CN104496781A - Synthesis method of alkyl cyclopentene alcohol ketone - Google Patents
Synthesis method of alkyl cyclopentene alcohol ketone Download PDFInfo
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- CN104496781A CN104496781A CN201410769261.XA CN201410769261A CN104496781A CN 104496781 A CN104496781 A CN 104496781A CN 201410769261 A CN201410769261 A CN 201410769261A CN 104496781 A CN104496781 A CN 104496781A
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- alcohol ketone
- alkylcyclopentenes
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- cyclopentene alcohol
- oxyethyl group
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Abstract
The invention discloses a synthesis method of alkyl cyclopentene alcohol ketone, which is characterized by comprising the following steps: A. by using 2-ethoxy acetaldehyde as the raw material and thiazole onium salt as a catalyst, reacting with conjugated ketene or Mannich base under alkaline conditions to obtain 1-ethoxy-2,5-dione; B. under the action of alkali, carrying out intramolecular condensation reaction on the 1-ethoxy-2,5-dione to generate an alkyl cyclopentene alcohol ketone methyl ether intermediate; and C. hydrolyzing the alkyl cyclopentene alcohol ketone methyl ether under acidic conditions to obtain the alkyl cyclopentene alcohol ketone. The synthesis route has the advantage of mild reaction conditions, and is a new synthesis route for synthesizing alkyl substituted cyclopentene alcohol ketone.
Description
Technical field
The invention belongs to organic synthesis field, be specifically related to a kind of synthetic method of alkylcyclopentenes alcohol ketone.
Background technology
Alkylcyclopentenes alcohol ketone compounds multi-band has caramel, fragrant and sweet fragrance, naturally be present in the goods such as wood tar oil, coffee, namely methyl cyclopentenyl ketone (2-hydroxy-3-methyl-2-cyclopentene-1-one) is wherein commonly called MCP, and ethylcyclopentenolone (3-ethyl-2-hydroxyl-2-cyclopentene-1-one) is extensively used in food, beverage and tobacco flavour formula; With 3,5-dimethylcyclopentene alcohol ketone in following formula (1) etc. also through being usually used in the essence allocating bread, coffee, maple etc.Owing to being widely used, the synthetic method domestic and foreign literature of MCP is quite a lot of, and other synthesis is less, therefore, makes us become interested to their synthetic method.
The people such as H.Gault at Compt.rend., 1937,205, in the research report delivered on 1416, with adjacent methyl-cyclopentanone for starting raw material, take tetracol phenixin as solvent, under light action, produce the chloro-5-methyl-cyclopentanone of 2,2-bis-with chlorine reaction, be then hydrolyzed and obtain methyl cyclopentenyl ketone.Because needs use tetracol phenixin and chlorine, environmental protection and safety problems larger.
Disclose in the patent German offen2313504 (1973) that Calame J.P. etc. declares, 2,5-hexanedione issues raw intramolecular condensation in alkali effect, obtains 3-methyl-2-cyclopentene-1-one, then use hydrogen peroxide epoxidation, then carry out acid catalyzed rearrangement and obtain methyl cyclopentenyl ketone.
The people such as Li Yunxia, Li Qiong are at " essence and flavoring agent makeup " 2008,1, introduce in 9-11 article, with 2-methyl furan for starting raw material, in acid condition with formaldehyde and dimethylamine generation Mannich reaction, the intermediate obtained under strongly acidic conditions hydrolysis obtains N, N dimethylamine base-2,, then there is intramolecular condensation in 5-hexanedione, hydrolysis obtains MCP then in the basic conditions.Because raw material is easy to get, it is also a kind of production method industrial at present; But owing to using dimethylamine and formaldehyde, the problem of environmental protection aspect is more outstanding.
Leir is at J.Org.Chem., 1970,35 (10), the synthetic method of methyl cyclopentenyl ketone and ethylcyclopentenolone has been delivered in one section of article on 3203, diekmann ring closure reaction is there is in dimethyl adipate under alkali effect, carry out methylating of carbonyl ortho position with methyl iodide again, the ortho position dichloro-cyclopentanone derivatives that the intermediate obtained and chlorine reaction produce, then be hydrolyzed and namely obtain methyl cyclopentenyl ketone.If ethylized with iodoethane, obtain ethylcyclopentenolone by identical process.
