CN101830853B - Nitroimidazoline derivatives and preparation method thereof and application thereof - Google Patents
Nitroimidazoline derivatives and preparation method thereof and application thereof Download PDFInfo
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- CN101830853B CN101830853B CN2010101602471A CN201010160247A CN101830853B CN 101830853 B CN101830853 B CN 101830853B CN 2010101602471 A CN2010101602471 A CN 2010101602471A CN 201010160247 A CN201010160247 A CN 201010160247A CN 101830853 B CN101830853 B CN 101830853B
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- 0 *CN(CCN1)C1=N[N+]([O-])=O Chemical compound *CN(CCN1)C1=N[N+]([O-])=O 0.000 description 1
- DJZWNSRUEJSEEB-UHFFFAOYSA-N [O-][N+](N=C1NCCN1)=O Chemical compound [O-][N+](N=C1NCCN1)=O DJZWNSRUEJSEEB-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to nitroimidazoline derivatives. The nitroimidazoline derivatives have a structural formula shown in a formula I, wherein R is substituted benzene, naphthalene, benzoxazole or benzimidazole. The preparation method comprises that different substituted chloromethylene compounds, N-nitroimidazoline, potassium carbonate and solvent are reacted to form the nitroimidazoline derivatives. The nitroimidazoline derivatives have the advantages that: 1) the synthetic method for the nitroimidazoline derivative compounds is simple; and 2) the nitroimidazoline derivative compounds havea structure different from that of imidacloprid and have high insecticidal activity, the structure of the compounds does not comprise pyridine rings, and the compounds have wide development prospect.
Description
Technical field
The present invention relates to Nitroimidazoline derivatives and its production and application.
Background technology
Anabasine insecticide, particularly Provado since putting on market in 1991, and for control piercing-sucking mouthparts aphid, plant hopper, leafhopper make a great contribution, the sterilant exploitation that acts on the nicotine aceticoceptor still has bigger potentiality.We can say do not have a kind of crop not use Provado at present, especially paddy rice, vegetables two big crops, per season the crop access times minimum more than twice, solved the problem of preventing and treating of piercing-sucking mouthparts aphid, plant hopper, leafhopper for a long time effectively.Provado is a kind of novel nitro-imine sterilant, and its insecticidal mechanism mainly is an insect neural system nAChR agonist, thereby the normal conduction of blocking-up insect central nervous system causes insect dead.It is a most salable insecticide variety on the present world market, because of its good root internal absorption characteristic, tag and stomach poison function and high long-lasting, can be used as soil treatment, seed treatment and foliar spray.But a kind of agricultural chemicals of long-term single use can make insect produce resistance, and Provado is no exception.In the area that long-term single repeatedly high dosage uses Provado, planthopper has produced tens times to hundreds of times to its resistance.In addition, Provado produces a large amount of pollutents owing to contain the pyridine ring production process, is difficult to administer.
Summary of the invention
Problem to be solved by this invention is to propose a kind of Nitroimidazoline derivatives to above-mentioned prior art, and this compound has higher virulence to aphid, plant hopper and leafhopper, and because this compound does not contain pyridine ring, can not produce pollution.
Another object of the present invention provides the preparation method of Nitroimidazoline derivatives.
The conduct that also has a purpose to provide Nitroimidazoline derivatives of the present invention is anti-to eliminate aphis, the application of the sterilant of plant hopper and leafhopper.
The present invention for the solution that problem adopted of the above-mentioned proposition of solution is: Nitroimidazoline derivatives has the represented structural formula of general formula I:
Wherein R is substituted benzene, naphthalene, benzoxazoles or benzoglyoxaline.
The present invention also provides the preparation method of above-mentioned Nitroimidazoline derivatives: with the N-Nitroimidazoline; Salt of wormwood and solvent join in the reaction vessel; Be heated to 30-100 ℃; After treating the dissolving of N-Nitroimidazoline; To wherein adding different substituted chloro methylene compounds; Wherein in the different substituted chloro methylene compounds of mole: N-Nitroimidazoline: salt of wormwood=1: 1-1.2: 1-1.5; Dropwise; Continuing reacting by heating 3.5-4.5h finishes to reacting; Filter, the filtrating evaporate to dryness, the gained bottom product is dissolved in water; Use dichloromethane extraction again; Precipitation gets crude product, obtains Nitroimidazoline derivatives with the butanone recrystallization.
