CN101838267A - Triazole compound and preparation and application thereof - Google Patents

Triazole compound and preparation and application thereof Download PDF

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CN101838267A
CN101838267A CN201010151995A CN201010151995A CN101838267A CN 101838267 A CN101838267 A CN 101838267A CN 201010151995 A CN201010151995 A CN 201010151995A CN 201010151995 A CN201010151995 A CN 201010151995A CN 101838267 A CN101838267 A CN 101838267A
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CN101838267B (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, world's agricultural chemicals complete works (sterilant volume) (weedicide volume), 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.﹠amp; 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 derivative 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 asphyxia neonatorum that cause and anti-heart disorder, anti-microbial infection, antiulcer agent, leukocyte increasing etc., 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, the piperazine (pyridine) of piperazine (pyridine) and replacement etc. is the group that contains physiologically active.In order to seek more highly active compound, consider a big class triazole compounds is arranged in the disinfectant use in agriculture, the contriver is at Tianjin science and technology support plan International Technology collaborative project (07ZCGHHZ01400), the intelligence plan is introduced in Tianjin, Tianjin natural science fund (07JCYBJC01200) and state natural sciences fund (20672062), under the subsidy of " 973 " plans (2003CB114402), the present invention wishes 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 intermediate 2-of the synthetic method of 3-triazole class compounds (general formula I) and synthetic these compounds replaces the synthetic method of fragrant diazanyl-2-cyano group 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:
Wherein: Ar is phenyl or is substituted single replacement of base or disubstituted phenyl that described 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 cycloalkyl 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 cycloalkyl 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 intermediate 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 is substituted single replacement of base or disubstituted phenyl that described 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 cycloalkyl 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 cycloalkyl 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 as follows:
Wherein: substituent A r in each general formula compound and R 1, R 2, NR 1R 2Definition see description in the above-mentioned general formula 1;
The step and the condition of concrete synthetic method are as follows:
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 as follows:
Figure GSA00000077878800032
Wherein: substituent A r, R 1, R 2, NR 1R 2As 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 as follows:
Wherein: substituent A r, R 1, R 2, NR 1R 2As the definition among the above-mentioned general formula compound I;
C. the operation steps of synthetic compound I is as follows:
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, filtering the back collects solid and gets Compound I with ethyl alcohol recrystallization, calculated yield, carry out fusing point and NMR, IR, MS and ultimate analysis, the consumption of synthetic compound enlarges by corresponding proportion or dwindles, 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 as follows:
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, filtering the back collects solid and gets Compound I I with ethyl alcohol recrystallization, calculated yield, 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 as follows:
Figure GSA00000077878800041
The concrete synthesis step of compound V and VI is as follows:
Tocosamine VII and 50 milliliters of ethanol of in 100 milliliters of round-bottomed flasks, adding 0.01 mole Compound I X or X and 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, filtering the back collects solid and gets compound VIII or XI with ethyl alcohol recrystallization, the neutralized verdigris that in filling 100 milliliters of round-bottomed flasks of 50 milliliters of pyridines, adds 0.005 mole compound VIII or XI and 0.011 mole, reaction mixture is spent stirring reactions 6 hours 60, the cooling back adds water in reaction mixture, filter the back and collect solid and get product V or VI with ethyl alcohol recrystallization.
The biological activity determination method and the step of each compound are as follows:
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, detailed process is: get 5 milligrams of sample dissolution at an amount of N, in the dinethylformamide, then with containing the medicament that a certain amount of polysorbas20 emulsifier aqueous solution is diluted to 500 mcg/ml, reagent agent is respectively drawn under aseptic condition in 1 milliliter of injection culture dish, add 9 milliliters of substratum more respectively, make 50 mcg/ml pastille flat boards after shaking up, do blank with the flat board that adds 1 milliliter of aqua sterilisa, punch tool with 4 millimeters of diameters cuts the bacterium dish along the mycelia outer rim, move on the pastille flat board, be equilateral triangle and put, every processing repeats 3 times, culture dish is placed in 24 ± 1 degree constant incubators cultivates, colony diameter to be contrasted expands to 2-3 centimetre of " Invest, Then Investigate " and respectively handles bacterium dish expansion diameter, average, relatively calculate relative bacteriostasis rate, comprise frequently seen plants pathogenic bacteria on the various agricultural for the examination bacterial classification with blank, 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 as follows: the mensuration of the direct antiviral activity that exsomatizes adopts half leaf method to carry out; Live test is the common cigarette with the seedling age unanimity, 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, check 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 treatment of seedling and seedling, treatment dosage is 750 gram/hectares, 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, 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, adopt 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 describe 1 by specific preparation and biological activity determination embodiment, 2,3-triazole class compounds I and synthetic its intermediate replace the synthetic and biological activity of fragrant hydrazone group ethanamidine Compound I I and in the application of agriculture field, but described embodiment only is used for specific description the present invention and unrestricted the present invention, especially its biological activity only illustrates, rather than the restriction this patent, concrete embodiment is as follows:
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, 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, measurement 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 measurement result of part of compounds yield and physical and chemical parameter is as follows:
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-)] the 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 are also-[1,2-a] [1,5]-diazacyclo oct-3-yl) 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 are also-[1,2-a] [1,5]-diazacyclo oct-3-yl) the 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 are also-[1,2-a] [1,5]-diazacyclo oct-3-yl) 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), and 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 are also-[1,2-a] [1,5]-diazacyclo oct-3-yl) 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 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 active 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, optimal reaction temperature is 60 degree, reaction finishes the cooling back and add water in reaction mixture, 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, measurement 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 measurement result of physical and chemical parameter are as follows:
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), and 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.
2-(3, the 5-difluorophenyl)-4-itrile group-5-[2-(1H-indol-3-yl) oxyethyl group [2H-[1,2,3]-triazole (I-18) .1.70 restrains (96%), (brown solid) fusing point: 139-141 ℃; 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), and 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), and 3.3-3.45 (m, 3H, CH), 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), and 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-1-base [2H-[1,2,3]-triazole (I-24) .1.30 restrains (65%), (gray solid), fusing point: 154-155 ℃ to 2-(4-chloro-phenyl-)-4-itrile group-5-[4-; 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), and 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 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 active 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 production of present China, and the name in the bracket is called the latin name of pathogenic bacteria here.Thalli growth rate method measurement result sees Table 1, table 1 shows, 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 intermediate 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, the enemy can be loose, derosal, procymidone, RP-26019, Vancide 89, the mould prestige of second, ester bacterium urea, fultolanil, F-1991, cyproconazole, methasulfocarb, fenpropidin, dislike acid amides, triazolone, thiophanate methyl, metaxanin, Metalaxyl-M, M 9834, hymexazol, dimethomorph, flumorph, tridemorph, fluzilazol, alkene azoles alcohol, tebuconazole, dislike mould spirit, difenoconazole, mepanipyrim, Azoxystrobin, Wocosin 50TK, diazosulfide, Whitfield's ointment, tiadinil, tisocromide, N-(5-methyl-1,3-thiazole-2-yl)-4-methyl-1,2,3-thiadiazole; In all Compound I of the present invention or II or V or VI and other the known any sterilant that can use on agricultural any one or two kinds are used in combination the control that also can be used for agricultural plants disease and gardening plant disease, can obtain same effect, controlling object comprises the Achyla of Oomycete, Aphanomyces, pythium, phytophthora, Sclerospora, Plasmopara, false Peronospora, a disease that genus produces surplus the Peronospora etc. 20, as seedling blight of rice, the tomato root rot, the late blight of potato, black shank, the millet Powdery Mildew, downy mildew of garpe, downy mildew of lettuce, other diseases of plurality of cereals crops such as cucumber downy mildew and cash crop etc., using formulation is 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, 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 composition can be that weight ratio is 1%-90%, the prevention effect of medicament is good, especially the effect of composition that contains compound 18e and 18f is remarkable, these compositions have synergism and summation action, do not find to have the composition of antagonistic action, the prevention 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, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-ethyl formate, the DL-beta-aminobutyric acid, virazole, Ningnanmycin, antofine, virus star and XY-13, in other known any medicament that can be used as Antiphytoviral such as XY-30 any one or two kinds are used in combination the control that can be used for agricultural plants and gardening plant virus disease, and controlling object comprises tobacco, tomato, vegetables, melon, fruit, the tobacco mosaic virus disease of grain and legume crop etc., the cucumber mosaic virus viral disease, tomato virus disease, the sweet potato viruses disease, pepper virus disease, potato virus disease, melon virus disease and corn short mosaic disease 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 composition can be that weight ratio is 1%-90%, the prevention effect ideal of medicament, these compositions have synergism and summation action, do not find to have the composition 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, the inferior Nong in ground, acetamiprid, Affirm (Merck Co.), Avrmectin, Cypermethrin, effective cypermethrin, thiophene worm piperazine, fenvalerate, alkynes mite spy, the butyl ether urea, benfuracarb, azocyclotin, Buprofezin, ether chrysanthemum ester, ethoprophos, fluorine worm nitrile, flufenoxuron, the desinsection list, disosultap, Provado, flufenoxuron, UC 62644, Avrmectin, pleocidin and sulfur-phosphor and worm hydrazides etc., using formulation is 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, 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 composition can be that weight ratio is 1%-90%, the prevention effect of medicament is good, these compositions have synergism and summation action, do not find to have the composition 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, 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, tribenuron-methyl, monosulfmeturon, single phonetic sulphur ester, pyrazosulfuronmethyl, azoles sulfometuron-methyl; Amino formate such as thiobencarb, Hydram; Organic phosphates such as glyphosate, careless ammonium phosphine; The bromoxynil of other classification weedicides such as nitrile, ioxynil, the dicamba 98 of benzoic acids, the Paraquat 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, using formulation is 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, 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 composition can be that weight ratio is 1%-90%, the prevention effect of medicament is good, these compositions have synergism and summation action, do not find to have the composition 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 sees Table 2 and table 3, table 2 and table 3 are as seen, most medicament all can be processed according to the method for statement, 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 the effect composition, other components such as tensio-active agent and filler, preparation to processing carries out cold storage test, liquid preparation is placed 1 week not have to precipitate at 0 ± 2 ℃ and is separated out, 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 synergy or doublely control and lighten one's labor
Agricultural chemicals and saving dispenser cost
Sodium lauryl sulphate 1-5-
Diatomite 5-30-
Sodium lignosulfonate 2-8-
Other compositions 1-5-
Kaolin supplies 100%-

