CN104892615B - Tetrahydro-pyrazole ketone triazin compound and preparation method and application - Google Patents

Tetrahydro-pyrazole ketone triazin compound and preparation method and application Download PDF

Info

Publication number
CN104892615B
CN104892615B CN201510314980.7A CN201510314980A CN104892615B CN 104892615 B CN104892615 B CN 104892615B CN 201510314980 A CN201510314980 A CN 201510314980A CN 104892615 B CN104892615 B CN 104892615B
Authority
CN
China
Prior art keywords
tetrahydro
acid
preparation
silicon
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201510314980.7A
Other languages
Chinese (zh)
Other versions
CN104892615A (en
Inventor
那日松
李洪连
刘佳
王长青
田佳轩
李文明
何睿
刘向阳
张猛
蒋世军
孙铖
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henan Agricultural University
Original Assignee
Henan Agricultural University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henan Agricultural University filed Critical Henan Agricultural University
Priority to CN201510314980.7A priority Critical patent/CN104892615B/en
Publication of CN104892615A publication Critical patent/CN104892615A/en
Application granted granted Critical
Publication of CN104892615B publication Critical patent/CN104892615B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system

Abstract

The invention discloses a kind of tetrahydro-pyrazole ketone triazin compound and preparation method and application, the tetrahydro-pyrazole ketone that the present invention is provided triaizine compounds, such as formula（Ⅰ）It is shown.Its preparation method such as following steps：Under Bronsted acid or Louis acid catalysis, by formula（Ⅱ）And formula（Ⅲ）Shown compound is reacted in being mixed in solvent, and reaction obtains formula（Ⅰ）Shown compound, the present invention provide a kind of simple new method to prepare tetrahydropyrazolonederivative derivative, and compound document prepared by the present invention has no report, is noval chemical compound.The preparation method that the present invention is provided is acid catalyzed cycloaddition method, and with molecular economy, catalyst is Bronsted acid or lewis acid, it is to avoid use transition metal, product to there is no heavy metal pollution risk for reaction itself.Expensive phosphine catalyst need not be used, it is with low cost.

