CN1061336C - 2,5-dimethyl-2,4 hexadiene and diazonium acetate cyclopropyl alkylation reaction and catalyst - Google Patents
2,5-dimethyl-2,4 hexadiene and diazonium acetate cyclopropyl alkylation reaction and catalyst Download PDFInfo
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- CN1061336C CN1061336C CN94112703A CN94112703A CN1061336C CN 1061336 C CN1061336 C CN 1061336C CN 94112703 A CN94112703 A CN 94112703A CN 94112703 A CN94112703 A CN 94112703A CN 1061336 C CN1061336 C CN 1061336C
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- dimethyl
- methylpropenyl
- carboxylic acid
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- acid ester
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Abstract
The present invention relates to a catalyst for synthesizing 2-(2'-methyl propenyl)-3, 3-dimethyl cyclopropane carboxylate in the cyclopropyl alkylation reaction of 2, 5-dimethyl-2, 4 hexadiene and diazonium acetate, which is characterized in that the catalyst is an aromatic amine type salicylal dehyde schiff base copper (II) complex compound. The catalyst of the present invention catalyzes the cyclopropyl alkylation reaction of the 2, 5-dimethyl-2, 4 hexadiene and the diazonium acetate to synthesize chrysanthemum, and has no induction period, smooth and easily controlled reaction, 95% of reaction yield (by diazonium acetate). The catalyst has the advantages of easy synthesis and low cost, and is suitable for industrial production.
Description
The invention belongs to catalyst for cyclopropanizing reaction of olefine, the catalyzer of specifically a kind of 2.5-dimethyl-2.4-hexadiene and diazonium acetate cyclopropanization reaction Synthetic 2-(2 '-methylpropenyl)-3.3-dimethyl cyclopropane carboxylic acid ester.
2-(2 '-methylpropenyl)-3.3-dimethyl cyclopropane carboxylic acid ester (hereinafter to be referred as chrysanthemum monocarboxylate) is a synthesizing propylene chrysanthemum ester, propine chrysanthemum ester,, phenothrin, Tetramethrin, the important intermediate of the contour effective sanitary insecticide of resmethrin is synthesized by a kind of 2.5-dimethyl-2.4-hexadiene (hereinafter to be referred as diene) and diazonium acetate catalysis cyclopropanization reaction usually, and its reaction process is as follows:
For realizing above-mentioned reaction, select appropriate catalyst very crucial, adopt inorganic, the organic salt or the complex compound of copper or copper usually.Copper powder [J.Chem.Soc., 10,283 (1945)] Cu (OTf)
2[Synthesis, 600 (1976)] etc. make catalyzer, the little what 70% of cyclopropanization reaction yield (in diazonium, down with).Company of nation of society adopts band-SO
3H or-CO
2Cu (II) makes catalyzer in the resene polymkeric substance of H, the exchange, and yield is 89.6%[U.S.Pat.4, and 709,085 (1987)].Cu (II) complex compound of aliphatic alpha-alkamine schiff base of salicylaldehyde is made catalyzer and is furtherd investigate, all little what 80% of yield, [Ger.Offn.2,240,259 (1973); Jpn.Kokai 74,14, and 448 (1974); Tetra.Lett.1907 (1975), 2955 (1977)].Described catalyzer or active low, lure the different phase long, reaction yield is low, or difficult synthetic, costs an arm and a leg, and does not reach not only economy but also safe suitability for industrialized production requirement.
The object of the present invention is to provide a kind of easy synthesizing, the catalyzer that price is low makes the cyclopropanization reaction of diene and diazonium acetate not have inductive phase, and is easy to control, and the reaction yield height.
The invention provides the catalyzer of a kind of 2.5-dimethyl-2.4-hexadiene and diazonium acetate cyclopropanization reaction Synthetic 2-(2 '-methylpropenyl)-3.3-dimethyl cyclopropane carboxylic acid ester, it is characterized in that described catalyzer is arylamine class schiff base of salicylaldehyde copper (II) complex compound, can by formula (
R wherein
1R
2R
3Be H, No
2, CN, OH, F, Cl, Br, the alkyl of I and C1-15;
The present invention also provides the method for a kind of 2.5-dimethyl-2.4-diene in the sixth of the twelve Earthly Branches and diazonium acetate cyclopropanization reaction Synthetic 2-(2 '-methylpropenyl)-3.3-dimethyl cyclopropane carboxylic acid ester, it is characterized in that, and aforementioned catalyzer, reaction process is as follows:
Wherein R is the C1-15 alkyl, and the mol ratio of its reactant diene and diazonium acetate is 1-5: 1, and temperature of reaction is 50～200 ℃, catalyst consumption is 0.1～5% of a diazonium acetate weight; Optimum temperature is 70～150 ℃; It is 0.5～3% that optimum week of catalyzer measures; Diazonium acetate can be the ethyl diazoacetate propyl ester butyl ester of low-carbon alcohol etc., also can be diazoacetic acid monooctyl ester, the ester of higher alcohols; Reaction can be at methylene dichloride, and ethylene dichloride carries out in the chlorobenzene equal solvent, also can do to carry out in the solvent with diene itself.
