CN101838267B - Triazole compound and preparation and application thereof - Google Patents

Triazole compound and preparation and application thereof Download PDF

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CN101838267B
CN101838267B CN2010101519953A CN201010151995A CN101838267B CN 101838267 B CN101838267 B CN 101838267B CN 2010101519953 A CN2010101519953 A CN 2010101519953A CN 201010151995 A CN201010151995 A CN 201010151995A CN 101838267 B CN101838267 B CN 101838267B
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amino
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vinyl cyanide
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CN101838267A (en
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范志金
张海科
米娜
贝尔斯卡娅·娜特丽娅·帕沃洛娃
巴库勒夫·瓦西里耶·阿勒克什维奇
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Nankai University
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Abstract

The invention provides a fast, simple and convenient method for synthesizing 2- substituted aryl-2-cyano-acetamidine II containing eulexine, tryptamine and other primary amine as well as secondary amine structural fragments, an application in the fields of agriculture and plant protection, a method for synthesizing a 2-substituted aryl-4-cyano-5-substituted amino-2H-1, 2, 3-triazole compound by utilizing the 2- substituted aryl-2-cyano-acetamidine II and an application in the fields of agriculture and plant protection. The invention relates to a nitrogenous heterocyclic compound, in particular to aryl-2-cyano-acetamidine the chemical structural formula of which is shown in the specification. The invention discloses the chemical structure and the synthetic method of the compounds, and the effect and application thereof in preventing and curing agricultural plant diseases and plant virus diseases; and the invention further discloses application of combination of the compounds and commercial pesticides in preventing and curing agricultural and horticultural harmful organisms, proportion of single use of the compounds or use of a combination, and a dosage-form processing method.

Description

Triazole class compounds and preparation thereof and application
Technical field
Technical scheme of the present invention relates to the heterogeneous ring compound that contains 1,2-diazole, is specifically related to contain the 1,2,3-triazoles compound.
Background technology
The heterogeneous ring compound that contains N has wide biological activity (Peterlin-Masic, L. and Kikelj, D.Tetrahedron, 2001,57, the 7073-7105 that comprises antidepressant, anticancer, antiplatelet and antimycotic and desinsection, weeding etc.; Liu Changling, complete works of (sterilant volume) (the weedicide volume) of world's agricultural chemicals, Chemical Industry Press); Many highly active compounds such as serpin, nitric oxide synthase inhibitor activity, the plain antagonist of integration all contain amino (Litzinger E.A.; Martasek P., Roman L.J.and Silverman R.B.Bioorgan.& Med.Chem.2006,14; 3185); Amidine compound is the important intermediate (Hammond M.C.and Bartlett P. A.J. Org.Chem.2007,72,3104) of synthesizing heterocyclic compounds.At present, natural product is usually introduced in vitochemical research in reaction system structure fragment has highly active verivate with synthetic, because aminated compounds is natural amino acid and polypeptide and alkaloidal important as precursors and be widely used in the organic synthesis.Tocosamine (cystisine) is the bioactive ingredients in pulse family and the Berberidaceae plant; Clinically be used for muscle or intravenous injection; Rescue is because of operation and various wound the reflectivity breathlessness, shock and the sleepy baby that cause and anti-heart disorder, anti-microbial infection, antiulcer agent, leukocyte increasing etc., and particularly this compounds has stronger antitumour activity (Li Ping, Yang Minli; The extraction process of the yellow Central China of lanceolata Tocosamine Alkaloid; The West China pharmaceutical journal, 2007,22 (1): 7-8); Pyridine, pyrroles, piperidine, tryptamines, piperazine (pyridine) and substituted piperazine (pyridine) etc. is the group that contains physiologically active.In order to seek more highly active compound; Consider one big type of triazole compounds is arranged in the disinfectant use in agriculture; The contriver introduces in Tianjin science and technology support plan International Technology collaborative project (07ZCGHHZ01400), Tianjin under the subsidy of intelligence plan, Tianjin natural science fund (07JCYBJC01200) and state natural sciences fund (20672062), " 973 " plans (2003CB114402), and the present invention hopes aminated compounds is especially carried out eco-friendly pesticide molecule design and activity research in the natural aminated compounds introduction triazole class compounds with biologically active.
Summary of the invention
Technical problem to be solved by this invention is: new 2-substituted aryl-5-substituted-amino-2H-1 is provided; 2; The midbody 2-of the compound method of 3-triazole class compounds (general formula I) and synthetic these compounds replaces the compound method of fragrant diazanyl-2-cyanic acid ethanamidine (general formula I I); The activity of this compounds inhibition pathogenic fungi and the measuring method of insecticidal activity and herbicidal activity are provided, and these compounds are as the purposes of bactericide, antiviral agent and sterilant and weedicide.
The present invention solves this technical problem the technical scheme that is adopted: have the 2-substituted aryl-5-substituted-amino-2H-1 of agricultural insecticidal, sterilization and weeding activity, and 2, the 3-triazole class compounds has the chemical structure of general formula I:
Figure GSA00000077878800021
Wherein: Ar is phenyl or replaces or disubstituted phenyl through the substituting group list that said substituting group is the group that is selected from methoxyl group, methyl, trifluoromethyl, nitro or halogen;
R 1Group for azacycloalkyl, tetrahydropyrrole base, piperidyl, 3-chloro-phenyl-piperazinyl, 3-chloro-phenyl-piperidyl, 3-methoxyphenylpiperazderivatives base, 3-p-methoxy-phenyl piperidyl, 3-pyridyl Phenylpiperazinyl, 3-pyridyl Phenylpiperidine base, 3-pyrimidyl Phenylpiperazinyl, tryptamines base, 3-pyrimidyl Phenylpiperidine base or the Flower of Chinese Peashrub base of the naphthenic base of the straight chained alkyl that is selected from H, C1-C6, C3-C6, C3-C6;
R 2Group for the straight chained alkyl, tetrahydropyrrole base, cyclohexyl, piperidyl, tryptamines base, 3-chloro-phenyl-piperazinyl, 3-chloro-phenyl-piperidyl, 3-methoxyphenylpiperazderivatives base, 3-p-methoxy-phenyl piperidyl, 3-pyridyl Phenylpiperazinyl, 3-pyridyl Phenylpiperidine base, 3-pyrimidyl Phenylpiperazinyl, 3-pyrimidyl Phenylpiperidine base, Flower of Chinese Peashrub base or the C3-C6 naphthenic base that are selected from H, methyl, C1-C6;
Or R 1With R 2Form the group that is selected from tetrahydropyrrole base, piperidyl, tryptamines base, 3-chloro-phenyl-piperazinyl, 3-chloro-phenyl-piperidyl, 3-methoxyphenylpiperazderivatives base, 3-p-methoxy-phenyl piperidyl, 3-pyridyl Phenylpiperazinyl, 3-pyridyl Phenylpiperidine base, 3-pyrimidyl Phenylpiperazinyl, 3-pyrimidyl Phenylpiperidine base or Flower of Chinese Peashrub base in the lump with the N atom that links to each other.
The midbody of synthetic compound I replaces fragrant hydrazone group ethanamidine compound, it is characterized in that having the chemical structure of following general formula I I:
Figure GSA00000077878800022
Wherein: Ar is phenyl or replaces or disubstituted phenyl through the substituting group list that said substituting group is the group that is selected from methoxyl group, methyl, trifluoromethyl, nitro or halogen;
R 1Group for azacycloalkyl, tetrahydropyrrole base, piperidyl, 3-chloro-phenyl-piperazinyl, 3-chloro-phenyl-piperidyl, 3-methoxyphenylpiperazderivatives base, 3-p-methoxy-phenyl piperidyl, 3-pyridyl Phenylpiperazinyl, 3-pyridyl Phenylpiperidine base, 3-pyrimidyl Phenylpiperazinyl, tryptamines base, 3-pyrimidyl Phenylpiperidine base or the Flower of Chinese Peashrub base of the naphthenic base of the straight chained alkyl that is selected from H, C1-C6, C3-C6, C3-C6;
R 2Group for the straight chained alkyl, tetrahydropyrrole base, cyclohexyl, piperidyl, tryptamines base, 3-chloro-phenyl-piperazinyl, 3-chloro-phenyl-piperidyl, 3-methoxyphenylpiperazderivatives base, 3-p-methoxy-phenyl piperidyl, 3-pyridyl Phenylpiperazinyl, 3-pyridyl Phenylpiperidine base, 3-pyrimidyl Phenylpiperazinyl, 3-pyrimidyl Phenylpiperidine base, Flower of Chinese Peashrub base or the C3-C6 naphthenic base that are selected from H, methyl, C1-C6;
Or R 1With R 2Form the group that is selected from tetrahydropyrrole base, piperidyl, tryptamines base, 3-chloro-phenyl-piperazinyl, 3-chloro-phenyl-piperidyl, 3-methoxyphenylpiperazderivatives base, 3-p-methoxy-phenyl piperidyl, 3-pyridyl Phenylpiperazinyl, 3-pyridyl Phenylpiperidine base, 3-pyrimidyl Phenylpiperazinyl, 3-pyrimidyl Phenylpiperidine base or Flower of Chinese Peashrub base in the lump with the N atom that links to each other.
The total synthetic route and the method for compound I of the present invention are following:
Figure GSA00000077878800031
Wherein: substituent A r in each general formula compound and R 1, R 2, NR 1R 2Definition see the description in the above-mentioned general formula 1;
The step and the condition of concrete compound method are following:
A. compound I is by the preparation of intermediate II and cupric acetate heating carrying out oxidation step cyclization, and reaction conditions is to be solvent with the pyridine, and room temperature or reflux 1 hour to 24 hours, concrete chemical reaction general formula was following:
Figure GSA00000077878800032
Wherein: substituent A r, R 1, R 2, NR 1R 2Like the definition among the above-mentioned general formula compound I;
B. intermediate II adds hot preparation by compound IV and compound III in ethanol, and reaction conditions is to be solvent with ethanol, reflux 1 hour to 24 hours, and concrete chemical reaction general formula is following:
Figure GSA00000077878800033
Wherein: substituent A r, R 1, R 2, NR 1R 2Like the definition among the above-mentioned general formula compound I;
C. the operation steps of synthetic compound I is following:
In filling 100 milliliters of round-bottomed flasks of 50 milliliters of pyridines, add 0.005 mole compound I I and 0.011 mole neutralized verdigris; Reaction mixture stirring reaction 1 hour to 24 hours under from room temperature to the reflux temperature condition; The cooling back adds water in reaction mixture, filter the back and collect solid and get compound I, calculated yield with ethyl alcohol recrystallization; Carry out fusing point and NMR, IR, MS and ultimate analysis; The consumption of synthetic compound enlarges by corresponding proportion or dwindles, and wherein compound I I is synthetic for the present invention, and commercial compound I I also obtains same effect;
D. the operation steps of synthetic intermediate compound I I is following:
In 100 milliliters of round-bottomed flasks, add 0.01 mole compound VI and compound III and 50 milliliters of ethanol of 1.3 moles; Reaction mixture is at room temperature stirring reaction 1 hour to 24 hours under the reflux temperature condition; After the cooling reaction mixture is joined in the trash ice, filter the back and collect solid and get compound I I, calculated yield with ethyl alcohol recrystallization; Carry out fusing point and NMR, IR, MS and ultimate analysis, the consumption of synthetic compound enlarges by corresponding proportion or dwindles; Compound VI of the present invention can be synthetic according to method provided by the invention, and commercial compound VI also obtains same effect;
In the synthetic new compound, 1,2,3-triazoles compounds V and VI have good biological activity, and its synthetic reaction formula is following:
Figure GSA00000077878800041
The concrete synthesis step of compound V and VI is following:
In 100 milliliters of round-bottomed flasks, add 0.01 mole compound I X or X and Tocosamine VII and 50 milliliters of ethanol of 1.3 moles; The temperature of reaction mixture is 70 degree; Reaction times is stirring reaction 10 hours, after the cooling reaction mixture is joined in the trash ice, filters the back and collects solid and get compound VIII or XI with ethyl alcohol recrystallization; In filling 100 milliliters of round-bottomed flasks of 50 milliliters of pyridines, add 0.005 mole compound VIII or XI and 0.011 mole neutralized verdigris; Reaction mixture is spent stirring reactions 6 hours 60, and the cooling back adds water in reaction mixture, filters back collection solid and gets product V or VI with ethyl alcohol recrystallization.