Description

Tetrahydro-pyrazole ketone triazin compound and preparation method and application
Technical field
The invention belongs to organic compound preparation technical field, and in particular to a kind of tetrahydro-pyrazole ketone triazin derivatives And preparation method and application.
Background technology
Tetrahydro-pyrazole ketone structure is a kind of important skeleton in new drug and pesticide developing, and its derivant shows extensive life Thing activity, for example, non-steroid analgesic C1, antidiabetic medicine C2, antibacterial C3, herbicide C4, insecticide C5, antibiotic C6 etc., some compounds enter market as FDA medicines and pesticide species.Therefore, relevant tetrahydropyrazolonederivative derivative High efficiency preparation method receive much concern always, specifically how efficiently, the tetrahydro-pyrazole ketone of economic acquisition molecular diversity spreads out It is biological.
Intermolecular cycloaddition reaction is to prepare one of heterocyclic compound most efficient method, is sent out in antibiotic C6 compounds Since existing, 1, the 3- Dipolar Cycloaddition that 1, the 3- dipoles body such as azo methylene time amine is participated in becomes and prepares heterocyclic compound Especially tetrahydropyrazolonederivative derivative important method.
Chinese patent CN 103497193, International Edition (2013), 52 (47), 12377-12380； Angewandte Chemie, International Edition (2013), 52 (48), 12641-12645) report and utilized Metal and Phosphine ligands catalysis are crossed, by azo methylene time amine and the ylide raw material containing drawing electron groups such as ester groups, system Contain the method for the tetrahydro-pyrazole ketone triazine structure compound of ester group in standby amino ortho position.
Above-mentioned preparation method is limited by ylide raw material, is needed using transition metal and expensive catalyst, and preparation method is multiple It is miscellaneous, high cost.
The content of the invention
It is an object of the invention to provide a kind of tetrahydro-pyrazole ketone triazin derivatives and preparation method and application.
The technical scheme is that：A kind of tetrahydro-pyrazole ketone triaizine compounds, the tetrahydro-pyrazole ketone triazine The chemical formula of compound is as shown in formula I：
Wherein R1For phenyl, alkyl phenyl, alkoxyl phenyl, halogenophenyl, polyhalo phenyl, naphthyl, nitrobenzophenone, alkane Base；R2For benzyl.
The preparation method of described tetrahydro-pyrazole ketone triaizine compounds：1,3- dipole body azos methylene time amine and N- first Under Bronsted acid and metal Lewis acids catalysis, the reaction in different solvents obtains tetrahydrochysene to epoxide-N- front three silicon methylbenzylamines Pyrazolone triaizine compounds, 1, the 3- dipoles body azo methylene time amine and N- methoxyl group-N- front three silicon methylbenzylamines The ratio of the amount of material is 1：4, the amount of the material of Bronsted acid and metal Lewis acids is 1,3- dipole body azos methylene time amine thing The 10% of the amount of matter, response time are 1-72 hours, and reaction temperature is from 0 DEG C to the reflux temperature of solvent, 1, the 3- dipole bodies , as shown in formula II, the chemical formula of the N- methoxyl groups-N- front three silicon methylbenzylamines is as led to for the chemical formula of azo methylene time amine Shown in formula III：
Wherein R1For phenyl, alkyl phenyl, alkoxyl phenyl, halogenophenyl, polyhalo phenyl, naphthyl, nitrobenzophenone, alkane Base；R2For benzyl.
The Bronsted acid is trifluoroacetic acid, acetic acid, phosphoric acid, hydrochloric acid；Lewis acid is trifluoromethanesulfonic acid zinc, trifluoromethanesulfonic acid Trimethylsilyl group, silver trifluoroacetate, silver acetate, titanium tetrachloride, lithium fluoride.
The solvent be dichloromethane, dichloroethanes, chloroform, DMF, tetrahydrofuran, in acetonitrile extremely Few one kind.
The reaction temperature is 10-15 DEG C.
Tetrahydro-pyrazole ketone application of the triaizine compounds in nematicide.
Tetrahydro-pyrazole ketone application of the triaizine compounds in antibacterial.
The invention has the beneficial effects as follows：The present invention proposes a kind of not by the limit of the ylide raw material containing drawing electron groups such as ester groups System, the method for not requiring the use of transition metal and expensive catalyst are directly prepared for the tetrahydro-pyrazole ketone of the various sex modification of a class simultaneously The compound of triazine structure.
Preparation method of the present invention is simple, and yield is high, and other methods are compared and do not need strict anhydrous and oxygen-free operation；Need not hold high Expensive Phosphine ligands, cost are more cheap；Cu or other transition-metal catalysts are not required the use of, it is dirty that product does not have metal residual Dye；Do not limited by the ylide raw material that must contain the drawing electron groups such as ester group；Compound prepared by the present invention has to nematodiasis There is eelworm-killing activity, can be as the effective ingredient of nematicide.Compound prepared by the present invention also has to plant soil-borne diseases There is bactericidal activity, can be as the effective ingredient of antibacterial.
Specific embodiment
Following examples further illustrate present disclosure, but should not be construed as limiting the invention.
