CN104892581A - 2-methyl-4-amino-5-(substituted-1,2,3-triazolyl)methylpyridine derivatives having bactericidal activity, and preparation method and application thereof - Google Patents

2-methyl-4-amino-5-(substituted-1,2,3-triazolyl)methylpyridine derivatives having bactericidal activity, and preparation method and application thereof Download PDF

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CN104892581A
CN104892581A CN201410082965.XA CN201410082965A CN104892581A CN 104892581 A CN104892581 A CN 104892581A CN 201410082965 A CN201410082965 A CN 201410082965A CN 104892581 A CN104892581 A CN 104892581A
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dmso
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贺红武
王威
贺军波
张�林
朱国中
郭新娟
邹鹏
谭效松
彭浩
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Huazhong Normal University
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
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Abstract

The invention discloses 2-methyl-4-amino-5-(substituted-1,2,3-triazolyl)methylpyridine derivatives having a bactericidal activity, and a preparation method and an application thereof, wherein the derivatives have the structural formula described in the specification, wherein R<1> represents H or I, X represents O, NH or S, Y represents benzoylamide thiocarbonyl or substituted benzoylamide thiocarbonyl, 2-phenyl-1,3,4-thiadiazole(oxadiazole)-5-yl or 2-substituted phenyl-1,3,4-thiadiazole(oxadiazole)-5-yl, benzophenone (acetophenone) imine or substituted benzophenone (acetophenone) imine, and Y-involved substituents on a benzene ring mainly comprise H, halogen, nitro, cyano group, CF3, C1-4 alkyl, methoxyl, C1-2 carboxylic group or carboxylate group. The compounds have a significant control effect on wheat gibberellic hypha, rice rhizoctonia solani, cucumber borrytis cinerea, tomato alternaria solani, alternaria alternata and cucumber colletrichum orbiculare, and can be used for bactericidal active ingredients.

Description

There is 2-methyl-4-amino-5-(replacement-1,2,3-triazoles base) the methylpyrimidine derivative of fungicidal activity, its preparation method and application
Technical field
The present invention relates to 2-methyl-4-amino-5-(replacement-1,2,3-triazoles base) methylpyrimidine derivative, its preparation method and application thereof.
Background technology
Pyruvate dehydrogenase system is the class important enzyme system in organism self-energy metabolic regulation process, and it is connected to the process that conversion of pyruvate that glycolysis-obtains is the substrate acetyl coenzyme A of tricarboxylic acid cycle.Based on the Biochemical Characteristics that it is important, pyruvate dehydrogenase system can be used as agricultural chemicals target completely and studies.In recent years, the present inventor is with pyruvate dehydrogenase system in microorganism for target, and design and synthesis has the novel texture compound as sterilant using value.Such as, category-A (application number is 201110268908.7 for He Hongwu etc., Chinese invention patent) compound then shows excellent fungicidal activity.
Summary of the invention
The object of the invention is to explore the novel cpd with fungicidal activity, and provide a kind of there is fungicidal activity 2-methyl-4-amino-5-(replacement-1,2,3-triazoles base) methylpyrimidine derivative, its preparation method and application.
The present invention is in the category-A compound basis enterprising one-step optimization structure type of Y, and propose a kind of novel cpd with fungicidal activity, it has the structure of general formula (I):
Wherein, R 1represent hydrogen or I; X represents O, NH or S; Y represents benzamide thiocarbonyl group or substituted benzamide thiocarbonyl group, 2-phenyl-1,3,4-thiophene (Evil) diazole-5-base or 2-substituted-phenyl-1,3,4-thiophene (Evil)-5-base, benzene first (ethyl ketone) imido grpup or substituted benzoyl (ethyl ketone) imido grpup; Substituting group on the phenyl ring involved by Y is mainly: H, halogen, nitro, cyano group, CF 3, C 1-4alkyl, methoxyl group, C 1-2carboxylic acid group or carboxylic acid ester groups; Monosubstituted or polysubstituted on phenyl ring optional position of substituting group, substituting group is identical or different.
Compound (I) comprise with general formula (I-1) represent [1-(2-methyl-4-aminopyrimidine-5-methyl)-1H-1, 2, 3-triazole]-4-methyl-(substituted benzoyl) thiocarbamate (thiocarbamide) compound, N-((1-((2-methyl-4-aminopyrimidine-5-the base represented with general formula (I-2)) methyl)-1H-1, 2, 3-triazole-4-yl) methyl)-2-substituted-phenyl-1, 3, 4-thiophene (Evil)-5-base sulfide compound, the O-that represents with general formula (I-3) [1-(2-methyl-4-aminopyrimidine-5-methyl)-1H-1, 2, 3-triazole-4-yl] substituted benzoyl (ethyl ketone) oxime ether compound.
The compound structure of general formula (I-1) proposed by the invention, general formula (I-2), general formula (I-3) is not reported, and the structure of general formula (I-1), general formula (I-2), general formula (I-3) is defined as follows respectively:
In general formula (I-1), X is oxygen or NH; R 1definition and the R of general formula (I) 1define identical; R 2for: H, halogen, nitro, methoxyl group or C 1-4alkyl; R 3for: H, halogen, nitro, cyano group, CF 3, C 1-4alkyl or methoxyl group; R 2with R 3position is interchangeable.
In general formula (I-2), X is oxygen or S; R 1definition and the R of general formula (I) 1define identical; R 2for: H, halogen, nitro or C 1-4alkyl; R 3for: H, halogen, nitro, CF 3, methoxyl group or C 1-4alkyl; R 2with R 3position is interchangeable.
In general formula (I-3), R 1definition and the R of general formula (I) 1define identical; R 2for H, nitro or halogen; R 3for: H, halogen, nitro, C 1-4alkyl or methoxyl group; R 2with R 3position is interchangeable; R 4for H or methyl.
The compound that the present invention has general formula (I) structure has significant preventive effect to fusarium graminearum, Rhizoctonia solani Kuhn, botrytis cinerea pers, tomato early blight bacterium, tobacco brown spot pathogen and cucumber anthracnose, can be used as the activeconstituents of sterilant.
Having the preparation method of the compound of general formula (I-1) structure, is at catalyzer and organic bases or only in the presence of a catalyst, compound (II) and alkynes intermediate (III) is reacted at-10 ~ 80 DEG C of temperature within 12-24 hour, close ring to generate, A method.Reaction formula is as follows:
In above-mentioned reaction formula (1), R in general formula (III) 1, R 2, R 3, R in the definition of X and general formula (I-1) 1, R 2, R 3, X definition identical.
In above-mentioned A method reaction, the mol ratio of compound (II), intermediate (III), catalyzer and organic bases is 1:(0.8-1.2): (0.01-0.15): 2; Reaction solvent adopts organic solvent: methylene dichloride, dioxane, ethylene dichloride, acetone, the trimethyl carbinol, water, benzene, ethyl acetate, tetrahydrofuran (THF), acetonitrile, DMF or dimethyl sulfoxide (DMSO); Catalyzer is: CuI, CuBr (PPh 3) 3, CuSO 45H 2o: sodium ascorbate, CuBr or Cu (OAc) 2; Organic bases is: triethylamine, diisopropyl ethyl amine, pyridine or hexahydropyridine.
Having the preparation method of the compound of general formula (I-2) structure, is at catalyzer and organic bases or only in the presence of a catalyst, compound (II) and intermediate (IV) is reacted at-10 ~ 80 DEG C of temperature within 12-24 hour, close ring to generate, B method.Reaction formula is as follows:
In above-mentioned reaction formula (2), R in general formula (IV) 1, R 2, R 3, R in the definition of X and general formula (I-2) 1, R 2, R 3, X definition identical.
In above-mentioned B method reaction, the mol ratio of compound (II), intermediate (IV), catalyzer and organic bases is 1:(0.8-1.2): (0.01-0.15): 2; Reaction solvent adopts organic solvent: methylene dichloride, dioxane, ethylene dichloride, acetone, the trimethyl carbinol: water, benzene, ethyl acetate, tetrahydrofuran (THF), acetonitrile, DMF or dimethyl sulfoxide (DMSO); Catalyzer is: CuI, CuBr (PPh 3) 3, CuSO 45H 2o: sodium ascorbate, CuBr or Cu (OAc) 2; Organic bases is: triethylamine, diisopropyl ethyl amine, pyridine or hexahydropyridine.
Having the preparation method of the compound of general formula (I-2) structure, is at catalyzer and organic bases or only in the presence of a catalyst, compound (II) and intermediate (V) is reacted at-10 ~ 80 DEG C of temperature within 12-24 hour, close ring to generate, C method.Reaction formula is as follows:
In above-mentioned reaction formula (3), R in logical formula V 1, R 2, R 3, R 4definition and general formula (I-3) in R 1, R 2, R 3, R 4definition identical.
In above-mentioned C method reaction, the mol ratio of compound (II), intermediate (V), catalyzer and organic bases is 1:(0.8-1.2): (0.01-0.15): 2; Reaction solvent adopts organic solvent: methylene dichloride, dioxane, ethylene dichloride, acetone, the trimethyl carbinol: water, benzene, ethyl acetate, tetrahydrofuran (THF), acetonitrile, DMF or dimethyl sulfoxide (DMSO); Catalyzer is: CuI, CuBr (PPh 3) 3, CuSO 45H 2o: sodium ascorbate, CuBr or Cu (OAc) 2; Organic bases is: triethylamine, diisopropyl ethyl amine, pyridine or hexahydropyridine.
Embodiment
Specifically describe the compounds of this invention (I) below by embodiment, comprise the preparation method of compound (I-1), (I-2), (I-3), only the present invention will be described for these embodiments, instead of limit the invention.
The compound (II) adopted in following embodiment can be prepared see the method recorded in document 1.
Embodiment 1: intermediate III-1 preparation
0.28g propargyl alcohol (5mmol), 0.5g triethylamine (5mmol) and 10mL acetonitrile is added in the 100mL three-necked bottle that drying tube, low-reading thermometer, constant pressure funnel are housed, 4 DEG C are cooled in cryogenic thermostat reactive bath technique, slowly add the acetonitrile solution of the benzoyl isothiocyanate of 10mL, wherein benzoyl isothiocyanate is 5mmol; Maintain reacting liquid temperature lower than 5 DEG C, after treating the acetonitrile solution dropwise of benzoyl isothiocyanate, be transferred to room temperature reaction, TLC(thin-layer chromatography) monitoring.Reaction terminate after, successively with 5% dilute hydrochloric acid, saturated sodium bicarbonate solution and saturated common salt water washing to solution in neutrality.Then use methylene dichloride (15mL × 3 time) aqueous phase extracted, organic phase, anhydrous sodium sulfate drying spend the night through merging, suction filtration, filtrate concentrates and obtain thick product, namely obtain sterling through silica gel column chromatography gradient elution (sherwood oil: ethyl acetate=3:1).
R 1, R 2, R 3, to be other substituent intermediate III obtain by intermediate III-1 similar approach X.
Embodiment 2: intermediate compound IV-1 preparation
5-phenyl-1,3,4-thiadiazoles-2-mercaptan, the 4.0mmol potassium carbonate powder of 4.0mmol is added in 50mL round-bottomed flask, be dissolved in the dry dimethyl sulfoxide (DMSO) of 15mL, 4.8mmol bromopropyl alcohol is added dropwise to, in stirred at ambient temperature reaction, TLC(thin-layer chromatography under room temperature) monitoring reaction disappears to raw material point, after stopped reaction, by in system impouring 100mL water, fully stir, have a large amount of solid to separate out, suction filtration obtains crude product IV-1, without the need to purifying.
R 1, R 2, R 3, to be other substituent intermediate compound IV obtain by intermediate compound IV-1 similar approach X.
Embodiment 3: intermediate V-1 preparation
Respectively 5mmol benzaldoxime, 5mmol propargyl bromide are dissolved in 20mL anhydrous acetonitrile, then add 5mmol sodium hydroxide, back flow reaction 8 hours, TLC(thin-layer chromatography) monitoring react completely.Decompression removing acetonitrile, then successively through dilute hydrochloric acid, saturated sodium bicarbonate solution, saturated common salt water washing, by ethyl acetate (20mL × 3 time) aqueous phase extracted, through merging organic phase, anhydrous sodium sulfate drying, concentrate to obtain thick product, acetone recrystallization obtains intermediate V-1.
R 1, R 2, R 3, R 4obtain for other substituent intermediate V press intermediate V-1 similar approach.