The biological activity determination method and the step of each compound are following:
E. each compound is to the mensuration of pathogenic fungi growth activity influence:
The mensuration of fungicidal activity or bacteriostatic activity adopts thalli growth rate assay method, and detailed process is: get 5 milligrams of sample dissolution at an amount of N, in the dinethylformamide; With containing the medicament that a certain amount of polysorbas20 emulsifier aqueous solution is diluted to 500 mcg/ml, will supply the reagent agent under aseptic condition, respectively to draw in 1 milliliter of injection petridish then, add 9 milliliters of substratum more respectively; It is dull and stereotyped to process 50 mcg/ml pastilles after shaking up, and does blank with the flat board that adds 1 milliliter of aqua sterilisa, cuts bacterium with the punch tool of 4 millimeters of diameters along the mycelia outer rim and coils; Move on the pastille flat board, be equilateral triangle and put, every processing repetition 3 times; Petridish is placed on cultivation in 24 ± 1 degree constant incubators, and colony diameter to be contrasted expands to 2-3 centimetre of " Invest, Then Investigate " and respectively handles bacterium dish expansion diameter, averages; Relatively calculate relative bacteriostasis rate with blank; Supply the examination bacterial classification to comprise frequently seen plants pathogenic bacteria on the various agricultural, as: A: sugar beet leaf spot bacteria, its Latin is called Cercospora beticola; B: cucumber fusarium axysporum, its Latin is called Fusarium oxysporum; C: peanut Cercospora bacteria, its Latin is called Cercosporaarachidicola; D: tomato early blight bacterium, its Latin is called Alternaria solani; E: fusarium graminearum, its Latin is called Gibberella zeae; F: the ring rot of apple bacterium, its Latin is called Physalospora piricola; G: Rhizoctonia solani Kuhn, its Latin is called Pellicularia sasakii; H: watermelon anthrax bacteria, its Latin is called Colletotrichumlagenarium; I: verticillium dahliae, its Latin is called Verticilium dahliae; J: phytophthora infestans, its Latin is called Phytophthora infestans (Mont.) de Bary; K: Sclerotinia sclerotiorum, its Latin is called Sclerotiniasclerotiorum; L: dry thread Pyrenomycetes, its Latin is called Rhizoctonia solani Kuhn;
F. the mensuration of each compound antiviral activity:
The screening method of anti-tobacco activity of resisting tobacco mosaic virus is following: the mensuration of the direct antiviral activity that exsomatizes adopts half leaf method to carry out; Live test is the common cigarette that seedling age is consistent, and 3 basins are one group, spray test compound solution 3 times; Each 10 milliliters, treat the dried back of blade face soup frictional inoculation tobacco resisting tobacco mosaic virus, be called for short TMV; After placing its growth optimal temperature and illumination to cultivate 3 days down the cigarette seedling, the inspection incidence, comprehensive scab number is calculated as follows out the antiviral effect of test compound to TMV; 3 repetitions are established in each processing, and contrast divides blank and standard chemicals treatment to contrast 2 kinds:
R = CK - T CK × 100
Wherein, R is the antiviral effect of new compound to the anti-TMV of tobacco, unit: %
CK is the average withered spot number of clear water contrast blade, unit: individual
T is the average withered spot number through the compound treatment rear blade, unit: individual;
G. the mensuration of each compound weeding activity:
The screening method of weeding activity adopts the greenhouse pot culture method to carry out; Cauline leaf is handled after dividing preceding soil treating of seedling and seedling, and treatment dosage is 750 gram/hectares, and application method is for spraying; 15 days mensuration overground part fresh weights suppress percentage after dispenser; Measure the examination material and comprise rape, its Latin is called Brassica campestris, barnyard grass grass, and its Latin is called Echinochloa crusgalli, three-coloured amaranth; Its Latin Amaranthus retroflexus L. by name and lady's-grass, its Latin is called Digitaria sanguinalis Scop;
H. the mensuration of each compound insecticidal activity:
The screening method of insecticidal activity: mythimna separata, its Latin is called Mythimna separata, adopts leaf dipping method; Impregnated in leaf of Semen Maydis in the soup of acetone preparation, its concentration is 100 mcg/ml, treats to insert 4 instar larvaes after soup is done; Main mensuration stomach toxicity and action of contace poison; 24 hours, 96 hours check test results mainly observe insect growth regulator(IGR) effect and death condition, represent the insecticidal activity height with per cent death loss.Aphid, its Latin is called Aphis laburni Kaltenbach, adopts leaf dipping method, and the broad bean seedling that is connected to aphid flood for 5 seconds in soup to be measured, drug concentration is 100 mcg/ml, preserve moisture cultivate 24 hours after check result, the calculating mortality ratio.Mosquito larvae, its Latin is called Culex pipiens pallens, and concrete grammar is the aqueous solution of 4 instar larvaes being put into the soup of 5 mcg/ml, the death condition of 24 hours inspection mosquito larvaes.
The invention has the beneficial effects as follows: synthetic new compound of the present invention has carried out the mensuration of agricultural biological activity such as bacteriostatic activity, antiviral activity, weeding activity and insecticidal activity, and this compounds can be used for the plant protection in agriculture field and gardening field.
The present invention will more specifically explain 1 through specific preparation and biological activity determination embodiment; 2; 3-triazole class compounds I and synthetic its midbody replace the synthetic and biological activity of fragrant hydrazone group ethanamidine compound I I and in the application of agriculture field, unrestricted the present invention, especially its biological activity only illustrate but said embodiment only is used for bright specifically the present invention; Rather than the restriction this patent, concrete embodiment is following:
Embodiment 1
Synthetic and the structure that replaces fragrant hydrazone group ethanamidine compound I I is identified
In 100 milliliters of round-bottomed flasks, add 0.01 mole compound IV and 1.3 moles compound R 1NHR 2With 50 milliliters of ethanol, reaction mixture is at room temperature stirring reaction 1 hour-24 hours under the solvent refluxing temperature, and optimal reaction temperature is 70 degree; Reaction finishes after the cooling reaction mixture to be joined in the trash ice; Filter the back and collect solid and get compound I I with ethyl alcohol recrystallization, calculated yield is carried out fusing point and NMR, IR, MS and ultimate analysis; Mensuration result shows, each compound of synthetic 1HNMR, 13CNMR is consistent with its chemical structure with the data presentation of MS and IR and ultimate analysis, and the substituting group of each general formula compound of conversion is easy to synthetic compound II, and the mensuration result of part of compounds yield and physical and chemical parameter is following:
3,3-diamino--2-(4-p-methoxy-phenyl azo) vinyl cyanide (II-1) .1.52 restrains (70%) (yellow solid), fusing point: 242-243 ℃; IR (KBr) v=3450,3420,3350,3250,3200 (NH), 3000,2930,2900,2830 (CH), 2180 (CN) cm -1 1HNMR (250MHz) δ=3.78 (s, 3H, OMe), 6.65-6.85 (m, 6H, 2NH 2+ H-Ar), 7.47 (d, 2H, H-Ar, J=8.8Hz); MS, m/z (%) 217 (M +, 62.5%); Anal. theoretical value C 10H 11N 5O:C, 55.29; H, 5.10; N, 32.24. measured value: C, 55.51; H, 5.23; N, 32.45.
3,3-diamino--2-phenylazo vinyl cyanide (II-2) .1.20 restrains (64%), (yellow solid), fusing point: 239-241 ℃; IR (KBr) v=3420,3410,3350,3250,3200 (NH), 2180 (CN) cm -1 1HNMR (250MHz) δ=6.97 (brs, 4H, 2NH 2), 7.06 (t, 1H, H-Ar, J=7.4Hz), 7.24 (t, 2H, H-Ar, J=7.3Hz), 7.49 (d, 2H, H-Ar, J=7.4Hz); MS, m/z (%) 187 (M +, 31.6%); Anal. theoretical value C 9H 9N 5: C, 57.74; H, 4.85; N, 37.41. measured value: C, 57.53; H, 4.71; N, 37.63.
3,3-diamino--2-(4-chloro-phenyl-azo) vinyl cyanide (II-3) .1.35 restrains (61%), (yellow solid), fusing point: 249-251 ℃; IR (KBr) v=3420,3410,3350,3250,3200 (NH), 2180 (CN) cm -1 1HNMR (400MHz) δ=7.18 (brs, 4H, 2NH 2), 7.29 and 7.57 (AA ' XX ', 4H, H-Ar, J=8.8Hz); 13CNMR (100MHz) δ=91.4,115.4,121.9 (2C), 128.5 (2C), 129.1,152.3,161.3; MS, m/z (%) 221 (M +, 39.5%); Anal. theoretical value C 9H 8ClN 5: C, 48.77; H, 3.64; N, 31.60. measured value: C, 48.89; H, 3.81; N, 31.45.
3-amino-2-(4-p-methoxy-phenyl azo-3-methylamino-) vinyl cyanide (II-4) .2.08 restrains (90%), (yellow crystals), fusing point: 313-315 ℃; IR (KBr) v=3440,3315,3260,3175,3100 (NH), 2950,2930,2,910 2825 (CH), 2180 (CN) cm -1 1HNMR (250MHz) δ=2.93 (d, 3H, Me, J=4.8Hz), 3.76 (s, 3H, OMe), 7.15 (brs, 4H, NH 2), 7.35-7.45 (m, 1H, NH), 6.80and 7.45 (AA ' XX ', 4H, H-Ar, J=8.8Hz); MS, m/z (%) 231 (M +, 67.6%); Anal. theoretical value C 11H 13N 5O:C, 57.13; H, 5.67; N, 30.28. measured value: C, 57.45; H, 5.75; N, 30.45.
3-amino-3-methylamino--2-phenylazo vinyl cyanide (II-5) .1.33 restrains (66%) (yellow crystals), fusing point: 225-227 ℃; IR (KBr) v=3430,3330,3260 (NH), 2180 (CN) cm -1 1HNMR (250MHz) δ=2.92 (d, 3H, Me, J=4.5Hz), 7.03 (t, 1H, H-Ar, J=7.3Hz), 7.3-7.4 (m, 3H, H-Ar+NH), 7.49 (d, 2H, H-Ar, J=8.0Hz), 7.56 (brs, 2H, NH 2); MS, m/z (%) 201 (M +, 41.6%); Anal. theoretical value C 10H 11N 5: C, 59.69; H, 5.51; N, 34.80. measured value: C, 59.41; H, 5.83; N, 35.03.
3-amino-2-(4-chloro-phenyl-azo-group-3-methylamino-) vinyl cyanide (II-6) .2.02 restrains (86%) (yellow crystals), fusing point: 219-220 ℃; 1HNMR (400MHz) δ=2.90 (d, 3H, Me, J=4.5Hz), 7.32and 7.57 (AA ' XX ', 4H, H-Ar, J=9.0Hz), 7.60 (brs, 2H, NH 2), 7.84 (q, 1H, NH); 13CNMR (100MHz): δ 28.6,91.5,115.6,121.8 (2C), 128.4 (2C), 128.6,152.5,160.0; MS, m/z (%) 235 (M +, 35.3%); Anal. theoretical value C 10H 10ClN 5: C, 50.96; H, 4.28; N, 29.72. measured value: C, 50.71; H, 4.36; N, 28.03.
3-amino-3-methylamino--2-(4-nitrophenyl azo-group) vinyl cyanide (II-7) .2.10 restrains (85%) (yellow crystals), fusing point: 290-291 ℃; 1HNMR (400MHz) δ=2.94 (d, 3H, Me, J=4.5Hz), 7.68and 8.12 (AA ' XX ', 4H, H-Ar, J=9.2Hz), 8.00 (brs, 2H, NH 2), 8.15 (q, 1H, NH); 13CNMR (100MHz): δ 28.9,95.5,114.5,120.1 (2C), 124.7 (2C), 142.7,159.1,159.5; Anal. theoretical value C 10H 10N 6O:C, 48.78; H, 4.09; N, 34.13. measured value: C, 48.55; H, 4.26; N, 34.33.
3-amino-3-hexamethylene amino-2-(4-p-methoxy-phenyl azo-group) vinyl cyanide (II-8) .2.48 restrains (83%) (yellow crystals), fusing point: 173-174 ℃; IR (KBr) v=3430,3330,3210,3160 (NH), 2940,2860,2830 (CH), 2180 (CN) cm -1 1HNMR (250MHz) δ=1.20-2.0 (m, 10H, 5CH 2), 3.60-3.75 (m, 1H, CH), 3.77 (s, 3H, OMe), 6.75-6.80 (m, 1H, NH), 7.25 (br s, 2H, NH 2), 6.82 and 7.40 (AA ' XX ', 4H, H-Ar, J=8.7Hz); MS, m/z (%) 299 (M +, 49.1%); Anal. theoretical value C 16H 21N 5O:C, 64.19; H, 7.07; N, 23.39. measured value: C, 64.41; H, 7.23; N, 23.54.
3-amino-3-hexamethylene amino-2-phenylazo vinyl cyanide (II-9) .2.25 restrains (84%) (yellow crystals), fusing point: 181-182 ℃; 1HNMR (250MHz) δ=1.02-2.04 (m, 10H, 5CH 2), 3.83-4.09 (m, 1H, CH), 7.17 (t, 1H, H-Ar, J=7.3Hz), 7.37 (t, 2H, H-Ar, J=7.2Hz), 7.74 (d, 2H, H-Ar, J=7.3Hz), 9.15 (d, 1H, NH, J=8.5Hz), 9.6 (br s, 2H, NH 2), MS, m/z (%) 269 (M +, 35.9); Anal. theoretical value C 15H 19N 5: C, 66.89; H, 7.11; N, 26.00. measured value: C, 66.59; H, 6.89; N, 26.23.
3-amino-2-(4-chloro-phenyl-azo-group)-3-hexamethylene aminoacrylonitrile (II-10) .1.90 restrains (63%) (yellow crystals), fusing point: 185-186 ℃; 1HNMR (250MHz) δ=1.10-2.00 (m, 10H, 5CH 2), 3.55-3.75 (m, 1H, CH), 6.97 (d, 1H, NH, J=9.0Hz), 7.42 (brs, 2H, NH 2), 7.24and 7.46 (AA ' XX ', 4H, H-Ar, J=8.6Hz); MS, m/z (%) 303 (M +, 53.7%); Anal. theoretical value C 15H 18ClN 5: C, 59.31; H, 5.97; N, 23.05. measured value: C, 59.55; H, 6.13; N, 23.33.
