CN105481839A - Preparation method for cycloxylidin enantiomer with photoactivity - Google Patents

Preparation method for cycloxylidin enantiomer with photoactivity Download PDF

Info

Publication number
CN105481839A
CN105481839A CN201510822732.3A CN201510822732A CN105481839A CN 105481839 A CN105481839 A CN 105481839A CN 201510822732 A CN201510822732 A CN 201510822732A CN 105481839 A CN105481839 A CN 105481839A
Authority
CN
China
Prior art keywords
nitroimidazoline
base amine
reaction
reactor
sodium hydride
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.)
Granted
Application number
CN201510822732.3A
Other languages
Chinese (zh)
Other versions
CN105481839B (en
Inventor
张千峰
夏佳美
徐文芳
范芳芳
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.)
ANHUI QIANHE NEW MATERIAL TECHNOLOGY DEVELOPMENT Co Ltd
Original Assignee
ANHUI QIANHE NEW MATERIAL TECHNOLOGY DEVELOPMENT Co Ltd
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 ANHUI QIANHE NEW MATERIAL TECHNOLOGY DEVELOPMENT Co Ltd filed Critical ANHUI QIANHE NEW MATERIAL TECHNOLOGY DEVELOPMENT Co Ltd
Priority to CN201510822732.3A priority Critical patent/CN105481839B/en
Publication of CN105481839A publication Critical patent/CN105481839A/en
Application granted granted Critical
Publication of CN105481839B publication Critical patent/CN105481839B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers

Abstract

The invention discloses a preparation method for a cycloxylidin enantiomer with photoactivity, which belongs to the technical field of asymmetric catalytic synthesis of medicines with optical activity. The method comprises a first step of synthesizing 1-allyl-N-2-nitroiminoimidazolidine and a second step of synthesizing the 1-(1,2-glycidyl)-N-2-nitroiminoimidazolidine enantiomer. The method employs sodium hydride to effectively completely remove hydrogen with weak acidity in a resonance structure of N-nitroiminoimidazolidine and convert the hydrogen into a sodium salt, wherein organic by-products are not produced; through asymmetric epoxidation, levorgyrate or dextrorotary enantiomer products with high yield can be obtained; and the method prepares high-purity enantiomer products, substantially improves insecticidal activity of the products and reduces environmental pollution.

