CN103058843A - Preparation method of improving content of gamma-isomers in ambrotone - Google Patents
Preparation method of improving content of gamma-isomers in ambrotone Download PDFInfo
- Publication number
- CN103058843A CN103058843A CN2012105711570A CN201210571157A CN103058843A CN 103058843 A CN103058843 A CN 103058843A CN 2012105711570 A CN2012105711570 A CN 2012105711570A CN 201210571157 A CN201210571157 A CN 201210571157A CN 103058843 A CN103058843 A CN 103058843A
- Authority
- CN
- China
- Prior art keywords
- ambrotone
- content
- isomer
- acid solution
- preparation
- 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.)
- Pending
Links
Abstract
The invention discloses a preparation method of improving content of gamma-isomers in ambrotone. The preparation method comprises the following steps: the ambrotone is obtained according to a conventional preparation method, content of beta--isomers in the ambrotone is above 65% , content of the gamma-isomers is less than 11%, the ambrotone with low content of the gamma-isomers and diene addition-compound products, namely iso-pooleysacramento ketone, are added in a container, then about two thirds of total quantity of catalyst of acid solution is added, and uniform mixing is carried out, thermostatic reaction is carried out at the temperature of 60-70 DEG C for 3-5 hours, then the rest of the acid solution is replenished, the thermostatic reaction is kept at the temperature of 60-70 DEG C for 5-8 hours, organic media and acid solution are stewed and separated, the separated acid solution can be used in a circulation and set mode, the separated organic media are neutralized through alkali to be neutral, then reduced pressure distillation is carried out, 126-130 DEG C-3mmHg of cut fraction is collected, and the ambrotone with high content of the gamma-isomers is obtained.
Description
Technical field:
The invention belongs to a kind of synthetic method of flavor compounds, specifically a kind of method that improves γ-content of isomer in the ambrotone.
Background technology:
Its chemical name of ambrotone is: 2-ethanoyl-1,2,3,4,5,6,7,8-octahydro-2,3,7,8-tetramethyl-naphthalene are the mixtures of several isomer, and it has the banksia rose, grane ambra concurrently, and fragrance is lasting, and stable in properties can be used as spices or fixative.
The synthetic route of at present common ambrotone is following three steps, and synthetic 3-methyl-3-amylene-2 ketone carries out Diene-addition with myrcene to 3-methyl-3-amylene-2 ketone more first, and the product with Diene-addition carries out cyclisation at last, carries out at last underpressure distillation and gets final product.But because it is higher to obtain ambrotone β-content of isomer, γ-content of isomer is on the low side only to be 9～11%, has greatly affected fragrance.
Summary of the invention:
Technical problem to be solved by this invention provides a kind of preparation method who improves γ-content of isomer in the ambrotone.
The technical scheme of technical solution problem of the present invention is:
A kind of preparation method who improves γ-content of isomer in the ambrotone comprises the following steps:
Prepare according to a conventional method ambrotone, β-content of isomer in the described ambrotone is more than 65%%, γ-content of isomer is below 11%%, the ambrotone that γ-content of isomer is low and Diene-addition product are that different Puli Sa Ke sliding door ketone adds in the container, adding about 2/3rds of catalyst acid solution total amount stirs again, 60～70 ℃ of isothermal reactions 3～5 hours, add again the acid solution of remainder, continue to keep 60～70 ℃ of isothermal reactions of temperature 5～8 hours, leave standstill and tell organic phase and acid solution, isolated acid solution can recycled, the organic phase of telling is neutralized to neutrality with alkali, carry out again underpressure distillation, collect 126-130 ℃/1-3mmHg cut, obtain the high ambrotone of γ-content of isomer.
Described acid solution is a kind of or its mixture in phosphoric acid solution or hydrochloric acid soln or the Lewis acid acid solution.
Described phosphoric acid solution mass concentration is 55～85%.
The mass ratio of the ambrotone that described γ-content of isomer is low and Diene-addition product, phosphoric acid solution is 1:2.25～2.50:0.06～0.08.
Described alkali is sodium hydroxide or potassium hydroxide.
The below is different Puli Sa Ke sliding door ketone is converted into ambrotone under sour existence condition three kinds of main isomer chemical equations, the present invention is that the ambrotone that β-content of isomer is high joins in the reaction, can effectively impel Puli Sa Ke sliding door ketone to transform to γ-isomer.
Different Puli Sa Ke sliding door ketone β-isomer
Alpha-isomer γ-isomer
The present invention compared with prior art has the following advantages:
The present invention has overcome that β-content of isomer is high in the ambrotone that prior art obtains, γ-content of isomer is low, causes ambrotone fragrance to bias toward the banksia rose, dry unabiding shortcoming.Ambrotone γ-content of isomer that the present invention obtains can reach 13～16%, and the fragrance grane ambra is thick and heavy, mellow and full clearly thoroughly, lasting is lasting.Simultaneously isolated acid solution can recycled, has reduced production cost.