Compound prepared by the present invention has certain preventing and treating effect to the plant soil-borne diseases that various cause of diseases such as nematicide, funguses cause Really, related cause of disease example is included but are not limited to：Plant nematode, such as Meloidogyne Meloidogyne, Heterodera Heterodera, Ditylenchus, grain Turbatrix Anguina, minute hand Turbatrix Longidorus, similes thorne Category Radophorus, Pratylenchus Pratylenchus are belonged to nematodes；Oomycetes, such as pythium Pythium, false downy mildew Category Pseudoperonospora, Phytophthora Phytophthora, Peronospora Peronospora, white Phytophthora Peronophythora, with other category；Fungi Imperfecti, such as Fusarium Fusarium, Rhizoctonia Rhizoctonia, colletotrichum Colletotrichum, Curvularia Curvularia, with other category；Ascomycota, such as cochliobolus belong to Cochliobolus, red Mould category Gibberella, Erysiphe Erysiphe, Valsa Valsa, Claviceps Claviceps, Exoascus Taphrina, Venturia Venturia, mycosphaerella Mycosphaerella, Neovossia Neovossia, with other Category；And other such as antibacterials etc. cause the pathogen of plant soil-borne diseases.Related disease example caused by related cause of disease include but It is not limited only to：The nematodiasises such as root knot nematode in tobacco, Semen Tritici aestivi cyst roundworm, sweet potato stem nematode, root-knot nematode, Semen Tritici aestivi stem foot Maize ear rot, root rotof flax, wheat sharp eyespot, wheat scab, Semen Tritici aestivi corruption mildew, take-all, Corn Stalk Rot, maize seedling The soil-borne diseases such as rot, Causal Organism of Maize Basal Stalk, Semen Maydiss corruption mildew.
Embodiment 1
By 2- (phenyl) pyrazolidine 3- ketone ylides (0.125mmol), N- methoxyl groups-N- front threes silicon methylbenzylamine (III) (0.125mmol), in, adding 15mL reaction tubes, it is subsequently adding CH2Cl2(1mL) with trifluoroacetic acid (0.0125mmol).Divide afterwards Batch add N- methoxyl groups-N- front threes silicon methylbenzylamine (III) (0.375mmol), reaction system stirs 72h at 10 DEG C, to having reacted Entirely.Reaction solution direct Jing silica gel column chromatography (eluant after being spin-dried for：Petrol ether/ethyl acetate=1/9) obtain white after purification Solid.71%yield, a white solid.1H NMR(400MHz,Chloroform-d)δ7.36–7.27(m,10H), 4.91 (d, J=11.3Hz, 1H), 3.78-3.68 (m, 4H), 3.36-3.25 (m, 1H), 2.96-2.89 (m, 1H), 2.84- 2.75(m,1H),2.69–2.60(m,2H),2.50–2.39(m,1H)；13C NMR(101MHz,CDCl3)δ170.35, 138.03,137.03,129.04,128.75,128.52,128.33,127.74,127.52,66.99,61.58,58.68, 57.61,47.96,30.09；IR(film)νmax 3029,2924,2844,1695,1602,1494,1453,1410,1328, 1280,1129,1065,1027,929,979,758,100,633,569,529,498,466cm-1；HRMS(MALDI)calcd for C19H22N3O+[M+H]+308.1757,found 308.1763。
Embodiment 2
By 2- (o-methyl-phenyl -) pyrazolidine 3- ketone ylides (0.125mmol), N- methoxyl group-N- front three silicon methylbenzylamines (III) (0.125mmol), in adding 15mL reaction tubes, it is subsequently adding CH2Cl2(1mL) with trifluoroacetic acid (0.0125mmol).It After be dividedly in some parts N- methoxyl groups-N- front threes silicon methylbenzylamine (III) (0.375mmol), reaction system stirs 72h at 10 DEG C, to anti- Should be complete.Reaction solution direct Jing silica gel column chromatography (eluant after being spin-dried for：Petrol ether/ethyl acetate=1/9) obtain after purification White solid.69%yield, a white solid.1H NMR (400MHz, Chloroform-d) δ 7.52 (d, J=7.5Hz, 0H), 7.58-7.48 (m, 2H), 7.40-7.08 (m, 9H), 4.93 (dd, J=11.4,1.9Hz, 1H), 4.03 (dd, J= 10.3,2.7Hz, 1H), 3.83-3.69 (m, 3H), 3.45-3.27 (m, 1H), 2.89 (dt, J=13.0,2.3Hz, 1H), 2.77–2.40(m,4H),2.28(s,3H)；13C NMR(101MHz,CDCl3)δ170.52,137.11,136.08,135.47, 130.54,129.00,128.51,127.59,127.54,126.96,126.57,62.07,61.71,57.41,57.36, 47.95,30.14,19.41；IR(film)νmax 3063,3027,2925,2244,1696,1603,1492,1454,1413, 1329,1279,1239,1172,1131,1069,1050,1027,1002,311,882,848,730,699,673,645,548, 480,452cm-1；HRMS(MALDI)calcd for C20H24N3O+[M+H]+322.1914,found 322.1922。
Embodiment 3
By 2- (aminomethyl phenyl) pyrazolidine 3- ketone ylides (0.125mmol), N- methoxyl group-N- front three silicon methylbenzylamines (III) (0.125mmol), in adding 15mL reaction tubes, it is subsequently adding CH2Cl2(1mL) with trifluoroacetic acid (0.0125mmol).It After be dividedly in some parts N- methoxyl groups-N- front threes silicon methylbenzylamine (III) (0.375mmol), reaction system stirs 72h at 10 DEG C, to anti- Should be complete.Reaction solution direct Jing silica gel column chromatography (eluant after being spin-dried for：Petrol ether/ethyl acetate=1/9) obtain after purification White solid.67%yield, a white solid.1H NMR (400MHz, Chloroform-d) δ 7.52 (d, J=7.6Hz, 1H), 7.39-7.32 (m, 3H), 7.30-7.11 (m, 5H), 4.93 (dd, J=11.4,1.9Hz, 1H), 4.03 (dd, J= 10.4,2.7Hz,1H),3.86–3.72(m,3H),3.42–3.31(m,1H),2.93–2.85(m,1H),2.75–2.42(m, 4H),2.28(s,3H)；13C NMR(101MHz,CDCl3)δ170.52,137.10,136.07,135.47,130.53, 129.00,128.51,127.58,127.53,126.96,126.56,62.08,61.71,57.41,57.35,47.95, 30.14,19.41；IR(film)νmax 3027,2924,1695,1603,1492,1412,1329,1279,1172,1131, 1070,1027,912,848,755,738,699,548,452cm-1；HRMS(MALDI)calcd for C20H24N3O+[M+H]+ 322.1914,found322.1928。
Embodiment 4
By 2- (p-methylphenyl) pyrazolidine 3- ketone ylides (0.125mmol), N- methoxyl group-N- front three silicon methylbenzylamines (III) (0.125mmol), in adding 15mL reaction tubes, it is subsequently adding CH2Cl2(1mL) with trifluoroacetic acid (0.0125mmol).It After be dividedly in some parts N- methoxyl groups-N- front threes silicon methylbenzylamine (III) (0.375mmol), reaction system stirs 72h at 10 DEG C, to anti- Should be complete.Reaction solution direct Jing silica gel column chromatography (eluant after being spin-dried for：Petrol ether/ethyl acetate=1/9) obtain after purification White solid.68%yield, a white solid.1H NMR(400MHz,Chloroform-d)δ7.35–7.28(m,4H), 7.22 (d, J=8.0Hz, 2H), 7.14 (d, J=8.0Hz, 2H), 4.90 (d, J=11.3Hz, 1H), 3.79-3.61 (m, 4H), 3.37–3.24(m,1H),2.95–2.86(m,1H),2.84–2.73(m,1H),2.68–2.58(m,2H),2.51–2.40(m, 1H),2.33(s,3H)；13C NMR(101MHz,CDCl3)δ170.35,138.14,137.04,134.99,129.42, 129.06,128.50,127.63,127.50,66.76,61.57,58.71,57.63,47.88,30.10,21.16；IR (film)νmax 3028,2923,2850,1696,1514,1454,1495,1454,1413,1327,1279,1238,1174, 1129,1070,1027,984,912,817,791,735,699,545cm-1；HRMS(MALDI)calcd for C20H24N3O+[M +H]+322.1914,found 322.1923。
Embodiment 5
By 2- (3,4- 3,5-dimethylphenyl) pyrazolidine 3- ketone ylides (0.125mmol), N- methoxyl group-N- front three silicon methyl Benzylamine (III) (0.125mmol), in adding 15mL reaction tubes, is subsequently adding CH2Cl2(1mL) and trifluoroacetic acid (0.0125mmol).N- methoxyl groups-N- front threes silicon methylbenzylamine (III) is dividedly in some parts afterwards (0.375mmol), and reaction system exists 10 DEG C of stirring 72h are complete to reacting.Reaction solution direct Jing silica gel column chromatography (eluant after being spin-dried for：Petrol ether/ethyl acetate =white solid 1/9) is obtained after purification.65%yield, a pale white solid.1H NMR(400MHz, Chloroform-d)δ7.45–7.22(m,5H),7.17–6.96(m,3H),4.99–4.88(m,1H),3.82–3.69(m, 2H), 3.69-3.60 (m, 2H), 3.36-3.24 (m, 2H), 2.89 (dt, J=12.6,2.3Hz, 1H), 2.86-2.74 (m, 1H), 2.73-2.57 (m, 2H), 2.52-2.39 (m, 1H), 2.24 (d, J=3.5Hz, 6H)；13C NMR(101MHz,CDCl3)δ 170.55,137.04,136.90,136.81,135.31,129.93,129.12,128.85,128.50,127.51,125.17, 66.77,61.59,58.51,57.57,47.87,30.04,19.80,19.50；IR(film)νmax 3029,2923,2852, 1690,1502,1497,1454,1416,1357,327,1281,1265,1241,1206,1182,1134,1074,1070, 1026,911,821,800,736,719,700cm-1；HRMS(MALDI)calcd for C21H26N3O+[M+H]+336.2070, found 336.2078。