Description

A kind of preparation method of photolytic activity epoxy quinoline enantiomorph
Technical field
The invention belongs to optics drugs asymmetry catalysis synthesis technical field, be specifically related to the preparation method of 1-(1,2-epoxypropyl)-N-Nitroimidazoline-2-base amine (i.e. epoxy quinoline) enantiomorph.
Background technology
Epoxy quinoline is that the one grown up on common pesticide imidacloprid basis is efficient, and low toxic pesticide, progressively promotes at present in the farm crop such as cucumber, cotton, is the best kind replacing organophosphorus, organochlorine insecticide.The raceme product (see Chinese patent CN101503406A) of what but synthesis main at present and production technique obtained is epoxy quinoline, if this can be split as left-handed (-) and dextrorotation (+) product to raceme, so this is bound to better to the medicinal effect with optical activity enantiomeric excess product, but the cost of industrial resolving racemic is very high, and be difficult to the popularization realizing industrialization; For this reason, the present invention designs and adopts that chlorine third is rare synthesizes 1-allyl group-N-Nitroimidazoline-2-base ammonia with N-nitro imido imidazolyl alkane, what be oxidized to 1-(1,2-epoxypropyl)-N-Nitroimidazoline-2-base amine (i.e. epoxy quinoline) by Sharpless asymmetric Epoxidation again has optical activity enantiomeric excess product.
The great advantage of Sharpless asymmetric Epoxidation is: reaction reagent is commercialization, and it is cheap and easy to get, and the yield of its epoxidation product has the e.e. value (Enantiomeric excess) more than 90% usually, the chirality of product can also be predicted in addition according to reaction model.There is optically active chipal compounds and have important application in fields such as medicine, agricultural chemicals, material, spices and food, and its value of optically active chipal compounds will far away higher than its racemic modification product, epoxy quinoline product is as the chipal compounds that can be separated and transform, the synthesis being necessary to study its left-handed (-) and dextrorotation (+) enantiomorph be separated and pharmacological properties and insecticidal activity, and the problem such as toxicity or environmental pollution may be there is.
Summary of the invention
The present invention is directed to above-mentioned prior art Problems existing, the preparation method of 1-(1,2-epoxypropyl)-N-Nitroimidazoline-2-base amine (i.e. epoxy quinoline) enantiomorph is provided.
Photolytic activity epoxy quinoline enantiomorph of the present invention, namely the structural formula of 1-(1,2-epoxypropyl)-N-Nitroimidazoline-2-base amine enantiomorph is:
Photolytic activity epoxy quinoline enantiomorph provided by the present invention: preparation method's concrete steps of 1-(2,3-epoxypropyl)-N-Nitroimidazoline-2-base amine are as follows:
(1) 1-allyl group-N-Nitroimidazoline-2-base amine is synthesized:
Under nitrogen protection, N-nitro imido imidazolyl alkane and organic solvent are joined in reactor, after N-nitro imido imidazolyl alkane dissolves substantially, under agitation in reactor, add sodium hydride in batches, continue stirring after adding sodium hydride 30 minutes, more slowly drip propenyl chloride in reactor, after dropwising, stirring reaction under temperature 35-40 DEG C of condition, and monitor reaction process with TLC or HPLC, until reaction terminates; After cooling, underpressure distillation goes out organic solvent, obtains orange-yellow oily liquids, adds the isopyknic ether of described orange-yellow oily liquids and separate out faint yellow crystalline solid at temperature-10 DEG C, take advantage of cold filtration, obtain thick product, with Gossypol recrystallized from chloroform, obtain the sterling of 1-allyl group-N-Nitroimidazoline-2-base amine.
Described organic solvent is the mixed solvent of DMF (N, N'-dimethyl formamide) or DMF and toluene, described propenyl chloride: N-nitro imido imidazolyl alkane: the mol ratio of sodium hydride is: 1:1.1-1.5:1.1-1.5; The purity of described sodium hydride is 60wt%; Described vacuum distillation temperature is 40 DEG C, and pressure is 0.3KPa; Can add a small amount of in whole reaction soln system molecular sieve.
(2) 1-(1,2-epoxypropyl)-N-Nitroimidazoline-2-base amine enantiomorph is synthesized:
Under nitrogen protection, in reactor, add a certain amount of organic solvents, chloroform, at-10-O DEG C of temperature, successively add tetra isopropyl oxygen titanium Ti (Oi-Pr) wherein 4, L (+)-diethyl tartrate ((+) DET) or L (-)-diethyl tartrate ((-) DET), stir the 1-allyl group-N-Nitroimidazoline-2-base amine adding step (1) after 15 minutes and prepare, finally add oxygenant metachloroperbenzoic acid (M-CPBA), the homogeneous phase solution of reaction gained is stirred 12h, period TLC or HPLC monitors the product conversion process of reaction, after desolventizing, by petroleum ether, thick product can be obtained, 1-(1 is obtained through chloroform-sherwood oil mixed solvent recrystallization, 2-epoxypropyl) sterling of-N-Nitroimidazoline-2-base amine enantiomorph.
Described tetra isopropyl oxygen titanium: L (+)-diethyl tartrate: 1-allyl group-N-Nitroimidazoline-2-base amine: the mol ratio of metachloroperbenzoic acid is 1:1:1:2; The volume ratio of described chloroform-sherwood oil is 2:1; Can add a small amount of in whole reaction soln system molecular sieve.
Wherein: in step (1), the temperature of reaction of synthesis 1-allyl group-N-Nitroimidazoline-2-base amine is 35-40 DEG C, and temperature height can cause unreacted propenyl chloride to vapor away, and affects the output of 1-allyl group-N-Nitroimidazoline-2-base amine; Sodium hydride purity used is 60wt%, and sodium hydride slowly adds in batches, to avoid the effusion that can produce a large amount of hydrogen in the process added; Sharpless asymmetric epoxidation reaction in step (2) is-10 DEG C-0 DEG C (available cryosel bath modulation).