Embodiment:
Carry out synthetic, the Diene-addition of 3-methyl-3-amylene-2 ketone according to prior art, obtain different Puli Sa Ke sliding door ketone.
Embodiment 1:
With 230g β-content of isomer more than 65%, γ-content of isomer is that the Diene-addition product of ambrotone below 11% and 518g is that different Puli Sa Ke sliding door ketone joins in three mouthfuls of reaction flasks, adding mass concentration is that 60% phosphoric acid solution 8.2g stirs again, be warming up to 60～70 ℃ of isothermal reactions 3～5 hours, add again the remaining phosphoric acid solution of 5.6g, continue to keep 60～70 ℃ of isothermal reactions of temperature 5～8 hours, leave standstill and tell organic phase and acid solution, isolated acid solution can recycled, the organic phase of telling is neutralized to neutrality with 10～15% sodium hydroxide, be decompressed to 1～3mmHg, collect 118～126 ℃ of cuts (1) 284g(γ-content of isomer 2～5%) can repeat to apply mechanically, collect 126～130 ℃ of cuts (2) 448g(γ-content of isomer 14%).
Embodiment 2:
The ambrotone of the high β-content of isomer of 230g and the Diene-addition product of 518g are joined in three mouthfuls of reaction flasks, the phosphoric acid solution that adds again 9.8g stirs, be warming up to 60～70 ℃ of isothermal reactions 3～4 hours, add again the phosphoric acid solution of 6.5g, continue to keep 60～70 ℃ of isothermal reactions of temperature 5～7 hours, leave standstill and tell organic phase and acid solution, isolated acid solution can recycled, the organic phase of telling is neutralized to neutrality with 10～15% sodium hydroxide, be decompressed to 1～3mmHg, collect 118～126 ℃ of cuts (1) 246g(γ-content of isomer 2～5%) can repeat to apply mechanically, collect 126～130 ℃ of cuts (2) 486g(γ-content of isomer 15%).All the other are implemented such as embodiment 1.
Embodiment 3:
The ambrotone of the high β-content of isomer of 230g and the Diene-addition product of 578g are joined in three mouthfuls of reaction flasks, the phosphoric acid solution that adds again 11.5g stirs, be warming up to 60～70 ℃ of isothermal reactions 3～5 hours, add again the phosphoric acid solution of 6.9g, continue to keep 60～70 ℃ of isothermal reactions of temperature 5～8 hours, leave standstill and tell organic phase and acid solution, isolated acid solution can recycled, the organic phase of telling is neutralized to neutrality with 10～15% sodium hydroxide, be decompressed to 1～3mmHg, collect 118～126 ℃ of cuts (1) 282g(γ-content of isomer 2～5%) can repeat to apply mechanically, collect 126～130 ℃ of cuts (2) 510g(γ-content of isomer 14.5%).All the other are implemented such as embodiment 1.
Claims (4)
1. the preparation method of γ-content of isomer in the raising ambrotone is characterized in that comprising the following steps:
Prepare according to a conventional method ambrotone, β-content of isomer in the described ambrotone is more than 65%%, γ-content of isomer is below 11%%, the ambrotone that γ-content of isomer is low and Diene-addition product are that different Puli Sa Ke sliding door ketone adds in the container, adding about 2/3rds of catalyst acid solution total amount stirs again, 60～70 ℃ of isothermal reactions 3～5 hours, add again the acid solution of remainder, continue to keep 60～70 ℃ of isothermal reactions of temperature 5～8 hours, leave standstill and tell organic phase, organic phase is neutralized to neutrality with alkali, carries out underpressure distillation again, collect 126-130 ℃/1-3mmHg cut, obtain the high ambrotone of γ-content of isomer.
2. a kind of preparation method who improves γ-content of isomer in the ambrotone as claimed in claim 1, it is characterized in that: described acid solution is a kind of or its mixture in phosphoric acid solution or hydrochloric acid soln or the Lewis acid acid solution.
3. a kind of preparation method who improves γ-content of isomer in the ambrotone as claimed in claim 1, it is characterized in that: the mass ratio of the ambrotone that described γ-content of isomer is low and Diene-addition product, phosphoric acid solution is 1:2.25～2.50:0.06～0.08.