Press such scheme, preferably in the different substituted chloro methylene compounds of mole: the N-Nitroimidazoline: salt of wormwood=be 1: 1.05: 1.
Press such scheme, preferred temperature of reaction is 0-90 ℃.
The reaction formula of said process is:
Nitroimidazoline derivatives of the present invention has higher virulence to aphid, plant hopper and leafhopper etc.
Beneficial effect of the present invention is:
1) compound Nitroimidazoline derivatives synthesis method of the present invention is simple;
2) compound Nitroimidazoline derivatives of the present invention has and the Provado various structure, has higher insecticidal activity, and does not contain pyridine ring in the structure of this compound, has bigger development prospect.
Embodiment
Come the represented compound of general formula I of the present invention is done explanation particularly through specific embodiment below, only the present invention will be described for these embodiment, rather than limit the invention.
Embodiment 1
The preparation of 1-(naphthalene-1-ylmethyl)-N-nitroimidazole alkane-2-imines
1. the preparation (I) of α-chloromethyl naphthalene intermediate
12.8g(0.1mol) naphthalene)37% formalin)36% hydrochloric acid, a spot of cetyl trimethylammonium bromide joins in the 100ml there-necked flask, is heated to 75 ℃ of reaction 6h under stirring; Reaction finishes; Reaction solution behind the extraction liquid evaporate to dryness, is crossed post with sherwood oil with 50ml hexanaphthene extracted twice; Get transparent liquid product 15.3g, yield 87%.Synthetic route is following:
2. (be N-Nitroimidazoline)0.260g(0.0021mol) with 2-nitro-imine base imidazolidine; Anhydrous potassium carbonate 0.28g(0.002mol); The 15ml anhydrous acetonitrile joins in the 50ml there-necked flask; Be heated to 40 ℃, be stirred to 2-Nitroimidazoline dissolving after, to wherein adding α-chloromethyl naphthalene intermediate (I)3.6g 0.002mol; Continue to be heated to 70 ℃ of following responses, reaction 4h is after reaction finishes; Filtered while hot; Filtrate decompression is concentrated into dried, and resistates adds the 20ml water dissolution, with 15ml * 3 chloroform extractions; Chloroform layer is used the 10ml water washing once again; Steaming desolventizes, and the butanone recrystallization promptly gets target compound.
White solid powder 0.31g, yield 57.4%, m.p.193-194 ℃.
1H?NMR(CDCl
3，300MHz)δ：3.33～3.36(q，2H)，3.65～3.68(t，2H)，4.98(s，2H)，7.41～7.45(m，J＝13.2Hz，2H)，7.54～7.58(m，2H)，7.85～7.89(m，2H)，8.06～8.07(d，1H)，8.17(s，1H)；MSm/z(％)：270(M
+，6)，269(18)，224(32)，210(9)，156(95)，129(100)，60(15)；Anal.calcd?for?C
14H
14N
4O
2：C?62.21，H?5.22，N?20.73；found?C?62.35，H?5.34，N?20.68。
Embodiment 2
The preparation of 1-(3-xenyl-4-ylmethyl)-N-nitroimidazole alkane-2-imines
1. the preparation (II of chloromethyl biphenyl intermediate)
Biphenyl 6.1g(0.0396mol); Paraformaldehyde 96 2.0g(0.0667mol), zinc chloride 9.7g(0.0965mol), 3.2ml 36% hydrochloric acid glacial acetic acid; The 40ml hexanaphthene, a small amount of cetyl trimethylammonium bromide joins in the 100ml there-necked flask; Till the following feeding of stirring exsiccant hydrogen chloride gas is extremely saturated; Be heated to 5-60 ℃ then, the TLC following response, reaction finishes; Add the dilution of 50ml water hexanaphthene, separatory, water layer are again with the extraction of 50ml hexanaphthene once; Merge oil reservoir; Cross post with sherwood oil behind the evaporate to dryness, get white solid 4.73g, yield 63%.
