CN103833690B - Utilize australene to prepare the method for 2,3-epoxypinane - Google Patents
Utilize australene to prepare the method for 2,3-epoxypinane Download PDFInfo
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- CN103833690B CN103833690B CN201410055738.8A CN201410055738A CN103833690B CN 103833690 B CN103833690 B CN 103833690B CN 201410055738 A CN201410055738 A CN 201410055738A CN 103833690 B CN103833690 B CN 103833690B
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- australene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides one and utilize australene to prepare the method for 2,3-epoxypinane, the method comprises the following steps: (1), preparation reactant liquor; (2), under agitation drip concentration and be 18% Peracetic acid and react to above-mentioned reactant liquor, reacting liquid temperature is controlled at below 20 DEG C; (3), the product of step 2 is carried out to suction filtration, obtain filtrate and filter cake; (4), the 200mL washing leaching cake that adds water, collect filtrate, filtrate stratification, separates water layer and organic layer. (5), respectively wash organic layer once with saturated nacl aqueous solution, saturated sodium thiosulfate solution successively, then with saturated nacl aqueous solution washing organic layer to neutral, after anhydrous sodium sulfate drying, normal temperature boils off solvent and obtains product. The present invention has improved the yield of product 2,3--epoxypinane, has reduced production cost, removes the danger with high concentration peroxy acid blast simultaneously.
Description
Technical field
The present invention relates to chemical field, relate in particular to one and utilize australene to prepare the method for 2,3-epoxypinane.
Background technology
The epoxidation reaction of α – firpene under organic peroxide acid effect carried out synthetic perfume intermediate, is an important channel in organic synthesis and flavor chemistry. At present adopting benzoyl hydroperoxide is oxidant, 2, the yield of 3-epoxypinane is 80%, but benzoyl hydroperoxide cost is higher; If adopt 40% Peracetic acid to make oxidant, 2, the yield of 3-epoxypinane rises to 85%, but 40% Peracetic acid is unstable, in preparation process, easily blasts, and inconvenience is produced. Therefore someone attempts to make oxidant by 20% Peracetic acid, and epoxypinane yield is very low is again 60～65%.
Summary of the invention
The object of the invention is to solve the defect that above-mentioned prior art exists, provide a kind of and under low concentration Peracetic acid, utilize australene to prepare the method for 2,3-epoxypinane.
One utilizes australene to prepare the method for 2,3-epoxypinane, comprises the following steps:
(1), preparation reactant liquor;
(2), under agitation drip concentration and be 18% Peracetic acid and react to above-mentioned reactant liquor, reacting liquid temperature is controlled at below 20 DEG C;
(3), the product of step 2 is carried out to suction filtration, obtain filtrate and filter cake;
(4), the 200mL washing leaching cake that adds water, collect filtrate, filtrate stratification, separates water layer and organic layer.
(5) respectively wash organic layer once with saturated nacl aqueous solution, saturated sodium thiosulfate solution successively, more extremely neutral with saturated nacl aqueous solution washing organic layer, after anhydrous sodium sulfate drying, normal temperature boils off solvent and obtains product;
Wherein, the preparation of described reactant liquor comprises the following steps:
A, australene is dissolved in organic solvent to the appropriate natrium carbonicum calcinatum of rear interpolation;
B, add appropriate TBAB in the solution of step 1, making TBAB obtain concentration is 0.02-0.08mol/L;
C, interpolation support type mesoporous molecular sieve catalyst, the consumption of support type mesoporous molecular sieve catalyst is the 2%-3.5% of australene quality; Wherein step b, c order interchangeable;
Described support type mesoporous molecular sieve catalyst, for SBA-15 is flooded to phosphotungstic acid 12h, then, after filtering, being dried, makes finally by crossing 450 DEG C of roastings;
The mole of described Peracetic acid is 2-3.5 times of australene.
Further, the method for utilizing australene to prepare 2,3-epoxypinane as above, the organic solvent that dissolves australene is chloroform.
Further, the method for utilizing australene to prepare 2,3-epoxypinane as above, described step 3 comprises filter cake is added to water washing, collects cleaning solution, cleaning solution stratification separates water layer and organic layer; With chloroform extraction water layer 1-2 time, obtain organic layer, this organic layer and separatory gained organic layer are merged.
Further, the method for utilizing australene to prepare 2,3-epoxypinane as above, in described step 2, reaction temperature is controlled at 4～16 DEG C, and the reaction time is controlled at 2～4 hours.