The reaction formula of above-mentioned preparation process is as follows:
The present invention compared with prior art has following technical characterstic:
(1) adopt sodium hydride effectively can be removed completely by hydrogen more weak for resonant for N-nitro imido imidazolyl alkane middle acidity, and can sodium salt be converted into, and can not organic by-products be produced.
(2) the preparation feedback temperature of the first step allyl group product is 35-40 DEG C, and heat condition is comparatively gentle, less energy consumption, can also avoid the autohemagglutination phenomenon of 1-allyl group-N-Nitroimidazoline-2-base amine product simultaneously.
(3) by Sharpless asymmetric Epoxidation, enantiomorph product that is left-handed or dextrorotation can be obtained respectively with higher productive rate, and required epoxidation catalyst low price be easy to obtain.
(4) highly purified enantiomorph product can be obtained, greatly improve the insecticidal activity of product, also correspondingly can reduce agricultural chemicals usage quantity in actual applications, reduce the pollution to environment.
Embodiment
Embodiment 1: concrete preparation method is as follows for 1-provided by the invention (1,2-epoxypropyl)-N-Nitroimidazoline-2-base amine enantiomorph:
(1): the preparation of 1-allyl group-N-Nitroimidazoline-2-base amine:
Under nitrogen protection, the N-nitro-imine base imidazolidine of 6.5g (0.05mol) is joined the N of 50mL, in N'-dimethyl formamide; stir after within 30 minutes, making it to dissolve completely; 2.4g sodium hydride is divided and adds for 3-5 time wherein, continue stir about 1h, obtain the pale yellow solution of homogeneous phase.Slowly be added drop-wise in above-mentioned solution by 4.9mL (0.06mol) propenyl chloride constant pressure dropping funnel, be slowly warmed up to 40 DEG C again after dropwising, TLC or HPLC method is in order to monitoring reaction course, until reaction is carried out completely.Pass through suction filtered through kieselguhr, the inorganic salt produced in removing reaction process, obtain yellow transparent solution, underpressure distillation at 40 DEG C (pressure: 0.3KPa) N, N'-solvent dimethylformamide, add isopyknic anhydrous diethyl ether again and can separate out faint yellow crystalline solid at-10 DEG C, take advantage of cold filtration, obtain thick product, with Gossypol recrystallized from chloroform, the sterling of 1-allyl group-N-Nitroimidazoline-2-base amine can be obtained, yield: 82%, m.p.:67-89 DEG C. 1HNMR(CDCl 3,400MHz，ppm):δ2.69(s,2H,NCH 2CH 2N),2.85(s,2H,NCH 2CH 2N),3.16(s,2H,NCH 2CH＝),3.16(s,2H,NCH 2CH＝),5.09-5.23(dd,J＝6.6Hz,2H,NCH 2CH＝CH 2),5.94(d,J＝6.4Hz,1H,NCH 2CH＝CH 2),8.22(s,1H,NH).MS(ESI):m/z170.17[M +],124.16[M +-NO 2].Anal.Calc.forC 6H 10N 4O 2:C,42.35；H,5.92；N,32.92％.Found:C,42.17；H,5.89；N,32.77％。
(2) L (-)-1-(1,2-epoxypropyl)-N-Nitroimidazoline-2-base amine and D (+)-1-(1,2-epoxypropyl)-N-Nitroimidazoline-2-base amine is prepared respectively:
The preparation of L (-)-1-(1,2-epoxypropyl)-N-Nitroimidazoline-2-base amine:
The chloroform of 20mL is joined in the three neck round-bottomed flasks of 100mL, cooling is stirred under-10 DEG C (cryosel bath), successively add the tetra isopropyl oxygen titanium of 0.297mL (1mmol) respectively, 0.172mL (0.206g, L (-)-diethyl tartrate 1mmol), stir about 10 minutes, solution is after homogeneous phase, add 0.17g (1mmol) 1-allyl group-N-Nitroimidazoline-2-imines again, add 0.345g (2mmol) metachloroperbenzoic acid for the last time; Gained homogeneous phase solution is at refrigerator stir about 12h at-10-0 DEG C, by TLC or HPLC method monitoring epoxidation conversion process between the reaction period, after question response thing all transfers product to, removing reaction solvent, obtains light yellow solid powder by petroleum ether, then uses chloroform-sherwood oil (2:1) recrystallization, obtain sterling, yield: 77%, ee value: 90%, m.p.:97 ~ 99 DEG C. 1HNMR(CDCl 3,400MHz，ppm):δ2.52(s,2H,CH 2-OCH-CH 2),2.69(s,2H,CH 2-OCH-CH 2),2.78(d,1H,J＝6.1Hz,CH 2-OCH-CH 2),2.81(s,2H,NCH 2CH 2N),2.89(s,2H,NCH 2CH 2N),8.14(s,1H,NH).MS(ESI):m/z188.17[M +],140.16[M +-NO 2].Anal.Calc.forC 6H 10N 4O 3:C,38.71；H,5.41；N,30.09％.Found:C,38.64；H,5.37；N,30.04％。
The preparation of D (+)-1-(1,2-epoxypropyl)-N-Nitroimidazoline-2-base amine:
The chloroform of 20mL is joined in the three neck round-bottomed flasks of 100mL, cooling is stirred under-10 DEG C (cryosel bath), successively add the tetra isopropyl oxygen titanium of 0.297mL (1mmol) respectively, 0.172mL (0.206g, D (+)-diethyl tartrate 1mmol), stir 10 minutes, solution is after homogeneous phase, add 0.17g (1mmol) 1-allyl group-N-Nitroimidazoline-2-imines again, add 0.345g (2mmol) metachloroperbenzoic acid for the last time; Gained homogeneous phase solution is at refrigerator stir about 12h at-10-0 DEG C, by TLC or HPLC method monitoring epoxidation conversion process between the reaction period, after question response thing all transfers product to, removing reaction solvent, obtains light yellow solid powder by petroleum ether, then uses chloroform-sherwood oil (2:1) recrystallization, obtain sterling, yield: 81%, ee value: 93%, m.p.:96 ~ 97 DEG C. 1HNMR(CDCl 3,400MHz，ppm):δ2.54(s,2H,CH 2-OCH-CH 2),2.67(s,2H,CH 2-OCH-CH 2),2.79(d,1H,J＝6.1Hz,CH 2-OCH-CH 2),2.84(s,2H,NCH 2CH 2N),2.91(s,2H,NCH 2CH 2N),8.17(s,1H,NH).MS(ESI):m/z188.17[M +],140.16[M +-NO 2].Anal.Calc.forC 6H 10N 4O 3:C,38.71；H,5.41；N,30.09％.Found:C,38.69；H,5.36；N,30.02％。

