CN110590524A - Method for preparing amyl cyclopentenone without isomerization of organic solvent in synthesis of methyl dihydrojasmonate - Google Patents
Method for preparing amyl cyclopentenone without isomerization of organic solvent in synthesis of methyl dihydrojasmonate Download PDFInfo
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- CN110590524A CN110590524A CN201910912460.4A CN201910912460A CN110590524A CN 110590524 A CN110590524 A CN 110590524A CN 201910912460 A CN201910912460 A CN 201910912460A CN 110590524 A CN110590524 A CN 110590524A
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- isomerization
- organic solvent
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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
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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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
Abstract
The invention discloses a method for preparing amyl cyclopentenone by organic solvent-free isomerization in methyl dihydrojasmonate synthesis, which comprises the following steps: stirring and mixing p-toluenesulfonic acid and acetic anhydride in a reactor, heating to 120 +/-2 ℃ under stirring, dropwise adding pentylene cyclopentanone, after dropwise adding, keeping the temperature at 118 ℃ and 122 ℃ and stirring for 2-4h, after the reaction is finished, cooling, adjusting the pH of the reaction solution to 7.5-9 by using a sodium carbonate solution, standing and layering, wherein the oil phase is a crude product of pentylcyclopentenone. In the isomerization process, no organic solvent is used, and clean and green production is realized.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, relates to synthesis of perfume compounds, and particularly relates to a method for preparing pentalenone by isomerization without organic solvent in synthesis of methyl dihydrojasmonate.
Background
Jasmine flower fragrance compounds have been studied for several tens of years, and with the increasing demand for such compounds, the industrialization rate is far from meeting the demand. Methyl Dihydrojasmonate (MDJ) belongs to jasmone compounds, is one of important artificially synthesized jasmine perfumes, has no related report that the methyl dihydrojasmonate exists in natural perfume, and is an important perfume variety in the modern perfume industry due to relatively low price and wide application range. The liquid fragrance agent is colorless or light yellow transparent liquid in appearance, has stable chemical property, and has the advantages of slow volatilization, long fragrance retention time, no discoloration when used for blending fragrance, and the like. Not only can be applied to cosmetics, but also can be used as a synergist in food essence and can be used as a coordinator of other flower fragrance essences.
Since the forties of the last century, people began to explore the artificial synthesis of methyl dihydrojasmonate, and through years of research, dozens of different synthetic routes have been developed, thus achieving considerable success. At present, the industrial production route of methyl dihydrojasmonate is mainly to obtain a key 2-pentyl-2-cyclopentenone intermediate from cyclopentanone and n-valeraldehyde through aldol condensation and strong acid isomerization, perform addition on the 2-pentyl-2-cyclopentenone intermediate by dimethyl malonate, and then perform decarboxylation to obtain a methyl dihydrojasmonate product.
The strong acid isomerization reaction adopts the process that xylene is used as a solvent, p-toluenesulfonic acid is used as an acid catalyst, acetic anhydride is used as an auxiliary catalyst, pentylene cyclopentanone is isomerized into pentylcyclopentenone, and a large amount of xylene is used in industrial production, so that the treatment cost of dangerous waste of enterprises is increased, great pressure is brought to the environment, and the sustainable development of economy and environment is not facilitated.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing the pentalenone by isomerization without an organic solvent in the synthesis of methyl dihydrojasmonate, and the clean and green production is realized without using the organic solvent in the isomerization process.
The invention is realized by the following technical scheme:
the method for preparing the pentylcyclopentenone without isomerization of an organic solvent in the synthesis of the methyl dihydrojasmonate comprises the following steps of:
stirring and mixing p-toluenesulfonic acid and acetic anhydride in a reactor, heating to 120 +/-2 ℃ under stirring, dropwise adding pentylene cyclopentanone, after dropwise adding, keeping the temperature at 118 ℃ and 122 ℃ and stirring for 2-4h, after the reaction is finished, cooling, adjusting the pH of the reaction solution to 7.5-9 by using a sodium carbonate solution, standing and layering, wherein the oil phase is a crude product of the pentylcyclopentenone, and the crude product is rectified to obtain the crude product of the pentylcyclopentenone.