Embodiment 6
By 2- (to tert-butyl-phenyl) pyrazolidine 3- ketone ylides (0.125mmol), N- methoxyl group-N- front three silicon methyl benzyls Amine (III) (0.125mmol), in adding 15mL reaction tubes, is subsequently adding CH2Cl2(1mL) with trifluoroacetic acid (0.0125mmol). N- methoxyl groups-N- front threes silicon methylbenzylamine (III) is dividedly in some parts afterwards (0.375mmol), and reaction system stirs 72h at 10 DEG C, extremely Reaction is complete.Reaction solution direct Jing silica gel column chromatography (eluant after being spin-dried for：Petrol ether/ethyl acetate=1/9) obtain after purification To white solid.64%yield, a pale white solid.1H NMR(400MHz,Chloroform-d)δ7.35–7.24 (m, 9H), 4.91 (d, J=11.1Hz, 1H), 3.77-3.64 (m, 4H), 3.35-3.27 (m, 1H), 2.94-2.88 (m, 1H), 2.85–2.76(m,1H),2.69–2.59(m,2H),2.49–2.38(m,1H),1.30(s,9H)；13C NMR(101MHz, CDCl3)δ170.41,151.31,137.09,134.91,129.04,128.50,127.49,127.38,125.60,66.64, 61.61,58.60,57.62,47.96,34.58,31.32,30.10；IR(film)νmax 2960,2925,2867,2853, 1697,1454,1409,1362,1278,1268,1131,1119,1108,1026,1017,832,736,699,570cm-1； HRMS(MALDI)calcd for C23H30N3O+[M+H]+364.2383,found 364.2391.
Embodiment 7
By 2- (o-methoxyphenyl) pyrazolidine 3- ketone ylides (0.125mmol), N- methoxyl group-N- front three silicon methyl benzyls Amine (III) (0.125mmol), in adding 15mL reaction tubes, is subsequently adding CH2Cl2(1mL) with trifluoroacetic acid (0.0125mmol). N- methoxyl groups-N- front threes silicon methylbenzylamine (III) is dividedly in some parts afterwards (0.375mmol), and reaction system stirs 72h at 10 DEG C, extremely Reaction is complete.Reaction solution direct Jing silica gel column chromatography (eluant after being spin-dried for：Petrol ether/ethyl acetate=1/9) obtain after purification To white solid.55%yield, a pale white solid.1H NMR(400MHz,Chloroform-d)δ7.46(dd,J =7.7,1.7Hz, 1H), 7.39-7.28 (m, 4H), 7.27-7.21 (m, 2H), 6.96 (t, J=7.5Hz, 1H), 6.85 (d, J =8.3Hz, 1H), 4.91 (d, J=11.7Hz, 1H), 4.39 (dd, J=10.3,2.3Hz, 1H), 3.84 (d, J=11.6Hz, 1H),3.78(s,3H),3.76(s,2H),3.42–3.33(m,1H),3.00–2.93(m,1H),2.85–2.76(m,1H), 2.73–2.55(m,2H),2.49–2.37(m,1H)；13C NMR(101MHz,CDCl3)δ170.39,137.01,135.50, 133.28,129.08,128.57,128.54,127.81,127.73,127.55,127.12,126.97,126.85,126.43, 126.27,67.11,61.60,58.70,57.66,48.04,30.11；IR(film)νmax 2957,2923,2850,1695, 1613,1516,1488,1423,1327,1273,1119,1072,1041,720,679,543cm-1；HRMS(MALDI)calcd for C20H24N3O2 +[M+H]+338.1863,found 338.1870。
Embodiment 8
By 2- (m-methoxyphenyl) pyrazolidine 3- ketone ylides (0.125mmol), N- methoxyl group-N- front three silicon methyl benzyls Amine (III) (0.125mmol), in adding 15mL reaction tubes, is subsequently adding CH2Cl2(1mL) with trifluoroacetic acid (0.0125mmol). N- methoxyl groups-N- front threes silicon methylbenzylamine (III) is dividedly in some parts afterwards (0.375mmol), and reaction system stirs 72h at 10 DEG C, extremely Reaction is complete.Reaction solution direct Jing silica gel column chromatography (eluant after being spin-dried for：Petrol ether/ethyl acetate=1/9) obtain after purification To white solid.53%yield, a pale white solid.1H NMR(400MHz,Chloroform-d)δ7.34–7.23 (m, 6H), 6.94-6.86 (m, 2H), 6.86-6.80 (m, 1H), 4.90 (d, J=11.2Hz, 1H), 3.81 (s, 3H), 3.77- 3.64(m,4H),3.38–3.29(m,1H),2.96–2.88(m,1H),2.85–2.75(m,1H),2.71–2.58(m,2H), 2.52–2.38(m,1H)；13C NMR(101MHz,CDCl3)δ170.38,159.85,139.66,137.02,129.76, 129.04,128.52,127.52,120.05,113.56,113.26,66.88,61.52,58.66,57.59,55.29, 47.93,30.06；IR(film)νmax 2957,2923,2852,1697,1613,1516,1488,1417,1339,1154, 1118,1076,861,781,746,720,679,543cm-1；HRMS(MALDI)calcd for C20H24N3O2 +[M+H]+ 338.1863,found338.1865。
Embodiment 9
By 2- (p-methoxyphenyl) pyrazolidine 3- ketone ylides (0.125mmol), N- methoxyl group-N- front three silicon methyl benzyls Amine (III) (0.125mmol), in adding 15mL reaction tubes, is subsequently adding CH2Cl2(1mL) with trifluoroacetic acid (0.0125mmol). N- methoxyl groups-N- front threes silicon methylbenzylamine (III) is dividedly in some parts afterwards (0.375mmol), and reaction system stirs 72h at 10 DEG C, extremely Reaction is complete.Reaction solution direct Jing silica gel column chromatography (eluant after being spin-dried for：Petrol ether/ethyl acetate=1/9) obtain after purification To white solid.60%yield, a pale white solid.1H NMR(400MHz,Chloroform-d)δ7.26–7.18 (m, 7H), 6.83-6.77 (m, 2H), 4.84 (d, J=11.3Hz, 1H), 3.73 (s, 3H), 3.69-3.57 (m, 4H), 3.26- 3.18(m,1H),2.86–2.80(m,1H),2.76–2.68(m,1H),2.62–2.52(m,2H),2.44–2.34(m,1H)；13C NMR(101MHz,CDCl3)δ170.32,159.55,137.05,130.00,129.05,128.85,128.50,127.50, 114.10,66.43,61.59,58.75,57.66,55.30,47.82,30.12；IR(film)νmax 2954,2925,2851, 1693,1611,1513,1495,1413,1327,1302,1278,1248,1174,1129,1110,1070,1030,911, 834,735,699,547cm-1；HRMS(MALDI)calcd for C20H24N3O2 +[M+H]+338.1863, found338.1870。
Embodiment 10
By 2- (Chloro-O-Phenyl) pyrazolidine 3- ketone ylides (0.125mmol), N- methoxyl group-N- front three silicon methylbenzylamines (III) (0.125mmol), in adding 15mL reaction tubes, it is subsequently adding CH2Cl2(1mL) with trifluoroacetic acid (0.0125mmol).It After be dividedly in some parts N- methoxyl groups-N- front threes silicon methylbenzylamine (III) (0.375mmol), reaction system stirs 72h at 10 DEG C, to anti- Should be complete.Reaction solution direct Jing silica gel column chromatography (eluant after being spin-dried for：Petrol ether/ethyl acetate=1/9) obtain after purification White solid.74%yield, a pale white solid.1H NMR (400MHz, Chloroform-d) δ 7.58 (dd, J= 7.7,1.8Hz, 1H), 7.36-7.19 (m, 8H), 4.92 (d, J=11.8Hz, 1H), 4.41 (dd, J=10.4,2.8Hz, 1H), 3.92–3.83(m,1H),3.79(s,2H),3.43–3.31(m,1H),3.06–2.98(m,1H),2.82–2.56(m,3H), 2.52–2.40(m,1H)；13C NMR(101MHz,CDCl3)δ170.77,137.18,135.47,133.38,129.71, 129.11,128.99,128.70,128.47,127.51,127.39,61.33,61.31,56.93,56.60,47.95, 29.92；IR(film)νmax 3063,3029,2924,2851,2245,1693,1495,1475,1442,1412,1329, 1280,1204,1124,1070,1037,1002,982,911,882,846,734,701,672,646,548,456cm-1；HRMS (MALDI)calcd for C19H21ClN3O+[M+H]+342.1368,found 342.1373。