Embodiment 4: compound 1 preparation
1mmol2-methyl-4-amino-5-azido-methyl pyrimidine and 1mmol O-proyl benzoyl-amido thiocarboxylic are dissolved in 20mL tetrahydrofuran (THF); add 2mmol triethylamine and 0.1mmol cuprous iodide CuI; at 60-70 DEG C of stirring reaction 10-15 hour; TLC(thin-layer chromatography) monitoring reaction is extremely completely; the solid that added water is separated out, through the crude product of filtration under diminished pressure, washing, oven dry.With DMF and water recrystallization, obtain the target compound of yellow solid, productive rate 88%, mp:120-122 DEG C.
Ultimate analysis/%: calculated value: C, 53.25; H, 4.47; N, 25.57; S, 8.36; Measured value: C, 53.09; H, 4.74; N, 25.33; S, 8.04; 1h NMR (400MHz, CDCl 3): δ 2.49 (s, 3H, CH 3), 5.35 (s, 2H, CH 2), 5.44 (s, 2H, CH 2), 5.66 (s, 2H, NH 2), 7.41-8.03 (m, 5H, Ar-H), 7.72 (s, 1H, CH), 8.19 (s, 1H, CH); 13c NMR (100MHz, DMSO-d 6): δ 25.2,46.9,57.9,108.2,125.0,128.8,129.2,133.5,142.0,156.4,161.6,165.5,167.2,179.3.IR (KBr): 1277 (C=S), 1702 (C=O), 3150 (N-H), 3512cm- 1.ESI-MS (m/z): 384 (M ++ 1).
Compound 2-20 presses compound 1 similar approach and obtains, and Structural Identification data are as follows:
Compound 2
Gained sterling is yellow solid, productive rate 87%, m.p.115-116 DEG C; .Ultimate analysis/%: calculated value: C, 48.86; H, 3.86; N, 23.46; S, 7.67; Measured value: C, 48.83; H, 4.20; N, 23.57; S, 7.82; 1h NMR (400MHz, CDCl 3): δ 2.50 (s, 3H, CH 3), 5.36 (s, 2H, CH 2), 5.45 (s, 2H, CH2), 5.58 (s, 2H, NH 2), 7.28-7.85 (m, 4H, Ar-H), 7.46 (s, 1H, CH), 8.19 (s, 1H, CH) .IR (KBr): 1265 (C=S), 1717 (C=O), 3145 (N-H), 3544cm -1.ESI-MS (m/z): 418 (M ++ 1).
Compound 3
Gained sterling is yellow solid, productive rate 84%, m.p.139-141 DEG C.Ultimate analysis/%: calculated value: C, 48.86; H, 3.86; N, 23.46; S, 7.67; Measured value: C, 49.24; H, 3.96; N, 23.53; S, 7.74; 1h NMR (400MHz, CDCl 3): δ 2.49 (s, 3H, CH 3), 5.38 (s, 2H, CH 2), 5.44 (s, 2H, CH2), 5.66 (s, 2H, NH 2), 7.35-7.99 (m, 4H, Ar-H), 7.72 (s, 1H, CH), 8.05 (s, 1H, CH) .IR (KBr): 1270 (C=S), 1722 (C=O), 3147 (N-H), 3454cm -1.ESI-MS (m/z): 418 (M ++ 1).
Compound 4
Gained sterling is yellow solid, productive rate 78%, m.p.124-125 DEG C.Ultimate analysis/%: calculated value: C, 48.86; H, 3.86; N, 23.46; S, 7.67; Measured value: C, 49.02; H, 4.05; N, 23.33; S, 7.75; 1h NMR (400MHz, CDCl 3): δ 2.49 (s, 3H, CH 3), 5.36 (s, 2H, CH 2), 5.43 (s, 2H, CH2), 5.63 (s, 2H, NH 2), 7.39-7.97 (m, 4H, Ar-H), 7.71 (s, 1H, CH), 8.20 (s, 1H, CH); 13c NMR (100MHz, DMSO-d 6): δ 25.2,46.8,58.1,108.2,125.0,128.1,131.0,138.4,141.7,156.3,161.5,164.6,167.6,180.3.IR (KBr): 1277 (C=S), 1708 (C=O), 3110 (N-H), 3452cm -1.ESI-MS (m/z): 418 (M ++ 1).
Compound 5
Gained sterling is light yellow solid, productive rate 73%, m.p.156-157 DEG C.Ultimate analysis/%: calculated value: C, 54.39; H, 4.82; N, 24.67; S, 8.07; Measured value: C, 54.69; H, 4.99; N, 24.65; S, 7.62; 1h NMR (400MHz, CDCl3): δ 2.49 (s, 3H, CH 3), 2.62 (s, 3H, CH 3), 5.36 (s, 2H, CH 2), 5.41 (s, 2H, CH2), 5.67 (s, 2H, NH 2), 7.22-7.96 (m, 4H, Ar-H), 7.71 (s, 1H, CH), 8.20 (s, 1H, CH) .IR (KBr): 1270 (C=S), 1702 (C=O), 3150 (N-H), 3512cm -1.ESI-MS (m/z): 398 (M ++ 1).
Compound 6
Gained sterling is yellow solid, productive rate 83%, m.p.123-125 DEG C.Ultimate analysis/%: calculated value: C, 54.39; H, 4.82; N, 24.67; S, 8.07; Measured value: C, 54.17; H, 4.73; N, 23.55; S, 8.01; 1h NMR (400MHz, CDCl 3): δ 2.51 (s, 3H, CH 3), 2.65 (s, 3H, CH 3), 5.38 (s, 2H, CH 2), 5.43 (s, 2H, CH2), 5.54 (s, 2H, NH 2), 7.32-7.93 (m, 4H, Ar-H), 7.71 (s, 1H, CH), 8.08 (s, 1H, CH) .IR (KBr): 1253 (C=S), 1709 (C=O), 3118 (N-H), 3452cm -1.ESI-MS (m/z): 398 (M ++ 1).
Compound 7
Gained sterling is light yellow solid, productive rate 71%, m.p.146-148 DEG C.Ultimate analysis/%: calculated value: C, 50.87; H, 4.02; N, 24.43; S, 7.99; Measured value: C, 51.04; H, 4.29; N, 24.32; S, 7.66; 1h NMR (400MHz, CDCl3): δ 2.49 (s, 3H, CH 3), 5.36 (s, 2H, CH 2), 5.46 (s, 2H, CH 2), 5.60 (s, 2H, NH 2), 7.11-7.93 (m, 4H, Ar-H), 7.52 (s, 1H, CH), 8.20 (s, 1H, CH) .IR (KBr): 1253 (C=S), 1729 (C=O), 3148 (N-H), 3453cm -1.ESI-MS (m/z): 402 (M ++ 1).
Compound 8
Gained sterling is yellow solid, productive rate 76%, m.p.132-133 DEG C.Ultimate analysis/%: calculated value: C, 50.87; H, 4.02; N, 24.43; S, 7.99; Measured value: C, 50.92; H, 4.34; N, 24.40; S, 7.80; 1h NMR (400MHz, CDCl 3): δ 2.50 (s, 3H, CH 3), 5.36 (s, 2H, CH 2), 5.43 (s, 2H, CH 2), 5.62 (s, 2H, NH 2), 7.07-8.06 (m, 4H, Ar-H), 7.71 (s, 1H, CH), 8.20 (s, 1H, CH) .IR (KBr): 1253 (C=S), 1721 (C=O), 3111 (N-H), 3454cm -1.ESI-MS (m/z): 402 (M ++ 1).
Compound 9
Gained sterling is yellow solid, productive rate 70%, m.p.134-136 DEG C.Ultimate analysis/%: calculated value: C, 44.16; H, 3.49; N, 21.21; S, 6.94; Measured value: C, 44.44; H, 3.77; N, 31.38; S, 6.84; 1h NMR (400MHz, CDCl 3): δ 2.50 (s, 3H, CH 3), 5.36 (s, 2H, CH 2), 5.45 (s, 2H, CH 2), 5.61 (s, 2H, NH 2), 7.33-7.80 (m, 4H, Ar-H), 7.66 (s, 1H, CH), 8.20 (s, 1H, CH) .IR (KBr): 1270 (C=S), 1721 (C=O), 3145 (N-H), 3453cm -1.ESI-MS (m/z): 463 (M ++ 1).
Compound 10
Gained sterling is yellow solid, productive rate 77%, m.p.141-142 DEG C.Ultimate analysis/%: calculated value: C, 48.68; H, 3.60; N, 23.38; S, 7.65; Measured value: C, 48.32; H, 3.86; N, 23.62; S, 7.54; 1h NMR (400MHz, CDCl 3): δ 2.49 (s, 3H, CH 3), 5.36 (s, 2H, CH 2), 5.42 (s, 2H, CH 2), 5.59 (s, 2H, NH 2), 6.92-7.71 (m, 4H, Ar-H), 7.71 (s, 1H, CH), 8.20 (s, 1H, CH) .IR (KBr): 1265 (C=S), 1725 (C=O), 3139 (N-H), 3440cm -1.ESI-MS (m/z): 420 (M ++ 1).
Compound 11
Gained sterling is yellow solid, productive rate 50%, m.p.73-75 DEG C.Element analysis/%: calculated value: C, 44.11; H, 3.27; N, 24.21; S, 6.93; Measured value: C, 44.25; H, 3.42; N, 24.22; S, 6.82; 1h NMR (600MHz, DMSO-d 6): δ 2.29 (s, 3H, CH 3), 5.44 (s, 2H, CH 2), 5.49 (s, 2H, CH 2), 6.98 (s, 2H, NH 2), 7.99-8.27 (m, 3H, Ar-H), 8.38 (s, 1H, CH); 13c NMR (100MHz, DMSO-d 6): δ 25.3,46.8,109.3,122.4,125.2,125.5,132.0,132.6,135.4,141.1,142.9,149.4,156.2,161.4,163.5,194.5.IR (KBr): 1243 (C=S), 1603 (C=O), 3369 (N-H) cm -1.EI-MS (m/z, %): 462 (M +, 2).
Compound 12
Gained sterling is yellow solid, productive rate 56%, m.p.62-64 DEG C.Ultimate analysis/%: calculated value: C, 45.14; H, 3.34; N, 21.68; S, 7.09; Measured value: C, 45.25; H, 3.56; N, 21.95; S, 7.25; 1h NMR (600MHz, DMSO-d 6): δ 2.30 (s, 3H, CH 3), 5.38 (s, 2H, CH 2), 5.47 (s, 2H, CH 2), 6.98 (s, 2H, NH 2), 7.53-7.81 (m, 3H, Ar-H), 8.25 (s, 1H, CH) .IR (KBr): 1245 (C=S), 1604 (C=O), 3366 (N-H) cm -1.EI-MS (m/z, %): 451 (M +, 2).
Compound 13
Gained sterling is yellow solid, productive rate 87%, m.p.96-98 DEG C.Ultimate analysis/%: calculated value: C, 51.46; H, 4.77; N, 22.11; S, 7.23; Measured value: C, 51.62; H, 4.59; N, 22.95; S, 6.98; 1h NMR (400MHz, DMSO-d 6): δ 2.30 (s, 3H, CH 3), 3.78 (s, 3H, OCH 3), 3.81 (s, 3H, OCH 3), 5.34 (s, 2H, CH 2), 5.45 (s, 2H, CH 2), 6.94 (s, 2H, NH 2), 7.05 (d, 1H, J=8.8Hz, Ar-H), 7.41 (s, 1H, Ar-H), 7.56 (d, 1H, J=7.2Hz, Ar-H), 8.22 (s, 1H, CH); 13c NMR (100MHz, DMSO-d 6): δ 25.3,46.7,55.5,55.7,57.6,111.0,111.6,121.4,123.3,124.9,142.2,148.4,153.1156.0,160.9,161.4,165.2,166.9,180.3.IR (KBr): 1271 (C=S), 1706 (C=O), 3365 (N-H) cm -1.EI-MS (m/z, %): 462 (M +, 2).
Compound 14
Gained sterling is yellow solid, productive rate 44%, m.p.>260 DEG C.Ultimate analysis/%: calculated value: C, 43.13; H, 3.19; N, 26.63; S, 6.77; Measured value: C, 43.35; H, 3.42; N, 26.12; S, 6.53; 1h NMR (600MHz, DMSO-d 6): δ 2.29 (s, 3H, CH 3), 5.50 (s, 2H, CH 2), 5.52 (s, 2H, CH 2), 7.00 (s, 2H, NH 2), 8.30 (s, 1H, CH), 8.87 (s, 1H, Ar-H), 9.03 (s, 1H, Ar-H) .IR (KBr): 1277 (C=S), 1726 (C=O), 3362 (N-H) cm -1.EI-MS (m/z, %): 473 (M +, 4).