Claims (1)

1. a preparation method for photolytic activity epoxy quinoline enantiomorph, is characterized in that these preparation method's concrete steps are as follows:
(1) 1-allyl group-N-Nitroimidazoline-2-base amine is synthesized:
Under nitrogen protection, N-nitro imido imidazolyl alkane and organic solvent are joined in reactor, after N-nitro imido imidazolyl alkane dissolves substantially, under agitation in reactor, add sodium hydride in batches, continue stirring after adding sodium hydride 30 minutes, more slowly drip propenyl chloride in reactor, after dropwising, stirring reaction under temperature 35-40 DEG C of condition, and monitor reaction process with TLC or HPLC, until reaction terminates; After cooling, underpressure distillation goes out organic solvent, obtains orange-yellow oily liquids, adds the isopyknic ether of described orange-yellow oily liquids and separate out faint yellow crystalline solid at temperature-10 DEG C, take advantage of cold filtration, obtain thick product, with Gossypol recrystallized from chloroform, obtain the sterling of 1-allyl group-N-Nitroimidazoline-2-base amine; Described organic solvent is the mixed solvent of N, N'-dimethyl formamide or N, N'-dimethyl formamide and toluene, described propenyl chloride: N-nitro imido imidazolyl alkane: the mol ratio of sodium hydride is: 1:1.1-1.5:1.1-1.5; The purity of described sodium hydride is 60wt%; Described vacuum distillation temperature is 40 DEG C, and pressure is 0.3KPa;
(2) 1-(1,2-epoxypropyl)-N-Nitroimidazoline-2-base amine enantiomorph is synthesized:
Under nitrogen protection, in reactor, add a certain amount of organic solvents, chloroform, at-10-O DEG C of temperature, first backward reactor adds tetra isopropyl oxygen titanium Ti (Oi-Pr) 4, L (+)-diethyl tartrate or L (-)-diethyl tartrate, stir after 15 minutes and add the obtained 1-allyl group-N-Nitroimidazoline-2-base amine of step (1), finally add oxygenant metachloroperbenzoic acid, the homogeneous phase solution of reaction gained is stirred 12h, period TLC or HPLC monitors the product conversion process of reaction, after desolventizing, by petroleum ether, thick product can be obtained, the sterling of 1-(1,2-epoxypropyl)-N-Nitroimidazoline-2-base amine enantiomorph is obtained through chloroform-sherwood oil mixed solvent recrystallization; Described tetra isopropyl oxygen titanium: L (+)-diethyl tartrate: 1-allyl group-N-Nitroimidazoline-2-base amine: the mol ratio of metachloroperbenzoic acid is 1:1:1:2; The volume ratio of described chloroform-sherwood oil is 2:1.
CN201510822732.3A 2015-11-23 2015-11-23 A kind of preparation method of photolytic activity epoxy quinoline enantiomer Expired - Fee Related CN105481839B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510822732.3A CN105481839B (en) 2015-11-23 2015-11-23 A kind of preparation method of photolytic activity epoxy quinoline enantiomer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510822732.3A CN105481839B (en) 2015-11-23 2015-11-23 A kind of preparation method of photolytic activity epoxy quinoline enantiomer