3-amino-3-hexamethylene amino-2-(4-nitrophenyl azo-group) vinyl cyanide (II-11) .2.15 restrains (68%) (yellow crystals), fusing point: 260-261 ℃; 1HNMR (400MHz) δ=1.20-1.50 (m, 5H, CH 2), 1.55-1.65 (m, 1H, CH 2), 1.70-1.80 (m, 2H, CH 2), 1.80-1.90 (m, 2H, CH 2), 3.60-3.70 (m, 1H, CH), 7.66 and 8.12 (AA ' XX ', 4H, H-Ar, J=9.0Hz), 7.82 (d, 1H, NH, J=9.0Hz), 7.99 (s, 2H, NH 2); 13CNMR (100MHz): δ 24.6,24.8,31.7,59.7,95.9,114.6,120.2 (2C), 124.7 (2C), 142.7,157.7,159.0; Anal. theoretical value C 15H 18N 6O 2: C, 57.31; H, 5.77; N, 26.73. measured value: C, 57.38; H, 5.91; N, 27.03.
3-amino-2-(4-p-methoxy-phenyl azo-group)-3-pyridine-1-base vinyl cyanide (II-12) .2.27 gram (84%) (yellow crystals), fusing point: 195-196 ℃; IR (KBr) v=3450,3340,3190 (NH), 2970,2940,2880,2840 (CH), 2180 (CN) cm -1 1HNMR (400MHz) δ=1.90-1.95 (m, 4H, 2CH 2), 3.61-3.65 (m, 4H, 2CH 2), 3.76 (s, 3H, OMe), 7.12 (br s, 2H, NH 2), 6.89 and 7.44 (AA ' XX ', 4H, H-Ar, J=9.0Hz); 13CNMR (100MHz) δ=24.8 (2C), 49.5 (2C), 55.2,91.5,113.9 (2C), 117.5,121.5 (2C), 147.7,157.4,158.3; MS, m/z (%) 271 (M +, 59.2%); Anal. theoretical value C 14H 17N 5O:C, 61.98; H, 6.32; N, 25.81. measured value: C, 61.74; H, 6.03; N, 26.06.
3-amino-2-(4-fluorophenyl azo-group)-3-pyridine-1-base vinyl cyanide (II-13) .2.02 gram (78%) (yellow crystals), fusing point: 190-191 ℃; 1HNMR (250MHz) δ=1.95-2.05 (m, 4H, 2CH 2), 3.60-3.78 (m, 4H, 2CH 2), 6.9-7.1 (m, 4H, H-Ar+NH 2), 7.42-7.55 (m, 2H, H-Ar); Anal. theoretical value C 13H 14FN 5: C, 60.22; H, 5.44; N, 27.01. measured value: C, 59.85; H, 5.25; N, 27.36.
3-amino-2-(3,5-difluorophenyl azo-group)-3-pyridine-1-base vinyl cyanide (II-14) .2.5 gram (85%) (yellow crystals), fusing point: 240-241 ℃; IR (KBr) v=3420,3400,3300 (NH), 2970,2950,2920,2870 (CH), 2190 (CN) cm -1 1HNMR (250MHz) δ=1.90-2.10 (m, 4H, 2CH 2), 3.60-3.80 (m, 4H, 2CH 2), 6.59 (tt, 1H, H-Ar, J=8.9,2.1Hz), 7.0-7.15 (m, 2H, H-Ar), 7.31 (br s, 2H, NH 2); Anal. theoretical value C 13H 13F 2N 5: C, 56.31; H, 4.73; N, 25.26. measured value: C, 56.16; H, 4.95; N, 25.52.
3-amino-2-(4-nitrophenyl azo-group)-3-pyridine-1-base vinyl cyanide (II-15) .2.4 gram (85%) (yellow crystals), fusing point: 259-260 ℃; IR (KBr) v=3420,3400,3300 (NH), 2970,2950,2920,2870 (CH), 2190 (CN) cm -1 1HNMR (250MHz) δ=1.95-2.10 (m, 4H, 2CH 2), 3.65-3.75 (m, 4H, 2CH 2), 7.54 (br s, 2H, NH 2), 7.57 and 8.10 (AA ' XX ', 4H, H-Ar, J=9.2Hz); 13CNMR (100MHz) δ=24.9 (2C), 50.5 (2C), 96.8,115.7,120.1 (2C), 124.7 (2C), 142.8,157.6,159.0; Anal. theoretical value C 13H 14N 6O 2: C, 54.54; H, 4.93; N, 29.35. measured value: C, 54.35; H, 5.17; N, 29.61.
Amino-2-(4-p-methoxy-phenyl azo-group)-3-piperidines-1-base vinyl cyanide (II-16) .1.85 gram (65%) (yellow crystals), fusing point: 134-136 ℃; IR (KBr) v=3415,3315,3205,3160 (NH), 2940,2860,2840 (CH), 2180 (CN) cm -1 1HNMR (250MHz) δ=1.70 (brs, 6H, 3CH 2), 3.57 (br s, 4H, 2CH 2), 3.78 (s, 3H, OMe), 7.18 (br s, 2H, NH 2), 6.83 and 7.43 (AA ' XX ', 4H, H-Ar, J=9.2Hz); MS m/z (%) 285 (M +, 56.9%); Anal. theoretical value C 15H 19N 5O:C, 63.14; H, 6.71; N, 24.54. measured value: C, 62.88; H, 6.89; N, 24.68.
3-amino-2-(4-fluorophenyl azo-group)-3-piperidines-1-base vinyl cyanide (II-17) .1.70 gram (62%) (yellow crystals), fusing point: 200-201 ℃; HNMR (250MHz) δ=1.70 (brs, 6H, 3CH 2), 3.59 (br s, 4H, 2CH 2), 7.02 (t, 2H, H-Ar, J=8.9Hz)), 7.32 (br s, 2H, NH 2), 7.46 (dd, 2H, H-Ar, J=9.0,5.0Hz); Anal. theoretical value C 14H 16FN 5: C, 61.52; H, 5.90; N, 25.62. measured value: C, 61.29; H, 5.76; N, 25.90.
3-amino-2-(3,5-difluorophenyl azo-group)-3-piperidines-1-base vinyl cyanide (II-18) .1.60 gram (55%) (yellow crystals), fusing point: 220-221 ℃; IR (KBr) v=3410,3310,3210 (NH), 2960,2940,2920,2865 (CH), 2180 (CN) cm -1HNMR (250MHz) δ=1.71 (brs, 6H, 3CH 2), 3.61 (brs, 4H, 2CH 2), 6.60 (tt, 1H, H-Ar, J=8.9,2.2Hz), 7.05-7.10 (m, 2H, H-Ar), 7.65 (br s, 2H, NH 2); Anal. theoretical value C 14H 15F 2LN 5: C, 57.72; H, 5.19; N, 24.04. measured value: C, 57.53; H, 5.27; N, 24.37.
3-amino-2-(4-fluorophenyl azo-group)-3-morpholine-4-base vinyl cyanide (II-19) .1.93 gram (70%) (yellow crystals), fusing point: 198-200 ℃; HNMR (250MHz) δ=3.55-3.75 (m, 8H, 4CH 2), 7.04 (brs, 2H, NH 2), 7.25 (t, 2H, H-Ar, J=8.5Hz), 7.40-7.50 (m, 4H, H-Ar+NH 2); Anal. theoretical value C 13H 14FN 5O:C, 56.72; H, 5.13; N, 25.44. measured value: C, 56.95; H, 5.32; N, 25.64.
3-amino-2-(3,5-difluorophenyl azo-group)-3-morpholine-4-base vinyl cyanide (II-20) .1.90 gram (65%) (yellow crystals), fusing point: 119-220 ℃; IR (KBr) v=3410,3300,3200 (NH), 2980,2920,2860 (CH), 2190 (CN) cm -1HNMR (250MHz) δ=3.60-3.80 (m, 8H, 4CH 2), 6.63 (tt, 1H, H-Ar, J=9.0,2.3Hz), 7.05-7.15 (m, 2H, H-Ar), 7.81 (brs, 2H, NH 2); Anal. theoretical value C 13H 13F 2N 5O:C, 53.24; H, 4.47; N, 23.88. measured value: C, 52.95; H, 4.63; N, 24.12.
3-amino-3-[2-(1H-indol-3-yl) ethylamino]-2-(4-p-methoxy-phenyl azo-group) vinyl cyanide (II-21) .3.15 restrains (87%) (yellow crystals), fusing point: 161-162 ℃; IR (KBr) v=3440,3310,3240 (NH), CH 2910,2865,2840, CN2180cm -1 1HNMR (250MHz): δ=3.06 (t, 2H, CH 2, J=5.0Hz), 3.61 (dt, 2H, CH 2, J=6.5,5.0Hz), 3.77 (s, 3H, OMe), 6.81 (d, 2H, H-Ar, J=9.3Hz), 6.99 (t, 2H, H-Ind, J=7.8Hz), 7.06 (s, 1H, H-Ind), 7.23 (m, 3H, NH+NH 2), 7.34 (m, 3H, H-Ar+H-Ind), 7.57 (d, 1H, H-Ind, J=7.5Hz), 10.7 (s, 1H, NH); EI ms:m/z 360 (M +, 41.15%); Anal. theoretical value C 20H 20N 6O (360.42): C, 66.65; H, 5.59; N, 23.32. measured value: C, 66.38; H, 5.78; N, 23.53.
3-amino-2-(4-chloro-phenyl-azo-group)-3-[2-(1H-indol-3-yl) ethylamino] vinyl cyanide (II-22) .3.1 restrains (87%) (yellow crystals), fusing point: 176-178 ℃; IR (KBr) v=3440,3310,3240 (NH), 2910,2865,2840 (CH), 2180 (CN) cm -1 1HNMR (400MHz): δ=3.02 (t, 2H, CH 2, J=7.6Hz), 3.62 (brs, 2H, CH 2), 6.99 (t, 1H, H-Ind, J=6.8Hz), 7.03 (t, 1H, H-Ind, J=7.8Hz); 7.16 (s, 1H, H-Ind), 7.24 (d, 2H, H-Ar, J=8.0Hz), 7.33-7.38 (3H, m; H-Ar+H-Ind), 7.56 (d, 1H, H-Ind, J=7.3Hz), 7.68-7.73 (m, 3H, NH+NH 2), 10.9 (s, 1H, NH); MS, m/z (%) 364 (M +, 17.6%); Anal. theoretical value C 19H 17ClN 6: C, 62.55; H, 4.70; N, 23.03. measured value: C, 62.31; H, 4.87; N, 23.31.
4-{2-amino-1-itrile group-2-[2-(ethylamino of 1H-indoles-3-)] vinyl azo-group } ethyl benzoate (II-23) .3.00 restrains (80%) (clear crystal), fusing point: 215-216 ℃; IR (KBr) v=3440,3310,3240 (NH), 2910,2865,2840 (CH), 2180 (CN) cm -1 1HNMR (250MHz): δ=3.06 (t, 2H, CH2, J=5.0Hz), 3.61 (dt, 2H, CH 2, J=6.5,5.0Hz), 3.77 (s, 3H, OMe), 6.81 (d, 2H, H-Ar, J=7.3Hz), 6.99 (t, 2H, the H-indoles, J=7.8Hz), 7.06 (s, 1H, H-indoles), 7.23 (m, 2H, H-Ind+NH 2), 7.46 (d, 1H, H-Ind, J=7.5Hz), 7.83-7.85 (m, 1H, NH), 7.45 and 7.87 (AA ' XX ', 4H, H-Ar, J=9.0Hz), 10.7 (s, 1H, NH); 13C (100MHz): δ=14.2,24.4,42.0,60.3,93.4,110.8,111.4,115.1 (2C), 118.3,118.4,120.0 (2C), 121.0,123.1,125.1,127.1,130.0,136.2,157.2,159.0,165.7; MS, (%) m/z402 (M +, 34.2%); Anal. theoretical value C 22H 22N 6O 2: C, 65.66; H, 5.51; N, 20.88. measured value: C, 65.41; H, 5.43; N, 20.67.
3-amino-2-(4-fluorophenyl azo-group)-3-[2-(1H-indol-3-yl) ethylamino] vinyl cyanide (II-24) .2.78 restrains (80%) (yellow crystals), fusing point: 218-220 ℃; 1HNMR (400MHz): δ=3.02 (t, 2H, CH 2, J=4.8Hz), 3.62 (br s, 2H, CH 2), 6.8-7.2 (m, 4H, H-Ar+H-Ind), 7.2 (s, 1H, H-Ind), 7.36 (d, 1H, H-Ind, J=7.5Hz), 7.4-7.7 (m 5H, H-Ar+H-Ind+NH 2), 10.89 (s, 1H, NH); 13C (100MHz): δ=24.6,42.0,90.9,110.9,111.4,115.2 (d, 2C, 2J CF=22.2Hz), 115.9118.4 (2C), 121.0,121.6 (d, 2C, 3J CF=7.9Hz), 123.1,127.0,136.2,150.4,159.3,160.0 (d, 1J CF=240Hz); Anal. theoretical value C 19H 17FN 6: C, 65.51; H, 4.92; N, 24.12. measured value: C, 65.32; H, 4.71; N, 24.35.