Compound 15
Gained sterling is yellow solid, productive rate 34%, m.p.206-208 DEG C.Ultimate analysis/%: calculated value: C, 51.46; H, 4.77; N, 22.11; S, 7.23; Measured value: C, 51.27; H, 4.49; N, 22.22; S, 7.38; 1h NMR (400MHz, DMSO-d 6): δ 2.29 (s, 3H, CH 3), 3.78 (s, 3H, OCH 3), 3.81 (s, 3H, OCH 3), 5.34 (s, 2H, CH 2), 5.48 (s, 2H, CH 2), 6.98 (s, 2H, NH 2), 7.04 (d, 1H, J=8.4Hz, Ar-H), 7.41 (d, 1H, J=1.8Hz, Ar-H), 7.56 (d, 1H, J=8.4Hz, Ar-H) .IR (KBr): 1271 (C=S), 1706 (C=O), 3369 (N-H) cm -1.EI-MS (m/z, %): 443 (M +, 4).
Compound 16
Gained sterling is yellow solid, productive rate 77%, m.p.141-142 DEG C.Ultimate analysis/%: calculated value: C, 48.68; H, 3.60; N, 23.38; S, 7.65; Measured value: C, 48.32; H, 3.86; N, 23.62; S, 7.54; 1h NMR (400MHz, CDCl 3): δ 2.49 (s, 3H, CH 3), 5.36 (s, 2H, CH 2), 5.42 (s, 2H, CH 2), 5.59 (s, 2H, NH 2), 6.92-7.71 (m, 4H, Ar-H), 7.71 (s, 1H, CH), 8.20 (s, 1H, CH) .IR (KBr): 1265 (C=S), 1725 (C=O), 3139 (N-H), 3440cm -1.EI-MS (m/z, %): 420 (M ++ 1,100).
Compound 17
Gained sterling is yellow solid, productive rate 33%, m.p.230-232 DEG C.Ultimate analysis/%: calculated value: C, 45.14; H, 3.34; N, 21.68; S, 7.09; Measured value: C, 45.22; H, 3.11; N, 21.88; S, 7.20; 1h NMR (400MHz, DMSO-d 6): δ 2.32 (s, 3H, CH 3), 5.39 (s, 2H, CH 2), 5.51 (s, 2H, CH 2), 7.06 (s, 2H, NH 2), 7.53-7.81 (m, 3H, Ar-H), 8.25 (s, 1H, CH) .IR (KBr): 1271 (C=S), 1712 (C=O), 3426 (N-H) cm -1.EI-MS (m/z, %): 451 (M +, 2).
Compound 18
Gained sterling is yellow solid, productive rate 30%, m.p.191-193 DEG C.Ultimate analysis/%: calculated value: C, 40.09; H, 3.17; N, 19.25; S, 6.30; Measured value: C, 40.20; H, 3.45; N, 19.18; S, 6.16; 1h NMR (600MHz, DMSO-d 6): δ 2.29 (s, 3H, CH 3), 4.49 (s, 2H, CH 2), 5.43 (s, 2H, CH 2), 6.97 (s, 2H, NH 2), 7.16-7.85 (m, 3H, Ar-H), 7.97 (s, 1H, CH) .IR (KBr): 1285 (C=S), 1715 (C=O), 3364 (N-H) cm -1.EI-MS (m/z, %): 509 (M +, 2).
Compound 19
Gained sterling is yellow solid, productive rate 40%, m.p.138-140 DEG C.Ultimate analysis/%: calculated value: C, 47.89; H, 3.57; N, 21.72; S, 7.10; Measured value: C, 47.05; H, 3.64; N, 21.67; S, 7.38; 1h NMR (600MHz, DMSO-d 6): δ 2.30 (s, 3H, CH 3), 5.25 (s, 2H, CH 2), 5.45 (s, 2H, CH 2), 6.95 (s, 2H, NH 2), 7.49-7.79 (m, 4H, Ar-H), 8.01 (s, 1H, CH), 8.03 (s, 1H, CH) .IR (KBr): 1323 (C=S), 1656 (C=O), 3376 (N-H) cm -1.EI-MS (m/z, %): 451 (M +, 2).
Compound 20
Gained sterling is yellow solid, productive rate 37%, m.p.>260 DEG C.Ultimate analysis/%: calculated value: C, 52.93; H, 3.95; N, 27.43; S, 7.85; Measured value: C, 52.78; H, 3.72; N, 27.12; S, 7.55; 1h NMR (400MHz, DMSO-d 6): δ 2.50 (s, 3H, CH 3), 4.52 (s, 2H, CH 2), 5.51 (s, 2H, CH 2), 7.11 (s, 2H, NH 2), 7.96 (m, 4H, Ar-H), 8.00 (s, 1H, CH), 9.28 (s, 1H, CH) .IR (KBr): 1271 (C=S), 1712 (C=O), 3426 (N-H) cm -1.EI-MS (m/z, %): 408 (M +, 2).
Embodiment 5: compound 21 preparation
1mmol2-methyl-4-amino-5-azido-methyl pyrimidine and 1mmol proyl benzoylthioureas are dissolved in 20mL acetonitrile; add 2mmol diisopropyl ethyl amine and 0.1mmol cuprous iodide; at 30-40 DEG C of stirring reaction 10-15 hour; TLC(thin-layer chromatography) monitoring reaction is extremely completely; the solid that added water is separated out; through filtration under diminished pressure, washing, oven dry, obtain crude product.With DMF and water recrystallization, obtaining target compound, is light yellow solid, productive rate 70%, mp:124-126 DEG C.
Ultimate analysis/%: calculated value: C, 53.39; H, 4.74; N, 29.30; S, 8.38; Measured value: C, 53.04; H, 4.65; N, 29.27; S, 8.35; 1h NMR (400MHz, CDCl 3): δ 2.49 (s, 3H, CH 3), 5.35 (s, 2H, CH 2), 5.44 (s, 2H, CH 2), 5.66 (s, 2H, NH 2), 7.41-8.03 (m, 5H, Ar-H), 7.72 (s, 1H, CH), 8.19 (s, 1H, CH) .IR (KBr): 1265 (C=S), 1692 (C=O), 3150 (N-H), 3410cm -1.EI-MS (m/z, %): 383 (M ++ 1,100).
Compound 22-40 presses compound 21 similar approach and obtains, and its Structural Identification data are as follows:
Compound 22
Gained sterling is yellow solid, productive rate 87%, m.p.115-116 DEG C.Ultimate analysis/%: calculated value: C, 48.98; H, 4.11; N, 26.88; S, 7.69; Measured value: C, 49.20; H, 4.36; N, 26.79; S, 7.74; 1h NMR (400MHz, CDCl 3): δ 2.50 (s, 3H, CH 3), 5.36 (s, 2H, CH 2), 5.45 (s, 2H, CH 2), 5.58 (s, 2H, NH 2), 7.28-7.85 (m, 4H, Ar-H), 7.46 (s, 1H, CH), 8.19 (s, 1H, CH) .IR (KBr): 1250 (C=S), 1717 (C=O), 3145 (N-H), 3544cm -1.EI-MS (m/z, %): 417 (M ++ 1,100).
Compound 23
Gained sterling is yellow solid, productive rate 85%, m.p.159-161 DEG C.Ultimate analysis/%: calculated value: C, 48.98; H, 4.11; N, 26.88; S, 7.69; Measured value: C, 48.99; H, 4.43; N, 26.52; S, 7.39; 1h NMR (400MHz, CDCl 3): δ 2.49 (s, 3H, CH 3), 5.38 (s, 2H, CH 2), 5.44 (s, 2H, CH 2), 5.66 (s, 2H, NH 2), 7.35-7.99 (m, 4H, Ar-H), 7.72 (s, 1H, CH), 8.05 (s, 1H, CH) .IR (KBr): 1250 (C=S), 1722 (C=O), 3147 (N-H), 3454cm -1.EI-MS (m/z, %): 417 (M ++ 1,100).
Compound 24
Gained sterling is yellow solid, productive rate 77%, m.p.124-125 DEG C; Ultimate analysis/%: calculated value: C, 48.98; H, 4.11; N, 26.88; S, 7.69; Measured value: C, 48.92; H, 4.54; N, 27.11; S, 7.50; 1h NMR (400MHz, CDCl 3): δ 2.49 (s, 3H, CH 3), 5.36 (s, 2H, CH 2), 5.43 (s, 2H, CH 2), 5.63 (s, 2H, NH 2), 7.39-7.97 (m, 4H, Ar-H), 7.71 (s, 1H, CH), 8.20 (s, 1H, CH) .IR (KBr): 1250 (C=S), 1708 (C=O), 3110 (N-H), 3452cm -1.EI-MS (m/z, %): 417 (M ++ 1,100).
Compound 25
Gained sterling is light yellow solid, productive rate 80%, m.p.156-157 DEG C.Ultimate analysis/%: calculated value: C, 54.53; H, 5.08; N, 28.26; S, 8.09; Measured value: C, 49.68; H, 4.85; N, 28.40; S, 8.14; 1h NMR (400MHz, CDCl3): δ 2.49 (s, 3H, CH 3), 2.62 (s, 3H, CH 3), 5.36 (s, 2H, CH 2), 5.41 (s, 2H, CH 2), 5.67 (s, 2H, NH 2), 7.22-7.96 (m, 4H, Ar-H), 7.71 (s, 1H, CH), 8.20 (s, 1H, CH) .IR (KBr): 1270 (C=S), 1702 (C=O), 3150 (N-H), 3512cm -1.EI-MS (m/z, %): 397 (M ++ 1,100).
Compound 26
Gained sterling is yellow solid, productive rate 80%, m.p.120-122 DEG C.Ultimate analysis/%: calculated value: C, 54.53; H, 5.08; N, 28.26; S, 8.09; Measured value: C, 54.31; H, 5.11; N, 28.17; S, 8.22; 1h NMR (400MHz, CDCl 3): δ 2.51 (s, 3H, CH 3), 2.65 (s, 3H, CH 3), 5.38 (s, 2H, CH 2), 5.43 (s, 2H, CH 2), 5.54 (s, 2H, NH 2), 7.32-7.93 (m, 4H, Ar-H), 7.71 (s, 1H, CH), 8.08 (s, 1H, CH) .IR (KBr): 1270 (C=S), 1709 (C=O), 3118 (N-H), 3452cm -1.EI-MS (m/z, %): 397 (M ++ 1,100).
Compound 27
Gained sterling is light yellow solid, productive rate 90%, m.p.141-143 DEG C.Ultimate analysis/%: calculated value: C, 50.99; H, 4.28; N, 27.98; S, 8.01; Measured value: C, 50.76; H, 4.06; N, 27.84; S, 8.26; 1h NMR (400MHz, CDCl3): δ 2.49 (s, 3H, CH 3), 5.36 (s, 2H, CH 2), 5.46 (s, 2H, CH 2), 5.60 (s, 2H, NH 2), 7.11-7.93 (m, 4H, Ar-H), 7.52 (s, 1H, CH), 8.20 (s, 1H, CH) .IR (KBr): 1270 (C=S), 1729 (C=O), 3148 (N-H), 3453cm -1.EI-MS (m/z, %): 401 (M ++ 1,100).
Compound 28
Gained sterling is yellow solid, productive rate 78%, m.p.152-153 DEG C.Ultimate analysis/%: calculated value: C, 50.99; H, 4.28; N, 27.98; S, 8.01; Measured value: C, 51.03; H, 4.01; N, 27.84; S, 8.26; 1h NMR (400MHz, CDCl 3): δ 2.50 (s, 3H, CH 3), 5.36 (s, 2H, CH 2), 5.43 (s, 2H, CH 2), 5.62 (s, 2H, NH 2), 7.10-8.06 (m, 4H, Ar-H), 7.71 (s, 1H, CH), 8.20 (s, 1H, CH) .IR (KBr): 1270 (C=S), 1721 (C=O), 3111 (N-H), 3454cm -1.EI-MS (m/z, %): 401 (M ++ 1,100).
Compound 29
Gained sterling is yellow solid, productive rate 86%, m.p.134-136 DEG C.Ultimate analysis/%: calculated value: C, 44.26; H, 3.71; N, 24.29; S, 6.95; Measured value: C, 44.04; H, 3.97; N, 24.11; S, 6.83; 1h NMR (400MHz, CDCl 3): δ 2.50 (s, 3H, CH 3), 5.36 (s, 2H, CH 2), 5.45 (s, 2H, CH 2), 5.61 (s, 2H, NH 2), 7.33-7.80 (m, 4H, Ar-H), 7.66 (s, 1H, CH), 8.20 (s, 1H, CH) .IR (KBr): 1270 (C=S), 1721 (C=O), 3145 (N-H), 3453cm -1.EI-MS (m/z, %): 462 (M ++ 1,100).