Embodiment 11
By 2- (chlorphenyl) pyrazolidine 3- ketone ylides (0.125mmol), N- methoxyl group-N- front three silicon methylbenzylamines (III) (0.125mmol), in adding 15mL reaction tubes, it is subsequently adding CH2Cl2(1mL) with trifluoroacetic acid (0.0125mmol).It After be dividedly in some parts N- methoxyl groups-N- front threes silicon methylbenzylamine (III) (0.375mmol), reaction system stirs 72h at 10 DEG C, to anti- Should be complete.Reaction solution direct Jing silica gel column chromatography (eluant after being spin-dried for：Petrol ether/ethyl acetate=1/9) obtain after purification White solid.72%yield, a pale white solid.1H NMR(400MHz,Chloroform-d)δ7.34–7.27 (m, 9H), 4.91 (d, J=11.3Hz, 1H), 3.79-3.67 (m, 4H), 3.36-3.23 (m, 1H), 2.95-2.90 (m, 1H), 2.83–2.75(m,1H),2.69–2.60(m,2H),2.49–2.39(m,1H)；13C NMR(101MHz,CDCl3)δ170.77, 137.18,135.47,133.38,129.71,129.11,128.99,128.70,128.47,127.51,127.39,61.33, 61.31,56.93,56.60,47.95,29.92；IR(film)νmax 3029,2925,2850,1693,1597,1573,1495, 1454,1431,1413,1357,1326,1281,1238,1204,1175,1130,1096,1078,1027,1001,984, 911,879,782,734,697,669,646cm-1；HRMS(MALDI)calcd for C19H21ClN3O+[M+H]+342.1368, found342.1377。
Embodiment 12
By 2- (rubigan) pyrazolidine 3- ketone ylides (0.125mmol), N- methoxyl group-N- front three silicon methylbenzylamines (III) (0.125mmol), in adding 15mL reaction tubes, it is subsequently adding CH2Cl2(1mL) with trifluoroacetic acid (0.0125mmol).It After be dividedly in some parts N- methoxyl groups-N- front threes silicon methylbenzylamine (III) (0.375mmol), reaction system stirs 72h at 10 DEG C, to anti- Should be complete.Reaction solution direct Jing silica gel column chromatography (eluant after being spin-dried for：Petrol ether/ethyl acetate=1/9) obtain after purification White solid.76%yield, a pale white solid.1H NMR(400MHz,Chloroform-d)1H NMR (400MHz, Chloroform-d) δ 7.37-7.27 (m, 9H), 4.91 (d, J=11.3Hz, 1H), 3.78-3.60 (m, 4H), 3.36–3.24(m,1H),2.93–2.86(m,1H),2.80–2.71(m,1H),2.67–2.54(m,2H),2.50–2.40(m, 1H)；13C NMR(101MHz,CDCl3)δ170.27,136.87,136.52,134.09,129.03,129.03,128.98, 128.55,127.58,66.30,61.53,58.61,57.57,47.97,30.00；IR(film)νmax 2954,2925,2850, 1693,1492,1454,1409,1280,1200,1175,1130,1089,1069,1027,014,830,737,719,700, 531cm-1；HRMS(MALDI)calcd for C19H21ClN3O+[M+H]+342.1368,found 342.1372。
Embodiment 13
By 2- (o-fluorophenyl) pyrazolidine 3- ketone ylides (0.125mmol), N- methoxyl group-N- front three silicon methylbenzylamines (III) (0.125mmol), in adding 15mL reaction tubes, it is subsequently adding CH2Cl2(1mL) with trifluoroacetic acid (0.0125mmol).It After be dividedly in some parts N- methoxyl groups-N- front threes silicon methylbenzylamine (III) (0.375mmol), reaction system stirs 72h at 10 DEG C, to anti- Should be complete.Reaction solution direct Jing silica gel column chromatography (eluant after being spin-dried for：Petrol ether/ethyl acetate=1/9) obtain after purification White solid.73%yield, a white solid.1H NMR (400MHz, Chloroform-d) δ 7.51 (t, J=8.1Hz, 1H),7.34–7.23(m,6H),7.19–7.12(m,1H),7.07–7.00(m,1H),4.97–4.87(m,1H),4.22(d,J =10.4Hz, 1H), 3.86-3.72 (m, 3H), 3.41-3.29 (m, 1H), 3.00-2.93 (m, 1H), 2.85-2.78 (m, 1H), 2.76–2.63(m,2H),2.51–2.40(m,1H)；13C NMR(101MHz,CDCl3)δ170.58,161.73,159.27, 137.08,129.49,129.41,129.10,128.51,127.52,124.99,124.87,124.63,124.60,115.69, 115.47,65.58,61.42,57.16,56.96,48.03,29.92；IR(film)νmax 3063,3029,2925,2852, 1696,1616,1586,1491,1455,1412,1347,1329,1280,1229,1182,1131,1098,1027,1002, 982,912,881,853,815,761,734,699,673,645,547,495cm-1；HRMS(MALDI)calcd for C19H21FN3O+[M+H]+326.1663,found 326.1670。
Embodiment 14
By 2- (fluorophenyl) pyrazolidine 3- ketone ylides (0.125mmol), N- methoxyl group-N- front three silicon methylbenzylamines (III) (0.125mmol), in adding 15mL reaction tubes, it is subsequently adding CH2Cl2(1mL) with trifluoroacetic acid (0.0125mmol).It After be dividedly in some parts N- methoxyl groups-N- front threes silicon methylbenzylamine (III) (0.375mmol), reaction system stirs 72h at 10 DEG C, to anti- Should be complete.Reaction solution direct Jing silica gel column chromatography (eluant after being spin-dried for：Petrol ether/ethyl acetate=1/9) obtain after purification White solid.73%yield, a white solid.1H NMR(400MHz,Chloroform-d)δ7.34–7.13(m,6H), 7.08-6.96 (m, 3H), 6.97-6.84 (m, 1H), 4.83 (dd, J=11.3,1.8Hz, 1H), 3.69-3.57 (m, 4H), 3.32–3.19(m,1H),2.90–2.78(m,1H),2.77–2.64(m,1H),2.65–2.50(m,2H),2.45–2.30(m, 1H)；13C NMR(101MHz,CDCl3)δ170.30,164.18,161.73,140.68,136.92,130.35,130.27, 129.02,128.55,127.58,123.42,123.39,115.38,115.17,114.66,114.44,66.38,61.50, 58.59,57.54,48.01,29.99；IR(film)νmax3063,3029,2925,2848,1696,1614,1590,1488, 1449,1413,1347,1328,1280,1267,1177,1126,1068,1027,975,912,787,734,697,669, 646,546,489cm-1；HRMS(MALDI)calcd for C19H21FN3O+[M+H]+326.1663,found 326.1672。
Embodiment 15
By 2- (p-fluorophenyl) pyrazolidine 3- ketone ylides (0.125mmol), N- methoxyl group-N- front three silicon methylbenzylamines (III) (0.125mmol), in adding 15mL reaction tubes, it is subsequently adding CH2Cl2(1mL) with trifluoroacetic acid (0.0125mmol).It After be dividedly in some parts N- methoxyl groups-N- front threes silicon methylbenzylamine (III) (0.375mmol), reaction system stirs 72h at 10 DEG C, to anti- Should be complete.Reaction solution direct Jing silica gel column chromatography (eluant after being spin-dried for：Petrol ether/ethyl acetate=1/9) obtain after purification White solid.75%yield, a white solid.1H NMR (400MHz, Chloroform-d) δ 7.32 (dd, J=8.2, 4.9Hz, 7H), 7.07-6.99 (m, 2H), 4.91 (d, J=11.3Hz, 1H), 3.76-3.64 (m, 4H), 3.29 (ddd, J= 10.7,9.3,5.9Hz,1H),2.93–2.86(m,1H),2.81–2.72(m,1H),2.68–2.55(m,2H),2.50–2.39 (m,1H)；13C NMR(101MHz,CDCl3)δ170.26,163.79,161.33,136.94,133.80,133.77,129.36, 129.28,129.02,128.54,127.56,115.81,115.60,66.28,61.57,58.77,57.62,47.90, 30.05；IR(film)νmax 3030,2925,2851,1695,1605,1510,1454,1414,1327,1279,1223, 1174,1157,1130,1097,1069,1027,920,88,838,793,700,669,591,545,524cm-1；HRMS (MALDI)calcd for C19H21FN3O+[M+H]+326.1663,found 326.1668。
Embodiment 16