Further, the method for utilizing australene to prepare 2,3-epoxypinane as above, in described support type mesoporous molecular sieve catalyst, phosphotungstic acid accounts for 20%～60% of gross mass.
The present invention by 18% Peracetic acid as epoxidation reagent, and make catalyst with homemade support type mesopore molecular sieve, in reactant liquor, add phase transfer catalyst TBAB, so both removed the danger of high concentration peroxy acid blast, the yield that can improve again α-epoxypinane, reduces production costs. Because the epoxidation speed of this reaction is mainly the too little decision of the concentration in organic phase by Peracetic acid, concentration is larger, and epoxidation speed is faster. And to improve the concentration of Peracetic acid in organic phase, only select the organic solvent of high polarity, therefore select chloroform as solvent. The present invention owing to reacting under acid condition, and ring-opening reaction easily occurs α-epoxypinane, and therefore, the acetic acid that adds natrium carbonicum calcinatum neutralization reaction to generate in reaction vessel, makes its buffer system that forms NaAC-HAC, and controlling pH value is 7 left and right. In a word, expect the α-epoxypinane of high yield, the generation that the most important thing is to select the organic solvent of high polarity and stop ring-opening reaction.
The present invention adopts support type mesoporous molecular sieve catalyst, makes oxidant by 18% low concentration Peracetic acid, improves the yield of product 2,3--epoxypinane, reduces production costs, and removes the danger with high concentration peroxy acid blast simultaneously. Be that 2,3-epoxypinane synthetic provides new approach.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearer, will the technical scheme in the present invention be clearly and completely described below, obviously, described embodiment is the present invention's part embodiment, instead of whole embodiment. Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
Below provide embodiment that effect of the present invention is described:
Embodiment 1:
Agitator is being housed, thermometer, in the four-hole boiling flask of dropping funel and condenser pipe, add the australene of 0.1mol, 25mL chloroform, 12.72g natrium carbonicum calcinatum is produced solution I, then add respectively TBAB and support type mesoporous molecular sieve catalyst to solution I, making TBAB shared concentration in solution I is 0.02mol/L, the consumption of support type mesoporous molecular sieve catalyst is 3% of australene quality, catalyst is the mesopore molecular sieve of load 40% phosphotungstic acid, under agitation drip concentration and be 18% Peracetic acid, the consumption of Peracetic acid is 0.2mol, cooling with cold water, temperature is controlled at 4 DEG C, reaction 3h,
Product is first poured in funnel, first carried out suction filtration, obtain filtrate and filter cake; The 200mL washing leaching cake that adds water, collects cleaning solution, and cleaning solution stratification separates water layer and organic layer. With chloroform extraction water layer 1-2 time, merge with organic layer; Respectively wash organic layer after merging once with saturated nacl aqueous solution, saturated sodium thiosulfate solution successively, extremely neutral with saturated nacl aqueous solution washing organic layer again, after anhydrous sodium sulfate drying, normal temperature boils off solvent and obtains product, and product is the liquid that water white transparency has cool smell. By product, through its content of gas chromatographic analysis, the conversion ratio of australene is 87.23%; 2,3 epoxypinanes be selectively 48.42%.
Embodiment 2:
Agitator is being housed, thermometer, in the four-hole boiling flask of dropping funel and condenser pipe, add the australene of 0.1mol, 25mL chloroform, 12.72g natrium carbonicum calcinatum is produced solution I, then add respectively TBAB and support type mesoporous molecular sieve catalyst to solution I, making TBAB shared concentration in solution I is 0.08mol/L, the consumption of support type mesoporous molecular sieve catalyst is the 3.5%(0.476g of australene quality), catalyst is the mesopore molecular sieve of load 40% phosphotungstic acid, under agitation drip concentration and be 18% Peracetic acid, the consumption of Peracetic acid is 0.35mol, cooling with cold water, temperature is controlled at 16 DEG C, reaction 2.5h,
Product is first poured in funnel, first carried out suction filtration, obtain filtrate and filter cake; The 200mL washing leaching cake that adds water, collects cleaning solution, and cleaning solution stratification separates water layer and organic layer. With chloroform extraction water layer 1-2 time, merge with organic layer; Respectively wash organic layer after merging once with saturated nacl aqueous solution, saturated sodium thiosulfate solution successively, extremely neutral with saturated nacl aqueous solution washing organic layer again, after anhydrous sodium sulfate drying, normal temperature boils off solvent and obtains product, and product is the liquid that water white transparency has cool smell. By product, through its content of gas chromatographic analysis, the conversion ratio of australene is 91.03%; 2,3 epoxypinanes be selectively 58.35%.