The people such as Meng Xianle describe the synthetic method of methyl cyclopentenyl ketone and several adjacent diketone in CN201310044882, and they use cyclic ketones for raw material, and cyclic ketones and nitrous acid ester react the oxime generating cyclic ketones, then hydrolysis obtains corresponding MCP and adjacent diketone.
Summary of the invention
The object of the invention is to: the new synthetic route that a kind of alkylcyclopentenes alcohol ketone is provided, with the conventional industrial chemicals that is easy to get, easy and simple to handle;
For achieving the above object, technical solution of the present invention is:
A synthetic method for alkylcyclopentenes alcohol ketone, is characterized in that, is made up of following steps:
A: with 2-oxyethyl group acetaldehyde for raw material, is catalyzer in the basic conditions with thiazole salt, with conjugation ketenes or Mannich alkali reaction, obtains 1-oxyethyl group-2,5-diketone;
Under alkali effect, there is intermolecular condensation in B:1-oxyethyl group-2,5-diketone, generates alkylcyclopentenes alcohol ketone methyl ether intermediate;
C: alkylcyclopentenes alcohol ketone methyl ether is hydrolyzed in acid condition and obtains alkylcyclopentenes alcohol ketone; Concrete reaction scheme is as follows:
In a preferred embodiment of the invention, described thiazole salt is selected from chlorination 3-benzyl-5-(2-hydroxyethyl)-4-methylthiazol salt.
In a preferred embodiment of the invention, described step (1) temperature of reaction is 70 DEG C ~ 80 DEG C.
Synthetic route of the present invention, reaction conditions is gentle.It is a kind of new synthetic route of synthesis of alkyl substituted cyclopentene alcohol ketone.
Embodiment
In order to make technique means of the present invention, character of innovation, reach object and effect is easy to understand, below in conjunction with embodiment, set forth the present invention further, but embodiments of the present invention are not limited thereto.
Following examples, except as otherwise noted, in literary composition, concentration is mass percent concentration.
Embodiment 1
The synthesis of 1-oxyethyl group-2,5-heptadione
250ml autoclave; Under stirring at room temperature and nitrogen protection, add 4.4g oxyethyl group acetaldehyde respectively, 5g ethyl vinyl ketone, chlorination 3-benzyl-5-(2-hydroxyethyl)-4-methylthiazol salt 2.19g, DMF (80ml); Close autoclave.In still, 3.4g triethylamine is shifted by nitrogen.Be heated to 70 DEG C, react 12 hours.Cool to room temperature, extracts material out.Add 100ml ethyl acetate in material, under frozen water cooling, with the neutralization of 1M dilute hydrochloric acid, oil phase is extremely neutral with saturated common salt water washing.Anhydrous sodium sulfate drying, water-ring pump is concentrated steams ethyl acetate.Concentrated solution underpressure distillation, obtains liquid 5.4g; Yield 62.1%.
Embodiment 2
The synthesis of ethylcyclopentenolone
At 250ml there-necked flask, induction stirring, ice-water bath, adds the ethanol solution 100ml being dissolved with 1.7g potassium hydroxide, maintains 10-15 DEG C, stirs the lower 50ml ethanol solution dripped containing 7.6g 1-oxyethyl group-2,5-heptadione, within about 2 hours, dropwises; Then stirring at room temperature 15 hours.Add 1.8g Glacial acetic acid, water-ring pump concentrating under reduced pressure.Add 50ml methyl tertiary butyl ether in concentrated solution, oil phase concentrates, crude product 5.9g.
Water-bath, induction stirring, adds 40ml 10% aqueous sulfuric acid in 5.9g crude product, stirring at room temperature 4 hours.3x 30ml methyl tertiary butyl ether extracts, and merges organic phase; Saturated brine washs.Normal pressure recycling design.77-79 DEG C/500Pa cut is collected in crude product underpressure distillation, obtains ethylcyclopentenolone weak yellow liquid 3.3g, yield 52.7%.
Embodiment 3
The synthesis of 1-oxyethyl group-3-methyl-2,5-hexanedione
500ml autoclave; Under stirring at room temperature and nitrogen protection, add 17.6g oxyethyl group acetaldehyde respectively, 32.2g 4-(N, N-dimethyl amido)-2 pentanone, chlorination 3-benzyl-5-(2-hydroxyethyl)-4-methylthiazol salt 5.5g, DMF (260ml); Close autoclave.In still, 14g triethylamine is shifted by nitrogen.Be heated to 80 DEG C, react 9 hours.Cool to room temperature, extracts material out.Add 200ml ethyl acetate in material, under frozen water cooling, with the neutralization of 1M dilute hydrochloric acid, oil phase is extremely neutral with saturated common salt water washing.Anhydrous sodium sulfate drying, water-ring pump is concentrated steams ethyl acetate.Concentrated solution underpressure distillation, obtains liquid 22.4g; Yield 65%.