Content of the present invention is described in detail below by real.In all examples, all adopt industrial raw material.Resultant usefulness gas one liquid-liquid chromatography carries out quantitative analysis, calculates reaction yield with diazonium acetate.
Example 1. catalysis cyclopropanization reactions experiment 1
At the bottom of having the 100ml garden of induction stirring, add 0.075g (0.14mmol) o-Nitraniline schiff base of salicylaldehyde copper complex (C26H18N4o6Cu) in the flask, 13.2g (120mmol) diene, reflux, dripping 7.6g concentration under the whipped state in 1-2 hour is the chlorobenzene solution of 60% ethyl diazoacetate (40mmol), steam chlorobenzene and diene after dropwising earlier, underpressure distillation again obtains faint yellow chrysanthemum monocarboxylate 8.1g, content 92%, yield are 95%;
Example 2 catalysis cyclopropanization reactions experiment 2
At the bottom of having the 100ml garden of induction stirring, add 0.1g (0.2mmol) in the flask to monomethylaniline schiff base of salicylaldehyde copper (II) complex compound (C28H24N2O2Cu), 13.2g (120mmol) diene, reflux, dripping 42.6g concentration under the whipped state in 1-2 hour is the dichloroethane solution of 20% diazoacetic acid butyl ester (60mmol), after dropwising, steams ethylene dichloride and diene earlier, underpressure distillation again, get faint yellow chrysanthemumic acid butyl ester 12.2g, content 90%, yield 82%;
Example 3 catalysis cyclopropanization reactions experiment 3
At the bottom of having the 100ml garden of induction stirring, add 0.2g (0.38mmol) p-Chlorobenzoic acid amide schiff base of salicylaldehyde copper (II) complex compound (C26H18N2O2Cl2Cu) in the flask, 22g (200mmol) diene, reflux, under the whipped state in 1-2 hour Dropwise 5 9.7g concentration be the dichloromethane solution of 15% diazoacetic acid propyl ester (70mmol), after dropwising, steam methylene dichloride and dioxane earlier, underpressure distillation then, get flaxen liquid 14.2g, chrysanthemumic acid propyl ester content is 92%, yield 89%;
Example 4, catalysis cyclopropanization reaction experiment 4
At the bottom of having the 100ml garden that induction stirring gives, add 0.1g (0.22mmol) aniline schiff base of salicylaldehyde copper (II) complex compound (C26H20N2O2Cu) in the flask, 13.2g (120mmol) diene, the 10g chlorobenzene, reflux, dripping 39.6g concentration under the whipped state in 1-2 hour is the dichloromethane solution of 30% diazoacetic acid monooctyl ester (60mmol), after dropwising, steam methylene dichloride earlier, diene, chlorobenzene subtracts the grave distillation then, gets weak yellow liquid 15.3g, chrysanthemumic acid monooctyl ester content is 88%, yield 80%;
Experiment 5, catalysis cyclopropanization reaction experiment 5
At the bottom of having the 100ml garden of induction stirring, add 0.15g (0.24mmol) alpha-naphthylamine schiff base of salicylaldehyde copper complex (C38H34N2O2Cu) in the flask, 16.5 (150mmol) diene, the 10g ethylene dichloride, reflux, in 1-3 hour, drip 28.5g concentration under the whipped state and be the chlorobenzene solution of 20% ethyl diazoacetate (50mmol), after dropwising, steam ethylene dichloride earlier, chlorobenzene, diene, underpressure distillation then gets weak yellow liquid 9.9g, chrysanthemumic acid ethyl ester content is 92%, yield 93%;
Experiment 6, catalysis cyclopropanization reaction experiment 6
The consumption of experimental technique and each reactant uses different copper complexs to make catalyst diene cyclopropanization reaction yield example and goes in the table 1 with example 5:
Table 1. catalysis diene cyclopropanization reaction is herded rate
| Catalyzer | Diazonium acetate N 2CHCOOR | Yield % |
| R 1=R 2=R 3=H | R=C 2H 5 | 80 |
| R 1=R 2=R 3=H | R=C 4H 9-n | 83 |
| R 1=R 2=H R 3=CH 3 | R=C 4H 9-n | 90 |
| R 1=CH 3 R 2=R 3=H | R=C 2H 5 | 86 |
| R 1=R 3=CH 3 R 2=H | R=C 5H 11-n | 92 |
| R 1=R 2=H R 3=C 2H 5 | R=C 2H 5 | 85 |
| R 1=R 2=H R 3=NO 2 | R=C 2H 5 | 92 |
| R 1=NO 2 R 2=R 3=H | R=C 4H 9-n | 90 |
| R 1=Cl R 2=R 3=H | R=C 2H 5 | 88 |
| R 1=Br R 2=R 3=H | R=C 2H 5 | 91 |
| R 1=R 3=H R 2=CN | R=C 2H 5 | 94 |
By above-mentioned example as can be known, utilize catalyst 2 of the present invention, 5-dimethyl-2,4-hexadiene and diazonium acetate cyclopropanization reaction synthesis of pyrethrin acid esters, no inductive phase, steadily easy to control, reaction yield can reach 95% in diazo ester, this catalyzer is easily synthetic, and cost is low, is suitable for adopting in industrial production.