3-amino-2-(3,5-difluorophenyl azo-group)-3-[2-(1H-indol-3-yl) ethylamino] vinyl cyanide (II-25) .1.8 restrains (50%) (yellow crystals), fusing point: 210-212 ℃; 1HNMR (400MHz): δ=3.08 (t, 2H, CH 2, J=7.0Hz), 3.72 (br s, 2H, CH 2), 6.72 (t, 1H, H-Ar, J=7.0Hz), 6.80-7.20 (m, 5H, H-Ind+H-Ar+NH 2), 7.32 (d, 1H, H-Ind, J=8.0Hz), 7.50-7.70 (m, 3H, H-Ind+H-Ar), 7.8 (t, 1H, NH, J=6.9Hz), 10.7 (brs, 1H, NH); 13C (100MHz): δ=24.4,42.1,92.6,99.3 (t, 2J CF=27.2Hz), 102.9 (d, 2C, 2J CF=25.5Hz), 110.9 (2C), 111.4,115.1,118.3,118.4,121.0,123.0,127.1,136.2,156.8 (t, 3J CF=9.6Hz), 158.9,163.0 (dd, 2C, 1J CF=242.3, 3J CF=15.0Hz); Anal. theoretical value C 19H 16F 2N 6: C, 62.29; H, 4.40; N, 22.94. measured value: C, 62.05; H, 4.53; N, 23.14.
3-amino-2-(4-nitrophenyl azo-group)-3-[2-(1H-indol-3-yl) ethylamino] vinyl cyanide (II-26) .3.1 restrains (63%) (yellow crystals), fusing point: 308-310 ℃; 1HNMR (400MHz): δ=3.03 (t, 2H, CH 2, J=7.2Hz), 3.66 (t, 2H, CH 2), 6.98 (t, 1H, H-Ind, J=6.8Hz), 7.08 (t, 1H, H-Ind, J=7.2Hz); 7.24 (s, 1H, H-Ind), 7.36 (d, 2H, H-Ar, J=8.0Hz), 7.33-7.38 (3H, m; H-Ar+H-Ind), 7.56 (d, 1H, H-Ind, J=7.3Hz), 7.68-7.73 (m, 3H, NH+NH 2), 10.9 (s, 1H, NH); 13C (100MHz): δ=24.2,42.1,95.7,110.7,111.4,114.5,118.3 (2C), 120.1 (2C), 121.0,123.2,124.7 (2C), 127.0,136.2,142.7,158.6,159.0; Anal. theoretical value C 19H 17ClN 6: C, 62.55; H, 4.70; N, 23.03. measured value: C, 62.31; H, 4.87; N, 23.31.
3-amino-2-(4-p-methoxy-phenyl azo-group)-3-(8-oxygen-1,5,6,8-tetrahydrochysene-2H, 4H-1,5-picoline be [1,5]-diazacyclo oct-3-yl also-[1,2-a]) vinyl cyanide (II-27) .2.93 restrains (75%) (yellow crystals), fusing point: 183-185 ℃; 1HNMR (250MHz): δ=1.99and 2.07 (AA ' BB ', 2H, CH2, J=12.8Hz), 2.58 (brs, 1H, CH), 3.23 (br s, 1H, CH), 3.39 (d, 1H; CH, J=13.1Hz), 3.54 (d, 1H, CH, J=13.1Hz), 3.68-3.72 (m, 1H, CH), 3.76 (s, 3H; OMe), 4.02 (d, 1H, CH, J=13.2Hz), 4.30 (d, 1H, CH, J=13.8Hz), 4.42 (d, 1H; CH, J=15.3Hz), 6.12 (d, 1H, H-Ar, J=6.5Hz), 6.20 (d, 1H, H-Ar, J=9.0Hz), 7.23 (br s; 2H, NH2), 7.26 (dd, 1H, H-Ar, J=9.0,6.5Hz), 6.84 and 7.42 (AA ' XX ', 4H, H-Ar, J=9.0Hz); 13C (100MHz): δ=24.94,27.0,33.9,47.8,53.0,55.2,55.4,92.1,104.8,113.9 (2C), 116.2,117.1,121.8 (2C), 139.0,147.4,149.4,157.8,162.38,162.7; MS, m/z (%) 390 (M +, 7.5%); Anal. theoretical value C 21H 22N 6O 2: C, 64.60; H, 5.68; N, 21.52. measured value: C, 64.43; H, 5.47; N, 21.63.
3-amino-3-(8-oxygen-1,5,6,8-tetrahydrochysene-2H, 4H-1,5-picoline be [1,5]-diazacyclo oct-3-yl also-[1,2-a])-2-phenylazo vinyl cyanide (II-28) .3.13 restrains (87%) (clear crystal), fusing point: 163-165 ℃; 1H NMR (250MHz): δ=1.97and 2.03 (AA ' BB ', 2H, CH 2, J=12.5Hz), 2.61 (brs, 1H, CH), 3.24 (s, 1H, CH), 3.40 (d, 1H, CH; J=13.6Hz), 3.55 (d, 1H, CH, J=12.8Hz), 3.70 (dd, 1H, CH, J=15.8,6.3Hz), 4.0-4.08 (m; 1H, CH), 4.33 (d, 1H, CH, J=13.2Hz), 4.43 (d, 1H, CH, J=16.1Hz), 6.12 (d; 1H, H-Ar, J=7.0Hz), 6.22 (d, 1H, H-Ar, J=8.8Hz), 7.05 (t, 1H, H-Ar, J=7.0Hz); 7.25-7.20 (m, 3H, H-Ar), 7.27 (d, 1H, H-Ar, J=8.5Hz), 7.30 (br s, 2H, NH 2); MS, (%) m/z360 (M +, 9.6%); Anal. theoretical value C 20H 20N 6O:C, 66.65; H, 5.59; N, 23.32. measured value: C, 66.89; H, 5.71; N, 23.12.
4-[2-amino-1-itrile group-2-(8-oxygen-1,5,6,8-tetrahydrochysene-2H, 4H-1,5-picoline be [1,5]-diazacyclo oct-3-yl also-[1,2-a]) vinyl azo-group] ethyl benzoate (II-29) .3.00 restrains (70%) (yellow crystals), fusing point: 245-246 ℃; 1HNMR (250MHz): δ=1.13 (t 3H, Me, J=7.1Hz), 1.96 and 2.05 (AA ' BB ', 2H, CH 2, J=12.8Hz), 2.60 (brs, 1H, CH), 3.30 (d, 1H, CH, J=8.3Hz), 3.43 (d, 1H; CH, J=13.2Hz), 3.58 (dd, 1H, CH, J=10.7), 3.69 (dd, 1H, CH, J=15.4,15.2Hz); 4.0 (d, 1H, CH, J=13.2Hz), 4.26-4.31 (m, 3H, CH), 4.37 (d, 1H, CH; J=15.4Hz), 6.19 (1H, d, H-Ar, J=7.0Hz), 6.24 (d, 1H, H-Ar, J=9.0Hz), 7.32 (dd; H-Ar, J=9.0,7.0Hz), 7.50and 7.88 (AA ' XX ', 4H, H-Ar, J=8.7Hz), 7.79 (brs, 2H, NH 2); MS:m/z432 (M +, 15.3%); 13CNMR (100MHz): δ=14.2,24.8,27.0,33.9,47.7,53.0,55.5,60.3,94.4,104.8,116.0,116.3,120.2 (2C), 125.7,130.0 (2C), 139.0,149.0,156.9,162.1,162.5,165.6; MS, m/z (%) 432 (M +, 13.2); Anal. theoretical value C 23H 24N 6O 3: C, 63.60; H, 5.59; N, 19.43. measured value: C, 63.86; H, 5.70; N, 19.61.
3-amino-2-(4-chloro-phenyl-azo-group)-3-(8-oxygen-1,5,6,8-tetrahydrochysene-2H, 4H-1,5-picoline be [1,5]-diazacyclo oct-3-yl also-[1,2-a]) vinyl cyanide (II-30) .3.7 restrains (93%) (yellow crystals), fusing point: 170-171 ℃; 1HNMR (400MHz): δ=2.00 and 2.11 (AB, 2H, CH 2, J=15.0Hz), 2.61 (s, 1H, CH), 3.24 (s, 1H, CH), 3.41 (d, 1H, CH; J=15.0Hz), 3.56 (dd, 1H, CH, J=13.0,12.7Hz), 3.69 (dd, 1H, CH, J=15.5,14.3Hz); 4.02 (m, 1H, CH), 4.31 (d, 1H, CH, J=13.5Hz), 4.42 (d, 1H, CH, J=15.7Hz); 6.12 (dd, 1H, CH, J=6.5,1.0Hz), 6.21 (1H, dd, CH, J=9.0,1.0Hz), 7.25 (dd; 1H, CH, J=9.0,6.5Hz), 7.25 and 7.43 (AA ' XX ', 4H, H-Ar, J=8.8Hz), 7.41 (s, 2H, NH 2); Anal. theoretical value C 20H 21ClN 6O:C, 60.53; H, 5.33; N, 21.18. measured value: C, 60.78; H, 5.15; N, 21.40.
3-amino-2-(4-fluorophenyl azo-group)-3-(8-oxygen-1,5,6,8-tetrahydrochysene-2H, 4H-1,5-picoline be [1,5]-diazacyclo oct-3-yl also-[1,2-a]) vinyl cyanide (II-31) .3.33 restrains (88%) (yellow crystals), fusing point: 173-175 ℃; 1HNMR (250MHz): δ=1.99 and 2.10 (AA ' BB ', 2H, CH 2, J=14.1Hz), 2.49 (brs, 1H, CH), 3.26 (brs, 1H, CH), 3.34-3.60 (m, 3H, CH), 3.70 (dd; 1H, CH, J=16.0,6.5Hz), 3.97-4.10 (m, 1H, CH), 4.31 (d, 1H, CH, J=13.2Hz), 4.42 (d; 1H, CH, J=15.8Hz), 6.12 (d, 1H, H-Ar, J=7.0Hz), 6.22 (d, 1H, H-Ar, J=9.0Hz); 6.96-7.09 (m, 2H, H-Ar), 7.26 (dd, 1H, H-Ar, J=9.0,7.0Hz), 7.33 (brs, 2H, NH 2), 7.42-7.52 (m, 2H, H-Ar); 13CNMR (100MHz): δ=24.8,26.9,33.9,47.7,52.9,55.4,92.6 104.8,115.3 (d, 2C, 2J CF=22.2Hz), 116.2,116.6,122.0 (d, 2C, 3J CF=8.1Hz), 139.0,149.2,150.1,160.3 (d, 1J CF=241Hz), 162.1,162.7; MS, m/z (%) 378 (M +, 9.4%); Anal. theoretical value C 20H 19FN 6O:C, 63.48; H, 5.06; N, 22.21. measured value: C, 63.69; H, 5.21; N, 22.12.
3-amino-2-(2,4 dichloro benzene base azo-group)-3-(8-oxygen-1,5,6,8-tetrahydrochysene-2H, 4H-1,5-picoline be [1,5]-diazacyclo oct-3-yl also-[1,2-a]) vinyl cyanide (II-32) .3.52 restrains (82%) (yellow crystals), fusing point: 223-224 ℃; 1H NMR (250MHz): δ=2.04and 2.17 (AA ' BB ', 2H, CH 2, J=12.5Hz), 2.62 (brs, 1H, CH), 3.26 (brs, 1H, CH), 3.4-3.5 (m, 1H, CH); 3.57 (d, 1H, CH, J=11.5Hz), 3.68 (dd, 1H, CH, J=15.5,6.3Hz), 4.0-4.1 (m, 1H; CH), 4.34 (d, 1H, H-Ar, J=13.8Hz), 4.43 (d, 1H, CH, J=15.8Hz), 6.13 (d, 1H; H-Ar, J=6.8Hz), 6.23 (d, 1H, H-Ar, J=8.0Hz), 7.15-7.3 (m, 2H, H-Ar), 7.34 (d; 1H, H-Ar, J=2.0Hz), 7.49 (d, 1H, H-Ar, J=8.5Hz), 7.6 (brs, 1H, NH 2); MS, m/z (%) 378 (M +, 9.5%); Anal. theoretical value C 20H 18Cl 2N 6O:C, 55.96; H, 4.23; N, 19.58. measured value: C, 56.16; H, 4.45; N, 19.39.
3-amino-2-(3,5-difluorophenyl azo-group)-3-(8-oxygen-1,5,6,8-tetrahydrochysene-2H, 4H-1,5-picoline be [1,5]-diazacyclo oct-3-yl also-[1,2-a]) vinyl cyanide (II-33) .2.45 restrains (62%) (yellow crystals), fusing point: 257-258 ℃; 1HNMR (250MHz): δ=2.05 and 2.11 (AA ' BB ', 2H, CH 2, J=12.5Hz), 2.66 (brs, 1H, CH), 3.30 (d, 1H, CH, J=13.8Hz); 3.45 (d, 1H, CH, J=14.5Hz), 3.78 (dd, 1H, CH, J=17.0,5.0Hz); 3.9-4.2 (m, 3H, CH), 7.1-6.4 (m, 2H, HAr), 7.12 (t, 1H, H-Ar; J=9.3Hz), 7.27 (t, 1H, H-Ar, J=7.5Hz), 7.49 (d, 2H, H-Ar, J=6.3Hz); MS, m/z 396 (M +, 12.6%); Anal. theoretical value C 20H 18Cl 2N 6O:C, 60.60; H, 4.58; N, 21.20. measured value: C, 60.86; H, 4.70; N, 21.43.