By 2- (2,4,6- trifluorophenyl) pyrazolidine 3- ketone ylides (0.125mmol), N- methoxyl group-N- front three silicon methyl Benzylamine (III) (0.125mmol), in adding 15mL reaction tubes, is subsequently adding CH2Cl2(1mL) with trifluoromethanesulfonic acid zinc (0.0125mmol).N- methoxyl groups-N- front threes silicon methylbenzylamine (III) is dividedly in some parts afterwards (0.375mmol), and reaction system exists 10 DEG C of stirring 72h are complete to reacting.Reaction solution direct Jing silica gel column chromatography (eluant after being spin-dried for：Petrol ether/ethyl acetate =white solid 1/9) is obtained after purification.85%yield, a white solid.1H NMR(400MHz,Chloroform-d)δ 7.63(s,1H),7.60–7.51(m,2H),7.50–7.44(m,1H),7.34(s,2H),7.33(s,2H),7.30–7.27(m, 1H), 4.92 (d, J=11.5Hz, 1H), 3.81-3.67 (m, 4H), 3.37-3.28 (m, 1H), 2.98-2.90 (m, 1H), 2.81–2.71(m,1H),2.71–2.58(m,2H),2.53–2.41(m,1H)；13C NMR(101MHz,CDCl3)δ170.23, 139.17,136.86,131.38,131.16,131.06,129.32,129.00,128.57,127.61,125.25,125.21, 124.44,124.40,122.55,66.55,61.52,58.69,57.56,48.08,29.97；IR(film)νmax 3031, 2925,2851,1696,1615,1586,1490,1455,1412,1347,1328,1280,1229,1180,1129,1097, 1027,1002,982,912,761,734,700,673,547cm-1；HRMS(MALDI)calcd for C19H19F3N3O+[M+H ]+362.1475,found 362.1483.
Embodiment 17
By 2- (p-nitrophenyl) pyrazolidine 3- ketone ylides (0.125mmol), N- methoxyl group-N- front three silicon methylbenzylamines (III) (0.125mmol), in adding 15mL reaction tubes, it is subsequently adding CH2Cl2(1mL) with trifluoroacetic acid (0.0125mmol).It After be dividedly in some parts N- methoxyl groups-N- front threes silicon methylbenzylamine (III) (0.375mmol), reaction system stirs 72h at 12 DEG C, to anti- Should be complete.Reaction solution direct Jing silica gel column chromatography (eluant after being spin-dried for：Petrol ether/ethyl acetate=1/9) obtain after purification Yellow solid.70%yield, a yellow solid.1H NMR(400MHz,Chloroform-d)δ8.26–8.17(m, 2H), 7.60-7.48 (m, 2H), 7.36-7.27 (m, 5H), 4.92 (d, J=11.5Hz, 1H), 3.85 (dd, J=10.4, 2.9Hz,1H),3.81–3.66(m,3H),3.39–3.30(m,1H),2.96–2.87(m,1H),2.79–2.56(m,3H), 2.54–2.42(m,1H)；13C NMR(101MHz,CDCl3)δ170.15,147.88,145.46,136.71,128.97, 128.58,128.55,127.67,124.01,66.19,61.44,58.45,57.44,48.18,29.83；IR(film)νmax 2954,2924,2852,1692,1599,1520,1454,412,1347,1280,1237,1128,107,1070,855,738, 751,740,698,668cm-1；HRMS(MALDI)calcd for C19H21N4O3 +[M+H]+353.1608,found 353.1613.
Embodiment 18
By 2- (1- naphthyls) pyrazolidine 3- ketone ylides (0.125mmol), N- methoxyl groups-N- front threes silicon methylbenzylamine (III) (0.125mmol), in, adding 15mL reaction tubes, it is subsequently adding CH2Cl2(1mL) with trifluoroacetic acid (0.0125mmol).Divide afterwards Batch add N- methoxyl groups-N- front threes silicon methylbenzylamine (III) (0.375mmol), reaction system stirs 72h at 15 DEG C, to having reacted Entirely.Reaction solution direct Jing silica gel column chromatography (eluant after being spin-dried for：Petrol ether/ethyl acetate=1/9) obtain white after purification Solid.65%yield, a white solid.1H NMR(400MHz,Chloroform-d)δ8.03–7.92(m,1H), 7.90-7.83 (m, 1H), 7.83-7.69 (m, 2H), 7.54-7.44 (m, 3H), 7.42-7.26 (m, 5H), 4.99 (dd, J= 11.5,1.9Hz, 1H), 4.67 (dd, J=10.3,2.7Hz, 1H), 3.95-3.72 (m, 3H), 3.54-3.33 (m, 1H), 3.21–3.07(m,1H),2.85–2.61(m,3H),2.54–2.41(m,1H)；13C NMR(101MHz,CDCl3)δ170.60, 137.01,133.79,133.70,130.98,129.23,129.04,128.54,128.23,127.59,126.55,125.74, 125.68,124.88,121.80,61.56,61.39,58.38,57.46,48.08,30.11；IR(film)νmax 3013, 2923,2852,1693,1660,1507,1447,1316,1275,1266,1133,1120,1072,1023,871,827,749, 720,668cm-1；HRMS(MALDI)calcd for C23H24N3O+[M+H]+358.1914,found 358.1915.
Embodiment 19
By 2- (2- naphthyls) pyrazolidine 3- ketone ylides (0.125mmol), N- methoxyl groups-N- front threes silicon methylbenzylamine (III) (0.125mmol), in, adding 15mL reaction tubes, it is subsequently adding CH2Cl2(1mL) with trifluoroacetic acid (0.0125mmol).Divide afterwards Batch add N- methoxyl groups-N- front threes silicon methylbenzylamine (III) (0.375mmol), reaction system stirs 72h at 10 DEG C, to having reacted Entirely.Reaction solution direct Jing silica gel column chromatography (eluant after being spin-dried for：Petrol ether/ethyl acetate=1/9) obtain white after purification Solid.69%yield, a white solid.1H NMR(400MHz,Chloroform-d)δ7.87–7.78(m,6H), 7.54-7.42 (m, 3H), 7.39-7.25 (m, 6H), 4.95 (dd, J=11.3,1.8Hz, 1H), 3.92-3.68 (m, 5H), 3.40-3.27 (m, 1H), 2.99 (ddd, J=12.7,2.9,1.9Hz, 1H), 2.90-2.61 (m, 3H), 2.54-2.41 (m, 1H)；13C NMR(101MHz,CDCl3)δ170.39,137.01,135.50,133.28,129.08,128.57,128.54, 127.81,127.73,127.55,127.12,126.97,126.85,126.43,126.27,67.11,61.60,58.70, 57.66,48.04,30.11；IR(film)νmax 3057,3029,2924,2849,1693,1661,1508,1495,1454, 1414,1352,1325,1283,1265,1179,1133,1121,1070,1027,909,883,859,820,737,700, 479cm-1；HRMS(MALDI)calcd for C23H24N3O+[M+H]+358.1914,found 358.1920.
Compound eelworm-killing activity is tested
Prepare 50ppm medicinal liquids；Two ages of the nematicides such as root knot nematode in tobacco, Semen Tritici aestivi Cyst nematode, sweet potato stem nematode will be collected The suspension of larva, is settled to 50mL, takes 1mL and instills counting ware, count, determine nematicide concentration under anatomical lens after shaking up.Match somebody with somebody 50ppm medicinal liquids processed, wherein contain sterilized water, DMSO and Tween 80 equal solvent and cosolvent.Eelworm-killing activity life is carried out with medicinal liquid Thing is determined, and so that as blank, each sample repeats test 3 times without liquid medicine, is tested each sample every time and is done at 4 repetitions Reason.Calculate 24 hours corrected mortalities.
Table 1 is medicine Nematicidal Activity result.
Compound is to root rotof flax, Semen Tritici aestivi base rot disease, the bactericidal activity test of Semen Tritici aestivi corruption mildew
Compound concentration 50ppm medicinal liquids, using the solution of sterilized water and solvent and cosolvent as negative control, with commercially available Ah Dimension rhzomorph medicinal liquid is positive control, pours culture dish after preparing the liquid medicine mixing for obtaining into, is solidified stand-by.Take the bacterium of a diameter of 6mm Cake, is seeded in PDA culture medium center, 25 DEG C of light cultures 6～8 days, and each concentration sets 3 repetitions.Bacterium is measured with crossing method Fall diameter, calculates the relative bacteriostasis rate of compound under the concentration.
I-17 78 75 80
I-18 75 73 82
I-19 73 75 83