Claims (7)
1. the catalyzer of 2.5-dimethyl-2.4-hexadiene and diazonium acetate cyclopropanization reaction Synthetic 2-(2 '-methylpropenyl)-3.3-dimethyl cyclopropane carboxylic acid ester, it is characterized in that described catalyzer is arylamine class schiff base of salicylaldehyde copper (II) complex compound, can (II) be represented by formula (I):
R wherein
1R
2R
3Be No
2, CN, OH, F, Cl, Br, the alkyl of I and C1-15.
2. the method for 2.5-dimethyl-2.4-hexadiene and diazonium acetate cyclopropanization reaction Synthetic 2-(2 '-methylpropenyl)-3.3-dimethyl cyclopropane carboxylic acid ester is characterized in that use the described catalyzer of claim 1, reactional equation is as follows:
Wherein R is the C1-15 alkyl, and the mol ratio of its reactant diene and diazonium acetate is 1-5: 1, and temperature of reaction is 50～200 ℃, catalyst consumption is 0.1～5% of a diazonium acetate weight.
3. by the method for the described Synthetic 2 of claim 2-(2 '-methylpropenyl)-3-dimethyl cyclopropane carboxylic acid ester, it is characterized in that: temperature is 70～1500 ℃.
4. by the method for the described Synthetic 2 of claim 2-(2 '-methylpropenyl)-3.3-dimethyl cyclopropane carboxylic acid ester, it is characterized in that: catalyst levels is 0.5～3%.
5. by the method for claim 2,3 or 4 described Synthetic 2s-(2 '-methylpropenyl)-3.3-dimethyl cyclopropane carboxylic acid ester, it is characterized in that: diazonium acetate is ethyl diazoacetate, propyl ester, the butyl ester of low-carbon alcohol, or the diazoacetic acid monooctyl ester of higher alcohols, ester.
6. by the method for claim 2,3 or 4 described Synthetic 2s-(2 '-methylpropenyl)-3.3-dimethyl cyclopropane carboxylic acid ester, it is characterized in that: be reflected at methylene dichloride, ethylene dichloride carries out in the chlorobenzene solvent, is perhaps doing to carry out in the solvent with diene itself.
7. by the method for the described Synthetic 2 of claim 5-(2 '-methylpropenyl)-3.3-dimethyl cyclopropane carboxylic acid ester, it is characterized in that: be reflected at methylene dichloride, two chloroethenes burn in the chlorobenzene solvent and carry out, and are perhaps doing to carry out in the solvent with diene itself.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94112703A CN1061336C (en) | 1994-12-21 | 1994-12-21 | 2,5-dimethyl-2,4 hexadiene and diazonium acetate cyclopropyl alkylation reaction and catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94112703A CN1061336C (en) | 1994-12-21 | 1994-12-21 | 2,5-dimethyl-2,4 hexadiene and diazonium acetate cyclopropyl alkylation reaction and catalyst |
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| Publication Number | Publication Date |
|---|---|
| CN1125220A CN1125220A (en) | 1996-06-26 |
| CN1061336C true CN1061336C (en) | 2001-01-31 |
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| CN94112703A Expired - Fee Related CN1061336C (en) | 1994-12-21 | 1994-12-21 | 2,5-dimethyl-2,4 hexadiene and diazonium acetate cyclopropyl alkylation reaction and catalyst |
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| CN103272644A (en) * | 2013-06-09 | 2013-09-04 | 江南大学 | Schiff base metal catalyst used in liquid phase epoxidation reaction and preparation method of schiff base metal catalyst |
| CN104710313A (en) * | 2013-12-13 | 2015-06-17 | 中国科学院大连化学物理研究所 | 3-acetoxy methyl-ethyl-2,2-dimethylcyclopropanecarboxylate synthesis method |
| CN110343040B (en) * | 2018-04-02 | 2021-12-21 | 中国科学院大连化学物理研究所 | Method for preparing chiral trans-first chrysanthemic acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0023075A1 (en) * | 1979-07-13 | 1981-01-28 | Imperial Chemical Industries Plc | Process for the preparation of cyclopropane carboxylic acid esters |
| CN1042713A (en) * | 1989-11-22 | 1990-06-06 | 北京农业大学 | A kind of synthetic method of catalyzer |
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1994
- 1994-12-21 CN CN94112703A patent/CN1061336C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0023075A1 (en) * | 1979-07-13 | 1981-01-28 | Imperial Chemical Industries Plc | Process for the preparation of cyclopropane carboxylic acid esters |
| CN1042713A (en) * | 1989-11-22 | 1990-06-06 | 北京农业大学 | A kind of synthetic method of catalyzer |
Non-Patent Citations (1)
| Title |
|---|
| ZH.OBSHCH.KHIM1984,54(3) 1984.1.1 POTAPOV,V.M.PANOVA G.V.SOLOZHENKO,E.G.OPTICALLLY ACTIVE COPPER(II)CHELATESFROMENAMINO KETONES AND * |
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