CN111548250A - Method for preparing 3-carene alcohol from 3-carene - Google Patents
Method for preparing 3-carene alcohol from 3-carene Download PDFInfo
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- CN111548250A CN111548250A CN202010363320.9A CN202010363320A CN111548250A CN 111548250 A CN111548250 A CN 111548250A CN 202010363320 A CN202010363320 A CN 202010363320A CN 111548250 A CN111548250 A CN 111548250A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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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
- C07C2602/20—All rings being cycloaliphatic the ring system containing seven carbon atoms
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Abstract
A method for preparing 3-carene alcohol from 3-carene relates to deep processing of 3-carene. Mixing 3-carene, an oxidant and a solvent, stirring and heating for reaction, adding acetic anhydride, washing and flashing to obtain 3, 4-epoxycarene; and (3) carrying out ring opening on the obtained 3, 4-epoxycarane by adopting a catalyst through hydrogenation, and carrying out rectification and purification to obtain the product 3-carane alcohol. The method converts 3-carene into 3-carene alcohol by epoxidation and hydrogenation ring opening, has higher yield, has the prospect of replacing other terpene alcohols such as terpineol, and can obtain higher economic benefit.
Description
Technical Field
The invention relates to deep processing of 3-carene, in particular to a method for preparing 3-carene alcohol from 3-carene.
Background
The 3-carene is a main component of monoterpene in the essential oil, has strong pine-like fragrance, can be mixed with oil, is insoluble in water, is easy to generate oxidation reaction, needs to be stored in a low-temperature closed manner, and is easy to oxidize quickly after being exposed in air. The chemical name of 3-carene is 3,7, 7-trimethylbicyclo [4.1.0] -3-heptene, and the molecular formula is C10H 16. The 3-carene is a chiral substance which is few and contains three-membered rings in nature, mainly exists in various essential oils such as turpentine, pepper oil, angelica rotundifolia oil and the like, for example, the content of the turpentine oil can reach 40-45 percent, and the content of the angelica rotundifolia oil can reach 3-12 percent, and belongs to natural equivalent spices. The product can be applied to various edible essence formulas, or can be directly used for medicines, pesticides and cosmetics, and can also be used as a synthetic intermediate of pesticides and medicines, and also be one of the irreplaceable raw materials in a plurality of noble chemicals such as plasticizers, non-infectious solvents and the like.
Chinese patent CN02150901.8 discloses a method for preparing epoxy pinane from pinene using sodium peroxycarbonate as a reagent. And (2) taking sodium percarbonate as a reagent, adding acetic anhydride during reaction, adding a phase transfer catalyst if necessary, controlling the reaction at the temperature below 60 ℃, and reacting for 1-24 hours to obtain the epoxy pinane.
Disclosure of Invention
The invention aims to provide a method for preparing 3-carene alcohol from 3-carene, which can fully utilize turpentine byproduct 3-carene, successfully prepare 3-carene alcohol and increase the application of monoterpene alcohol products.
The invention comprises the following steps:
1) mixing 3-carene, an oxidant and a solvent, stirring and heating for reaction, adding acetic anhydride, washing and flashing to obtain 3, 4-epoxycarene;
in the step 1), the molar ratio of the 3-carene to the oxidant can be 1: 1-1.2, the molar ratio of the oxidant to the acetic anhydride can be 1: 0.8-1.0, and the molar ratio of the solvent to the 3-carene can be 2-2.6: 1; the oxidant can be selected from sodium peroxycarbonate and the like; the solvent can be selected from 2, 4-dioxane, etc.; the temperature of the heating reaction can be 50-60 ℃, and the time of the heating reaction can be 6-10 h.
2) Carrying out hydrogenation ring opening on the 3, 4-epoxy carane obtained in the step 1) by adopting a catalyst, and carrying out rectification purification to obtain a product 3-carane alcohol.
In step 2), the catalyst may be a Raney-Ni catalyst; the hydrogenation ring opening can be carried out at the temperature of 120-135 ℃ and the hydrogen pressure of 3-3.5 MPa.
A large amount of by-product 3-carene can be obtained in the process of extracting pinene from turpentine, the by-product 3-carene is normally treated as waste solvent oil and is not fully developed and utilized, the hydration reaction for directly preparing 3-carene from 3-carene is not easy to carry out, the yield is low, the method converts the 3-carene into the 3-carene through epoxidation and hydrogenation ring-opening methods, and meanwhile, the yield is high, the prospect of replacing other terpene alcohols such as terpineol is realized, and higher economic benefit can be obtained.
Detailed Description
The following examples further illustrate the invention.