Compound 30
Gained sterling is yellow solid, productive rate 65%, m.p.165-167 DEG C.Ultimate analysis/%: calculated value: C, 48.80; H, 3.85; N, 26.78; S, 7.66; Measured value: C, 48.65; H, 3.82; N, 26.88; S, 7.82; 1h NMR (400MHz, CDCl 3): δ 2.49 (s, 3H, CH 3), 5.36 (s, 2H, CH 2), 5.42 (s, 2H, CH 2), 5.59 (s, 2H, NH 2), 6.92-7.71 (m, 4H, Ar-H), 7.71 (s, 1H, CH), 8.20 (s, 1H, CH) .IR (KBr): 1270 (C=S), 1725 (C=O), 3139 (N-H), 3440cm -1.EI-MS (m/z, %): 419 (M ++ 1,100).
Compound 31
Gained sterling is yellow solid, productive rate 42%, m.p.240-242 DEG C.Ultimate analysis/%: calculated value: C, 44.21; H, 3.49; N, 27.29; S, 6.94; Measured value: C, 44.55; H, 3.67; N, 27.46; S, 6.62; 1h NMR (600MHz, DMSO-d 6): δ 2.29 (s, 3H, CH 3), 4.48 (s, 2H, J=6.0Hz, CH 2), 5.48 (s, 2H, CH 2), 6.97 (s, 2H, NH 2), 7.68 (d, 1H, J=8.4Hz, Ar-H), 8.02 (s, 1H, CH), 8.21 (d, 1H, J=8.4Hz, Ar-H), 8.32 (s, 1H, Ar-H), 9.23 (s, 1H, CH) .IR (KBr): 1355 (C=S), 1679 (C=O), 3218 (N-H) cm -1.EI-MS (m/z, %): 461 (M +, 2).
Compound 32
Gained sterling is yellow solid, productive rate 50%, m.p.186-188 DEG C.Ultimate analysis/%: calculated value: C, 45.24; H, 3.57; N, 24.83; S, 7.10; Measured value: C, 45.02; H, 3.30; N, 24.00; S, 7.46; 1h NMR (400MHz, DMSO-d 6): δ 2.29 (s, 3H, CH 3), 4.48 (s, 2H, J=6.0Hz, CH 2), 5.63 (s, 2H, CH 2), 7.08 (s, 2H, NH 2), 7.48 (s, 2H, Ar-H), 7.68 (s, 1H, Ar-H), 8.02 (s, 1H, Ar-H), 8.32 (s, 1H, Ar-H), 9.23 (s, 1H, CH) .IR (KBr): 1299 (C=S), 1666 (C=O), 3363 (N-H) cm -1.EI-MS (m/z, %): 450 (M +, 2).
Compound 33
Gained sterling is yellow solid, productive rate 62%, m.p.208-209 DEG C.Ultimate analysis/%: calculated value: C, 51.57; H, 5.01; N, 25.32; S, 7.25; Measured value: C, 51.22; H, 5.47; N, 25.04; S, 7.48; 1h NMR (400MHz, DMSO-d 6): δ 2.30 (s, 3H, CH 3), 3.82 (s, 6H, OCH 3), 4.47 (s, 2H, CH 2), 5.42 (s, 2H, CH 2), 6.97 (s, 2H, NH 2), 7.04 (s, 2H, Ar-H), 7.60 (s, 2H, Ar-H), 8.02 (s, 1H, Ar-H), 8.32 (s, 1H, Ar-H), 9.12 (s, 1H, CH); 13c NMR (100MHz, DMSO-d 6): δ 27.4,34.7,47.2,56.0,113.7,127.1,128.9,130.0,131.0,132.3,134.4,135.1,138.3,140.6,160.3,161.1,165.3,169.2,192.4.IR (KBr): 1267 (C=S), 1695 (C=O), 3334 (N-H) cm -1.EI-MS (m/z, %): 442 (M +, 2).
Compound 34
Gained sterling is yellow solid, productive rate 44%, m.p.181-183 DEG C.Ultimate analysis/%: calculated value: C, 43.22; H, 3.41; N, 29.65; S, 6.79; Measured value: C, 42.48; H, 3.47; N, 29.76; S, 6.52; 1h NMR (400MHz, DMSO-d 6): δ 2.28 (s, 3H, CH 3), 4.57 (s, 2H, CH 2), 5.42 (s, 2H, CH 2), 6.93 (s, 2H, NH 2), 8.07 (s, 1H, CH), 8.95 (s, 1H, Ar-H), 9.07 (s, 2H, Ar-H), 9.75 (s, 1H, CH) .IR (KBr): 1344 (C=S), 1672 (C=O), 3414 (N-H) cm -1.EI-MS (m/z, %): 472 (M +, 2).
Compound 35
Gained sterling is yellow solid, productive rate 34%, m.p.191-193 DEG C.Ultimate analysis/%: calculated value: C, 51.57; H, 5.01; N, 25.32; S, 7.25; Measured value: C, 50.60; H, 5.42; N, 25.17; S, 7.05; 1h NMR (400MHz, DMSO-d 6): δ 2.32 (s, 3H, CH 3), 3.75 (s, 3H, OCH 3), 3.78 (s, 3H, OCH 3), 4.85 (s, 2H, CH 2), 5.48 (s, 2H, CH 2), 6.97 (s, 2H, NH 2), 6.67-7.34 (m, 3H, Ar-H), 8.13 (s, 1H, CH), 11.00 (s, 1H, NH), 11.76 (s, 1H, NH) .IR (KBr): 1288 (C=S), 1631 (C=O), 3432 (N-H) cm -1.EI-MS (m/z, %): 442 (M +, 5).
Compound 36
Gained sterling is yellow solid, productive rate 97%, m.p.228-230 DEG C.Ultimate analysis/%: calculated value: C, 48.80; H, 3.85; N, 26.78; S, 7.66; Measured value: C, 48.63; H, 3.73; N, 26.13; S, 7.48; 1h NMR (400MHz, DMSO-d 6): δ 2.30 (s, 3H, CH 3), 4.48 (d, 2H, J=5.2Hz, CH 2), 5.43 (s, 2H, CH 2), 6.94 (s, 2H, NH 2), 7.14-7.71 (m, 3H, Ar-H), 8.00 (s, 1H, CH), 8.83 (s, 1H, CH); 13c NMR (100MHz, DMSO-d 6): δ 25.2,46.6,67.0,104.2,104.5,104.8,111.6,111.8,120.2,120.4,123.0,131.8,131.9,144.8,158.5,158.6,161.0,161.1,161.4,162.1,162.2,162.8,164.7.IR (KBr): 1432 (C=S), 1663 (C=O), 3309 (N-H) cm -1.EI-MS (m/z, %): 442 (M +, 5).
Compound 37
Gained sterling is yellow solid, productive rate 45%, m.p.164-166 DEG C.Ultimate analysis/%: calculated value: C, 45.24; H, 3.57; N, 24.83; S, 7.10; Measured value: C, 45.60; H, 3.44; N, 24.13; S, 7.36; 1h NMR (400MHz, DMSO-d 6): δ 2.32 (s, 3H, CH 3), 4.39 (s, 2H, CH 2), 5.51 (s, 2H, CH 2), 7.06 (s, 2H, NH 2), 7.53-7.81 (m, 3H, Ar-H), 8.25 (s, 1H, CH) .IR (KBr): 1431 (C=S), 1644 (C=O), 3428 (N-H) cm -1.EI-MS (m/z, %): 450 (M +, 2).
Compound 38
Gained sterling is yellow solid, and productive rate is 30%, m.p.206-208 DEG C.Ultimate analysis/%: calculated value: C, 40.17; H, 3.37; N, 22.04; S, 6.31; Measured value: C, 40.32; H, 3.55; N, 22.77; S, 6.19; 1h NMR (400MHz, DMSO-d 6): δ 2.30 (s, 3H, CH 3), 4.43 (s, 2H, CH 2), 5.44 (s, 2H, CH 2), 6.98 (s, 2H, NH 2), 7.16-7.85 (m, 4H, Ar-H), 8.00 (s, 1H, CH), 8.91 (s, 1H, CH) .IR (KBr): 1389 (C=S), 1664 (C=O), 3335 (N-H) cm -1.EI-MS (m/z, %): 508 (M +, 2).
Compound 39
Gained sterling is yellow solid, productive rate 40%, m.p.230-232 DEG C.Ultimate analysis/%: calculated value: C, 48.00; H, 3.80; N, 24.88; S, 7.12; Measured value: C, 48.18; H, 3.95; N, 24.44; S, 7.55; 1h NMR (400MHz, DMSO-d 6): δ 2.29 (s, 3H, CH 3), 4.52 (s, 2H, CH 2), 5.39 (s, 2H, CH 2), 6.91 (s, 2H, NH 2), 7.85 (s, 2H, Ar-H), 8.02 (s, 2H, Ar-H), 8.04 (s, 1H, CH), 9.26 (s, 1H, CH) .IR (KBr): 1336 (C=S), 1631 (C=O), 3423 (N-H) cm -1.EI-MS (m/z, %): 450 (M +, 2).
Compound 40
Gained sterling is yellow solid, productive rate 35%, m.p.193-195 DEG C.Ultimate analysis/%: calculated value: C, 53.06; H, 4.21; N, 30.94; S, 7.87; Measured value: C, 53.14; H, 4.06; N, 30.01; S, 7.65; 1h NMR (400MHz, DMSO-d 6): δ 2.40 (s, 3H, CH 3), 4.51 (s, 2H, CH 2), 5.46 (s, 2H, CH 2), 7.02 (s, 2H, NH 2), 7.99 (m, 4H, Ar-H), 7.99 (s, 2H, Ar-H), 9.28 (s, 1H, CH) .IR (KBr): 1285 (C=S), 1663 (C=O), 3416 (N-H) cm -1.EI-MS (m/z, %): 407 (M +, 2).
Embodiment 6: compound 41 preparation
2.0mmol2-methyl-4-amino-5-azido-methyl pyrimidine, 2.0mmol triethylamine, 10mL anhydrous acetonitrile, 2.1mmol5-phenyl-(1 is added in 50mL round-bottomed flask, 3,4-thiadiazoles)-2-sulfenyl propine, stirring and dissolving, add the CuI of 0.1mmol again, stirred at ambient temperature reacts, TLC(thin-layer chromatography) monitoring reaction is extremely completely, the stirring that adds water has solid to separate out, the crude product of suction filtration, washing, oven dry, through ethyl alcohol recrystallization, obtains target compound, is white solid, productive rate 91%, mp:121-123 DEG C.
1H NMR(600MHz,DMSO-d 6)δ(ppm):2.32(s,3H,CH 3),4.65(s,2H,-SCH 2-),5.44(s,2H,CH 2),7.04(s,2H,NH 2),7.58-7.97(m,5H,H-Ph),8.16(s,1H,pyrimidin-5-yl-H);IR(KBr):ν3385(N-H),3140,2361,2356,1663,1594,1574,1471,1430,1224,1195,1120,1064,995,837,814,780,706;HRMS(calcd.)[M+Na] +:419.0837(419.0740).
Compound 42-74 presses compound 41 similar approach and obtains, and its Structural Identification data are as follows:
Compound 42
Gained sterling is yellow solid, productive rate 90%, m.p.128-130 DEG C; 1h NMR (400MHz, DMSO-d 6) δ (ppm): 2.29 (s, 3H, CH 3), 4.63 (s, 2H ,-SCH 2-), 5.42 (s, 2H, CH 2), 6.93 (s, 2H, NH 2), 7.57-8.25 (m, 4H, 1H, H 3,5and6-Ph, pyrimidin-5-yl-H); IR (KBr): 3337 (N-H), 3196,2369,2359,2100,1600,1564 (N=O), 1466,1345 (N=O), 1260,1228,1194,1121,1089,1048,855,807,725.
Compound 43
Gained sterling is yellow solid, productive rate 91%; M.p.137-139 DEG C; 1h NMR (400MHz, DMSO-d 6) δ (ppm): 2.28 (s, 3H, CH 3), 4.66 (s, 2H ,-SCH 2-), 5.41 (s, 2H, CH 2), 6.91 (s, 2H, NH 2), 8.14 (s, 1H, pyrimidin-5-yl-H), 8.20-8.43 (m, 4H, H 2,3,5and6-Ph); IR (KBr): 3400 (N-H), 3142,2363,2354,1632,1595,1558,1521 (N=O), 1463,1346 (N=O), 1190,1115,1069,855,808,790,708; HRMS (calcd.) [M+Na] +: 464.0688 (464.0695).
Compound 44
Gained sterling is white solid, productive rate 91%; M.p.157-160 DEG C; 1h NMR (400MHz, DMSO-d 6) δ (ppm): 2.29 (s, 3H, CH 3), 4.63 (s, 2H ,-SCH 2-), 5.43 (s, 2H, CH 2), 6.97 (s, 2H, NH 2), 7.55-7.95 (m, 4H, H 3,4,5and6-Ph), 8.14 (s, 1H, pyrimidin-5-yl-H); IR (KBr): 3379 (N-H), 3140,2364,2355,1660,1595,1572,1478,1431,1196,1120,1091,1050,814,779,762,729; HRMS (calcd.) [M+Na] +: 453.0447 (453.0393).