Publications (2)

Publication Number Publication Date
CN105481839A true CN105481839A (en) 2016-04-13
CN105481839B CN105481839B (en) 2018-05-11

Family

ID=55669158

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510822732.3A Expired - Fee Related CN105481839B (en) 2015-11-23 2015-11-23 A kind of preparation method of photolytic activity epoxy quinoline enantiomer

Country Status (1)

Country Link
CN (1) CN105481839B (en)

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018177970A1 (en) 2017-03-31 2018-10-04 Basf Se Process for preparing chiral 2,3-dihydrothiazolo[3,2-a]pyrimidin-4-ium compounds
WO2018197466A1 (en) 2017-04-26 2018-11-01 Basf Se Substituted succinimide derivatives as pesticides
CN109053699A (en) * 2018-09-26 2018-12-21 四川和邦生物科技股份有限公司 A kind of preparation method of cycolxylidin
WO2019043183A1 (en) 2017-08-31 2019-03-07 Basf Se Method of controlling rice pests in rice
EP3453706A1 (en) 2017-09-08 2019-03-13 Basf Se Pesticidal imidazole compounds
WO2019072906A1 (en) 2017-10-13 2019-04-18 Basf Se Imidazolidine pyrimidinium compounds for combating animal pests
WO2019121143A1 (en) 2017-12-20 2019-06-27 Basf Se Substituted cyclopropyl derivatives
WO2019137995A1 (en) 2018-01-11 2019-07-18 Basf Se Novel pyridazine compounds for controlling invertebrate pests
WO2019145140A1 (en) 2018-01-09 2019-08-01 Basf Se Silylethynyl hetaryl compounds as nitrification inhibitors
WO2019166558A1 (en) 2018-02-28 2019-09-06 Basf Se Use of pyrazole propargyl ethers as nitrification inhibitors
WO2019166560A1 (en) 2018-02-28 2019-09-06 Basf Se Use of n-functionalized alkoxy pyrazole compounds as nitrification inhibitors
WO2019166561A1 (en) 2018-02-28 2019-09-06 Basf Se Use of alkoxypyrazoles as nitrification inhibitors
WO2019175712A1 (en) 2018-03-14 2019-09-19 Basf Corporation New uses for catechol molecules as inhibitors to glutathione s-transferase metabolic pathways
WO2019175713A1 (en) 2018-03-14 2019-09-19 Basf Corporation New catechol molecules and their use as inhibitors to p450 related metabolic pathways
WO2019219529A1 (en) 2018-05-15 2019-11-21 Basf Se Mixtures comprising benzpyrimoxan and oxazosulfyl and uses and methods of applying them
WO2019224092A1 (en) 2018-05-22 2019-11-28 Basf Se Pesticidally active c15-derivatives of ginkgolides
WO2020002472A1 (en) 2018-06-28 2020-01-02 Basf Se Use of alkynylthiophenes as nitrification inhibitors
WO2020020777A1 (en) 2018-07-23 2020-01-30 Basf Se Use of substituted 2-thiazolines as nitrification inhibitors
WO2020020765A1 (en) 2018-07-23 2020-01-30 Basf Se Use of a substituted thiazolidine compound as nitrification inhibitor
EP3613736A1 (en) 2018-08-22 2020-02-26 Basf Se Substituted glutarimide derivatives
EP3628157A1 (en) 2018-09-28 2020-04-01 Basf Se Method of controlling insecticide resistant insects and virus transmission to plants
EP3628156A1 (en) 2018-09-28 2020-04-01 Basf Se Method for controlling pests of sugarcane, citrus, rapeseed, and potato plants
EP3628158A1 (en) 2018-09-28 2020-04-01 Basf Se Pesticidal mixture comprising a mesoionic compound and a biopesticide
WO2020064492A1 (en) 2018-09-28 2020-04-02 Basf Se Method of controlling pests by seed treatment application of a mesoionic compound or mixture thereof
EP3643705A1 (en) 2018-10-24 2020-04-29 Basf Se Pesticidal compounds
EP3696177A1 (en) 2019-02-12 2020-08-19 Basf Se Heterocyclic compounds for the control of invertebrate pests
WO2020239517A1 (en) 2019-05-29 2020-12-03 Basf Se Mesoionic imidazolium compounds and derivatives for combating animal pests
EP3766879A1 (en) 2019-07-19 2021-01-20 Basf Se Pesticidal pyrazole derivatives
EP3769623A1 (en) 2019-07-22 2021-01-27 Basf Se Mesoionic imidazolium compounds and derivatives for combating animal pests
WO2022167488A1 (en) 2021-02-02 2022-08-11 Basf Se Synergistic action of dcd and alkoxypyrazoles as nitrification inhibitors
WO2022243521A1 (en) 2021-05-21 2022-11-24 Basf Se Use of ethynylpyridine compounds as nitrification inhibitors
WO2022243523A1 (en) 2021-05-21 2022-11-24 Basf Se Use of an n-functionalized alkoxy pyrazole compound as nitrification inhibitor
WO2022268810A1 (en) 2021-06-21 2022-12-29 Basf Se Metal-organic frameworks with pyrazole-based building blocks
WO2023203066A1 (en) 2022-04-21 2023-10-26 Basf Se Synergistic action as nitrification inhibitors of dcd oligomers with alkoxypyrazole and its oligomers
WO2024028243A1 (en) 2022-08-02 2024-02-08 Basf Se Pyrazolo pesticidal compounds