Embodiment 4
The synthesis synthesis of 3,5-dimethylcyclopentene alcohol ketone
At 500ml there-necked flask, induction stirring, ice-water bath, add the ethanol solution 220ml being dissolved with 4.3g potassium hydroxide, maintain 5-10 DEG C, stir lower dropping and contain 19g 1-oxyethyl group-3-methyl-2, the 100ml ethanol solution of 5-hexanedione, dropwises for about 3 hours; Then stirring at room temperature 10 hours.Add 4.6g Glacial acetic acid, water-ring pump concentrating under reduced pressure.Add 150ml methyl tertiary butyl ether in concentrated solution, oil phase concentrates, crude product 16.2g.
Water-bath, induction stirring, adds 80ml 10% aqueous sulfuric acid in the above-mentioned crude product of 16.2g, stirring at room temperature 5 hours.3x 100ml methyl tertiary butyl ether extracts, and merges organic phase; Saturated brine washs.Normal pressure recycling design.75-78 DEG C/1300Pa cut is collected in crude product underpressure distillation, obtains product 6.9g, yield 48.6%.
Claims (3)
1. a synthetic method for alkylcyclopentenes alcohol ketone, is characterized in that, is made up of following steps:
A: with 2-oxyethyl group acetaldehyde for raw material, is catalyzer in the basic conditions with thiazole salt, with conjugation ketenes or Mannich alkali reaction, obtains 1-oxyethyl group-2,5-diketone;
Under alkali effect, there is intermolecular condensation in B:1-oxyethyl group-2,5-diketone, generates alkylcyclopentenes alcohol ketone methyl ether intermediate;
C: alkylcyclopentenes alcohol ketone methyl ether is hydrolyzed in acid condition and obtains alkylcyclopentenes alcohol ketone; Concrete reaction scheme is as follows:
2. the synthetic method of a kind of alkylcyclopentenes alcohol ketone as claimed in claim 1, is characterized in that, described thiazole salt is selected from chlorination 3-benzyl-5-(2-hydroxyethyl)-4-methylthiazol salt.
3. the synthetic method of a kind of alkylcyclopentenes alcohol ketone as claimed in claim 1, is characterized in that, described step (1) temperature of reaction is 70 DEG C ~ 80 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410769261.XA CN104496781A (en) | 2014-12-12 | 2014-12-12 | Synthesis method of alkyl cyclopentene alcohol ketone |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142582A (en) * | 2020-09-16 | 2020-12-29 | 上海应用技术大学 | Synthetic method of methyl cyclopentenolone |
| CN113122098A (en) * | 2021-05-06 | 2021-07-16 | 湖北巴乐福化工科技有限公司 | Environment-friendly health-care coating and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3907896A (en) * | 1972-04-07 | 1975-09-23 | Givaudan Corp | Process for preparation of cyclopentenones |
| US4892966A (en) * | 1985-11-20 | 1990-01-09 | Givaudan Corporation | Acetoacetic acid ester derivatives for the manufacture of α-hydroxycarbonyl compounds |
-
2014
- 2014-12-12 CN CN201410769261.XA patent/CN104496781A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3907896A (en) * | 1972-04-07 | 1975-09-23 | Givaudan Corp | Process for preparation of cyclopentenones |
| US4892966A (en) * | 1985-11-20 | 1990-01-09 | Givaudan Corporation | Acetoacetic acid ester derivatives for the manufacture of α-hydroxycarbonyl compounds |
Non-Patent Citations (1)
| Title |
|---|
| STETTER HERMANN ET AL: "Addition of aldehydes to activated double bonds. XXVIII. Preparations and reactions of alkoxy and acetoxy 2,5-diketones", 《CHEMISCHE BERICHTE》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142582A (en) * | 2020-09-16 | 2020-12-29 | 上海应用技术大学 | Synthetic method of methyl cyclopentenolone |
| CN113122098A (en) * | 2021-05-06 | 2021-07-16 | 湖北巴乐福化工科技有限公司 | Environment-friendly health-care coating and preparation method thereof |
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