Compound 45
Gained sterling is white solid, productive rate 91%; M.p.169-171 DEG C; 1h NMR (400MHz, DMSO-d 6) δ (ppm): 2.30 (s, 3H, CH 3), 4.62 (s, 2H ,-SCH 2-), 5.42 (s, 2H, CH 2), 6.93 (s, 2H, NH 2), 6.93-7.40 (m, 4H, H 2,3,5and6-Ph), 8.13 (s, 1H, pyrimidin-5-yl-H); IR (KBr): 3334 (N-H), 3162,2364,2359,1664,1593,1571,1472,1426,1222,1197,1118,1094,1068,1054,839,813,782,729.
Compound 46
Gained sterling is yellow solid, productive rate 92%; M.p.117-120 DEG C; 1h NMR (400MHz, DMSO-d 6) δ (ppm): 2.29 (s, 3H, CH 3), 4.63 (s, 2H ,-SCH 2-), 5.42 (s, 2H, CH 2), 6.93 (s, 2H, NH 2), 7.93-8.19 (m, 4H, 1H, H 3,4,5and6-Ph, pyrimidin-5-yl-H); IR (KBr): 3411 (N-H), 3144,2453,2353,1662,1647,1596,1572,1528 (N=O), 1465,1432,1352 (N=O), 1196,1118,1065,996,857,809,789,726; HRMS (calcd.) [M+Na] +: 464.0688 (464.0676).
Compound 47
Gained sterling is white solid, productive rate 93%; M.p.133-135 DEG C; 1h NMR (400MHz, DMSO-d 6) δ (ppm): 2.29 (s, 3H, CH 3), 4.63 (s, 2H ,-SCH 2-), 5.42 (s, 2H, CH 2), 6.93 (s, 2H, NH 2), 7.07-7.63 (m, 3H, H 3, 5and6-Ph), 8.13 (s, 1H, pyrimidin-5-yl-H); IR (KBr): 3327 (N-H), 3167,2394,2354,1658,1593,1568,1474,1426,1373,1194,1148,1118,1089,1051,864,813,777,731.
Compound 48
Gained sterling is white solid, productive rate 93%; M.p.137-139 DEG C; 1h NMR (600MHz, DMSO-d 6) δ (ppm): 2.29 (s, 3H, CH 3), 4.61 (s, 2H ,-SCH 2-), 5.43 (s, 2H, CH 2), 6.96 (s, 2H, NH 2), 7.41-7.44 (m, 2H, H 2,6-Ph), 7.99-8.00 (m, 2H, H 3,5-Ph), 8.13 (s, 1H, pyrimidin-5-yl-H); IR (KBr): 3334 (N-H), 3150,2432,2354,1665,1609,1594,1573,1501,1473,1426,1357,1228,1192,1119,1066,845,814,781,732; HRMS (calcd.) [M+Na] +: 437.0743 (437.0713).
Compound 49
Gained sterling is white solid, productive rate 91%; M.p.115-117 DEG C; 1h NMR (600MHz, DMSO-d 6) δ (ppm): 2.28 (s, 3H, CH 3), 4.65 (s, 2H ,-SCH 2-), 5.41 (s, 2H, CH 2), 6.94 (s, 2H, NH 2), 7.96-7.98 (m, 2H, H 2,6-Ph), 8.13-8.15 (m, 3H, H 3,5-Ph, pyrimidin-5-yl-H); IR (KBr): 3389 (N-H), 3069,2400,2354,1664,1595,1558,1505,1468,1416,1324,1197,1166,1111,1077,1058,857,812,791; HRMS (calcd.) [M+Na] +: 487.0711 (487.0722).
Compound 50
Gained sterling is yellow solid, productive rate 85%; M.p.144-147 DEG C; 1h NMR (400MHz, DMSO-d 6) δ (ppm): 2.30 (s, 3H, CH 3), 4.65 (s, 2H ,-SCH 2-), 5.43 (s, 2H, CH 2), 6.91 (s, 2H, NH 2), 7.55-7.78 (m, 3H, H 2,4and6-Ph), 8.15 (s, 1H, pyrimidin-5-yl-H); IR (KBr): 3364 (N-H), 3222,2363,2354,1633,1598,1561,1531 (N=O), 1470,1346, (N=O) 1283,1235,1180,1102,991,865,811,750,720.
Compound 51
Gained sterling is yellow solid, productive rate 88%; M.p.151-153 DEG C; 1h NMR (400MHz, DMSO-d 6) δ (ppm): 2.28 (s, 3H, CH 3), 4.67 (s, 2H ,-SCH 2-), 5.42 (s, 2H, CH 2), 6.94 (s, 2H, NH 2), 7.87 (s, 1H, H 1-Ph), 8.15 (s, 1H, pyrimidin-5-yl-H), 8.35-8.63 (m, 3H, H 4,5and6-Ph); IR (KBr): 3370 (N-H), 2355,2335,1629,1597,1557,1528 (N=O), 1462,1433,1352 (N=O), 1229,1198,1113,1058,972,871,811,789,744,709; HRMS (calcd.) [M+Na] +: 464.0688 (464.0638).
Compound 52
Gained sterling is white solid, productive rate 90%; M. pdEG C .139-141; 1h NMR (400MHz, DMSO-d 6) δ (ppm): 2.31 (s, 3H, CH 3), 4.63 (s, 2H ,-SCH 2-), 5.48 (s, 2H, CH 2), 7.02 (s, 2H, NH 2), 7.40-7.99 (m, 4H, H 3,4,5and6-Ph), 8.15 (s, 1H, pyrimidin-5-yl-H); IR (KBr): 3401 (N-H), 3132,2440,2356,1666,1600,1564,1493,1477,1437,1337,1222,1183,1118,1054,814,790,771,736; HRMS (calcd.) [M+Na] +: 437.0743 (437.0700).
Compound 53
Gained sterling is yellow solid, and productive rate is 70%; M.p.170-171 DEG C; Ultimate analysis/%: calculated value: C, 42.95; H, 3.18; N, 23.57; S, 13.49; Measured value: C, 43.36; H, 3.39; N, 23.21; S, 13.14; 1hNMR (400MHz, DMSO-d6 (ppm): 2.28 (s, 3H, CH 3), 4.62 (s, 2H ,-SCH 2-), 5.41 (s, 2H, CH 2), 6.91 (s, 2H, NH 2), 7.54-7.58 (m, 2H, H-Ph), 7.84-7.89 (m, 2H, H-Ph), 8.02 (s, 1H, 1,2,3-triazol-4-yl-H); (8.14 s, 1H, pyrimidin-5-yl-H), 13cNMR (100MHz, DMSO-d 6) δ (ppm): 25.4,26.9,47.0,109.7,120.9,124.4,128.5,131.8,133.6,134.6,142.6,148.1,156.3,161.6,164.3.
Compound 54
Gained sterling is light yellow solid, productive rate 52%; M.p.180-182 DEG C; Ultimate analysis/%: calculated value: C, 50.69; H, 4.25; N, 26.27; S, 15.04; Measured value: C, 50.42; H, 4.46; N, 26.24; S, 15.15; 1h NMR (400MHz, DMSO-d6) δ (ppm): 2.29 (s, 3H, CH 3), 3.84 (s, 3H, OCH 3), 4.61 (s, 2H ,-SCH 2-), 5.42 (s, 2H, CH 2), 6.94 (s, 2H, NH 2), 7.13 (d, 2H, J=10.8Hz, Ar-H), 7.89 (d, 2H, J=10.8Hz, Ar-H), 8.14 (s, 1H, pyrimidin-5-yl-H).
Compound 55
Gained sterling is light yellow solid, productive rate 71%; M.p.209-211 DEG C; Ultimate analysis/%: calculated value: C, 52.66; H, 4.42; N, 27.30; S, 15.62; Measured value: C, 52.68; H, 4.49; N, 27.27; S, 15.48; 1h NMR (400MHz, DMSO-d6) δ (ppm): 2.28 (s, 3H, CH 3), 2.38 (s, 3H, CH 3), 4.61 (s, 2H ,-SCH 2-), 5.40 (s, 2H, CH 2), 6.93 (s, 2H, NH 2), 7.39 (d, 2H, J=8.0Hz, Ar-H), 7.84 (d, 2H, J=8.0Hz, Ar-H), 7.98 (s, 1H, 1,2,3-triazol-4-yl-H), 8.14 (s, 1H, pyrimidin-5-yl-H).
Compound 56
Gained sterling is brown solid, productive rate 62%; M.p.155-156 DEG C; Ultimate analysis/%: calculated value: C, 52.66; H, 4.42; N, 27.30; S, 15.62; Measured value: C, 51.90; H, 4.85; N, 26.66; S, 15.39; 1h NMR (600MHz, DMSO-d6) δ (ppm): 2.39 (s, 3H, CH 3), 2.61 (s, 3H, CH 3), 4.75 (s, 2H ,-SCH 2-), 5.52 (s, 2H, CH 2), 7.05 (s, 2H, NH 2), 7.55-7.59 (m, 2H, Ar-H), 7.86-7.90 (m, 2H, Ar-H), 8.08 (s, 1H, 1,2,3-triazol-4-yl-H), 8.25 (s, 1H, pyrimidin-5-yl-H).
Compound 57
Gained sterling is light yellow solid, productive rate 74%; M.p.149-151 DEG C; 1h NMR (600MHz, DMSO-d6) δ (ppm): 2.29 (s, 3H, CH 3), 2.57 (s, 3H, CH 3), 4.64 (s, 2H ,-SCH 2-), 5.42 (s, 2H, CH 2), 6.95 (s, 2H, NH 2), 7.41 (d, 2H, J=27.0Hz, H-Ph), 7.49 (d, H, H-Ph), 7.85 (d, 2H, J=7.2Hz, Ar-H), 7.90 (s, 1H, 1,2,3-triazol-4-yl-H), 8.06 (s, 1H, pyrimidin-5-yl-H).
Compound 58
Gained sterling is yellow solid, productive rate 93%; M.p.162-164 DEG C; 1h NMR (400MHz, DMSO-d 6) δ (ppm): 2.32 (s, 3H, CH 3), 4.64 (s, 2H ,-SCH 2-), 5.42 (s, 2H, CH 2), 7.00 (s, 2H, NH 2), 7.52-7.99 (m, 3H, H 3,5and6-Ph), 8.13 (s, 1H, pyrimidin-5-yl-H); IR (KBr): 3356 (N-H), 3132,2355,2332,2097,1629,1594,1559 (N=O), 1467,1345 (N=O), 1260,1227,1193,1089,1050,883,806,729.
Compound 59
Gained sterling is yellow solid, productive rate 90%; M.p.143-145 DEG C; 1h NMR (400MHz, DMSO-d 6) δ (ppm): 2.31 (s, 3H, CH 3), 4.63 (s, 2H ,-SCH 2-), 5.44 (s, 2H, CH 2), 6.97 (s, 2H, NH 2), 7.91-8.18 (m, 4H, 1H, H 3,4,5and6-Ph, pyrimidin-5-yl-H); 13c NMR (100MHz, DMSO-d 6) δ (ppm): 25.11,26.86,46.78,108.35,123.92,124.56,127.74,128.48,142.25,149.15,155.89,161.45,163.98,164.51,167.18; HRMS (calcd.) [M+H] +: 426.1097 (426.1102).
Compound 60
Gained sterling is yellow solid, productive rate 86%; M.p.126-128 DEG C; 1h NMR (400MHz, DMSO-d 6) δ (ppm): 2.31 (s, 3H, CH 3), 4.63 (s, 2H ,-SCH 2-), 5.44 (s, 2H, CH 2), 6.97 (s, 2H, NH 2), 7.08-7.41 (m, 4H, H 3,4,5and6-Ph), 8.11 (s, 1H, pyrimidin-5-yl-H); IR (KBr): 3382 (N-H), 3141,2355,2334,1660,1595,1572,1468,1431,1359,1196,1120,1091,1071,1051,998,863,815,779,763,729; HRMS (calcd.) [M+H] +: 415.0856 (415.0831).
Compound 61
Gained sterling is white solid, productive rate 93%; M.p.189-191 DEG C; 1h NMR (400MHz, DMSO-d 6) δ (ppm): 2.31 (s, 3H, CH 3), 4.63 (s, 2H ,-SCH 2-), 5.44 (s, 2H, CH 2), 6.97 (s, 2H, NH 2), 6.93-7.40 (m, 4H, H 2,3,5and6-Ph), 8.13 (s, 1H, pyrimidin-5-yl-H); IR (KBr): 3337 (N-H), 3157,2462,2357,1664,1591,1570,1475,1426,1406,1222,1197,1117,1095,1068,1053,1012,839,813,782,729; HRMS (calcd.) [M+H] +: 415.0856 (415.0890).
