CN110746262A - Synthesis process of compound - Google Patents
Synthesis process of compound Download PDFInfo
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- CN110746262A CN110746262A CN201810822337.9A CN201810822337A CN110746262A CN 110746262 A CN110746262 A CN 110746262A CN 201810822337 A CN201810822337 A CN 201810822337A CN 110746262 A CN110746262 A CN 110746262A
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- Prior art keywords
- pentadecadiene
- synthesis
- cyclododecanone
- methylbicyclo
- isobutenyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2527/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
- C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/14—All rings being cycloaliphatic
- C07C2602/32—All rings being cycloaliphatic the ring system containing at least eleven carbon atoms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of chemical synthesis of flavors and fragrances, and particularly relates to an industrial synthesis process of 14-methylbicyclo [10.3.0] -1, 13-pentadecadiene, which is a key intermediate for synthesizing rare flavor muscone, wherein cyclododecanone is taken as a starting raw material, and nucleophilic substitution reaction is firstly carried out on the cyclododecanone and isobutenyl chloride under alkaline conditions to generate 2-isobutenyl cyclododecanone; then gas phase cyclization is carried out under the catalysis of a solid heteropoly acid catalyst to directly obtain 14-methyl bicyclo [10.3.0] -1, 13-pentadecadiene. The synthesis process provided by the invention has the main advantages that: the synthesis route is simple, the total yield is high, the method is environment-friendly, and the industrial production is easy to realize; the gas phase ring-closing production process catalyzed by heteropoly acid needs no reaction solvent, hardly produces waste water and waste gas, can recycle the catalyst, and has high raw material conversion rate and high product purity.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis of perfume and essence, and particularly relates to a novel synthesis process for industrially producing 14-methyl bicyclo [10.3.0] -1, 13-pentadecadiene, wherein the compound is a key intermediate for synthesizing rare perfume muscone.
Background
Muscone (Muscone, formula 1), the chemical name of which is 3-methylcyclopentadecanone, is the main component of natural musk and has a strong and pleasant musk fragrance. Muscone is not only a rare spice, but also has multiple pharmacological actions (von skillful; food and medicine 2015,17,212 of Liu military field) such as resuscitation inducing, blood circulation promoting, pain relieving, dementia resisting, cerebral ischemia resisting, and anti-inflammatory effects. Although the musk ketone is widely applied to the fields of flavors and fragrances and medicines, the natural sources of the musk ketone are extremely limited and the musk ketone is expensive and cannot meet the needs of people. Therefore, the research on the artificial synthesis of the muscone has important practical significance.
The key point of synthesizing muscone is the construction of pentadecenyl ring, and 14-methylbicyclo [10.3.0] -1, 13-pentadecene (14-methylbicyclo [10,3,0] pentadec-1,13-diene, formula 1) is the key intermediate for synthesizing muscone. At present, the synthesis of 14-methyl bicyclo [10.3.0] -1, 13-pentadecadiene reported in the literature mainly adopts two schemes to expand the ring of cyclododecanone.
(1) Cyclododecanone is taken as a raw material, firstly reacts with isobutenyl chlorine to generate 2-isobutenyl cyclododecanone, then is subjected to ozone reduction hydrolysis to obtain 2- (2-acetonyl) -cyclododecanone, then is subjected to intramolecular aldol condensation reaction, then is reacted with methyl Grignard reagent, and finally is subjected to elimination reaction under acidic condition to prepare 14-methyl bicyclo [10.3.0] -1, 13-pentadecadiene (Baumann, M Patent DE 2916418A1,1979,4,23.Mahaim, C.J. Patent EP 381964A1,1990,1, 18.).
(2) Cyclododecanone is taken as a raw material, firstly, the cyclododecanone reacts with isobutenyl chloride to generate 2-isobutenyl cyclododecanone, and then, the gas phase ring closing is directly carried out under the catalysis of alumina or silicon oxide to obtain 14-methyl bicyclo [10.3.0] -1, 13-pentadecadiene (Schelper, M.; Stock, C.; Ebel, K.; Teles, J.H.; Pelzer, R.Patent US20120088935A1,2013,10,22. Liu Xiling, Zhangming, patent, CN 101624326B,2012,9, 5.).
Although some researches on the synthesis of 14-methylbicyclo [10.3.0] -1, 13-pentadecadiene have been reported, the existing method has the problems of high cost, complex operation, long route and the like, and is difficult to realize industrial production. Therefore, the research on the synthesis process for industrially producing 14-methyl bicyclo [10.3.0] -1, 13-pentadecadiene is a key problem for solving the industrial production of muscone at present, and has great application value.
Disclosure of Invention
Aiming at solving the key problem of the industrial production of the musk ketone, the invention provides a synthesis process for industrially producing 14-methyl bicyclo [10.3.0] -1, 13-pentadecadiene, which has simple synthesis route, high total yield and environmental friendliness. The synthesis process takes cyclododecanone (marked as 1 in a formula 2) as a starting material, and firstly carries out nucleophilic substitution reaction with isobutenyl chlorine (marked as 2 in the formula 2) under alkaline conditions to generate 2-isobutenyl cyclododecanone (marked as 3 in the formula 2); then gas phase cyclization is carried out under the catalysis of a solid heteropoly acid catalyst to directly obtain 14-methyl bicyclo [10.3.0] -1, 13-pentadecadiene. The specific synthetic route of the 14-methyl bicyclo [10.3.0] -1, 13-pentadecadiene adopted by the invention is shown in formula 2.
The invention aims to provide a synthesis process for industrially producing 14-methyl bicyclo [10.3.0] -1, 13-pentadecadiene, which comprises the following steps:
(1) preparation of 2-isobutenylcyclododecanone
Adding cyclododecanone and toluene into a reaction kettle, stirring for dissolving, then adding a phase transfer catalyst and a sodium hydroxide aqueous solution, uniformly stirring, dropwise adding isobutenyl chloride, heating and stirring for reaction, carrying out GC monitoring reaction, separating liquid after the reaction is finished, washing an organic phase to be neutral by using dilute hydrochloric acid, then washing the organic phase by using a saturated NaCl aqueous solution, recovering the toluene and unreacted cyclododecanone, sending the residual organic phase into a rectifying kettle, and rectifying to obtain 2-isobutenyl cyclododecanone;
(2) preparation of 14-methylbicyclo [10.3.0] -1, 13-pentadecadiene
Loading a solid heteropoly acid catalyst into a gas phase reactor, heating to 230 ℃ under nitrogen purging, then decompressing, sending 2-isobutenyl cyclododecanone into the gas phase reactor, continuing to heat and react at 300 ℃, cooling reaction gas in a cooling tower, and rectifying to obtain 14-methyl bicyclo [10.3.0] -1, 13-pentadecadiene;
the synthesis process provided by the invention has the main advantages that: the method has the advantages of simple and direct route, high total yield, environmental friendliness and easy realization of industrial production; the gas phase ring-closing production process catalyzed by heteropoly acid needs no reaction solvent, hardly produces waste water and waste gas, can recycle the catalyst, and has high raw material conversion rate and high product purity.
Detailed Description
Example 1
Preparation of 2-isobutenylcyclododecanone
Adding cyclododecanone (364Kg,2000mol) and toluene (200L) into a reaction kettle, stirring for dissolving, then adding a phase transfer catalyst TEBA (9.1Kg,40mol) and a 50% sodium hydroxide aqueous solution (480Kg,6000mol), stirring uniformly, dropwise adding isobutenyl chloride (198Kg, 2200mol), heating the reaction system to 80 ℃, continuing stirring for reaction, monitoring the reaction by GC, and stopping the reaction when the content of the cyclododecanone is lower than 10%. And (6) separating. The organic phase was washed with 10% HCl to pH 7 and then with saturated aqueous NaCl to recover toluene and unreacted cyclododecanone, and the remaining organic phase was fed to a rectifying still and rectified to obtain 2-isobutenylcyclododecanone (331Kg, 70% yield).
Example 2
Preparation of 14-methylbicyclo [10.3.0] -1, 13-pentadecadiene
Loading 11.5Kg of phosphotungstic acid (4 mol) as a solid heteropolyacid catalyst into a gas phase reactor with the diameter of 0.16 m and the length of 5 m, heating the gas phase reactor to 230 ℃ under the purging of nitrogen, reducing the pressure in the gas phase reactor to 30mmHg, sending 2-isobutenyl cyclododecanone (47Kg,200mol) into the gas phase reactor at the speed of 6.0Kg/h by using a quantitative pump, continuously maintaining the reaction at the temperature of 230 ℃ for 300 ℃, after the reaction is finished, sending the reaction gas into a cooling tower for cooling, sending the cooled mixed solution into a rectifying kettle, and rectifying to obtain 14-methylbicyclo [10.3.0] -1, 13-pentadecadiene (39Kg, the yield is 90%, the conversion rate is 99%, and the purity is 95%). The solid heteropoly acid catalyst phosphotungstic acid is continuously recycled for 6 times.
TABLE 1 Effect of catalyst recycle on conversion and yield
Claims (5)
1. A synthesis process for industrially producing 14-methylbicyclo [10.3.0] -1, 13-pentadecadiene is characterized by comprising the following steps: cyclododecanone is taken as a starting material, and nucleophilic substitution reaction is firstly carried out on the cyclododecanone and isobutenyl chlorine under the alkaline condition to generate 2-isobutenyl cyclododecanone; then gas phase cyclization is carried out under the catalysis of a solid heteropoly acid catalyst to directly obtain 14-methyl bicyclo [10.3.0] -1, 13-pentadecadiene.
2. The synthesis process for industrially producing 14-methylbicyclo [10.3.0] -1, 13-pentadecadiene according to claim 1, wherein the gas-phase cyclization is carried out under the catalysis of a solid heteropolyacid catalyst, and the gas-phase cyclization comprises the following steps: the solid heteropoly acid catalyst is filled into a gas phase reactor, heated to 230 ℃ under the nitrogen purging, decompressed, sent into the gas phase reactor, continuously heated to 300 ℃ for reaction at 230-.
3. The synthesis step according to claim 2, characterized in that the solid heteropolyacid catalyst used for the synthesis of 14-methylbicyclo [10.3.0] -1, 13-pentadecadiene is phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, silicomolybdic acid, preferably the solid heteropolyacid catalyst phosphotungstic acid.
4. The synthesis procedure according to claim 2, characterized in that the amount of phosphotungstic acid as solid heteropolyacid catalyst used for the synthesis of 14-methylbicyclo [10.3.0] -1, 13-pentadecadiene is 1-5%, preferably 2%.
5. The synthesis step according to claim 2, characterized in that the temperature range for the synthesis of 14-methylbicyclo [10.3.0] -1, 13-pentadecadiene is 230-300 ℃, preferably 250-260 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201810822337.9A CN110746262A (en) | 2018-07-24 | 2018-07-24 | Synthesis process of compound |
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| CN201810822337.9A CN110746262A (en) | 2018-07-24 | 2018-07-24 | Synthesis process of compound |
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| CN110746262A true CN110746262A (en) | 2020-02-04 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08239332A (en) * | 1994-12-29 | 1996-09-17 | Nippon Petrochem Co Ltd | Production of cyclopentadiene |
| CN1827563A (en) * | 2006-04-06 | 2006-09-06 | 武汉大学 | Process for preparing 1,1'-spiro indan or derivatives thereof |
| CN101624326A (en) * | 2009-08-20 | 2010-01-13 | 上海力智生化科技有限公司 | Synthesis method of macro cyclic ketone intermediate 14-methyl bicycle [10, 3, 0] pentadecyl-1-alkene |
| WO2012045786A1 (en) * | 2010-10-07 | 2012-04-12 | Basf Se | Process for preparing ketones, in particular macrocyclic ketones |
-
2018
- 2018-07-24 CN CN201810822337.9A patent/CN110746262A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08239332A (en) * | 1994-12-29 | 1996-09-17 | Nippon Petrochem Co Ltd | Production of cyclopentadiene |
| CN1827563A (en) * | 2006-04-06 | 2006-09-06 | 武汉大学 | Process for preparing 1,1'-spiro indan or derivatives thereof |
| CN101624326A (en) * | 2009-08-20 | 2010-01-13 | 上海力智生化科技有限公司 | Synthesis method of macro cyclic ketone intermediate 14-methyl bicycle [10, 3, 0] pentadecyl-1-alkene |
| WO2012045786A1 (en) * | 2010-10-07 | 2012-04-12 | Basf Se | Process for preparing ketones, in particular macrocyclic ketones |
Non-Patent Citations (1)
| Title |
|---|
| KOSCHINSKY, RAINER ET AL: "Synthesis of highly alkylated functionalized cyclopentadienes", 《TETRAHEDRON LETTERS》 * |
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