Claims (6)

1. a kind of tetrahydro-pyrazole ketone triaizine compounds, it is characterised in that：The chemistry of the tetrahydro-pyrazole ketone triaizine compounds Formula is as shown in formula I：
Wherein R1For phenyl, halogenophenyl, naphthyl, nitrobenzophenone；R2For benzyl.
2. the preparation method of tetrahydro-pyrazole ketone according to claim 1 triaizine compounds, it is characterised in that：1,3- dipole Body azo methylene time amine with N- methoxyl group-N- front three silicon methylbenzylamines under Bronsted acid and metal Lewis acids catalysis, not Reaction in same solvent obtains tetrahydro-pyrazole ketone triaizine compounds, 1, the 3- dipoles body azo methylene time amine and N- methoxies The ratio of the amount of the material of base-N- front three silicon methylbenzylamines is 1: 4, and the amount of the material of Bronsted acid and metal Lewis acids is 1,3- idols The 10% of the amount of polar body azo methylene time amine material, the response time is 1-72 hours, and reaction temperature is from 0 DEG C to the backflow of solvent Temperature, the chemical formula of 1, the 3- dipoles body azo methylene time amine as shown in formula II, the N- methoxyl groups-N- front three silicon first The chemical formula of base benzylamine is as shown in general formula III：
Wherein R1For phenyl, halogenophenyl, naphthyl, nitrobenzophenone；R2For benzyl.
3. the preparation method of tetrahydro-pyrazole ketone according to claim 2 triaizine compounds, it is characterised in that：The proton Acid is trifluoroacetic acid, acetic acid, phosphoric acid, hydrochloric acid；Lewis acid is trifluoromethanesulfonic acid zinc, Trimethylsilyl trifluoromethanesulfonate, trifluoro Silver acetate, silver acetate, titanium tetrachloride, lithium fluoride.
4. the preparation method of tetrahydro-pyrazole ketone according to claim 2 triaizine compounds, it is characterised in that：The solvent For at least one in dichloromethane, dichloroethanes, chloroform, DMF, tetrahydrofuran, acetonitrile.
5. the preparation method of tetrahydro-pyrazole ketone according to claim 2 triaizine compounds, it is characterised in that：The reaction Temperature is 10-15 DEG C.
6. tetrahydro-pyrazole ketone as claimed in claim 1 application of the triaizine compounds in nematicide.
CN201510314980.7A 2015-06-10 2015-06-10 Tetrahydro-pyrazole ketone triazin compound and preparation method and application Active CN104892615B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510314980.7A CN104892615B (en) 2015-06-10 2015-06-10 Tetrahydro-pyrazole ketone triazin compound and preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510314980.7A CN104892615B (en) 2015-06-10 2015-06-10 Tetrahydro-pyrazole ketone triazin compound and preparation method and application