Compound 62
Gained sterling is yellow solid, productive rate 90%; M.p.171-173 DEG C; 1h NMR (400MHz, DMSO-d 6) δ (ppm): 2.31 (s, 3H, CH 3), 4.63 (s, 2H ,-SCH 2-), 5.44 (s, 2H, CH 2), 6.97 (s, 2H, NH 2), 7.91-8.18 (m, 4H, 1H, H 3,4,5and6-Ph, pyrimidin-5-yl-H); IR (KBr): 3415 (N-H), 3145,2353,1648,1597,1569,1527 (N=O), 1465,1431,1352 (N=O), 1195,1118,1065,986,857,808,751,725; HRMS (calcd.) [M+H] +: 426.1097 (426.1082).
Compound 63
Obtaining sterling is white solid, productive rate 91%; M.p.173-175 DEG C; 1h NMR (600MHz, DMSO-d 6) δ (ppm): 2.31 (s, 3H, CH 3), 4.64 (s, 2H ,-SCH 2-), 5.45 (s, 2H, CH 2), 7.00 (s, 2H, NH 2), 7.63-7.97 (m, 3H, H 3, 5and6-Ph), 8.15 (s, 1H, pyrimidin-5-yl-H); IR (KBr): 3336 (N-H), 3174,2418,2360,1657,1594,1568,1475,1430,1217,1195,1119,1090,1052,1037,865,832,814,778,732; HRMS (calcd.) [M+Na] +: 471.0286 (471.0320).
Compound 64
Gained sterling is white solid, productive rate 89%; 132-134 DEG C; 1h NMR (600MHz, DMSO-d 6) δ (ppm): 2.31 (s, 3H, CH 3), 4.63 (s, 2H ,-SCH 2-), 5.43 (s, 2H, CH 2), 7.01 (s, 2H, NH 2), 7.40-7.44 (m, 2H, H 2,6-Ph), 7.99-8.01 (m, 2H, H 3,5-Ph), 8.15 (s, 1H, pyrimidin-5-yl-H); IR (KBr): 3428 (N-H), 3152,2360,2357,1665,1595,1574,1502,1474,1426,1228,1192,1158,1121,1067,997,956,846,815,782,733; HRMS (calcd.) [M+H] +: 399.1152 (399.1151).
Compound 65
Gained sterling is white solid, productive rate 89%; 132-134 DEG C; 1h NMR (600MHz, DMSO-d 6) δ (ppm): 2.29 (s, 3H, CH 3), 4.66 (s, 2H ,-SCH 2-), 5.42 (s, 2H, CH 2), 6.98 (s, 2H, NH 2), 7.96-7.97 (m, 2H, H 2,6-Ph), 8.14-8.16 (m, 3H, H 3,5-Ph, pyrimidin-5-yl-H); IR (KBr): 3423 (N-H), 3069,2360,2357,1665,1595,1559,1508,1468,1416,1325,1198,1167,1110,1077,1058,1015,857,812,792; HRMS (calcd.) [M+H] +: 449.1120 (449.1133).
Compound 66
Gained sterling is white solid, productive rate 88%; M.p.138-140 DEG C; 1h NMR (400MHz, DMSO-d 6) δ (ppm): 2.37 (s, 3H, CH 3), 4.66 (s, 2H ,-SCH 2-), 5.47 (s, 2H, CH 2), 7.10 (s, 2H, NH 2), 7.58-7.95 (m, 5H, H-Ph), 8.18 (s, 1H, pyrimidin-5-yl-H); HRMS (calcd.) [M+H] +: 381.1246 (381.1236).
Compound 67
Gained sterling is yellow solid, productive rate 87%; M.p.163-165 DEG C; 1h NMR (400MHz, DMSO-d 6) δ (ppm): 2.31 (s, 3H, CH 3), 4.65 (s, 2H ,-SCH 2-), 5.43 (s, 2H, CH 2), 6.97 (s, 2H, NH 2), 7.52-7.75 (m, 3H, H 2,4and6-Ph), 8.14 (s, 1H, pyrimidin-5-yl-H); IR (KBr): 3369 (N-H), 3230,2366,2359,1640,1595,1567,1544 (N=O), 1472,1351 (N=O), 1279,1231,1180,1102,990,868,811,750,723.
Compound 68
Gained sterling is yellow solid, productive rate 90%; M.p.171-173 DEG C; 1h NMR (400MHz, DMSO-d 6) δ (ppm): 2.28 (s, 3H, CH 3), 4.66 (s, 2H ,-SCH 2-), 5.43 (s, 2H, CH 2), 6.91 (s, 2H, NH 2), 7.89 (s, 1H, H 1-Ph), 8.14 (s, 1H, pyrimidin-5-yl-H), 8.41-8.65 (m, 3H, H 4,5and6-Ph); IR (KBr): 3399 (N-H), 3132,2362,2355,1660,1593,1562,1527 (N=O), 1471,1353 (N=O), 1233,1123,1063,994,868,813,742,710; HRMS (calcd.) [M+H] +: 426.1097 (426.1069).
Compound 69
Gained sterling is white solid, productive rate 90%; M.p.165-168 DEG C; 1h NMR (400MHz, DMSO-d 6) δ (ppm): 2.31 (s, 3H, CH 3), 4.62 (s, 2H ,-SCH 2-), 5.43 (s, 2H, CH 2), 7.08 (s, 2H, NH 2), 7.41-7.97 (m, 4H, H 3,4,5and6-Ph), 8.13 (s, 1H, pyrimidin-5-yl-H); IR (KBr): 3401 (N-H), 3133,2440,1665,1619,1598,1565,1494,1476,1438,1338,1223,1185,1119,1054,994,959,813,790,770,737; HRMS (calcd.) [M+H] +: 399.1152 (399.1143).
Compound 70
Gained sterling is brown solid, productive rate 72%; M.p.167-168 DEG C; 1h NMR (400MHz, DMSO-d6) δ (ppm): 2.29 (s, 3H, CH 3), 4.64 (s, 2H ,-SCH 2-), 5.42 (s, 2H, CH 2), 6.94 (s, 2H, NH 2), 7.56 (s, 2H, H-Ph), 7.88 (s, 2H, H-Ph), 8.01 (s, 1H, 1,2,3-triazol-4-yl-H), 8.15 (s, 1H, pyrimidin-5-yl-H).
Compound 71
Gained sterling is light yellow solid, productive rate 88%; M.p.180-181 DEG C; Ultimate analysis/%: calculated value: C, 52.67; H, 4.42; N, 27.30; O, 7.80; S, 7.81; Measured value: C, 52.38; H, 4.16; N, 27.63; S, 7.83; 1h NMR (600MHz, DMSO-d6) δ (ppm): 2.28 (s, 3H, CH 3), 3.84 (s, 3H, OCH 3), 4.60 (s, 2H ,-SCH 2-), 5.40 (s, 2H, CH 2), 6.93 (s, 2H, NH 2), 7.11 (d, 2H, J=12Hz, Ar-H), 7.88 (d, 2H, J=12Hz, Ar-H), 7.98 (s, 1H, 1,2,3-triazol-4-yl-H), 8.15 (s, 1H, pyrimidin-5-yl-H).
Compound 72
Gained sterling is light yellow solid, productive rate 79%; M.p.215-217 DEG C; 1h NMR (400MHz, DMSO-d6) δ (ppm): 2.40 (s, 3H, CH 3), 2.61 (s, 3H, CH 3), 4.73 (s, 2H ,-SCH 2-), 5.52 (s, 2H, CH 2), 7.04 (s, 2H, NH 2), 7.52 (s, 2H, H-Ph), 7.95 (d, 2H, J=5.6Hz, Ar-H), 8.08 (s, 1H, 1,2,3-triazol-4-yl-H), 8.27 (s, 1H, pyrimidin-5-yl-H).
Compound 73
Gained sterling is brown solid, productive rate 85%; M.p.152-153 DEG C; Ultimate analysis/%: calculated value: C, 54.81; H, 4.60; N, 28.41; S, 8.13; Measured value: C, 54.59; H, 4.85; N, 27.94; S, 8.20; 1h NMR (600MHz, DMSO-d6) δ (ppm): 2.40 (s, 3H, CH 3), 2.62 (s, 3H, CH 3), 4.75 (s, 2H ,-SCH 2-), 5.52 (s, 2H, CH 2), 7.05 (s, 2H, NH 2), 7.56-7.60 (m, 2H, Ar-H), 7.87-7.91 (m, 2H, Ar-H), 8.07 (s, 1H, 1,2,3-triazol-4-yl-H), 8.25 (s, 1H, pyrimidin-5-yl-H).
Compound 74
Gained sterling is brown solid, productive rate 65%; M.p.152-153 DEG C; Ultimate analysis/%: calculated value: C, 54.81; H, 4.60; N, 28.41; S, 8.13; Measured value: C, 54.89; H, 4.38; N, 28.86; S, 7.85; 1h NMR (600MHz, DMSO-d6) δ (ppm): 2.29 (s, 3H, CH 3), 2.58 (s, 3H, CH 3), 4.63 (s, 2H ,-SCH 2-), 5.41 (s, 2H, CH 2), 6.94 (s, 2H, NH 2), 7.39-7.50 (m, 3H, H-Ph), 7.85 (d, H, J=8.4Hz, Ar-H), 7.96 (s, 1H, 1,2,3-triazol-4-yl-H), 8.14 (s, 1H, pyrimidin-5-yl-H).
Embodiment 7: compound 75 preparation
1mmol2-methyl-4-amino-5-azido-methyl pyrimidine, 1mmol O-propargyl-4-fluorophenethyl ketoxime ether, 2mmol triethylamine is added successively in 100mL round-bottomed flask, be dissolved in 10mL anhydrous tetrahydro furan (THF), stirred at ambient temperature, after dissolution of solid, add 0.1mmol cuprous iodide, 10-15 hour is reacted under room temperature, TLC(thin-layer chromatography) reaction is extremely completely, the stirring that adds water has solid to separate out, the crude product of decompress filter, washing, oven dry, with dimethyl formamide (DMF) and water recrystallization, obtains yellow solid, productive rate 71%, mp:96-97 DEG C.
Ultimate analysis/%: calculated value: C, 57.46; H, 5.11; N, 27.59; Measured value: C, 57.65; H, 5.18; N, 27.26; 1hNMR (600MHz, DMSO-d 6): δ 2.14 (s, 3H, CH 3), 2.29 (s, 3H, CH 3), 5.20 (s, 2H, CH 2), 5.44 (s, 2H, CH 2), 6.95 (s, 2H, NH 2), 7.23 (d, 2H, J=8.4Hz, Ar-H), 7.67 (s, 2H, J=6.0Hz, Ar-H), 8.01 (s, 1H, CH), 8.18 (s, 1H, CH); 13c NMR (100MHz, DMSO-d 6): δ 12.5,25.2,46.7,66.9,108.4,115.2,115.8,124.6,128.1,128.2,132.3,143.5,153.9,156.2,161.5,164.0,167.2.IR (KBr): 1663 (C=N), 3431 (N-H) cm -1.EI-MS (m/z, %): 355 (M +, 11).
Compound 76-95 presses compound 75 similar approach and obtains, and its Structural Identification data are as follows:
Compound 76
Gained sterling is yellow solid, productive rate 66%, m.p.180-183 DEG C; Ultimate analysis/%: calculated value: C, 49.05; H, 4.36; N, 23.55; Measured value: C, 49.23; H, 4.54; N, 23.91; 1h NMR (600MHz, DMSO-d 6): δ 2.13 (s, 3H, CH 3), 2.29 (s, 3H, CH 3), 5.20 (s, 2H, CH 2), 5.49 (s, 2H, CH 2), 7.02 (s, 2H, NH 2), 7.56-7.61 (m, 4H, Ar-H), 8.19 (s, 1H, CH); 13c NMR (100MHz, DMSO-d 6): δ 12.5,25.5,46.7,66.9,111.0,122.6,124.6,127.8,130.0,131.3,134.8,143.5,155.7,161.3,168.7.IR (KBr): 1674 (C=N), 3296 (N-H) cm -1.EI-MS (m/z, %): 415 (M +, 7).
