazoles and pyrimidine Va:
Figure A2004800156910007C1
Make Va and organometallic compound reaction, obtain the compound of formula XIIa according to the formula IX of claim 10:
Figure A2004800156910007C2
Wherein X ' is CN or C 1-C 4Alkoxyl group and M such as claim 10 definition; Halogenation XIIa then obtains the compound of formula XIIIa:
Figure A2004800156910007C3
And the amine of the compound of XIIIa and formula VI is according to Claim 8 reacted, obtain formula I.D compound:
Figure A2004800156910007C4
14. the intermediate of 9,12 or 13 formula IV, V, Va, VIII, XII, XIIa, XIII or XIIIa according to Claim 8.
15. a composition that is suitable for preventing and treating harmful fungoid, said composition comprise solid or liquid vehicle and according to the formula I compound of claim 1.
16. a method of preventing and treating the plant-pathogenic harmful fungoid comprises maybe will preventing material, plant, soil or the seed of fungal attack with significant quantity according to the formula I compound treatment fungi of claim 1.
CN 200480015691 2003-06-03 2004-05-27 Substituted pyrazolopyrimidines, methods for the production thereof, use of the same for controlling pathogenic fungi, and agents containing said compounds Pending CN1829717A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105980386A (en) * 2013-03-13 2016-09-28 基因泰克公司 Pyrazolo compounds and uses thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105980386A (en) * 2013-03-13 2016-09-28 基因泰克公司 Pyrazolo compounds and uses thereof
CN105980386B (en) * 2013-03-13 2021-08-13 基因泰克公司 Pyrazolo compounds and uses thereof

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