Publications (2)

Publication Number Publication Date
CN104892615A CN104892615A (en) 2015-09-09
CN104892615B true CN104892615B (en) 2017-04-05

Family

ID=54025628

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510314980.7A Active CN104892615B (en) 2015-06-10 2015-06-10 Tetrahydro-pyrazole ketone triazin compound and preparation method and application

Country Status (1)

Country Link
CN (1) CN104892615B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114591337A (en) * 2022-03-31 2022-06-07 武汉工程大学 Pyrazolo [1,2-a ] [1,2,4] triazine-3, 6-dione derivative and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0187012B1 (en) * 1984-12-22 1989-06-21 Beecham Group Plc Novel compositions
CN103497193B (en) * 2013-09-25 2015-09-02 武汉大学 There is derivative and the synthetic method thereof of 1,2,4-triazine skeleton structure

Also Published As

Publication number Publication date
CN104892615A (en) 2015-09-09

Similar Documents

Publication Publication Date Title
CN106916084B (en) A kind of malononitrile oximido ether compound and application thereof
CN103896963B (en) Ben Bing Evil Qin oxazolidinone compounds and its production and use
EP2539335B1 (en) Process for the preparation of isoxazoline derivatives
CN104412985B (en) Apply containing luxuriant and rich with fragrance heterocycle compound and preparation method thereof and Antiphytoviral
CN102675303B (en) 4-alkyl-2-arylamino-5-(1,2,4-triazole-1-group) thiazole and application thereof to preparation of medicaments for resisting cancer
CN104892615B (en) Tetrahydro-pyrazole ketone triazin compound and preparation method and application
CN103360379B (en) Oxazolidinone compound
CN108299255A (en) Histone deacetylase 8 selective depressant and its preparation method and application
CN102367239B (en) 2-aryl-2,3-dihydro-4H-1,3-benzothiazine-4-ketone derivatives and uses thereof
RO108869B1 (en) DERIVATES OF 6-ARYL-5,6DIHYDROIMIDAZO-[2,1-b]-TIAZOLE, PREPARATION PROCESSES AND INTERMEDIARIES THEREFOR
CN107556276B (en) C- triaryl glucoside compounds and its preparation method and application
CN107973807A (en) A kind of triazol benzothiazole derivant and its preparation method and application
CN102993105B (en) 1-methyl-2, 4-quinazoline diketone derivative and preparation method and application thereof
CN112574215B (en) Preparation method and application of benzoxazole compound for hospital disinfection
CN109851560A (en) Biphenyl diazole analog derivative and its preparation method and application
CN102835394A (en) Application of 2, 4-dichlorphenoxy acetyl-containing dihydrazide compound as herbicide
CN108440414B (en) Pyrazolone amide antifungal drug and preparation method and application thereof
US11155566B2 (en) 2-OXO-1-pyrrolidinyl imidazothiadiazole derivatives
CN103141486B (en) Application of 4-(benzofuran-5-yl)-2-phenzyl aminothiazole as bactericide
CN104926804A (en) Compounds with anti-tumor effect, and preparation method and application of compounds
CN102558018B (en) Benzene sulphenamide derivative and the purposes in preparation antibacterials thereof
CN106146559B (en) A kind of preparation method of Oxazolidinone derivative
CN103319367B (en) Caproamide derivative, its preparation method, intermediate and application
CN108148049B (en) Preparation method and application of 5-pyrazole amide compound with triazinone structure
CN105936633A (en) 5-(3-isopropyl benzisoxazol)pyrazin-2-amine and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant