CN1308279C - Purification method of 6,10,14-trimethyl-5E, 9E, 13-pentadecatricene-2-ketone - Google Patents
Purification method of 6,10,14-trimethyl-5E, 9E, 13-pentadecatricene-2-ketone Download PDFInfo
- Publication number
- CN1308279C CN1308279C CNB2004100161601A CN200410016160A CN1308279C CN 1308279 C CN1308279 C CN 1308279C CN B2004100161601 A CNB2004100161601 A CN B2004100161601A CN 200410016160 A CN200410016160 A CN 200410016160A CN 1308279 C CN1308279 C CN 1308279C
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- China
- Prior art keywords
- farnesyl acetone
- ketone
- farnesyl
- fractionation
- acetone
- 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.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 8
- 238000000746 purification Methods 0.000 title claims abstract description 8
- LTUMRKDLVGQMJU-IUBLYSDUSA-N farnesyl acetone Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C\CCC(C)=O LTUMRKDLVGQMJU-IUBLYSDUSA-N 0.000 claims abstract description 28
- LTUMRKDLVGQMJU-UHFFFAOYSA-N famesylacetone Natural products CC(C)=CCCC(C)=CCCC(C)=CCCC(C)=O LTUMRKDLVGQMJU-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 8
- FQTLCLSUCSAZDY-UHFFFAOYSA-N (+) E(S) nerolidol Natural products CC(C)=CCCC(C)=CCCC(C)(O)C=C FQTLCLSUCSAZDY-UHFFFAOYSA-N 0.000 claims abstract description 5
- FQTLCLSUCSAZDY-ATGUSINASA-N Nerolidol Chemical compound CC(C)=CCC\C(C)=C\CC[C@](C)(O)C=C FQTLCLSUCSAZDY-ATGUSINASA-N 0.000 claims abstract description 5
- WASNIKZYIWZQIP-AWEZNQCLSA-N nerolidol Natural products CC(=CCCC(=CCC[C@@H](O)C=C)C)C WASNIKZYIWZQIP-AWEZNQCLSA-N 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000005194 fractionation Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 3
- 238000003457 Shi epoxidation reaction Methods 0.000 claims description 2
- 230000009183 running Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 241000222290 Cladosporium Species 0.000 abstract 1
- 238000004508 fractional distillation Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- LTUMRKDLVGQMJU-ADPXBSPTSA-N (5z,9e)-6,10,14-trimethylpentadeca-5,9,13-trien-2-one Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C/CCC(C)=O LTUMRKDLVGQMJU-ADPXBSPTSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- DJAHKBBSJCDSOZ-AJLBTXRUSA-N (5z,9e,13e)-6,10,14,18-tetramethylnonadeca-5,9,13,17-tetraen-2-one;(5e,9e,13e)-6,10,14,18-tetramethylnonadeca-5,9,13,17-tetraen-2-one Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C\CC\C(C)=C/CCC(C)=O.CC(C)=CCC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CCC(C)=O DJAHKBBSJCDSOZ-AJLBTXRUSA-N 0.000 description 2
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229950006156 teprenone Drugs 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 208000007107 Stomach Ulcer Diseases 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 230000002467 anti-pepsin effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 201000005917 gastric ulcer Diseases 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to purification method of 6, 10, 14-trimethyl-5E, 9E, 13-pentadecanotriene-2-ketone (5E, 9E Farnesyl acetone for short). In the method, nerolidol is used as a raw material, the 5E, 9E Farnesyl acetone and 5Z, 9E Farnesyl acetone mixture are obtained via Cladosporium reaction; a Heli-Pack packed tower is used for fractional distillation to obtain the 5E, 9E Farnesyl acetone with high purity. The method has the advantage of simple operation and is suitable for industrial production.
Description
Technical field
The invention belongs to the field of chemical synthesis.Be specifically related to 6,10,14-trimethylammonium-5E, 9E, the 13-15 carbon triolefin-2-ketone (purification process that is called for short (5E, 9E) farnesyl acetone).
Background technology
6,10,14-trimethylammonium-5E, 9E, 13-15 carbon triolefin-2-ketone promptly (5E, 9E) farnesyl acetone is anti-peptic gastric ulcer medicine---the important intermediate of teprenone (Teprenone).Document (JP 9004726) has been reported (5E, 9E) the preparation method of farnesyl acetone, it promptly is starting raw material with the nerolidol, obtain (5E, 9E) farnesyl acetone and (5Z, 9E) farnesyl acetone mixture through Ka Shi reaction (carrall reaction), then through-30 ℃--55 ℃ of deep refrigerations, isolate (5E, 9E) farnesyl acetone, its synthetic route as shown in the formula:
But this separation method condition harshness, complicated operation, promptly (5E, 9E) farnesyl acetone purity is lower, only is 90.1% for the product that obtains.
Summary of the invention
Technical problem to be solved by this invention is according to (5E, 9E) farnesyl acetone is with (5Z, the 9E) characteristic of farnesyl acetone provide a kind of easy and simple to handle, are suitable for suitability for industrialized production (5E, 9E) purification process of farnesyl acetone.
(5E disclosed by the invention, 9E) the farnesyl acetone purification process is the mixture that obtains after the above-mentioned reaction, adopt fractionating method, obtain purity greater than more than 97% (its concrete steps comprise for 5E, 9E) farnesyl acetone: be raw material with the nerolidol, make (5E through Ka Shi (Carrall) reaction, 9E) farnesyl acetone and (adopting theoretical plate number is 80 Heli-Pack packed tower for 5Z, 9E) farnesyl acetone mixture; Reflux ratio is 10: 1-30: 1; Tower top temperature 175-195 ℃; 230-260 ℃ of still temperature; Vacuum tightness 5-15mmHg carries out fractionation, collect (5E, 9E) purity of farnesyl acetone reaches more than 97%, total recovery 19.2% (not comprising recovery set usefulness), middle runnings can be applied mechanically.
(5E, 9E) farnesyl acetone boiling range under the 10mmHg vacuum degree condition is 186-188 ℃, and (5Z, 9E) boiling range of farnesyl acetone is 182-184 ℃ under the similarity condition.The present invention adopts the Heli-Pack packed tower to separate (5E, 9E) farnesyl acetone that has obtained higher degree according to the boiling range difference of two materials under vacuum condition.The inventive method is simple to operate, is suitable for suitability for industrialized production.
Below in conjunction with embodiment, the invention will be further described.
Embodiment
Embodiment 1
In reactor, drop into nerolidol 1675 grams, methyl acetoacetate 1500 grams, aluminum isopropylate 50 grams, stirring is warming up to 100 ℃, begins to reclaim methyl alcohol, slowly is warming up to 175 ℃ again, reclaim excessive methyl acetoacetate, be cooled to room temperature then, add 5% dilute sulphuric acid and decompose layering, organic layer is water 1500ml * 2 successively, 5%NaHCO
3The 1500ml washing, get organic layer, carry out simple distillation, collect bp130-145 ℃/4-6mmHg cut, obtain (5E, 9E) farnesyl acetone and (5Z, 9E) farnesyl acetone mixture 1600 grams, yield 80%, (5E wherein, 9E) farnesyl acetone accounts for 60%, and (5Z, 9E) farnesyl acetone accounts for 40%.
In the fractionation still, drop into above-mentioned (5E, 9E) farnesyl acetone and (5Z, 9E) farnesyl acetone mixture 1600 grams, with theoretical plate number is that 80 Heli-Pack packed tower carries out fractionation, and reflux ratio is 12: 1,240 ℃ of still temperature, tower top temperature 184-188 ℃, vacuum tightness is 10mmHg.
Obtain cut IV (5E, 9E) farnesyl acetone 384 grams, content＞97% (GC).
Cut III can be inserted in down the fractionation again of batch reaction liquid,
Cut II after isomerization, fractionation again.
Claims (2)
1,6,10,14-trimethylammonium-5E, 9E, the purification process of 13-15 carbon triolefin-2-ketone, this method is to be raw material with the nerolidol, obtains (5E, 9E) farnesyl acetone and (5Z through the Ka Shi reaction, 9E) farnesyl acetone mixture, it is characterized in that described mixture employing theoretical plate number is 80 Heli-Pack packed tower, reflux ratio is 10: 1-30: 1, and tower top temperature is 175-195 ℃, the still temperature is 230-260 ℃, vacuum tightness is that 5-15mmHg carries out fractionation, and acquisition purity is 97% (5E, 9E) farnesyl acetone at least.
2, purification process according to claim 1 is characterized in that the middle runnings of collecting repeats fractionation in fractionation process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100161601A CN1308279C (en) | 2004-02-06 | 2004-02-06 | Purification method of 6,10,14-trimethyl-5E, 9E, 13-pentadecatricene-2-ketone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100161601A CN1308279C (en) | 2004-02-06 | 2004-02-06 | Purification method of 6,10,14-trimethyl-5E, 9E, 13-pentadecatricene-2-ketone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1651382A CN1651382A (en) | 2005-08-10 |
| CN1308279C true CN1308279C (en) | 2007-04-04 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2004100161601A Expired - Fee Related CN1308279C (en) | 2004-02-06 | 2004-02-06 | Purification method of 6,10,14-trimethyl-5E, 9E, 13-pentadecatricene-2-ketone |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101778810A (en) | 2007-08-08 | 2010-07-14 | 帝斯曼知识产权资产管理有限公司 | Preparation method of (E, E) -farnesyl acetone |
| CN101343219B (en) * | 2008-08-21 | 2012-03-21 | 成都理工大学 | Synthesis method of Teprenone |
| CN101830868B (en) * | 2009-12-09 | 2011-11-16 | 云南大学 | Oligosporol derivatives and application thereof |
| CN113666813A (en) * | 2021-08-25 | 2021-11-19 | 江苏宏邦化工科技有限公司 | Synthesis method of farnesyl acetone |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1251832A (en) * | 1998-09-07 | 2000-05-03 | Basf公司 | Method for continuous preparation of unsaturated ketone |
| CN1271716A (en) * | 1998-11-16 | 2000-11-01 | Basf公司 | Preparation of higher unsaturated ketone |
-
2004
- 2004-02-06 CN CNB2004100161601A patent/CN1308279C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1251832A (en) * | 1998-09-07 | 2000-05-03 | Basf公司 | Method for continuous preparation of unsaturated ketone |
| CN1271716A (en) * | 1998-11-16 | 2000-11-01 | Basf公司 | Preparation of higher unsaturated ketone |
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| Publication number | Publication date |
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| CN1651382A (en) | 2005-08-10 |
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Owner name: SHANGHAI ZHONGXI SUNVE PHARMACEUTICAL CO., LTD. Free format text: FORMER NAME: SHANGHAI SUNVE PHARMACEUTICAL CO., LTD. |
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Address after: 200331 No. 50, Yongdeng Road, Shanghai, China Patentee after: Shanghai Zhongxi Sunve Pharmaceutical Co., Ltd. Address before: 200331 No. 50, Yongdeng Road, Shanghai, Putuo District Patentee before: Shanghai Sunve Pharmaceutical Co., Ltd. |
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Granted publication date: 20070404 Termination date: 20140206 |