3-amino-2-(4-chloro-phenyl-azo-group)-3-[4-(3-chloro-phenylpiperazine-1-yl] vinyl cyanide (II-34) .2.60 restrains (65%) (clear crystal), fusing point: 154-155 ℃; 1HNMR (250MHz): δ=3.20-3.50 (m, 4H, CH 2), 3.60-3.95 (m 4H, CH 2), 6.74 (dd, 1H, H-Ar, J=7.4,1.4Hz), 6.85 (dd, 1H, H-Ar; J=8.8,2.0Hz), 6.85-6.90 (m, 1H, H-Ar), 7.18 (dd, 1H, H-Ar, J=8.5; 1.9Hz), 7.27 and 7.50 (AA ' XX ', 4H, H-Ar, J=8.8Hz), 7.60 (brs, 2H, NH 2); MS, m/z (%) 401 (M +, 13.5%); Anal. theoretical value C 19H 18Cl 2N 6: C, 56.87; H, 4.52; N, 20.94. measured value: C, 56.62; H, 4.43; N, 20.51.
3-amino-2-(4-chloro-phenyl-azo-group)-3-[4-(3-methoxyphenylpiperazderivatives-1-yl] vinyl cyanide (II-35) .3.05 restrains (77%) (yellow crystals), fusing point: 178-179 ℃; 1HNMR (250MHz): δ=3.08-3.28 (m, 4H, 2CH 2), 3.66-3.88 (m, 4H, 2CH 2), 3.71 (s 3H, OMe), 6.85-6.90 (m, 1H, H-Ar), 6.78 (d, 2H, H-Ar, J=8.8Hz), 7.16 (d, 1H, H-Ar, J=8.9Hz), 7.27 and 7.50 (AA ' XX ', 4H, H-Ar, J=8.5Hz), 7.56 (brs, 2H, NH 2); MS, m/z (%) 396 (M +, 18.3%); Anal. theoretical value C 20H 21ClN 6O:C, 60.53; H, 5.33; N, 21.18. measured value: C, 60.22; H, 5.49; N, 21.41.
3-amino-2-(4-chloro-phenyl-azo-group)-3-(4-pyridine-2-base piperazine-1-yl) vinyl cyanide (II-36) .2.17 restrains (59%) (yellow crystals), fusing point: 169-171 ℃; 1H NMR (250MHz): δ=3.35 (brs, 4H, 2CH 2), 3.63 (brs, 4H, 2CH 2), 6.69 (t, 1H, H-Pyr, J=4.9Hz), 6.85 (d, 1H, H-Pyr, J=8.6Hz), 7.28 (brs, 2H, NH 2), 7.34 (t, 1H, H-Pyr, J=8.4Hz), 7.51 and 7.90 (AA ' XX ', 4H, H-Ar, J=8.8Hz), 7.57 (t, 1H, H-Pyr, J=4.9Hz); MS, m/z (%) 367 (M +, 23.5%); Anal. theoretical value C 18H 18ClN 7: C, 58.78; H, 4.93; N, 26.65. measured value: C, 58.51; H, 4.71; N, 26.82.
3-amino-2-(4-chloro-phenyl-azo-group)-3-(4-pyrimidine-2-base piperazine-1-yl) vinyl cyanide (II-37) .2.32 restrains (63%) (yellow crystals), fusing point: 169-171 ℃; 1H NMR (250MHz): δ=3.50-3.59 (m, 4H, 2CH 2), 3.80-3.95 (m, 4H, 2CH 2), 6.55 (t, 1H, H-Pyrim, J=4.3Hz), 7.50 and 7.85 (AA ' XX ', 4H, H-Ar, J=9.3Hz), 8.20 (d, 2H, HPyrim, J=4.3Hz), 7.22 (brs, 2H, NH 2), MS, m/z (%) 368 (M +, 16.5%); Anal. theoretical value C 18H 18ClN 7: C, 55.36; H, 4.65; N, 30.38. measured value: C, 55.58; H, 4.80; N, 30.57.
Theory according to organic chemical reactions; When substituting group is not the substituting group described in the embodiment, adopt method of the present invention can react fully, and other compounds that obtain representing in the general structure; Principle and bioisostere principle according to reactive group addition in the agricultural chemicals initiative; These compounds also have same biological activity effect as above-mentioned compound, its effect is seen embodiment 3, embodiment 4, embodiment 5, embodiment 6, embodiment 7, embodiment 8.
Embodiment 2
Synthetic and the structure of 2-substituted aryl-5-substituted-amino-2H-4-itrile group-1,2,3-triazoles compounds I is identified
In filling 100 milliliters of round-bottomed flasks of 50 milliliters of pyridines, add 0.005 mole compound I I and 0.011 mole neutralized verdigris, reaction mixture is at chambers temp stirring reaction 1 hour to 24 hours under the temperature of solvent refluxing, and optimal reaction temperature is 60 degree; Reaction finishes the cooling back and in reaction mixture, adds water; Filter the back and collect solid and get product I with ethyl alcohol recrystallization, calculated yield is carried out fusing point and NMR, IR, MS and ultimate analysis; Mensuration result shows, each compound of synthetic 1HNMR, 13CNMR is consistent with its chemical structure with the data presentation of MS and IR and ultimate analysis, and the substituting group of each general formula compound of conversion is easy to synthetic compound I, and the yield of part of compounds and the mensuration result of physical and chemical parameter are following:
2-(4-p-methoxy-phenyl)-4-itrile group-5-methylamino--2H-[1,2,3]-triazole (I-1) .0.80 restrains (70%) (gray solid), fusing point: 168-169 ℃; IR (KBr) v=3380 (NH), 3000,2950,2920,2840,2810 (CH), 2230 (CN) cm -1. 1H NMR (250MHz): δ=2.89 (d, 3H, NHMe, J=5.0Hz), 3.83 (s, 3H, OMe), 6.68 (q, 1H, NH, J=5.0Hz), 6.99 and 7.83 (AA ' XX ', H-Ar, 4H, J=8.9Hz); MS, m/z (%) 229 (M +, 100%); Anal. theoretical value C 11H 11N 5O:C, 57.63; H, 4.84; N, 30.55. measured value: C, 57.49; H, 4.75; N, 30.37.
2-phenyl-4-itrile group-5-methylamino--2H-[1,2,3]-triazole (I-2) .0.58 restrains (57%) (gray solid), fusing point: 130-131 ℃; IR (KBr) v=3380 (NH), 2950,2910,2880,2810 (CH), 2240 (CN) cm -1. 1HNMR (250MHz): δ=2.91 (d, 3H, NHMe, J=4.6Hz), 6.76 (q, 1H, NH, J=4.6Hz), 7.36 (t, 1H, H-Ar, J=7.3Hz), 7.49 (t, 2H, H-Ar, J=7.3Hz), 7.93 (d, 2H, H-Ar, J=7.7Hz); 13C NMR (100MHz): δ=29.9,106.4,112.5,118.3 (2C), 128.2,129.7 (2C), 138.4,157.6; MS, m/z (%) 199 (M +, 100%); Anal. theoretical value C 10H 9N 5: C, 60.29; H, 4.55; N, 35.15. measured value: C, 60.49; H, 4.38; N, 35.35.
2-(3-nitrophenyl)-4-itrile group-5-methylamino--2H-[1,2,3]-triazole (I-3) .1.16 restrains (95%), (brown solid), fusing point: 189-90 ℃; 1HNMR (250MHz): δ=2.9 (d, 3H, Me, J=3.5Hz), 7.2 (br, 1H, NH), 8.1 and 8.3 (AA ' XX ', H-Ar, 4H, J=8.9Hz); Anal. theoretical value C 10H 8N 6O 2: C, 49.18; H, 3.30; N, 34.41. measured value: C, 49.33; H, 3.48; N, 34.68.
2-(4-p-methoxy-phenyl)-4-itrile group-5-hexamethylene amino-2H-[1,2,3]-triazole (I-4) .1.25 restrains (84%), (gray solid), fusing point: 153-155 ℃; IR (KBr) v=3350 (NH), 2930,2850 (CH), 2230 (CN) cm -1. 1H NMR (250MHz): δ=0.99-2.11 (m, 10H, 5CH 2), 3.57-3.30 (m, 1H, CH), 3.83 (s, 3H, OMe), 6.44-6.67 (d, 1H, NH, J=6.2Hz), 7.00 and 7.81 (AA ' XX ', 4H, H-Ar, J=9.3Hz); 13C NMR (100MHz) δ=24.5 (2C), 25.3,32.2 (2C), 55.5,105.5,113.0,114.7 (2C), 120.0 (2C), 132.1,156.0,159.0; MS, m/z (%) (M +, 100%); Anal. theoretical value C 16H 19N 5O:C, 64.63; H, 6.44; N, 23.55. measured value: C, 64.41; H, 6.28; N, 23.67.
2-phenyl-4-itrile group-5-hexamethylene amino-2H-[1,2,3]-triazole (I-5) .0.99 restrains (84%), (gray solid), fusing point: 171-173 ℃; IR (KBr) v=3350 (NH), 2930,2850 (CH), 2230 (CN) cm -1. 1H NMR (250MHz): δ=1.20-1.45 (m, 5H, CH), 1.85-1.60 (m, 3H, CH 2), 1.90-2.15 (m, 2H, CH 2), 3.56-3.34 (m, 1H, CH), 6.67 (d, 1H, NH, J=8.0Hz), 7.29-7.46 (m, 1H, H-Ar), 7.90 (d, 2H, H-Ar, J=7.9Hz), 7.50 (t, 2H, H-Ar, J=7.5Hz); 13C NMR (400MHz) δ=24.6 (2C), 25.3,32.2 (2C), 52.4,106.5,112.8,118.3 (2C), 128.2,129.7 (2C), 138.4,156.0; MS, m/z (%) 267 (M +, 53.8%); Anal. theoretical value C 15H 17N 5: C, 67.39; H, 6.41; N, 26.20. measured value: C, 67.61; H, 6.28; N, 26.45.
2-(4-p-methoxy-phenyl)-4-itrile group-5-tetrahydropyrrole-1-base-2H-[1,2,3]-triazole (I-6) .1.25 restrains (89%), (gray solid) fusing point: 126-127 ℃; IR (KBr) v=3380 (NH), 2980,2940,2880,2840, (CH), 2220 (CN) cm -1 1H NMR (400MHz) δ=1.94-1.99 (m, 4H, 2CH 2), 3.47-3.52 (m, 4H, 2CH 2), 3.81 (s, 3H, OMe), 6.85 (d, 1H, NH, J=6.8Hz), 7.11and 7.85 (AA ' XX ', 4H, H-Ar, J=9.3Hz); 13C NMR (100MHz): δ=24.8 (2C), 48.2 (2C), 55.5,104.8,113.9,114.8 (2C), 120.1 (2C), 132.0,155.7,159.2; MS, m/z (%) 269 (M +, 100%); Anal. theoretical value C 14H 15N 5O:C, 62.44; H, 5.61; N, 26.00. measured value: C, 62.31; H, 5.38; N, 26.31.
2-phenyl-4-itrile group-5-tetrahydropyrrole-1-base-2H-[1,2,3]-triazole (I-7) .1.15 restrains (95%), (gray solid) fusing point: 102-103 ℃; IR (KBr) v=3380 (NH), 2980,2940,2880 (CH), 2230 (CN) cm -1 1H NMR (250MHz): δ=2.14-1.93 (m, 2H, 2CH 2), 3.36-3.68 (m, 4H, 2CH 2), 7.39 (t, 1H, H-Ar, J=7.5Hz), 7.51 (t, 2H, H-Ar, J=7.5Hz); 7.93 (d, 2H, H-Ar, J=6.5Hz); 13C NMR (100MHz): δ=25.0 (2C), 48.2 (2C), 105.7,113.7,118.4 (2C), 128.4,129.7,138.3,161.9 (2C); MS, m/z (%) 239 (M +, 100%); Anal. theoretical value C 13H 13N 5: C, 65.26; H, 5.48; N, 29.27. measured value: C, 65.01; H, 5.25; N, 29.42.
2-(4-chloro-phenyl-)-4-itrile group-5-tetrahydropyrrole-1-base-2H-[1,2,3]-triazole (I-8) .2.15 restrains (78%), (gray solid) fusing point: 132-133 ℃; 1H NMR (250MHz): δ=1.95-2.10 (m, 4H, 2CH 2), 3.45-3.60 (m, 4H, 2CH 2), 7.51and 7.91 (AA ' XX ', 4H, H-Ar, J=8.8Hz); MS, m/z (%) 273 (M +, 100%); Anal. theoretical value C 13H 12ClN 5: C, 57.04; H, 4.42; N, 25.59. measured value: C, 56.81; H, 4.20; N, 25.82.