2. with 2-nitro-imine base imidazolidine 0.520g(0.0046mol); Anhydrous potassium carbonate 0.6g(0.0043mol); The 30ml anhydrous acetonitrile joins in the 100ml there-necked flask; Be heated to 60 ℃, be stirred to 2-Nitroimidazoline dissolving after, to wherein adding intermediate chloromethyl biphenyl intermediate (II)1.5g(0.004mol); Continue to be heated to 80 ℃ of following responses, reaction 4.5h is after reaction finishes; Filtered while hot; Filtrate decompression is concentrated into dried, and resistates adds the 40ml water dissolution, with 35ml * 3 chloroform extractions; Chloroform layer is used the 20ml water washing once again; Steaming desolventizes, and the butanone recrystallization promptly gets target compound.
White needle-like crystals 0.45g, yield 4.7%, m.p.155-156 ℃.
1H?NMR(CDCl
3，300MHz)δ：3.51～3.54(q，2H)，3.76～3.79(t，2H)，4.59(s，2H)，7.35～7.38(m，J＝7.8Hz，2H)，7.44～7.46(m，2H)，7.57～7.59(m，2H)，8.18(s，1H)；MSm/z(％)：296(M
+，100)，295(21)，250(8)，187(48)，153(14)，77(18)；Anal.calcd?for?C
16H
16N
4O
2：C?64.85，H?5.44，N?18.91；found?C?64.65，H?5.52，N18.82。
Embodiment 3
The preparation of 1-(benzoxazole-2-ylmethyl)-N-nitroimidazole alkane-2-imines
1.2-the preparation (III) of chloromethyl benzo oxazole
In the 50ml there-necked flask, stir add Ortho-Aminophenol 5.45g(0.05mol down successively), dry chlorobenzene of 20ml and 0.5ml pyridine, dropping chloro-acetyl chloride 5.85g(0.052mol) the 10ml chlorobenzene solution.Reacting liquid temperature rises to 80 ℃, crosses 1h, is warming up to 100 ℃ of reaction 2h, does not emit to there being hydrogen chloride gas, continues back flow reaction 4h, water pump pressure reducing and steaming chlorobenzene, and it is product that 115 ℃/1330Pa fraction is collected in residual thing underpressure distillation, faint yellow sticking shape liquid.Get product 4.02g, yield 48%.
2.1-(the preparation of benzoxazole-2-ylmethyl)-N-nitroimidazole alkane-2-imines
With 2-nitro-imine base imidazolidine (0.250g(0.002mol); Anhydrous potassium carbonate 0.38g(0.0026mol); The 20ml anhydrous acetonitrile joins in the 50ml there-necked flask; Be heated to 50 ℃, be stirred to 2-Nitroimidazoline dissolving after, to wherein adding intermediate 2-chloromethyl benzo oxazole (III)0.32g(0.0018mol); Continue to be heated to 65 ℃ of following responses, reaction 4h is after reaction finishes; Filtered while hot; Filtrate decompression is concentrated into dried, and resistates adds the 18ml water dissolution, with 15ml * 3 chloroform extractions; Chloroform layer is used the 10ml water washing once again; Steaming desolventizes, and the butanone recrystallization promptly gets target compound.
White needle-like crystals 0.25g, yield 48.1%, m.p.197-198 ℃.
1H?NMR(CDCl
3，300MHz)δ：3.82～3.85(q，2H)，3.90～3.92(t，2H)，4.87(s，2H)，7.35～7.37(m，J＝5.7Hz，2H)，7.52～7.53(d，1H)，7.70～7.71(q，1H)，8.29(s，1H)；MSm/z(％)：261(M
+，23)，260(100)，132(3)，129(27)，126(49)，118(17)；Anal.calcd?for?C
11H
11N
5O
3：C?50.57，H?4.24，N?26.81；found?C50.15，H?4.39，N?27.14。
Embodiment 4
Adopt spray method that compound of the present invention has been carried out evaluated biological activity.Use earlier dimethyl sulfoxide (DMSO) (DMSO) with 1-(3-xenyl-4-ylmethyl)-N-nitroimidazole alkane-2-imines (compound of preparation among the embodiment 2) dissolving; Add a certain amount of soil temperature-20 with deionized water then sample is made into 100 mcg/ml concentration; Soup evenly is sprayed onto on the stem and leaf of Wheat of a certain amount of aphid of inoculation, and does blank with clear water.Every concentration is handled repetition 3 times.Processing is placed in 27 ± 1 ℃ the illumination box (illumination in 12 hours, 12 hours dark).The dead borer population of inspection calculates mortality ratio after 48 hours.Through measuring all compounds under the concentration of 100 mcg/ml, the mortality ratio of aphid illustrates that greater than 50% compound of the present invention has higher killing aphis activity.