Example 1
Adding 180g of 3-carene, 210g of sodium peroxycarbonate and 450g of 2, 4-dioxane into a 1000ml three-necked bottle, heating to 50 ℃ under a rapid stirring state, dropwise adding 159g of acetic anhydride, keeping the reaction temperature at 50-55 ℃, continuously stirring for 2h after the addition, sampling, injecting and tracking by using GC (gas chromatography) sample introduction until the 3-carene basically reacts completely, wherein the required time is 7-9 h, adding 400g of water to dissolve solid inorganic salt after the reaction is finished, washing the oil layer once by 200g of 10% sodium hydroxide solution and once by 200g of 10% sodium chloride solution after liquid separation, and measuring the pH value to be approximately 8. And recovering the solvent, rectifying, and collecting fractions of 118-122/20 kPa. The GC content of the 3, 4-epoxycarane is more than 99 percent, and the yield is 80 to 85 percent.
Adding 20g of 3, 4-epoxycarane, 15g of absolute ethyl alcohol, 1g of Raney-Ni catalyst and 0.04g of sodium hydroxide into a hydrogenation kettle, replacing a gas triplet in the kettle with nitrogen, maintaining the pressure of hydrogen in the kettle at 2.5-3.0 mPa at the reaction temperature of 120 ℃ for 10-15 h, filtering the catalyst after the reaction is finished, removing the ethanol solvent, and carrying out flash evaporation to obtain the 3-carane alcohol. The content of the 3-carane alcohol is more than 90 percent, and the yield is 78 to 83 percent.
Example 2
Adding 90g of 3-carene, 105g of sodium peroxycarbonate and 225g of 2, 4-dioxane into a 500ml three-necked bottle, heating to 50 ℃ under a rapid stirring state, dropwise adding 80g of acetic anhydride, keeping the reaction temperature at 50-55 ℃, continuously stirring for 2h after the addition, sampling, injecting and tracking by using GC (gas chromatography) sample introduction until the 3-carene basically reacts completely, wherein the required time is 7-9 h, adding 200g of water to dissolve solid inorganic salt after the reaction is finished, washing the oil layer once by using 100g of 10% sodium hydroxide solution and once by using 100g of 10% sodium chloride solution after the liquid separation is finished, and measuring the pH value to be approximately 8. And recovering the solvent, rectifying, and collecting fractions of 118-122/20 kPa. The GC content of the 3, 4-epoxycarane is more than 99 percent, and the yield is 80 to 85 percent. The ring opening of the 3, 4-epoxy carane is carried out by hydrogenation according to the embodiment 1, the content of the 3-carane alcohol is more than 90 percent, and the yield is 78 to 83 percent.
Example 3
Adding 45g of 3-carene, 52.5g of sodium percarbonate and 112.5g of 2, 4-dioxane into a 250ml three-necked bottle, heating to 50 ℃ under a rapid stirring state, dropwise adding 40g of acetic anhydride, keeping the reaction temperature at 50-55 ℃, continuously stirring for 2h after the addition, sampling, carrying out sample injection tracking by using GC (gas chromatography), until the 3-carene basically reacts completely, wherein the required time is 7-9 h, adding 100g of water to dissolve solid inorganic salt after the reaction is finished, washing the oil layer once by using 50g of 10% sodium hydroxide solution after the liquid separation, then washing once by using 50g of 10% sodium chloride solution, and measuring the pH value to be approximately 8. And recovering the solvent, rectifying, and collecting fractions of 118-122/20 kPa. The GC content of the 3, 4-epoxycarane is more than 99 percent, and the yield is 80 to 85 percent. The ring opening of the 3, 4-epoxy carane is carried out by hydrogenation according to the embodiment 1, the content of the 3-carane alcohol is more than 90 percent, and the yield is 78 to 83 percent.
The above-described embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the scope of the invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (9)
1. A method for preparing 3-carene alcohol from 3-carene is characterized by comprising the following steps:
1) mixing 3-carene, an oxidant and a solvent, stirring and heating for reaction, adding acetic anhydride, washing and flashing to obtain 3, 4-epoxycarene;
2) carrying out hydrogenation ring opening on the 3, 4-epoxy carane obtained in the step 1) by adopting a catalyst, and carrying out rectification purification to obtain a product 3-carane alcohol.
2. The method for preparing 3-carene alcohol from 3-carene of claim 1, wherein in the step 1), the 3-carene and the oxidant are added in a molar ratio of 1: 1-1.2.
3. The method for preparing 3-carene alcohol from 3-carene of claim 1, wherein in the step 1), the oxidant and the acetic anhydride are added in a molar ratio of 1: 0.8-1.0.