The invention further improves the scheme as follows:
when the pentamethylene cyclopentanone is added, the temperature of the reaction solution is controlled at 118-122 ℃.
The dropping speed of the addition of the pentamethylene cyclopentanone is 16 ~ 24 kg/min.
The concentration of the sodium carbonate solution is 10% -13%.
The mass ratio of the pentylidene cyclopentanone to the toluenesulfonic acid to the acetic anhydride is 200:0.8 ~ 1.2.2: 20 ~ 30.
The invention has the beneficial effects that:
according to the preparation method, an organic solvent is not used, after the reaction is finished, the obtained crude product of the pentylcyclopentenone is directly obtained, distillation is not needed, and the crude product of the pentylcyclopentenone is directly rectified to obtain the finished product of the pentylcyclopentenone, so that the cost and the energy are saved, and the method is clean and pollution-free.
The acetic anhydride used in the invention is used as an auxiliary catalyst to promote the isomerization of the pentamethylene cyclopentanone to generate the pentamethylene cyclopentenone, is also used as a reaction solvent, and is also used as a water absorbent to reduce the moisture in the system, thereby being more beneficial to the isomerization.
Detailed Description
Example 1
Adding 2500kg of p-toluenesulfonic acid and 300kg of acetic anhydride into a reaction kettle, stirring uniformly, heating to 120 +/-2 ℃, stirring stably for 5min, dropwise adding 12.5kg of amylidene cyclopentanone at the dropping speed of 1250kg/min, keeping the reaction temperature of 118-122 ℃ in the dropwise adding process, keeping the temperature of 118-122 ℃ after the dropwise adding is completed, stirring for 2-4h under heat preservation at the temperature of 118-122 ℃, cooling after the reaction is completed, adjusting the pH of the reaction solution to 7.5-9 by using 10-13% sodium carbonate solution, standing for layering, removing the lower layer of water, obtaining the upper layer of oil phase which is a crude product of the amylcyclopentenone, and removing the upper layer of oil phase which is a crude product of the amylcyclopentenone to obtain 2298g of the finished product of the amylcyclopentenone, wherein the purity is 94.1% and the yield.
Example 2
Adding 2500kg of p-toluenesulfonic acid and 250kg of acetic anhydride into a reaction kettle, stirring uniformly, heating to 120 +/-2 ℃, stirring stably for 5min, dropwise adding 10kg of amylidene cyclopentanone at the dropping speed of 1250kg/min, keeping the reaction temperature of 118 plus one 122 ℃ in the dropwise adding process, keeping the temperature of 118 plus one 122 ℃ after the dropwise adding is finished, stirring for 2-4h at the temperature of 118 plus one 122 ℃, cooling after the reaction is finished, adjusting the pH of the reaction solution to 7.5-9 by using 10-13% sodium carbonate solution, standing for layering, removing the lower water layer, obtaining the upper oil phase which is a crude product of the amylcyclopentenone, rectifying to obtain a finished product of the amylcyclopentenone, namely 2329g of the finished product of the amylcyclopentenone, wherein the purity is 93.6%, and the yield is 87.2%.
Example 3
Adding 2500kg of p-toluenesulfonic acid and 375kg of acetic anhydride into a reaction kettle, stirring uniformly, heating to 120 +/-2 ℃, stirring stably for 5min, dropwise adding 15kg of pentamethylene cyclopentanone, wherein the dropping speed is 1250kg/min, keeping the reaction temperature at 118 plus and 122 ℃ in the dropwise adding process, keeping the temperature at 118 plus and 122 ℃ after the dropwise adding is finished, stirring for 2-4h under heat preservation at 118 plus and 122 ℃, cooling after the reaction is finished, adjusting the pH of the reaction solution to 7.5-9 by using 10-13% sodium carbonate solution, standing for layering, removing lower water, obtaining an upper oil phase which is a crude product of the pentylcyclopentenone, rectifying to obtain a finished product of the pentylcyclopentenone, wherein 2294g of the finished product of the pentylcyclopentenone is obtained, the purity is 94.5%, and the yield is 86.7%.
Claims (5)
1. The method for preparing the pentylcyclopentenone without isomerization of an organic solvent in the synthesis of methyl dihydrojasmonate is characterized by comprising the following steps of:
stirring and mixing p-toluenesulfonic acid and acetic anhydride in a reactor, heating to 120 +/-2 ℃ under stirring, dropwise adding pentylene cyclopentanone, after dropwise adding, keeping the temperature at 118 ℃ and 122 ℃ and stirring for 2-4h, after the reaction is finished, cooling, adjusting the pH of the reaction solution to 7.5-9 by using a sodium carbonate solution, standing and layering, wherein the oil phase is a crude product of the pentylcyclopentenone, and the crude product is rectified to obtain the crude product of the pentylcyclopentenone.
2. The method for preparing the pentylcyclopentenone without isomerization of an organic solvent in the synthesis of methyl dihydrojasmonate according to claim 1, wherein: when the pentamethylene cyclopentanone is added, the temperature of the reaction solution is controlled at 118-122 ℃.
3. The method for preparing the pentylcyclopentenone without isomerization of an organic solvent in the synthesis of methyl dihydrojasmonate according to claim 1, wherein the dropping speed of the pentylenecyclopentanone is 16 ~ 24 kg/min.
4. The method for preparing the pentylcyclopentenone without isomerization of an organic solvent in the synthesis of methyl dihydrojasmonate according to claim 1, wherein: the concentration of the sodium carbonate solution is 10% -13%.
5. The method for preparing the pentylcyclopentenone without isomerization of organic solvent in the synthesis of methyl dihydrojasmonate according to claim 1, wherein the mass ratio of pentylidene cyclopentanone, toluene sulfonic acid, and acetic anhydride is 200:0.8 ~ 1.2.2: 20 ~ 30.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112321399A (en) * | 2020-12-01 | 2021-02-05 | 山东卓俊实业有限公司 | Preparation method of chemical intermediate |
| CN112479838A (en) * | 2020-12-02 | 2021-03-12 | 山东卓俊实业有限公司 | Application of imidazole carbonate in preparation of chemical intermediates |
| CN114478217A (en) * | 2022-02-18 | 2022-05-13 | 山东新和成药业有限公司 | Preparation method of 2-n-pentylcyclopent-2-enone |
Citations (1)
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| CN103058846A (en) * | 2013-01-17 | 2013-04-24 | 福州大学 | Benzoquinone derivative from aspergillus aculeatus and application of benzoquinone derivative |
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- 2019-09-25 CN CN201910912460.4A patent/CN110590524A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058846A (en) * | 2013-01-17 | 2013-04-24 | 福州大学 | Benzoquinone derivative from aspergillus aculeatus and application of benzoquinone derivative |
Non-Patent Citations (1)
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| 镇晓华: ""二氢茉莉酮酸甲酯合成工艺研究"", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112321399A (en) * | 2020-12-01 | 2021-02-05 | 山东卓俊实业有限公司 | Preparation method of chemical intermediate |
| CN112479838A (en) * | 2020-12-02 | 2021-03-12 | 山东卓俊实业有限公司 | Application of imidazole carbonate in preparation of chemical intermediates |
| CN114478217A (en) * | 2022-02-18 | 2022-05-13 | 山东新和成药业有限公司 | Preparation method of 2-n-pentylcyclopent-2-enone |
| CN114478217B (en) * | 2022-02-18 | 2023-08-08 | 山东新和成药业有限公司 | Preparation method of 2-n-amyl cyclopent-2-enone |
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Application publication date: 20191220 |