Embodiment 5
Adopt spray method that compound of the present invention has been carried out the field evaluated biological activity.Earlier compound 1-(benzoxazole-2-ylmethyl)-N-nitroimidazole alkane-2-imines (compound of preparation among the embodiment 3) and wilkinite, white carbon black, sodium lignosulfonate are processed 10% wettable powder; Water spray is prevented and treated plant hopper and leafhopper on paddy rice; Under 1 gram/mu effective dose; Prevention effect to plant hopper and leafhopper was respectively 85% and 90% in 48 hours, illustrated that compound of the present invention has higher biological activity.
Above-mentioned is raw material with replacement chlorination Bian, to phenyl chlorination Bian, chlorine methylene radical benzo imidazoles etc., and warp and Nitroimidazoline reaction generate target compound.The compounds of this invention is measured through spray method, finds that it has higher insecticidal effect to aphid.
Claims (3)
1. Nitroimidazoline derivatives, it is 1-(benzoxazole-2-ylmethyl)-N-nitroimidazole alkane-2-imines.
2. the preparation method of the described Nitroimidazoline derivatives of claim 1 is characterized in that including following steps:
1) preparation (III) of 2-chloromethyl benzo oxazole
In the 50ml there-necked flask, add Ortho-Aminophenol 5.45g successively under stirring, dry chlorobenzene of 20ml and 0.5ml pyridine; Drip the 10ml chlorobenzene solution of chloro-acetyl chloride 5.85g, reacting liquid temperature rises to 80 ℃, crosses 1h; Be warming up to 100 ℃ of reaction 2h, do not emit, continue back flow reaction 4h to there being hydrogen chloride gas; Water pump pressure reducing and steaming chlorobenzene; It is product that 115 ℃/1330Pa fraction is collected in residual thing underpressure distillation, and faint yellow sticking shape liquid gets product 4.02g; Yield 48%
The preparation of 2)1-(benzoxazole-2-ylmethyl)-N-nitroimidazole alkane-2-imines
With 2-nitro-imine base imidazolidine 0.250g; Anhydrous potassium carbonate 0.38g; The 20ml anhydrous acetonitrile joins in the 50ml there-necked flask, is heated to 50 ℃, be stirred to 2-Nitroimidazoline dissolving after; To wherein adding intermediate 2-chloromethyl benzo oxazole (III)0.32g; Continue to be heated to 65 ℃, TLC following response, reaction 4h; After reaction finishes; Filtered while hot, filtrate decompression is concentrated into dried, and resistates adds the 18ml water dissolution; With 15ml * 3 chloroform extractions; Chloroform layer is used the 10ml water washing once again, and steaming desolventizes, the butanone recrystallization; Promptly get target compound
White needle-like crystals 0.25g, yield 48.1%, m.p.197-198 ℃.
The described Nitroimidazoline derivatives of claim 1 as anti-ly eliminate aphis, the application of the sterilant of plant hopper and leafhopper.
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| CN105168205A (en) * | 2015-08-18 | 2015-12-23 | 泰力特医药（湖北）有限公司 | Preparation method for dual inhibitor LCZ696 of angiotensin II receptor and neprilysin |
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| US4845106A (en) * | 1985-02-04 | 1989-07-04 | Nihon Tokushu Noyaku Seizo K.K. | Heterocyclic thiazole compounds |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4845106A (en) * | 1985-02-04 | 1989-07-04 | Nihon Tokushu Noyaku Seizo K.K. | Heterocyclic thiazole compounds |
| 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 |
Non-Patent Citations (1)
| Title |
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| 卢伦等.吡虫啉衍生物的合成.《合成化学》.2009,第17卷(第1期),第85页图1. * |
Cited By (1)
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| CN105168205A (en) * | 2015-08-18 | 2015-12-23 | 泰力特医药（湖北）有限公司 | Preparation method for dual inhibitor LCZ696 of angiotensin II receptor and neprilysin |
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