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4880933A (en) * 1986-12-19 1989-11-14 Nihon Tokushu Noyaku Seizo K.K. Nitro- or cyano-derivatives of 2-imino-imidazolines and 2-imino-tetrahydropyrimidines
CN1437602A (en) * 2000-06-22 2003-08-20 詹森药业有限公司 Compounds for treating impaired fundic relaxation
CN101503406A (en) * 2008-12-17 2009-08-12 武汉工程大学 1-(1,2-epoxy propyl)-N-nitroimidazolene amine-2, preparation and use thereof
CN101830853A (en) * 2010-04-23 2010-09-15 武汉工程大学 Nitroimidazoline derivatives and preparation method thereof and application thereof
CN103896927A (en) * 2014-04-01 2014-07-02 武汉工程大学 Method for preparing (R)/(S)-1-(2,3-glycidyl)-N-nitroimidazoline-2-imine

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4880933A (en) * 1986-12-19 1989-11-14 Nihon Tokushu Noyaku Seizo K.K. Nitro- or cyano-derivatives of 2-imino-imidazolines and 2-imino-tetrahydropyrimidines
EP0277317B1 (en) * 1986-12-19 1991-04-03 Nihon Tokushu Noyaku Seizo K.K. Nitro derivatives of 2-iminoimidazolidines and 2-iminotetrahydropyrimidines
CN1437602A (en) * 2000-06-22 2003-08-20 詹森药业有限公司 Compounds for treating impaired fundic relaxation
CN101503406A (en) * 2008-12-17 2009-08-12 武汉工程大学 1-(1,2-epoxy propyl)-N-nitroimidazolene amine-2, preparation and use thereof
CN101830853A (en) * 2010-04-23 2010-09-15 武汉工程大学 Nitroimidazoline derivatives and preparation method thereof and application thereof
CN103896927A (en) * 2014-04-01 2014-07-02 武汉工程大学 Method for preparing (R)/(S)-1-(2,3-glycidyl)-N-nitroimidazoline-2-imine

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
闻韧: "《药物合成反应 第二版》", 31 January 2003 *