Compound 77
Gained sterling is yellow solid, productive rate 90%, m.p.184-186 DEG C; Ultimate analysis/%: calculated value: C, 54.91; H, 4.88; N, 26.37; Measured value: C, 54.45; H, 4.75; N, 26.18; 1h NMR (600MHz, DMSO-d 6): δ 2.14 (s, 3H, CH 3), 2.30 (s, 3H, CH 3), 5.20 (s, 2H, CH 2), 5.44 (s, 2H, CH 2), 6.98 (s, 2H, NH 2), 7.47 (s, 2H, Ar-H), 7.64 (s, 2H, Ar-H), 8.19 (s, 1H, CH); 13c NMR (100MHz, DMSO-d 6): δ 12.5,25.5,46.7,66.9,111.0,122.6,124.6,127.8,130.0,131.3,134.8,143.5,155.7,161.3,168.7.IR (KBr): 1676 (C=N), 3299 (N-H) cm -1.EI-MS (m/z, %): 371 (M +, 7).
Compound 78
Gained sterling is yellow solid, productive rate 73%, m.p.131-132 DEG C; Ultimate analysis/%: calculated value: C, 60.52; H, 5.68; N, 29.06; Measured value: C, 59.85; H, 5.65; N, 29.35; 1h NMR (600MHz, DMSO-d 6): δ 2.15 (s, 3H, CH 3), 2.29 (s, 3H, CH 3), 5.20 (s, 2H, CH 2), 5.44 (s, 2H, CH 2), 6.98 (s, 2H, NH 2), 7.40 (d, 2H, J=2.4Hz, Ar-H), 7.63 (d, 2H, J=3.0Hz, Ar-H), 8.01 (s, 1H, Ar-H), 8.19 (s, 1H, CH); 13c NMR (100MHz, DMSO-d 6): δ 12.5,25.2,46.7,66.8,108.3,124.6,125.9,128.4,129.2,135.8,143.5,154.7,156.2,161.5,167.0.IR (KBr): 1664 (C=N), 3327 (N-H) cm -1.EI-MS (m/z, %): 337 (M +, 8).
Compound 79
Gained sterling is yellow solid, productive rate 64%, m.p.154-156 DEG C; Ultimate analysis/%: calculated value: C, 58.84; H, 5.76; N, 26.69; Measured value: C, 58.58; H, 5.62; N, 26.13; 1h NMR (600MHz, DMSO-d 6): δ 2.12 (s, 3H, CH 3), 2.29 (s, 3H, CH 3), 3.37 (s, 3H, OCH 3), 5.16 (s, 2H, CH 2), 5.43 (s, 2H, CH 2), 6.94 (s, 2H, NH 2), 6.96 (s, 2H, Ar-H), 7.58 (d, 2H, J=3.0Hz, Ar-H), 8.17 (s, 1H, Ar-H); 13c NMR (100MHz, DMSO-d 6): δ 12.4,25.2,46.6,55.1,66.7,108.4,113.8,124.5,127.3,128.2,143.6,156.2,160.1,161.5,167.0,183.0.IR (KBr): 1669 (C=N), 3323 (N-H) cm -1.EI-MS (m/z, %): 367 (M +, 10).
Compound 80
Gained sterling is yellow solid, productive rate 66%, m.p.222-224 DEG C; Ultimate analysis/%: calculated value: C, 53.40; H, 4.74; N, 29.30; Measured value: C, 53.61; H, 4.31; N, 29.12; 1h NMR (600MHz, DMSO-d 6): δ 2.21 (s, 3H, CH 3), 2.30 (s, 3H, CH 3), 5.27 (s, 2H, CH 2), 5.47 (s, 2H, CH 2), 6.98 (s, 2H, NH), 7.89 (s, 2H, Ar-H), 8.21 (s, 1H, CH), 8.25 (d, 2H, J=7.2Hz, Ar-H); IR (KBr): 1673 (C=N), 3302 (N-H) cm -1.
Compound 81
Gained sterling is yellow solid, productive rate 50%, m.p.126-127 DEG C; Ultimate analysis/%: calculated value: C, 57.46; H, 5.11; N, 27.59; Measured value: C, 57.15; H, 5.12; N, 27.32; 1h NMR (600MHz, DMSO-d 6): δ 2.13 (s, 3H, CH 3), 2.30 (s, 3H, CH 3), 5.20 (s, 2H, CH 2), 5.45 (s, 2H, CH 2), 6.98 (s, 2H, NH), 7.22-7.46 (s, 4H, Ar-H), 8.04 (s, 1H, CH), 8.17 (s, 1H, CH); IR (KBr): 1639 (C=N), 3384 (N-H) cm -1.
Compound 82
Gained sterling is yellow solid, productive rate 67%, m.p.188-190 DEG C; Ultimate analysis/%: calculated value: C, 54.91; H, 4.88; N, 26.37; Measured value: 54.18; H, 4.72; N, 26.46; 1h NMR (600MHz, DMSO-d 6): δ 2.14 (s, 3H, CH 3), 2.29 (s, 3H, CH 3), 5.20 (s, 2H, CH 2), 5.45 (s, 2H, CH 2), 6.98 (s, 2H, NH), 7.46 (s, 2H, Ar-H), 7.64 (s, 2H, Ar-H), 8.19 (s, 1H, CH); IR (KBr): 1676 (C=N), 3297 (N-H) cm -1.
Compound 83
Gained sterling is yellow solid, productive rate 64%, m.p.131-133 DEG C; Ultimate analysis/%: calculated value: C, 54.91; H, 4.88; N, 26.37; Measured value: C, 54.48; H, 4.62; N, 26.26; 1h NMR (600MHz, DMSO-d 6): δ 2.15 (s, 3H, CH 3), 2.29 (s, 3H, CH 3), 5.22 (s, 2H, CH 2), 5.44 (s, 2H, CH 2), 6.95 (s, 2H, NH), 7.42-7.48 (m, 2H, Ar-H); 7.60 (d, 1H, J=7.2Hz, Ar-H), 7.67 (s, 1H, Ar-H); 8.00 (s, 1H, CH), 8.19 (s, 1H, CH); IR (KBr): 1670 (C=N), 3389 (N-H) cm -1.
Compound 84
Gained sterling is yellow solid, productive rate 34%, m.p.109-110 DEG C; Ultimate analysis/%: calculated value: C, 53.40; H, 4.74; N, 29.30; Measured value: C, 53.11; H, 4.69; N, 29.57; 1h NMR (600MHz, DMSO-d 6): δ 2.10 (s, 3H, CH 3), 2.30 (s, 3H, CH 3), 5.12 (s, 2H, CH 2), 5.43 (s, 2H, CH 2), 6.95 (s, 2H, NH), 7.56 (d; 1H, J=7.8Hz, Ar-H), 7.67 (t, 1H; J=7.2Hz, Ar-H), 7.78 (t, 1H; J=7.2Hz, Ar-H), 8.00 (s, 1H; CH), 8.02 (d, 1H, J=8.4Hz; Ar-H), 8.11 (s, 1H, CH); IR (KBr): 1669 (C=N), 3385 (N-H) cm -1.
Compound 85
The sterling of gained is white solid, productive rate 74%, 1h NMR (600MHz, DMSO-d6) δ (ppm): 2.10 (s, 3H, CH 3), 2.32 (s, 3H, CH 3), 5.19 (s, 2H, CH 2), 5.46 (s, 2H, CH 2), 7.00 (s, 2H, NH 2), 7.34 (s, 1H, Ar-H), 7.50 (s, 1H, Ar-H), 7.70 (s, 1H, Ar-H) .IR (KBr) υ (cm -1): 3414 (NH 2), 2972 (CH 3), 1667 (C=N), 1646-1227 (Ar).
Compound 86
Gained sterling is yellow solid, productive rate 70%, m.p.190-192 DEG C; Ultimate analysis/%: calculated value: C, 48.99; H, 3.85; N, 25.00; Measured value: C, 48.29; H, 3.88; N, 25.12; 1h NMR (600MHz, DMSO-d 6): δ 2.30 (s, 3H, CH 3), 5.25 (s, 2H, CH 2), 5.45 (s, 2H, CH 2), 6.95 (s, 2H, NH), 7.49-7.79 (m, 3H, Ar-H), 8.01 (s, 1H, CH), 8.22 (s, 1H, CH), 8.39 (s, 1H, CH); IR (KBr): 1676 (C=N), 3346 (N-H) cm -1.
Compound 87
Gained sterling is yellow solid, productive rate 78%, m.p.185-187 DEG C; Ultimate analysis/%: calculated value: C, 53.71; H, 4.51; N, 27.40; Measured value: C, 53.32; H, 4.56; N, 27.02; 1h NMR (600MHz, DMSO-d 6): δ 2.28 (s, 3H, CH 3), 5.18 (s, 2H, CH 2), 5.43 (s, 2H, CH 2), 6.94 (s, 2H, NH), 7.48 (d, 2H, J=8.4Hz, Ar-H), 7.61 (d, 2H, J=8.4Hz, Ar-H), 7.94 (s, 2H, CH), 8.19 (s, 1H, CH), 8.25 (s, 1H, CH).
Compound 88
Gained sterling is yellow solid, productive rate 86%, m.p.179-181 DEG C; Ultimate analysis/%: calculated value: C, 47.44; H, 4.01; N, 24.37; Measured value: C, 46.95; H, 4.10; N, 24.21; 1h NMR (600MHz, DMSO-d 6): δ 2.31 (s, 3H, CH 3), 3.78 (s, 3H, CH 3), 5.15 (s, 2H, CH 2), 5.47 (s, 2H, CH 2), 6.98 (s, 2H, NH), 6.98 (s, 4H, Ar-H), 7.62 (d, 2H, J=7.8Hz, Ar-H), 7.94 (s, 1H, CH), 8.19 (s, 1H, CH), 8.24 (s, 1H, CH).
Compound 89
Gained sterling is yellow solid, productive rate 74%, m.p.168-170 DEG C; Ultimate analysis/%: calculated value: C, 56.30; H, 4.72; N, 28.72; Measured value: C, 56.49; H, 4.38; N, 28.52; 1h NMR (600MHz, DMSO-d 6): δ 2.30 (s, 3H, CH 3), 5.18 (s, 2H, CH 2), 5.46 (s, 2H, CH 2), 6.99 (s, 2H, NH), 7.26 (s, 2H, Ar-H), 7.94 (s, 1H, CH), 8.19 (s, 1H, CH), 8.25 (s, 1H, CH).
Compound 90
Gained sterling is yellow solid, productive rate 30%, m.p.100-101 DEG C; Ultimate analysis/%: calculated value: C, 57.78; H, 5.42; N, 27.75; Measured value: C, 57.30; H, 5.41; N, 27.56; 1h NMR (600MHz, DMSO-d 6): δ 2.31 (s, 3H, CH 3), 3.78 (s, 3H, OCH 3), 5.15 (s, 2H, CH 2), 5.47 (s, 2H, CH 2), 6.98 (s, 4H, Ar+NH), 7.54 (s, 2H, Ar-H), 8.17 (s, 2H, CH).
Compound 91
Gained sterling is yellow solid, productive rate 92%, m.p.170-172 DEG C; Ultimate analysis/%: calculated value: C, C, 59.43; H, 5.30; N, 30.32; Measured value: C, 59.65; H, 5.44; N, 30.24; 1h NMR (600MHz, DMSO-d 6): δ 2.29 (s, 3H, CH 3), 5.18 (s, 2H, CH 2), 5.44 (s, 2H, CH 2), 6.95 (s, 2H, NH 2), 7.41-7.59 (m, 5H, Ar-H), 8.02 (s, 1H, CH), 8.19 (s, 1H, CH), 8.24 (s, 1H, CH).
Compound 92
Gained sterling is yellow solid, productive rate 65%, m.p.214-216 DEG C; Ultimate analysis/%: calculated value: C, 52.17; H, 4.38; N, 30.42; Measured value: C, 51.72; H, 4.23; N, 30.89; 1h NMR (600MHz, DMSO-d 6): δ 2.29 (s, 3H, CH 3), 5.26 (s, 2H, CH 2), 5.43 (s, 2H, CH 2), 6.96 (s, 2H, NH), 7.86 (d, 2H, J=9.0Hz, Ar-H), 8.22 (s, 1H, CH), 8.27 (d, 2H, J=8.4Hz, CH), 8.42 (s, 1H, CH).
Compound 93
Gained sterling is yellow solid, productive rate 32%, m.p.180-182 DEG C; Ultimate analysis/%: calculated value: C, 52.17; H, 4.38; N, 30.42; Measured value: C, 52.73; H, 4.45; N, 30.08; 1h NMR (600MHz, DMSO-d 6): δ 2.30 (s, 3H, CH 3), 5.32 (s, 2H, CH 2), 5.46 (s, 2H, CH 2), 6.96 (s, 2H, NH 2), 7.10 (t, 1H, J=7.2Hz, Ar-H), 7.46 (d, 1H, J=8.4Hz, Ar-H), 7.67 (t, 1H, J=7.8Hz, Ar-H), 7.32 (d, 1H, J=7.2Hz, Ar-H), 7.98 (s, 1H, CH), 7.99 (s, 1H, CH), 8.27 (s, 1H, CH).