2-(4-fluorophenyl)-4-itrile group-5-tetrahydropyrrole-1-base-2H-[1,2,3]-triazole (I-9) 1.0 grams (77%), (white solid) fusing point: 120-121 ℃; 1H NMR (250MHz): δ=2.05 (brs, 4H, 2CH 2), 3.54 (brs, 4H, 2CH 2), 7.29 (m, 2H, H-Ar), 7.92 (m, 2H, H-Ar); Anal. theoretical value C 13H 12FN 5: C, 60.69; H, 4.70; N, 27.22. measured value: C, 60.93; H, 4.550; N, 26.96.
2-(3, the 5-difluorophenyl)-4-itrile group-5-tetrahydropyrrole-1-base-2H-[1,2,3]-triazole (I-10) .1.38 restrains (100%), (greyish-green solid) fusing point: 160-162 ℃; 1H NMR (250MHz): δ=1.85 (brs, 4H, 2CH 2), 3.54 (brs, 4H, 2CH 2), 7.0-7.25 (m, 1H, H-Ar), 7.45-7.6 (m, 2H, H-Ar); Anal. theoretical value C 13H 11F 2N 5: C, 56.73; H, 4.03; N, 25.44. measured value: C, 56.53; H, 4.20; N, 25.62.275.
2-(4-p-methoxy-phenyl)-4-itrile group-5-piperidines-1-base-2H-[1,2,3]-triazole (I-11) .1.36 restrains (96%), (gray solid) fusing point: 96-97 ℃; . 1H NMR (250MHz): δ=1.67 (br s, 6H, 3CH 2), 1.90-2.10 (m, 4H, 2CH 2), 3.40-3.52 (m, 4H, 2CH 2), 3.84 (s, 3H, Me), 7.01 and 7.83 (AA ' XX ', 4H, H-Ar, J=9.3Hz); 13CNMR (100MHz): δ=23.3,24.3 (2C), 48.0 (2C), 55.5,106.1,113.7,114.7 (2C), 120.1 (2C), 131.9,157.9,159.3; MS, m/z (%) 283 (M +, 100%); Anal. theoretical value C 15H 17N 5O:C, 63.59; H, 6.05; N, 24.72. measured value: C, 63.73; H, 5.83; N, 24.21.
2-(4-chloro-phenyl-)-4-itrile group-5-piperidines-1-base-2H-[1,2,3]-triazole (I-12) .1.00 restrains (78%), (gray solid) fusing point: 84-85 ℃; . 1H NMR (250MHz): δ=1.68 (br s, 6H, 3CH 2), 3.40-3.50 (br s, 4H, 2CH 2), 7.52and 7.91 (AA ' XX ', 4H, H-Ar, J=8.3Hz); 13C NMR (100MHz): δ=23.3.24.3 (2C), 47.9 (2C), 107.4,113.4,120.1 (2C), 129.7 (2C), 132.8,136.9,157.8; MS, m/z (%) 287 (M +, 36%); Anal. theoretical value C 14H 14ClN 5: C, 58.44; H, 4.90; N, 24.34. measured value: C, 58.63; H, 4.72; N, 24.65.
2-(4-fluorophenyl)-4-itrile group-5-piperidines-1-base-2H-[1,2,3]-triazole (I-13) .0.72 restrains (50%), (purple solid) fusing point: 121-122 ℃; 1H NMR (250MHz): δ=1.61 (br s, 6H, 3CH 2), 3.50 (br s, 4H, 2CH 2), 7.25-7.35 (m, 2H, H-Ar), 7.8-8.05 (m, 2H, H-Ar); MS, m/z (%) 287 (M +, 36%); Anal. theoretical value C 14H 14FN 5: C, 61.98; H, 5.20; N, 25.81. measured value: C, 61.67; H, 4.96; N, 26.05.271.
2-(3, the 5-difluorophenyl)-4-itrile group-5-piperidines-1-base-2H-[1,2,3]-triazole (I-14) .1.4 restrains (97%), (gray solid) fusing point: 130-131 ℃; 1H NMR (250MHz): δ=1.63 (br s, 6H, 3CH 2), 3.49 (br s, 4H, 2CH 2), 7.35 (t, 1H, H-Ar, J=13.2Hz), 7.57 (d, 2H, H-Ar, J=6.0Hz); MS, m/z (%) 287 (M +, 36%); Anal. theoretical value C 14H 13F 2N 5: C, 58.13; H, 4.53; N, 24.21. measured value: C, 58.36; H, 4.65; N, 24.45.
2-(4-p-methoxy-phenyl)-4-itrile group-5-[2-(1H-indol-3-yl) oxyethyl group]-2H-[1,2,3]-triazole (I-15) .1.54 restrains (86%), (gray solid) fusing point: 96-98 ℃; IR (KBr) v=3400,3360, (NH), 2960,2930,2860,2840 (CH), 2230 (CN) cm -1 1HNMR (250MHz): δ=3.04 (br s, 2H, CH 2), 3.55 (br s, 2H, CH 2), 3.83 (s, 3H, OMe), 6.80-7.19 (m, 5H, H-Ind+HAr), 7.32 (d, 2H, H-Ind, J=7.0Hz), 7.58 (d, 1H, H-Ind, J=6.3Hz), 7.83 (d, 2H, H-Ar, J=7.8Hz), 10.60 (br s, 1H, NH); 13CNMR (100MHz): δ=24.8,44.3,55.5,111.4,111.6,112.8 (2C), 114.7 (2C), 118.2 (2C), 119.9,120.9 (2C), 122.8,127.2,132.1,136.2,156.9,159.0; MS, m/z (%) 358 (M +, 10.5%); Aanl. theoretical value C 20H 18N 6O:C, 67.03; H, 5.06; N, 23.45. measured value: C, 67.31; H, 5.18; N, 23.58.
4-{4-itrile group-5-[2-(1H-indol-3-yl) oxyethyl group]-[1,2,3]-triazole-2-yl }-ethyl benzoate (I-16) .1.24 restrains (62%), (gray solid), fusing point: 221-222 ℃; 1HNMR (400MHz): δ=1.37 (t, 3H, Me, J=7.2Hz), 3.03 (t, 2H, CH 2, J=6.8Hz), 3.65 (dt, 2H, CH 2, J=6.5,6.8Hz), 4.30 (q, 2H, CH 2, J=7.2Hz), 6.95 (t, 1H, H-Ind J=6.8Hz), 7.04 (t, 1H; H-Ind, J=7.0Hz), 7.12-7.16 (m, 1H, H-Ind), 7.33 (d, 1H; H-Ind, J=8.3Hz), 7.5-7.7 (m, 2H, NH+H-Ind), 7.45and 7.87 (AA ' XX '; H-Ar, 4H, J=8.5Hz), 10.60 (br s, 1H, NH); MS, m/z (%) 400 (M +, 15.5%); Anal. theoretical value C 22H 22N 6O 2: C, 65.99; H, 5.03; N, 20.99. measured value: C, 65.68; H, 5.25; N, 21.28.
2-(4-fluorophenyl)-4-itrile group-5-[2-(1H-indol-3-yl) oxyethyl group]-2H-[1,2,3]-triazole (I-17) .1.20 restrains (70%), (gray solid) fusing point: 220-221 ℃; 1H NMR (400MHz): δ=3.0 (brs, 2H, CH 2), 3.5 (brs, 2H, CH 2), 7.0-7.15 (m, 2H, H-Ind+H-Ar), 7.2 (s, 1H, H-Ind), 7.25-7.65 (m, 4H, H-Ar+H-Ind), 7.60-7.63 (m, 1H, H-Ind), 7.90-7.97 (m, 2H, H-Ind+NH), 10.8 (brs, 1H, NH); Anal. theoretical value C 19H 15FN 6: C, 65.89; H, 4.37; N, 24.26. measured value: C, 65.68; H, 4.55; N, 24.47.
[[2H-[1,2,3]-triazole (I-18) .1.70 restrains (96%), (brown solid) fusing point: 139-141 ℃ to 2-(1H-indol-3-yl) oxyethyl group to 2-(3, the 5-difluorophenyl)-4-itrile group-5-; 1H NMR (400MHz): δ=3.09 (t, 2H, CH 2, J=7.0Hz), 3.76 (brs, 2H, CH 2), 6.59 (br, 1H, H-Ar), 6.90-7.1 (m, 3H, H-Ind+H-Ar), 7.18 (brs, 1H, H-Ind), 7.30-7.60 (m, 4H, H-Ind+H-Ar+NH), 10.7 (brs, 1H, NH); Anal. theoretical value C 19H 14F 2N 6: C, 62.63; H, 3.87; N, 23.0. measured value: C, 62.41; H, 4.01; N, 23.32.
2-(4-p-methoxy-phenyl)-4-itrile group-5-(8-oxygen-1,5,6,8-tetrahydrochysene-2H, 4H-1,5-picoline be [1,5]-diazacyclo oct-3-yl also-[1,2-a])-2H-[1,2,3]-triazole (I-19) .2.93 restrains (75%), (yellow crystals), fusing point: 148-150 ℃; 1HNMR (250MHz): δ=2.03 (brs, 2H, CH 2), 2.65 (brs, 1H, CH), 3.26 (brs, 1H, CH), 3.39 (d, 1H, CH, J=13.0Hz), 3.80 (brs, 1H, CH), 3.82 (s, 3H, OMe), 3.90-4.15 (m, 3H, CH 2), 6.15 (d, 2H, H-Ar, J=6.8Hz), 6.98 and 7.75 (AA ' XX ', 4H, H-Ar, J=8.3Hz), 7.23 (t, 1H, H-Ar, J=6.5Hz); MS, m/z (%) 390 (M +, 7.5%); Anal. theoretical value C 21H 22N 6O 2: C, 64.60; H, 5.68; N, 21.52. measured value: C, 64.43; H, 5.47; N, 21.63.
2-phenyl-4-itrile group-5-(8-oxygen-1,5,6,8-tetrahydrochysene-2H, 4H-1,5-picoline be [1,5]-diazacyclo oct-3-yl also-[1,2-a])-2H-[1,2,3]-triazole (I-20) .1.31 restrains (67%), (gray solid), fusing point: 172-173 ℃; 1HNMR (400MHz): δ=2.04 (s, 2H, CH 2), 2.66 (s, 1H, CH), 3.32 (m, 3H, CH), 3.78 (dd, 1H; CH, J=15.0,14.0Hz), 4.1 (m, 3H, CH), 6.16 (d, 2H, H-Ar; J=7.5Hz), 7.27 (dd, 1H, CH J=7.5,8.0Hz), 7.51 and7.87 (AA ' XX ', 4H, H-Ar, J=8.5Hz); Anal. theoretical value C 20H 17ClN 6O:C, 61.15; H, 4.36; N, 21.39. measured value: C, 61.33; H, 4.16; N, 21.54.
2-(4-fluorophenyl)-4-itrile group-5-(8-oxygen-1,5,6,8-tetrahydrochysene-2H, 4H-1,5-picoline be [1,5]-diazacyclo oct-3-yl also-[1,2-a])-2H-[1,2,3]-triazole (I-21) .1.35 restrains (72%), (gray solid), fusing point: 107-109 ℃; 1HNMR (250MHz): δ=2.04 (brs, 2H, CH 2), 2.65 (brs, 1H, CH), 3.25-3.40 (m, 3H, CH), 3.90 (d, 1H, CH; J=15.5,6.3Hz), 3.85-4.05 (m, 2H, CH), 4.11 (d, 1H, CH, J=13.0Hz), 6.16 (d; 2H, H-Ar, J=7.0Hz), 7.24-7.31 (m, 3H, H-Ar), 7.87-7.93 (m, 2H, H-Ar); 13CNMR (100MHz): δ=24.3,26.4,33.3,48.9,53.4,54.5,104.6,107.0,113.0,116.5 (d, 2C, J=23.4Hz), 120.9 (d, 2C, J=8.9Hz), 138.9,149.9,157.7,161.6 (d, J=244.8Hz), 162.0; MS, m/z (%) 376 (M +, 25); Anal. theoretical value C 20H 17FN 6O:C, 63.82; H, 4.55; N, 22.33. measured value: C, 63.57; H, 4.28; N, 22.21.
2-(2,4 dichloro benzene base)-4-itrile group-5-(8-oxygen-1,5,6,8-tetrahydrochysene-2H; 4H-1,5-methyl-pyrido-[1,2-a] [1,5]-diazacyclo oct-3-yl)-2H-[1; 2,3]-triazole (I-22) .1.62 restrains (76%), (gray solid), fusing point: 138-139 ℃; 1H NMR (250MHz): δ=2.04 (brs, 1H, CH), 2.63 (brs, 1H, CH), 3.3-3.45 (m, 3H; CH), and 3.65-3.72 (m, 1H, CH), 3.9-4.2 (m, 3H, CH), 6.14 (d; 2H, H-Ar, J=7.0Hz), 7.26 (t, 1H, HAr, J=7.0Hz); 7.53 (d, 1H, H-Ar, J=8.0Hz), 7.60-7.75 (m, 2H, H-Ar); MS, m/z (%) 427 (M +, 26.4%); Anal. theoretical value C 20H 16Cl 2N 6O:C, 56.22; H, 3.77; N, 19.67. measured value: C, 56.47; H, 3.58; N, 19.43.