Cited By (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018177970A1 (en) 2017-03-31 2018-10-04 Basf Se Process for preparing chiral 2,3-dihydrothiazolo[3,2-a]pyrimidin-4-ium compounds
EP3978504A1 (en) 2017-03-31 2022-04-06 Basf Se Chiral 2,3-dihydrothiazolo[3,2-a]pyrimidine derivatives for combating animal pests
WO2018197466A1 (en) 2017-04-26 2018-11-01 Basf Se Substituted succinimide derivatives as pesticides
WO2019043183A1 (en) 2017-08-31 2019-03-07 Basf Se Method of controlling rice pests in rice
WO2019042932A1 (en) 2017-08-31 2019-03-07 Basf Se Method of controlling rice pests in rice
EP3453706A1 (en) 2017-09-08 2019-03-13 Basf Se Pesticidal imidazole compounds
WO2019072906A1 (en) 2017-10-13 2019-04-18 Basf Se Imidazolidine pyrimidinium compounds for combating animal pests
WO2019121143A1 (en) 2017-12-20 2019-06-27 Basf Se Substituted cyclopropyl derivatives
WO2019145140A1 (en) 2018-01-09 2019-08-01 Basf Se Silylethynyl hetaryl compounds as nitrification inhibitors
WO2019137995A1 (en) 2018-01-11 2019-07-18 Basf Se Novel pyridazine compounds for controlling invertebrate pests
WO2019166558A1 (en) 2018-02-28 2019-09-06 Basf Se Use of pyrazole propargyl ethers as nitrification inhibitors
WO2019166560A1 (en) 2018-02-28 2019-09-06 Basf Se Use of n-functionalized alkoxy pyrazole compounds as nitrification inhibitors
WO2019166561A1 (en) 2018-02-28 2019-09-06 Basf Se Use of alkoxypyrazoles as nitrification inhibitors
WO2019175712A1 (en) 2018-03-14 2019-09-19 Basf Corporation New uses for catechol molecules as inhibitors to glutathione s-transferase metabolic pathways
WO2019175713A1 (en) 2018-03-14 2019-09-19 Basf Corporation New catechol molecules and their use as inhibitors to p450 related metabolic pathways
WO2019219529A1 (en) 2018-05-15 2019-11-21 Basf Se Mixtures comprising benzpyrimoxan and oxazosulfyl and uses and methods of applying them
WO2019224092A1 (en) 2018-05-22 2019-11-28 Basf Se Pesticidally active c15-derivatives of ginkgolides
WO2020002472A1 (en) 2018-06-28 2020-01-02 Basf Se Use of alkynylthiophenes as nitrification inhibitors
WO2020020777A1 (en) 2018-07-23 2020-01-30 Basf Se Use of substituted 2-thiazolines as nitrification inhibitors
WO2020020765A1 (en) 2018-07-23 2020-01-30 Basf Se Use of a substituted thiazolidine compound as nitrification inhibitor
EP3613736A1 (en) 2018-08-22 2020-02-26 Basf Se Substituted glutarimide derivatives
CN109053699A (en) * 2018-09-26 2018-12-21 四川和邦生物科技股份有限公司 A kind of preparation method of cycolxylidin
EP3628156A1 (en) 2018-09-28 2020-04-01 Basf Se Method for controlling pests of sugarcane, citrus, rapeseed, and potato plants
EP3628158A1 (en) 2018-09-28 2020-04-01 Basf Se Pesticidal mixture comprising a mesoionic compound and a biopesticide
WO2020064480A1 (en) 2018-09-28 2020-04-02 Basf Se Pesticidal mixture comprising a mesoionic compound and a biopesticide
WO2020064492A1 (en) 2018-09-28 2020-04-02 Basf Se Method of controlling pests by seed treatment application of a mesoionic compound or mixture thereof
WO2020064408A1 (en) 2018-09-28 2020-04-02 Basf Se Method of controlling insecticide resistant insects and virus transmission to plants
EP3628157A1 (en) 2018-09-28 2020-04-01 Basf Se Method of controlling insecticide resistant insects and virus transmission to plants
EP3643705A1 (en) 2018-10-24 2020-04-29 Basf Se Pesticidal compounds
WO2020083733A1 (en) 2018-10-24 2020-04-30 Basf Se Pesticidal compounds
EP3696177A1 (en) 2019-02-12 2020-08-19 Basf Se Heterocyclic compounds for the control of invertebrate pests
WO2020239517A1 (en) 2019-05-29 2020-12-03 Basf Se Mesoionic imidazolium compounds and derivatives for combating animal pests
EP3766879A1 (en) 2019-07-19 2021-01-20 Basf Se Pesticidal pyrazole derivatives
WO2021013561A1 (en) 2019-07-19 2021-01-28 Basf Se Pesticidal pyrazole and triazole derivatives
EP3769623A1 (en) 2019-07-22 2021-01-27 Basf Se Mesoionic imidazolium compounds and derivatives for combating animal pests
WO2022167488A1 (en) 2021-02-02 2022-08-11 Basf Se Synergistic action of dcd and alkoxypyrazoles as nitrification inhibitors
WO2022243521A1 (en) 2021-05-21 2022-11-24 Basf Se Use of ethynylpyridine compounds as nitrification inhibitors
WO2022243523A1 (en) 2021-05-21 2022-11-24 Basf Se Use of an n-functionalized alkoxy pyrazole compound as nitrification inhibitor
WO2022268810A1 (en) 2021-06-21 2022-12-29 Basf Se Metal-organic frameworks with pyrazole-based building blocks
WO2023203066A1 (en) 2022-04-21 2023-10-26 Basf Se Synergistic action as nitrification inhibitors of dcd oligomers with alkoxypyrazole and its oligomers
WO2024028243A1 (en) 2022-08-02 2024-02-08 Basf Se Pyrazolo pesticidal compounds