Compound 94
Gained sterling is yellow solid, productive rate 46%, m.p.154-155 DEG C; Ultimate analysis/%: calculated value: C, 53.71; H, 4.51; N, 27.40; Measured value: C, 53.51; H, 4.58; N, 27.69; 1h NMR (600MHz, DMSO-d 6): δ 2.29 (s, 3H, CH 3), 5.21 (s, 2H, CH 2), 5.44 (s, 2H, CH 2), 6.94 (s, 2H, NH), 7.44-7.50 (m, 2H, Ar-H), 7.57 (d, 1H, J=9.0Hz, Ar-H), 7.65 (s, 2H, CH), 7.99 (s, 1H, CH), 8.20 (s, 1H, CH), (8.26 s, 1H, CH).
Compound 95
Gained sterling is yellow solid, productive rate 46%, m.p.154-155 DEG C; Ultimate analysis/%: calculated value: C, 53.71; H, 4.51; N, 27.40; Measured value: C, 53.51; H, 4.58; N, 27.69; 1h NMR (600MHz, DMSO-d 6): δ 2.29 (s, 3H, CH 3), 5.21 (s, 2H, CH 2), 5.44 (s, 2H, CH 2), 6.94 (s, 2H, NH), 7.44-7.50 (m, 2H, Ar-H), 7.57 (d, 1H, J=9.0Hz, Ar-H), 7.65 (s, 2H, CH), 7.99 (s, 1H, CH), 8.20 (s, 1H, CH), (8.26 s, 1H, CH).
Embodiment 8: compound 96 preparation
1mmol2-methyl-4-amino-5-azido-methyl pyrimidine and 1mmol iodo-O-propargyl-4-chloro-acetophenone oxime ether are dissolved in 5mL anhydrous acetonitrile, add 0.1mmol cuprous iodide and 2mmol triethylamine, stirring reaction 12 hours under room temperature condition, the stirring that adds water has solid to separate out, suction filtration, dry yellow solid, productive rate 72%; 1h NMR (600MHz, DMSO-d6) δ (ppm): 2.16 (s, 3H, CH 3), 2.30 (s, 3H, CH 3), 5.17 (s, 2H, CH 2), 5.45 (s, 2H, CH 2), 6.90 (s, 2H, NH 2), 7.44 (d, 2H, J=8.4Hz, Ar-H), 7.66 (d, 2H, J=8.4, Ar-H).
Compound 97-104 presses compound 96 similar approach and obtains, and its Structural Identification data are as follows:
Compound 97
Gained sterling is white solid, productive rate 75%,
1H NMR(600MHz,DMSO-d6)δ(ppm):2.16(s,3H,CH 3),2.30(s,3H,CH 3),5.16(s,2H,CH 2),5.46(s,2H,CH 2),6.90(s,2H,NH 2),7.22(s,2H,Ar-H),7.70(s,2H,Ar-H).
Compound 98
Gained sterling is white solid, productive rate 69%, 1h NMR (600MHz, DMSO-d6) δ (ppm): 2.13 (s, 3H, CH 3), 2.29 (s, 3H, CH 3), 5.15 (s, 2H, CH 2), 5.43 (s, 2H, CH 2), 6.90 (s, 2H, NH 2), 7.42 (s, 2H, Ar-H), 7.64 (s, 2H, Ar-H).
Compound 99
Gained sterling is white solid, productive rate 79%, 1h NMR (600MHz, DMSO-d6) δ (ppm): 2.16 (s, 3H, CH 3), 2.31 (s, 3H, CH 3), 5.16 (s, 2H, CH 2), 5.46 (s, 2H, CH 2), 6.96 (s, 2H, NH 2), 7.39 (s, 3H, Ar-H), 7.65 (s, 2H, Ar-H).
Compound 100
The sterling of gained is white solid, productive rate 81%, 1h NMR (600MHz, DMSO-d6) δ (ppm): 2.22 (s, 3H, CH 3), 2.33 (s, 3H, CH 3), 5.24 (s, 2H, CH 2), 5.49 (s, 2H, CH 2), 6.94 (s, 2H, NH 2), 7.91 (d, 2H, J=7.8Hz, Ar-H), 8.23 (d, 2H, J=8.4Hz, Ar-H).
Compound 101
The sterling of gained is white solid, productive rate 80%,
1H NMR(600MHz,DMSO-d6)δ(ppm):2.16(s,3H,CH 3),2.30(s,3H,CH 3),5.18(s,2H,CH 2),5.44(s,2H,CH 2),6.91(s,2H,NH 2),7.42(s,1H,Ar-H),7.47(s,1H,Ar-H),7.62(s,1H,Ar-H),7.69(s,1H,Ar-H).EI-MS(m/z,%):497(M +,5.21).
Compound 102
The sterling of gained is white solid, productive rate 76%, 1h NMR (600MHz, DMSO-d6) δ (ppm): 2.15 (s, 3H, CH 3), 2.31 (s, 3H, CH 3), 5.17 (s, 2H, CH 2), 5.45 (s, 2H, CH 2), 6.91 (s, 2H, NH 2), 7.58 (s, 4H, Ar-H).
Compound 103
The sterling of gained is white solid, productive rate 78%, 1h NMR (600MHz, DMSO-d6) δ (ppm): 2.15 (s, 3H, CH 3), 2.31 (s, 3H, CH 3), 5.17 (s, 2H, CH 2), 5.44 (s, 2H, CH 2), 6.91 (s, 2H, NH 2), 7.22 (d, 1H, J=7.8Hz, Ar-H), 7.25 (d, 1H, J=8.4Hz, Ar-H), 7.43-7.46 (t, 2H, J=7.8Hz, 7.2Hz, Ar-H), 7.65 (s, 1H, pyrimidine CH).
Compound 104
The sterling of gained is white solid, productive rate 74%, 1h NMR (600MHz, DMSO-d6) δ (ppm): 2.10 (s, 3H, CH 3), 2.32 (s, 3H, CH 3), 5.19 (s, 2H, CH 2), 5.46 (s, 2H, CH 2), 7.00 (s, 2H, NH 2), 7.34 (s, 1H, Ar-H), 7.50 (s, 1H, Ar-H), 7.70 (s, 1H, Ar-H).
The compound of above-described embodiment synthesis is in table 1.
The compound that table 1 synthesizes
The compound that the present invention has general formula (I) structure has excellent fungicidal activity, can be used for preventing and treating fusarium graminearum, Rhizoctonia solani Kuhn, botrytis cinerea pers, tomato early blight bacterium, tobacco brown spot pathogen and cucumber anthracnose, part of compounds to the prevention effect of fungi with contrast commercialization sterilant quite or better.
Embodiment 9 fungicidal activity is tested
With the growth velocity of mycelia for foundation measures fungicidal activity.Choose the six kind common mushrooms relevant with cash crop, greengrocery crop, fruits crop: rice sheath blight disease, gray mold of cucumber, wheat scab, early blight of tomato, Alternaria alternate and cucumber anthracnose are as trying target.The compounds of this invention acetone solution, tween-80 emulsification, adding distilled water, to be made into finite concentration liquid stand-by.Potato 200 grams, glucose 15 grams, 15 grams, agar, after 1000 grams, water is made into substratum, in the culture dish high-temperature pressure-reduction sterilizing 25min of diameter 9cm, being mixed by substratum 13.5mL and liquid 1.5mL while hot after sterilizing is distributed in two culture dish, horizontal positioned, after cooling, gets 5mm respectively with sterilized bacteria taker and is with bacterio-agar from the nutrient solution of bacterial classification, put into each culture dish mycelia to face down, every ware puts 2-3 kind bacterium.If two groups of blanks, to be then placed in sterile constant-temperature loft drier 48 hours, the diameter measuring bacterial plaque, according to blank, represents drug effect with diameter: inhibiting rate %=(contrasts-process)/contrast × 100%.
Experiment material:
For examination bacterial classification: fusarium graminearum (Gibberella zeae), botrytis cinerea pers (Botrytis cinerea), tomato early blight bacterium (Alternaria solania), tobacco brown spot pathogen (Alternaria alternata (Fries) Keissler), cucumber anthracnose (GloeosporiumorbiculareArs).
Test result is in table 2.
The test result (test concentrations 100 μ g/g) of table 2 part of compounds
The document related in literary composition is as follows:
Document 1:Karl M.Erixon, Chester L.Dabalos, Finian J.Leeper.Synthesis and biological evaluation of pyrophosphate mimics of thiamine pyrophosphate based on a triazole scaffold.Organic & Biomolecular Chemistry, 2008,6,3561-3572.

Claims (9)

1. there is 2-methyl-4-amino-5-(replacement-1,2,3-triazoles base) the methylpyrimidine derivative of fungicidal activity, it is characterized in that the compound for having general formula (I) structure:
Wherein:
R 1represent hydrogen or I;
X represents O, NH or S;
Y represents benzamide thiocarbonyl group or substituted benzamide thiocarbonyl group, 2-phenyl-1,3,4-thiophene (Evil) diazole-5-base or 2-substituted-phenyl-1,3,4-thiophene (Evil)-5-base, benzene first (ethyl ketone) imido grpup or substituted benzoyl (ethyl ketone) imido grpup; Substituting group on the phenyl ring involved by Y is mainly: H, halogen, nitro, cyano group, CF 3, C 1-4alkyl, methoxyl group, C 1-2carboxylic acid group or carboxylic acid ester groups; Monosubstituted or polysubstituted on phenyl ring optional position of substituting group, substituting group is identical or different.
2. 2-methyl-4-amino-5-(replacement-1,2,3-triazoles base) methylpyrimidine derivative as claimed in claim 1, is characterized in that, comprise the compound with general formula (I-1) structure:
Wherein:
X represents oxygen or NH;
R 1represent hydrogen;
R 2represent H, halogen, nitro, methoxyl group or C 1-4alkyl;
R 3represent H, halogen, nitro, cyano group, CF 3, C 1-4alkyl or methoxyl group, R 2with R 3position is interchangeable.
3. 2-methyl-4-amino-5-(replacement-1,2,3-triazoles base) methylpyrimidine derivative as claimed in claim 1, is characterized in that, comprise the compound with general formula (I-2) structure:
Wherein:
X is oxygen or S;
R 1represent hydrogen;
R 2represent H, halogen, nitro or C 1-4alkyl;
R 3represent H, halogen, nitro, CF 3, methoxyl group or C 1-4alkyl, R 2with R 3position is interchangeable.
4. 2-methyl-4-amino-5-(replacement-1,2,3-triazoles base) methylpyrimidine derivative as claimed in claim 1, is characterized in that, comprise the compound with general formula (I-3) structure:
Wherein:
R 1represent hydrogen or I;
R 2represent H, nitro or halogen;
R 3represent H, halogen, nitro, C 1-4alkyl or methoxyl group, R 2with R 3position is interchangeable;
R 4for H or methyl.
5. the 2-methyl-4-amino-5-that general formula according to claim 2 (I-1) represents (replaces-1,2,3-triazolyl) preparation method of methylpyrimidine derivative, the compound that the compound that it is characterized in that general formula (II) is represented and general formula (III) represent reacts:
R in general formula (III) 1, R 2, R 3, X definition respectively with general formula (I-1) in R 1, R 2, R 3, X definition identical.
6. the 2-methyl-4-amino-5-that general formula according to claim 3 (I-2) represents (replaces-1,2,3-triazolyl) preparation method of methylpyrimidine derivative, the compound that the compound that it is characterized in that general formula (II) is represented and general formula (IV) represent reacts:
R in general formula (IV) 1, R 2, R 3, X definition respectively with general formula (I-2) in R 1, R 2, R 3, X definition identical.
7. the 2-methyl-4-amino-5-that general formula according to claim 4 (I-3) represents (replaces-1,2,3-triazolyl) preparation method of methylpyrimidine derivative, the compound that the compound that it is characterized in that general formula (II) is represented and logical formula V represent reacts:
R in logical formula V 1, R 2, R 3, R 4definition respectively with general formula (I-3) in R 1, R 2, R 3, R 4definition identical.
8. the application of 2-methyl-4-amino-5-(replacement-1,2,3-triazoles base) methylpyrimidine derivative that represents of general formula according to claim 1 (I), is characterized in that: as the effective constituent of sterilant.
9. the 2-methyl-4-amino-5-that general formula according to claim 1 (I) represents (replaces-1,2,3-triazolyl) application of methylpyrimidine derivative, it is characterized in that: as the effective constituent to fusarium graminearum, Rhizoctonia solani Kuhn, botrytis cinerea pers, tomato early blight bacterium, tobacco brown spot pathogen and cucumber anthracnose sterilant.
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