4. a kind of preparation method who improves γ-content of isomer in the ambrotone as claimed in claim 1, it is characterized in that: described alkali is sodium hydroxide or potassium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105711570A CN103058843A (en) | 2012-12-26 | 2012-12-26 | Preparation method of improving content of gamma-isomers in ambrotone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105711570A CN103058843A (en) | 2012-12-26 | 2012-12-26 | Preparation method of improving content of gamma-isomers in ambrotone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103058843A true CN103058843A (en) | 2013-04-24 |
Family
ID=48101778
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012105711570A Pending CN103058843A (en) | 2012-12-26 | 2012-12-26 | Preparation method of improving content of gamma-isomers in ambrotone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103058843A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105541589A (en) * | 2015-12-16 | 2016-05-04 | 广州百花香料股份有限公司 | Preparation method of ambrotone for improving fragrance quality of ambergris |
| CN106831382A (en) * | 2016-12-26 | 2017-06-13 | 广州百花香料股份有限公司 | A kind of preparation method for improving αisomer yield in irisone product |
| CN116217365A (en) * | 2023-03-23 | 2023-06-06 | 福州大学 | Improved ambroxol synthesis method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3911018A (en) * | 1973-02-27 | 1975-10-07 | Int Flavors & Fragrances Inc | Novel process and products produced by said process |
| US6160182A (en) * | 1998-08-19 | 2000-12-12 | Millennium Specialty Chemicals | Process for obtaining mixtures of isomeric acyloctahydronaphthalenes |
| CN102586015A (en) * | 2011-01-13 | 2012-07-18 | 国际香料和香精公司 | 2-acetyl-1,2,3,4,6,7,8,8a-octahydro-2,3,8,8-tetramethylnaphtho |
-
2012
- 2012-12-26 CN CN2012105711570A patent/CN103058843A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3911018A (en) * | 1973-02-27 | 1975-10-07 | Int Flavors & Fragrances Inc | Novel process and products produced by said process |
| US6160182A (en) * | 1998-08-19 | 2000-12-12 | Millennium Specialty Chemicals | Process for obtaining mixtures of isomeric acyloctahydronaphthalenes |
| CN102586015A (en) * | 2011-01-13 | 2012-07-18 | 国际香料和香精公司 | 2-acetyl-1,2,3,4,6,7,8,8a-octahydro-2,3,8,8-tetramethylnaphtho |
Non-Patent Citations (1)
| Title |
|---|
| 邹勇飞等: "月桂烯加成反应及产物的香气评估", 《香料香精化妆品》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105541589A (en) * | 2015-12-16 | 2016-05-04 | 广州百花香料股份有限公司 | Preparation method of ambrotone for improving fragrance quality of ambergris |
| CN106831382A (en) * | 2016-12-26 | 2017-06-13 | 广州百花香料股份有限公司 | A kind of preparation method for improving αisomer yield in irisone product |
| CN116217365A (en) * | 2023-03-23 | 2023-06-06 | 福州大学 | Improved ambroxol synthesis method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103058843A (en) | Preparation method of improving content of gamma-isomers in ambrotone | |
| BR112015011466A2 (en) | recombinant fungal host cell, recombinant nucleic acid construct, isolated polypeptide sequence, and methods for producing a fermentation product and at least one end product from at least one cellulosic substrate | |
| CN103058842A (en) | Preparation method of ambrotone | |
| KR20140105185A (en) | Method for preparation of anhydrosugar alcohols with reduced formation of polymeric reaction byproducts | |
| UA109671C2 (en) | Normal;heading 1;heading 2;heading 3;IMPROVED METHOD FOR ISOMERISATION OF HOP ALPHA-ACIDS TO ISO-ALPHA-ACIDS | |
| AU2014390000B2 (en) | Dehydration of a sugar alcohol with mixed combination of acid catalysts | |
| WO2014181716A1 (en) | Glycation inhibitor | |
| CN105130754A (en) | Method for extracting cyclohexanol from cyclohexanone waste liquid by using composite extractant | |
| CN103588633B (en) | The preparation technology of 5 (6)-decylenic acids | |
| CN102172537A (en) | Biomimetic catalyst for preparing acetal or ketal compounds and using method thereof | |
| Gao et al. | Optimization of ultrasound-assisted aqueous two-phase extraction of polyphenols from mango seed kernel | |
| CN102586015A (en) | 2-acetyl-1,2,3,4,6,7,8,8a-octahydro-2,3,8,8-tetramethylnaphtho | |
| JP2010090037A (en) | Filaggrin production promoter | |
| CN105766896A (en) | Dispersible oil suspending agent | |
| CN103274911A (en) | Novel preparation method of 1,3-dihydroxyl-2-acetone | |
| CN105646311A (en) | Method for preparing beta-Apo-8'-carotenal | |
| CN101244993A (en) | Method for synthesizing oxo-jonone by oxidizing jonone | |
| CN103073404B (en) | Method for by-producing dipentene in preparation process of ambergris ketone | |
| WO2007073240A1 (en) | Catalyst, a method for the production thereof and a dihydroxyalkane production method | |
| CN105567880B (en) | A kind of method and its application of lignocellulose degradation | |
| CN104262419A (en) | Alkyl glycoside and dealcoholization process thereof | |
| CN110330406A (en) | A kind of environmental friendly catalysis method of australene hydration reaction | |
| CN107983334A (en) | A kind of graphene-supported tin tungsten bimetallic catalyst and its preparation method and application | |
| JP6002730B2 (en) | Preservative composition | |
| CN100453630C (en) | Synthetic spice composition possessing auckandia root ambergris flavor and its preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130424 |