Also Published As

Publication number Publication date
CN105481839B (en) 2018-05-11

Similar Documents

Publication Publication Date Title
CN105481839A (en) Preparation method for cycloxylidin enantiomer with photoactivity
Hsieh et al. Silicon amine reagents for the photocatalytic synthesis of piperazines from aldehydes and ketones
CN101166722A (en) Process for preparing 3,3-disubstituted oxindoles and thio-oxindoles
CN110028489B (en) Method for preparing benzamide compound by pressure reduction method
CN103113308A (en) Method for preparing dihydropyrimidinone derivative
CN110627690A (en) Novel p-coumaric acid sulfonate derivative and preparation method and application thereof
CN102070473B (en) Method for synthesizing D-valine
CN106365986A (en) Compounds and preparation methods thereof, and uses of compounds in synthesis of brivaracetam
CN102816150B (en) Indole with bacteriostatic activity and derivatives thereof-triazole compounds, and preparation method thereof
CN104341333A (en) Preparation method of Pramiracetam sulfate
CN105693598A (en) Method for synthesis of 3-piperidone derivatives through iridium catalytic hydrogenation
CN104610267B (en) Method for efficiently synthesizing 6-alkyl pyrazolo [1,5-c ] quinazoline framework compound under non-catalytic condition
CN102249962B (en) Preparation method of 1,1-disulfur-1-olefin
CN103319417A (en) Method for preparing triclabendazole sulfoxide
CN105085582B (en) Different part cyclopentadienyl titanium complex crystal and its application in β aminocarboxyl compounds are prepared
CN103172497A (en) Industrialized production process of new medicament benvitimod for treating psoriasis
CN106008326A (en) Synthetic method for hydronopyl pyridine quaternary ammonium salts
CN103044192A (en) Method for synthesizing luliconazole intermediate-(S)-2,4-dichloro-1-(1,2-dichloroethyl) benzene
CN106234387B (en) A kind of application of the 1,2,4- triazole derivative of the structure of benzopyrazines containing methyl as fungicide
KR101416920B1 (en) Method for preparation of δ-nitro ketone derivatives
CN104910033A (en) Method for preparing 5-aminolevulinic acid hydrochloride
CN102276537A (en) Preparation method of 2-cyan-5-amiopyrimidine
CN106234385B (en) A kind of application of 1,2,4- triazole derivatives of the structure containing benzopyrazines as fungicide
CN103724324A (en) Imidacloprid-like ramification and preparing method thereof
CN104130197A (en) Chemical synthetic method of 2,4,6-triamido-5-cyano pyrimidine

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
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20180511

Termination date: 20181123

CF01 Termination of patent right due to non-payment of annual fee