2-(3, the 5-difluorophenyl)-4-itrile group-5-(8-oxygen-1,5,6,8-tetrahydrochysene-2H, 4H-1,5-picoline be [1,5]-diazacyclo oct-3-yl also-[1,2-a])-2H-[1,2,3]-triazole (I-23) .1.35 restrains (72%), (gray solid), fusing point: 107-109 ℃; 1HNMR (250MHz): δ=2.04 (brs, 2H, CH 2), 2.65 (brs, 1H, CH), 3.25-3.40 (m, 3H, CH), 3.90 (d, 1H, CH; J=15.5,6.3Hz), 3.85-4.05 (m, 2H, CH), 4.11 (d, 1H, CH, J=13.0Hz), 6.16 (d; 2H, H-Ar, J=7.0Hz), 7.24-7.31 (m, 3H, H-Ar), 7.87-7.93 (m, 2H, H-Ar); 13C NMR (100MHz): δ=24.3,26.4,33.3,48.9,53.4,54.5,104.6,107.0,113.0,116.5 (d, 2C, J=23.4), 120.9 (d, 2C, J=8.9Hz), 138.9,149.9,157.7,161.6 (d, J=244.8Hz), 162.0; MS, m/z (%) 376 (M +, 25); Anal. theoretical value C 20H 17FN 6O:C, 63.82; H, 4.55; N, 22.33. measured value: C, 63.57; H, 4.28; N, 22.21.
[(3-chloro-phenyl-piperazine-[2H-[1,2,3]-triazole (I-24) .1.30 restrains (65%), (gray solid), fusing point: 154-155 ℃ to the 1-base to 4-to 2-(4-chloro-phenyl-)-4-itrile group-5-; 1H NMR (250MHz): δ=3.19-3.43 (m, 4H, 2CH 2), 3.43-3.65 (m, 4H, 2CH 2), 6.78 (d, 1H, H-Ar, J=7.8Hz), 6.90 (d, 1H, H-Ar, J=8.2Hz), 6.90-7.0 (m, 1H, H-Ar), 7.19 (dd, 1H, H-Ar, J=8.0,1.9Hz), 7.54 and 7.95 (AA ' XX, ' 4H, H-Ar, J=8.3Hz) 7; MS, m/z (%) 399 (M +); Anal. theoretical value C 19H 16Cl 2N 6: C, 57.16; H, 4.04; N, 21.05. measured value: C, 57.38; H, 4.25; N, 21.36.
2-(4-chloro-phenyl-)-4-itrile group-5-[4-(3-methoxyphenylpiperazderivatives-1-yl]-2H-[1,2,3]-triazole (I-25) .0.91 restrains (55%), (gray solid), fusing point: 170-171 ℃; 1HNMR (250MHz): δ=3.31-3.35 (m, 4H, 2CH 2), 3.63-3.67 (m, 4H, 2CH 2), 3.75 (s, 3H, OMe), 6.36 (dd, 1H, H-Ar, J=7.8,2.1Hz); 6.47-6.50 (m, 1H, H-Ar), 6.55 (dd, 1H, H-Ar, J=8.3,1.8Hz), 7.10 (dd; 1H, H-Ar, J=8.3,1.8Hz), 7.54 and 7.96 (AA ' XX, ' 4H, H-Ar, J=8.5Hz); MS, m/z (%) 394 (M +); Anal. theoretical value C 20H 19ClN 6O:C, 60.84; H, 4.85; N, 21.28. measured value: C, 60.57; H, 4.95; N, 21.47.
2-(4-chloro-phenyl-)-4-itrile group-5-(4-pyridine-2-base piperazine-1-yl)-2H-[1,2,3]-triazole (I-26) .1.50 restrains (90%), (gray solid), fusing point: 146-148 ℃; 1HNMR (250MHz): δ=3.58-3.61 (m, 4H, 2CH 2), 3.69-3.72 (m, 4H, 2CH 2), 6.69 (t, 1H, H-Pyr, J=4.9Hz), 6.92 (d, 1H, H-Pyr, J=5.0Hz), 7.58 (t, 1H, H-Ar, J=7.4Hz), 7.65 and 7.98 (AA ' XX, ' 4H, H-Ar, J=9.0Hz), 7.57 (t, 1H, H-Pyr, J=4.9Hz); 13CNMR (100MHz): δ=43.7 (2C), 46.7 (2C), 107.4,107.8,113.3.113.5,118.6 (2C), 128.7,129.8 (2C), 137.6,138.2,147.6,157.8,158.7; MS, m/z (%) 331 (M +); Anal. theoretical value C 18H 17N 7: C, 59.10; H, 4.41; N, 26.80. measured value: C, 59.35; H, 4.65; N, 26.57.
2-(4-chloro-phenyl-)-4-itrile group-5-(4-pyrimidyl-2-base piperazine-1-yl)-2H-[1,2,3]-triazole (I-27) .1.55 restrains (85%), (gray solid), fusing point: 116-117 ℃; 1H NMR (250MHz): δ=3.52-3.61 (m, 4H, 2CH 2), 3.95-3.99 (m, 4H, 2CH 2), 6.61 (t, 1H, H-Pyr, J=4.3Hz), 7.54and 7.95 (AA ' XX, ' 4H, H-Ar, J=8.8Hz), 8.33 (d, 1H, H-Pyrim, J=4.3Hz); MS, m/z (%) 366 (M +, 54.5%); Anal. theoretical value C 17H 15ClN 8: C, 55.67; H, 4.12; N, 30.55. measured value: C, 55.45; H, 4.25; N, 30.27.
2-(4-chloro-phenyl-)-4-itrile group-5-(8-oxygen-1,5,6,8-tetrahydrochysene-2H, 4H-1,5-picoline be [1,5]-diazacyclo oct-3-yl also-[1,2-a])-2H-[1,2,3]-triazole (I-24) .1.35 restrains (72%), (gray solid), fusing point: 110-111 ℃; 1H NMR (250MHz): δ=2.04 (brs, 2H, CH 2), 2.65 (brs, 1H, CH), 3.25-3.40 (m, 3H, CH), 3.90 (d, 1H, CH; J=15.5,6.3Hz), 3.85-4.05 (m, 2H, CH), 4.11 (d, 1H, CH, J=13.0Hz), 6.16 (d; 2H, H-Ar, J=7.0Hz), 7.24-7.31 (m, 3H, H-Ar), 7.87-7.93 (m, 2H, H-Ar); 13C NMR (100MHz): δ=24.3,26.4,33.3,48.9,53.4,54.5,104.6,107.0,113.0,116.5 (d, 2C, J=23.4Hz), 120.9 (d, 2C, J=8.9Hz), 138.9,149.9,157.7,161.6 (d, J=244.8Hz), 162.0; MS, m/z (%) 393 (M +, 25).
Theory according to organic chemical reactions; When substituting group is not the substituting group described in the embodiment, adopt method of the present invention can react fully, and other compounds that obtain representing in the general structure; Principle and bioisostere principle according to reactive group addition in the agricultural chemicals initiative; These compounds also have same biological activity effect as above-mentioned compound, its effect is seen embodiment 3, embodiment 4, embodiment 5, embodiment 6, embodiment 7, embodiment 8.
Embodiment 3
The bacteriostatic activity of compound I of the present invention or II or V or VI:
The title and the code name of the frequently seen plants pathogenic fungi of the present invention's test comprise A: sugar beet leaf spot bacteria (Cercosporabeticoa); B: cucumber fusarium axysporum (Fusarium oxysporum); C: peanut Cercospora bacteria (Cercosporaarachidicola); D: tomato early blight bacterium (Alternaria solani); E: fusarium graminearum (Gibberella zeae); F: the ring rot of apple bacterium) (Physalospora piricola); G: Rhizoctonia solani Kuhn (Pellicularia sasakii); H: watermelon anthrax bacteria: (Colletotrichum lagenarium); I: verticillium dahliae (Verticilium dahliae); J: phytophthora infestans (Phytophthora infestans (Mont.) de Bary); K: Sclerotinia sclerotiorum (Sclerotinia sclerotiorum); L: dry thread Pyrenomycetes (Rhizoctonia solani Kuhn) etc., these bacterial classifications have good representativeness, can represent the kind of most of pathogenic bacteria that the field takes place in the agriculture prodn of present China, and the name in the bracket is called the latin name of pathogenic bacteria here.Thalli growth rate method is measured the result and is seen table 1, and table 1 shows that synthetic majority of compounds of the present invention has bacteriostatic action in various degree to the growth of the part pathogenic fungi of mensuration; When 50 mcg/ml, II-13, I-13, I-22 and I-23 all greater than 50%, have excellent bactericidal activity to the inhibiting rate of most of pathogenic fungi of test; Wherein, II-13 is the midbody amidine compound, and document is seldom reported the fungicidal activity of this compounds, and I-13, I-22 and I-23 are triazole class compounds.
The fungicidal activity of the compound among table 1 the present invention (/ %)
Figure GSA00000077878800181
-: undetermined
Embodiment 4
The application of compound I of the present invention or II or V or VI and other pesticide combination control agricultural and gardening plant disease:
The result of preliminary biological assay test shows, one or more in all compound I of the present invention or II or V or VI and the sterilant of organizing down mix use: white urea cyanogen, thiram, ziram, zinc manganese ethylenebisdithiocarbamate, phosethyl Al, thiophanate_methyl, m-tetrachlorophthalodinitrile, enemy can pines, derosal, procymidone, RP-26019, Vancide 89, the mould prestige of second, ester bacterium urea, fultolanil, F-1991, cyproconazole, methasulfocarb, fenpropidin, evil acid amides, triazolone, thiophanate methyl, metaxanin, Metalaxyl-M, M 9834, hymexazol, HSDB 6915, SYP-L190, tridemorph, fluzilazol, alkene azoles alcohol, tebuconazole, the mould spirit of evil, difenoconazole, mepanipyrim, ICIA 5504, Wocosin 50TK, diazosulfide, Whitfield's ointment, tiadinil, tisocromide, N-(5-methyl-1,3-thiazole-2-yl)-4-methyl-1,2,3-thiadiazole; The control that also can be used for agricultural plants disease and gardening plant disease is used in all compound I of the present invention or II or V or VI and other the known any sterilant that can on agricultural, use any one or two kinds of combinations; Can obtain same effect; Controlling object comprises surplus the Achyla, Aphanomyces, pythium, phytophthora, Sclerospora, Plasmopara, false Peronospora, Peronospora of Oomycete etc. 20 and to belong to the disease that produces; Like other diseases of plurality of cereals crops such as seedling blight of rice, tomato root rot, the late blight of potato, black shank, millet Powdery Mildew, downy mildew of garpe, downy mildew of lettuce, cucumber downy mildew and cash crop etc.; To use formulation be wettable powder, sustained release dosage, pulvis, micro-capsule suspension, can disperse dense dose, seed treatment emulsion, aqueous emulsion, big granula, granule, microemulsion, oil-suspending agent, finish, the seed with coated pesticidal, suspension concentrates, suspended emulsion agent, water-soluble granule, soluble thick agent, water-dispersible granules or the like; Compound I of the present invention or II or V or the VI ratio in compsn can be that weight ratio is 1%-90%; The control effect of medicament is good; Especially the effect of compsn that contains compound 18e and 18f is remarkable; These compsns have synergism and summation action; Do not find to have the compsn of antagonistic action, the control effect of all medicaments all is higher than forms the effect that these mixed preparations use separately.
Embodiment 5
The antiviral activity of compound I of the present invention or II or V or VI:
Synthetic majority of compounds of the present invention has certain restraining effect to the growth of tobacco mosaic virus(TMV): when 500 mcg/ml, all compounds to the restraining effect of tobacco mosaic virus(TMV) greater than 20%.
The result of preliminary biological assay test shows; All compound I of the present invention or II or V or VI and existing Antiphytoviral medicament such as diazosulfide, Whitfield's ointment, tiadinil, tisocromide, N-(5-methyl-1,3-thiazole-2-yl)-4-methyl-1,2,3-thiadiazole and 4-methyl isophthalic acid;-2; 3-thiadiazoles-5-formic acid, 4-methyl isophthalic acid; 2; The control that can be used for agricultural plants and gardening plant virus disease is used in other known any medicament that can be used as Antiphytoviral such as 3-thiadiazoles-5-ethyl formate, DL-beta-aminobutyric acid, virazole, Ningnanmycin, antofine, viral star and XY-13, XY-30 etc. any one or two kinds of combinations, and controlling object comprises tobacco mosaic virus disease, cucumber mosaic virus viral disease, tomato virus disease, sweet potato viruses disease, pepper virus disease, potato virus disease, melon virus disease and the corn short mosaic disease etc. of tobacco, tomato, vegetables, melon, fruit, grain and legume crop etc.To use formulation be wettable powder, sustained release dosage, pulvis, micro-capsule suspension, can disperse dense dose, seed treatment emulsion, aqueous emulsion, big granula, granule, microemulsion, oil-suspending agent, finish, the seed with coated pesticidal, suspension concentrates, suspended emulsion agent, water-soluble granule, soluble thick agent, water-dispersible granules or the like; Compound I of the present invention or II or V or the VI ratio in compsn can be that weight ratio is 1%-90%; The control effect of medicament is desirable; These compsns have synergism and summation action, do not find to have the compsn of antagonistic action.