4. The method for preparing 3-carene alcohol from 3-carene in the step 1), wherein the adding amount of the solvent and the 3-carene in the molar ratio of (2.0-2.6): 1 is performed in the step 1).
5. The process for preparing 3-carene alcohol from 3-carene according to claim 1, wherein in step 1), the oxidizing agent is selected from sodium percarbonate peroxide.
6. The process for preparing 3-carene alcohol from 3-carene according to claim 1, wherein in the step 1), the solvent is selected from 2, 4-dioxane.
7. The method for preparing 3-carene alcohol from 3-carene according to claim 1, wherein in the step 1), the temperature of the heating reaction is 50-60 ℃, and the time of the heating reaction is 6-10 h.
8. The process for preparing 3-carene alcohol from 3-carene of claim 1, wherein in step 2), the catalyst is Raney-Ni catalyst.
9. The method for preparing 3-carene alcohol from 3-carene according to claim 1, wherein in the step 2), the ring opening by hydrogenation is performed under the conditions of the temperature of 120-135 ℃ and the hydrogen introducing pressure of 3-3.5 MPa.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1422853A (en) * | 2002-11-28 | 2003-06-11 | 复旦大学 | Method for preparing epoxy pinane using sodium percarbonate as reagent |
| CN101973838A (en) * | 2010-10-28 | 2011-02-16 | 岳阳昌德化工实业有限公司 | Method for purifying beta-pinene and preparing alpha-epoxy pinane from turpentine oil |
| CN102060671A (en) * | 2010-12-16 | 2011-05-18 | 上海应用技术学院 | Method for preparing 3,4-carane diol as mosquito and fly evading agent |
| CN102173975A (en) * | 2011-03-25 | 2011-09-07 | 中国林业科学研究院林产化学工业研究所 | Preparation method of carane |
| CN103755665A (en) * | 2014-02-21 | 2014-04-30 | 广西民族大学 | Preparation method of 3,4-epoxycarane |
| CN104151126A (en) * | 2014-08-13 | 2014-11-19 | 广西梧松林化集团有限公司 | Method for synthesizing carane through 3-carene hydrogenation |
| CN104151141A (en) * | 2014-08-26 | 2014-11-19 | 广西梧松林化集团有限公司 | Method for preparing 3-carane-2-ol from 3-carane |
| CN104230666A (en) * | 2014-08-26 | 2014-12-24 | 广西梧松林化集团有限公司 | Method for preparing terpineol from 3-carene |
| CN110668915A (en) * | 2018-07-03 | 2020-01-10 | 岳阳昌德环境科技有限公司 | Method for preparing cyclohexanol |
-
2020
- 2020-04-30 CN CN202010363320.9A patent/CN111548250B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1422853A (en) * | 2002-11-28 | 2003-06-11 | 复旦大学 | Method for preparing epoxy pinane using sodium percarbonate as reagent |
| CN101973838A (en) * | 2010-10-28 | 2011-02-16 | 岳阳昌德化工实业有限公司 | Method for purifying beta-pinene and preparing alpha-epoxy pinane from turpentine oil |
| CN102060671A (en) * | 2010-12-16 | 2011-05-18 | 上海应用技术学院 | Method for preparing 3,4-carane diol as mosquito and fly evading agent |
| CN102173975A (en) * | 2011-03-25 | 2011-09-07 | 中国林业科学研究院林产化学工业研究所 | Preparation method of carane |
| CN103755665A (en) * | 2014-02-21 | 2014-04-30 | 广西民族大学 | Preparation method of 3,4-epoxycarane |
| CN104151126A (en) * | 2014-08-13 | 2014-11-19 | 广西梧松林化集团有限公司 | Method for synthesizing carane through 3-carene hydrogenation |
| CN104151141A (en) * | 2014-08-26 | 2014-11-19 | 广西梧松林化集团有限公司 | Method for preparing 3-carane-2-ol from 3-carane |
| CN104230666A (en) * | 2014-08-26 | 2014-12-24 | 广西梧松林化集团有限公司 | Method for preparing terpineol from 3-carene |
| CN110668915A (en) * | 2018-07-03 | 2020-01-10 | 岳阳昌德环境科技有限公司 | Method for preparing cyclohexanol |
Non-Patent Citations (2)
| Title |
|---|
| MISRA,A.N.等: "Monoterpenoids. VI.On the optical purity of (+)-car-3-ene from Pinus roxburghii and the source of racemization of (-)-menthol derived therefrom", 《TETRAHEDRON(1988)》, vol. 44, no. 22, 31 December 1988 (1988-12-31), pages 5 - 6 * |
| MORRIS FREIFELDER: "中等专业学校教学用书，基本有机合成工艺学", 安徽省化工研究所, pages: 199 * |
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