Embodiment 3:
Agitator is being housed, thermometer, in the four-hole boiling flask of dropping funel and condenser pipe, add the australene of 0.1mol, 25mL chloroform, 12.72g natrium carbonicum calcinatum is produced solution I, then add respectively TBAB and support type mesoporous molecular sieve catalyst to solution I, making TBAB shared concentration in solution I is 0.06mol/L, the consumption of support type mesoporous molecular sieve catalyst is the 2%(0.272g of australene quality), catalyst is the mesopore molecular sieve of load 40% phosphotungstic acid, under agitation drip concentration and be 18% Peracetic acid, the consumption of Peracetic acid is 0.35mol, cooling with cold water, temperature is controlled at 16 DEG C, reaction 2.5h,
Product is first poured in funnel, first carried out suction filtration, obtain filtrate and filter cake; The 200mL washing leaching cake that adds water, collects cleaning solution, and cleaning solution stratification separates water layer and organic layer. With chloroform extraction water layer 1-2 time, merge with organic layer; Respectively wash organic layer after merging once with saturated nacl aqueous solution, saturated sodium thiosulfate solution successively, extremely neutral with saturated nacl aqueous solution washing organic layer again, after anhydrous sodium sulfate drying, normal temperature boils off solvent and obtains product, and product is the liquid that water white transparency has cool smell. By product, through its content of gas chromatographic analysis, the conversion ratio of australene is 87.14%; 2,3 epoxypinanes be selectively 72.89%.
Embodiment 4:
Agitator is being housed, thermometer, in the four-hole boiling flask of dropping funel and condenser pipe, add the australene of 0.1mol, 25mL chloroform, 12.72g natrium carbonicum calcinatum is produced solution I, then add respectively TBAB and support type mesoporous molecular sieve catalyst to solution I, making TBAB shared concentration in solution I is 0.02mol/L, the consumption of support type mesoporous molecular sieve catalyst is the 3%(0.408g of australene quality), catalyst is the mesopore molecular sieve of load 40% phosphotungstic acid, under agitation drip concentration and be 18% Peracetic acid, the consumption of Peracetic acid is 0.25mol, cooling with cold water, temperature is controlled at 16 DEG C, reaction 3h,
Product is first poured in funnel, first carried out suction filtration, obtain filtrate and filter cake; The 200mL washing leaching cake that adds water, collects cleaning solution, and cleaning solution stratification separates water layer and organic layer. With chloroform extraction water layer 1-2 time, merge with organic layer; Respectively wash organic layer after merging once with saturated nacl aqueous solution, saturated sodium thiosulfate solution successively, extremely neutral with saturated nacl aqueous solution washing organic layer again, after anhydrous sodium sulfate drying, normal temperature boils off solvent and obtains product, and product is the liquid that water white transparency has cool smell. By product, through its content of gas chromatographic analysis, the conversion ratio of australene is 87.68%; 2,3 epoxypinanes be selectively 79.17%.
Embodiment 5:
Agitator is being housed, thermometer, in the four-hole boiling flask of dropping funel and condenser pipe, add the australene of 0.1mol, 25mL chloroform, 12.72g natrium carbonicum calcinatum is produced solution I, then add respectively TBAB and support type mesoporous molecular sieve catalyst to solution I, making TBAB shared concentration in solution I is 0.06mol/L, the consumption of support type mesoporous molecular sieve catalyst is the 3.5%(0.476g of australene quality), catalyst is the mesopore molecular sieve of load 40% phosphotungstic acid, under agitation drip concentration and be 18% Peracetic acid, the consumption of Peracetic acid is 0.25mol, cooling with cold water, temperature is controlled at 4 DEG C, reaction 4h,
Product is first poured in funnel, first carried out suction filtration, obtain filtrate and filter cake; The 200mL washing leaching cake that adds water, collects cleaning solution, and cleaning solution stratification separates water layer and organic layer. With chloroform extraction water layer 1-2 time, merge with organic layer; Respectively wash organic layer after merging once with saturated nacl aqueous solution, saturated sodium thiosulfate solution successively, extremely neutral with saturated nacl aqueous solution washing organic layer again, after anhydrous sodium sulfate drying, normal temperature boils off solvent and obtains product, and product is the liquid that water white transparency has cool smell. By product, through its content of gas chromatographic analysis, the conversion ratio of australene is 85.90%%; 2,3 epoxypinanes be selectively 80.84%.