Embodiment 6
The insecticidal activity of compound I of the present invention or II or V or VI:
Synthetic majority of compounds of the present invention has bacteriostatic action in various degree to the growth of mythimna separata (Mythimna separata) and mosquito larvae (Culex pipiens pallens) and aphid (Aphis laburni Kaltenbach): when 100 mcg/ml; All compounds to the restraining effect of mythimna separata and aphid greater than 60%; When 5 mcg/ml, all compounds to the restraining effect of mosquito larvae greater than 80%.
Compound of the present invention can with the sterilant of following group in one or more mix use: Chlorpyrifos 94, inferior Nong, acetamiprid, Affirm (Merck Co.), Avrmectin, PP-383, beta_cypermethrin, thiophene worm piperazine, fenvalerate, alkynes mite spy, butyl ether urea, benfuracarb, azocyclotin, PP618, ether chrysanthemum ester, ethoprophos, fluorine worm nitrile, WL 115110, desinsection list, disosultap, Provado, WL 115110, UC 62644, Avrmectin, pleocidin and sulfur-phosphor and worm hydrazides etc.; To use formulation be wettable powder, sustained release dosage, pulvis, micro-capsule suspension, can disperse dense dose, seed treatment emulsion, aqueous emulsion, big granula, granule, microemulsion, oil-suspending agent, finish, the seed with coated pesticidal, suspension concentrates, suspended emulsion agent, water-soluble granule, soluble thick agent, water-dispersible granules or the like; Compound I of the present invention or II or V or the VI ratio in compsn can be that weight ratio is 1%-90%; The control effect of medicament is good; These compsns have synergism and summation action, do not find to have the compsn of antagonistic action.Above-mentioned medicament can be converted water spray and use; Controlling object comprises: aphid, aleyrodid, leafhopper, thrips, heart-eating worm, cabbage caterpillar, snout moth's larva and common Agricultural pests such as sanitary insect pest such as plant hopper and mosquitos and flies.
Embodiment 7
The weeding activity of compound I of the present invention or II or V or VI:
Synthetic majority of compounds of the present invention has bacteriostatic action in various degree to the growth of 4 kinds of weeds of mensuration: when 750 gram/hectare dispenser dosage; All compounds are very little to the restraining effect of monocotyledon weed barnyard grass grass (Echinochloa crusgalli) and lady's-grass (Digitariasanguinalis (L.) Scop); Less than 30%, to the restraining effect of broadleaf weed rape (Brassica campestris) and three-coloured amaranth (Amaranthus retroflexus L.) greater than 60%.
Compound of the present invention can with the weedicide of following group in one or more mix use: phenoxy carboxylic acid is as 2,4-D butyl ester, 2 first, 4 chlorine; Virtue phenoxy base propionic acid ester such as quizalofop, surely kill, cover grass energy etc.; Dinitroaniline such as trifluralin, pendimethalin; Triazine such as simazine, atrazine, prometryn, ametryn 80WP, bladex etc.; Amides such as alachlor, acetochlor, the third careless amine, Butachlor technical 92, propisochlor, metolachlor etc.; Substituted urea class such as Diuron Tech, methoxydiuron, chlorotoluron, isoproturon; Diphenyl ether such as acifluorfen, fomesafen, lactofen, fluoroglycofenethyl; Cyclic imide class such as oxadiazon, methylarsonic acid, flumioxazin; Kinds such as sulfonylurea such as metsulfuronmethyl, green sulphur swell, benbbensulfuronmethyl, tribenuronmethyl, monosulfmeturon, single phonetic sulphur ester, pyrazosulfuronmethyl, azoles sulfometuron-methyl; Amino formate such as thiobencarb, Hydram; Organic phosphates such as Glyphosate 62 IPA Salt, careless ammonium phosphine; Bromoxynil, the ioxynil of other classification weedicides such as nitrile; The dicamba 98 of benzoic acids; The Paraquat 20 of bipyridyliums; The Imazethapyr of imidazolone type, imazamox, the pyrimidine Whitfield's ointment of pyrimidine salicylic acid, Nong Meili, the sethoxydim of cyclohexenone analog, clethodim etc.; The bentazone of heterocyclic, quinclorac, clomazone, fluroxypyr or the like; To use formulation be wettable powder, sustained release dosage, pulvis, micro-capsule suspension, can disperse dense dose, seed treatment emulsion, aqueous emulsion, big granula, granule, microemulsion, oil-suspending agent, finish, the seed with coated pesticidal, suspension concentrates, suspended emulsion agent, water-soluble granule, soluble thick agent, water-dispersible granules or the like, and compound I of the present invention or II or V or the VI ratio in compsn can be that weight ratio is 1%-90%, and the control effect of medicament is good; These compsns have synergism and summation action, do not find to have the compsn of antagonistic action.Above-mentioned medicament can be converted water spray and use; Controlling object comprises monocotyledon weed and the broadleaf weed that crop fields such as the extensive wheat of planting of China, corn, millet, cotton, peanut, fruit tree, vegetables take place, and crop is all had good selectivity.
Embodiment 8
Compound I of the present invention or II or V or VI mix working method and the stability of using compound preparation with common agricultural chemicals
The mixed preparation working method of compound I of the present invention or II or V or VI and common agricultural chemicals is seen table 2 and table 3; Table 2 and table 3 are visible, and most medicament all can be processed according to the method for statement, and the main component of liquid preparation is other a component of effective constituent and solubility promoter and tensio-active agent and synergistic agent and antifreezing agent etc.; The composition of solid preparation mainly includes other components such as imitating composition, tensio-active agent and filler; Preparation to processing carries out cold storage test, and liquid preparation is placed 1 all nothing depositions at 0 ± 2 ℃ and separated out, and solid preparation placed for 2 weeks at 54 ± 2 ℃; Caking phenomenon does not appear in medicament; The medicament drug effect that all preparations store before and after placing does not have significant difference, the rate of decomposition of mixing effective constituent in 5%, the medicament qualified stability.
The processing that other agriculture upward acceptable assistant or synergistic agent and filler and auxiliary material are used for the liquid or solid preparation also can obtain same effect.
Table 2 compound I of the present invention or II or V or VI mix the working method of using liquid preparation with conventional pesticide
Form content (%) explanation
The principle of other agricultural chemicals of compound I or II or V or VI+ 1-90 combination is expanding prevention spectrum or synergy
Solubility promoter 2-8-
Tensio-active agent 2-10-
Antifreezing agent 2-5-
Synergistic agent 2-8-
Other compositions 1-5-
Toluene (water) supplies 100%-
Table 3 compound I of the present invention or II or V or VI mix the working method of using solid preparation with conventional pesticide
Form content (%) explanation
The principle of other 1-90 of compound I or II or V or VI+ combination is to consider that synergy or double controls and lighten one's labor
Agricultural chemicals and saving dispenser cost
Sodium lauryl sulphate 1-5-
Zeyssatite 5-30-
Sodium lignosulfonate 2-8-
Other compositions 1-5-
Kaolin supplies 100%-

Claims (5)

1. replace fragrant hydrazone group ethanamidine compound, it is characterized in that having the chemical structure of following general formula I I:
Compound I I is following compound: 3-amino-2-(4-fluorophenyl azo-group)-3-pyridine-1-base vinyl cyanide, 3-amino-2-(3,5-difluorophenyl azo-group)-3-pyridine-1-base vinyl cyanide, 3-amino-2-(4-fluorophenyl azo-group)-3-piperidines-1-base vinyl cyanide, 3-amino-2-(3,5-difluorophenyl azo-group)-3-piperidines-1-base vinyl cyanide, 3-amino-2-(4-fluorophenyl azo-group)-3-morpholine-4-base vinyl cyanide, 3-amino-2-(3; 5-difluorophenyl azo-group)-3-morpholine-4-base vinyl cyanide, 3-amino-2-(4-fluorophenyl azo-group)-3-[2-(1H-indol-3-yl) ethylamino] vinyl cyanide, 3-amino-2-(3,5-difluorophenyl azo-group)-3-[2-(1H-indol-3-yl) ethylamino] vinyl cyanide, 3-amino-2-(4-fluorophenyl azo-group)-3-(8-oxygen-1,5; 6,8-tetrahydrochysene-2H, 4H-1; The 5-picoline is [1,5]-diazacyclo oct-3-yl also-[1,2-a]) vinyl cyanide, 3-amino-2-(2; 4-dichlorophenyl azo-group)-3-(8-oxygen-1; 5,6,8-tetrahydrochysene-2H; 4H-1; The 5-picoline is [1,5]-diazacyclo oct-3-yl also-[1,2-a]) vinyl cyanide.
2. the compound method of compound I I according to claim 1 is characterized in that total synthetic route is following:
Compound I I is by compound III and compound IV prepared in reaction, and reaction conditions is to be solvent with ethanol, temperature of reaction be room temperature to the temperature that makes solvent refluxing, the reaction times is 1 hour to 24 hours, concrete chemical reaction general formula is following:
Compound I I is following compound: 3-amino-2-(4-fluorophenyl azo-group)-3-pyridine-1-base vinyl cyanide, 3-amino-2-(3,5-difluorophenyl azo-group)-3-pyridine-1-base vinyl cyanide, 3-amino-2-(4-fluorophenyl azo-group)-3-piperidines-1-base vinyl cyanide, 3-amino-2-(3,5-difluorophenyl azo-group)-3-piperidines-1-base vinyl cyanide, 3-amino-2-(4-fluorophenyl azo-group)-3-morpholine-4-base vinyl cyanide, 3-amino-2-(3; 5-difluorophenyl azo-group)-3-morpholine-4-base vinyl cyanide, 3-amino-2-(4-fluorophenyl azo-group)-3-[2-(1H-indol-3-yl) ethylamino] vinyl cyanide, 3-amino-2-(3,5-difluorophenyl azo-group)-3-[2-(1H-indol-3-yl) ethylamino] vinyl cyanide, 3-amino-2-(4-fluorophenyl azo-group)-3-(8-oxygen-1,5; 6,8-tetrahydrochysene-2H, 4H-1; The 5-picoline is [1,5]-diazacyclo oct-3-yl also-[1,2-a]) vinyl cyanide, 3-amino-2-(2; 4-dichlorophenyl azo-group)-3-(8-oxygen-1; 5,6,8-tetrahydrochysene-2H; 4H-1; The 5-picoline is [1,5]-diazacyclo oct-3-yl also-[1,2-a]) vinyl cyanide;
The concrete synthesis step of compound I I is following:
In 100 milliliters of round-bottomed flasks, add 0.01 mole compound IV and compound III and 50 milliliters of ethanol of 1.3 moles; Reaction mixture is at room temperature stirring reaction 1 hour to 24 hours under the reflux temperature condition; After the cooling reaction mixture is joined in the trash ice; Filter the back and collect solid and get compound I I with ethyl alcohol recrystallization, the consumption of synthetic compound can or dwindle by corresponding proportion expansion.
3. the described compound I I of claim 1 is as the purposes of bactericide.
4. a biocide preparation is characterized in that: contain compound I I as claimed in claim 1 in this biocide preparation and go up acceptable assistant with agricultural.
5. bactericidal composition; It is characterized in that: contain compound I I as claimed in claim 1 in the said composition and be selected from down the bactericide of group: white urea cyanogen with one or more; Thiram; Ziram; Mancozeb; Aliette; Thiophanate-methyl; Bravo; The enemy can be loose; Carbendazim; Procymidone; Iprodione; Captan; The mould prestige of second; Ester bacterium urea; Flutolanil; Benomyl; Cyproconazole; Methasulfocarb; Fenpropidin; Dislike acid amides; Triazolone; Thiophanate methyl; Metalaxyl; Metalaxyl-M; M 9834; Hydroxyisoxazole; Dimethomorph; Flumorph; Tridemorph; Flusilazole; Alkene azoles alcohol; Tebuconazole; Dislike mould spirit; Difenoconazole; Mepanipyrim; Fluoxastrobin; Propiconazole; Diazosulfide; Salicylic acid; Tiadinil; Tisocromide; N-(5-methyl-1,3-thiazole-2-yl)-4-methyl-1,2,3-thiadiazole, the ratio of wherein said compound I I in composition are 1-90 weight %.
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Title
M. A. Demina et al.,.synthesis of 1-azolylcytizines.《Chemistry of Heterocyclic Compounds》.2007,第43卷(第5期),第671-672页. *
Vinata V Mulwad et al.,.Synthesis and antimicrobial screening of 5-(4, 7-dimethyl-2-oxo-2H-benzopyran-6-ylazo)-2-methyl-6-morpholin-4-yl-2, 3-dihydro-3H-pyrimidin-4-one and 5-(4, 7-dimethyl-2-oxo-2H-benzopyran-6-ylazo)-2-methyl-6-piperidin-1-yl-2, 3-dihydro-3H-pyrimidin-4-one.《Indian Journal of Chemistry》.2007,第46B卷第1873-1878页. *
Y A Ammar et al.,.Activated nitriles in heterocyclic chemistry: facile synthesis and antimicrobial activity of some pyrimidine, pyrazolopyrimidine and prazolotriazine derivatives containing sulfonamide moiety.《Indian Journal of Chemisty》.2004,第43B卷第2203-2211页. *

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