Claims (6)

1. replace fragrant hydrazone group ethanamidine compound, replacing fragrant hydrazone group ethanamidine compound is the important intermediate of direct synthetic compound I, it is characterized in that having the chemical structure of following general formula I I:
Figure FSA00000077878700011
Wherein: Ar is phenyl or is substituted single replacement of base or disubstituted phenyl that described substituting group is the group that is selected from methoxyl group, methyl, trifluoromethyl, nitro or halogen;
R 1Group for azacycloalkyl, 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 cycloalkyl of the straight chained alkyl that is selected from H, C1-C6, C3-C6, C3-C6;
R 2Group for the straight chained alkyl, 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 cycloalkyl that are selected from H, C1-C6;
Or R 1With R 2Form the group that is selected from tryptamines base, 3-chloro-phenyl-piperazinyl, 3-chloro-phenyl-piperidyl, 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.
Do not comprise in the above-claimed cpd that R1 is that to be methyl or tetrahydropyrrole base, R1 form the compound of tetrahydropyrrole base, piperidyl, 3-methoxyphenylpiperazderivatives base in the lump with R2 and the N atom that links to each other for methyl, R2.
2. according to the synthetic method of the Compound I I of claim 1, it is characterized in that total synthetic route is as follows:
Intermediate II 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 as follows:
Figure FSA00000077878700012
Wherein: substituent A r, R 1, R 2, NR 1R 2Definition such as claim 1 definition.
The concrete synthesis step of intermediate II is as follows: add 0.01 mole compound IV and compound III and 50 milliliters of ethanol of 1.3 moles in 100 milliliters of round-bottomed flasks, 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. biocide preparation is characterized in that: the described bactericide of claim 3 contains Compound I I as claimed in claim 1 and agricultural goes up acceptable assistant or synergistic agent.
5. fungicidal 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 sterilant of group: white urea cyanogen with one or more, thiram, ziram, zinc manganese ethylenebisdithiocarbamate, phosethyl Al, thiophanate_methyl, m-tetrachlorophthalodinitrile, the enemy can be loose, 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, dimethomorph, flumorph, tridemorph, fluzilazol, alkene azoles alcohol, tebuconazole hymexazo, difenoconazole, mepanipyrim, Azoxystrobin, Wocosin 50TK, diazosulfide, Whitfield's ointment, 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 %.
6. the composition of an antiviral agent, it is characterized in that: contain Compound I I as claimed in claim 1 in the said composition and be selected from down the antiviral agent of group: 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 with one or more, 2,3-thiadiazoles-5-formic acid, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-ethyl formate, DL-beta-aminobutyric acid, virazole, Ningnanmycin, antofine and agricultural go up acceptable assistant, and the ratio of wherein said Compound I I in composition is 1-90 weight %.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020169047A1 (en) * 2019-02-22 2020-08-27 沈阳化工大学 1,1-dicyanohydrazone compound and use therefor

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020169047A1 (en) * 2019-02-22 2020-08-27 沈阳化工大学 1,1-dicyanohydrazone compound and use therefor

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