Finally it should be noted that: above embodiment only, in order to technical scheme of the present invention to be described, is not intended to limit; Although the present invention is had been described in detail with reference to previous embodiment, those of ordinary skill in the art is to be understood that: its technical scheme that still can record aforementioned each embodiment is modified, or part technical characterictic is wherein equal to replacement; And these amendments or replacement do not make the essence of appropriate technical solution depart from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (2)
1. a method of utilizing australene to prepare 2,3-epoxypinane, is characterized in that, comprises the following steps:
(1), preparation reactant liquor;
(2), under agitation drip concentration and be 18% Peracetic acid and react to above-mentioned reactant liquor, wherein, reaction temperatureDegree is controlled at 16 DEG C, and the reaction time is controlled at 2 hours;
(3), the product of step 2 is carried out to suction filtration, obtain filtrate and filter cake; Be specially: filter cake is added to water washing,Collect cleaning solution, cleaning solution stratification, separates water layer and organic layer; With chloroform extraction water layer 1-2 time, obtainOrganic layer, merges this organic layer and separatory gained organic layer;
(4), the 200mL washing leaching cake that adds water, collect filtrate, filtrate stratification, separates water layer and organic layer;
(5) respectively wash organic layer once with saturated nacl aqueous solution, saturated sodium thiosulfate solution successively, then use saturated chlorineChange sodium solution washing organic layer to neutral, after anhydrous sodium sulfate drying, normal temperature boils off solvent and obtains product; Wherein, described inThe preparation of reactant liquor comprises the following steps:
A, australene is dissolved in organic solvent to the appropriate natrium carbonicum calcinatum of rear interpolation;
B, add appropriate TBAB in the solution of step a, make TBAB obtain concentration to be0.02-0.08mol/L；
C, interpolation support type mesoporous molecular sieve catalyst, the consumption of support type mesoporous molecular sieve catalyst is australene quality2%-3.5%; Wherein step b, c order interchangeable;
Described support type mesoporous molecular sieve catalyst is for to flood phosphotungstic acid 12h by SBA-15, then through filtering, dry after,Make finally by crossing 450 DEG C of roastings;
The mole of described Peracetic acid is 2-3.5 times of australene;
The organic solvent that dissolves australene is chloroform.
2. the method for utilizing australene to prepare 2,3-epoxypinane according to claim 1, is characterized in that, instituteState phosphotungstic acid in support type mesoporous molecular sieve catalyst and account for 40% of gross mass.
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| CN103833690B true CN103833690B (en) | 2016-05-04 |
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| CN106588819B (en) * | 2016-11-02 | 2018-10-23 | 昆明理工大学 | A kind of preparation method of highly selective epoxypinane |
| CN107597190B (en) * | 2017-08-14 | 2019-12-06 | 湖北大学 | preparation method and application of zeolite molecular sieve crystal grain surface assembled metal organic framework film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1422853A (en) * | 2002-11-28 | 2003-06-11 | 复旦大学 | Method for preparing epoxy pinane using sodium percarbonate as reagent |
| CN102471297A (en) * | 2009-07-24 | 2012-05-23 | 荒川化学工业株式会社 | Method for manufacturing an epoxy compound and method for epoxidizing a carbon-carbon double bond |
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| GB0423586D0 (en) * | 2004-10-22 | 2004-11-24 | United States Borax Inc | Selective oxidation of organic compounds |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1422853A (en) * | 2002-11-28 | 2003-06-11 | 复旦大学 | Method for preparing epoxy pinane using sodium percarbonate as reagent |
| CN102471297A (en) * | 2009-07-24 | 2012-05-23 | 荒川化学工业株式会社 | Method for manufacturing an epoxy compound and method for epoxidizing a carbon-carbon double bond |
Non-Patent Citations (2)
| Title |
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| 吴春华等.杂多酸负载介孔分子筛催化α-蒎烯的环氧化反应.《西南林业大学学报》.2011,第31卷(第4期),85-88. * |
| 负载型纳米复合杂多酸催化α-蒎烯的环氧化反应研究;吴春华等;《化学工业与工程》;20090531;第26卷(第3期);203-206 * |
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