CN111548250B

CN111548250B - Method for preparing 3-carenol from 3-carene

Info

Publication number: CN111548250B
Application number: CN202010363320.9A
Authority: CN
Inventors: 郑启航; 张剑平; 郑艺辉; 郑祎敏; 杨毅融
Original assignee: Xiamen Doingcom Chemical Co ltd
Current assignee: Xiamen Doingcom Chemical Co ltd
Priority date: 2020-04-30
Filing date: 2020-04-30
Publication date: 2023-10-20
Anticipated expiration: 2040-04-30
Also published as: CN111548250A

Abstract

A method for preparing 3-carene from 3-carene, which relates to the deep processing of 3-carene. Mixing 3-carene, an oxidant and a solvent, stirring, heating, reacting, adding acetic anhydride, washing and flash evaporating to obtain 3, 4-epoxycarene; the 3, 4-epoxycarane is hydrogenated and ring-opened by a catalyst, and the 3-carane alcohol is obtained after rectification and purification. The 3-carene is converted into 3-carene alcohol by epoxidation and hydrogenation ring opening, and the 3-carene alcohol has higher yield, has the prospect of replacing other terpene alcohols such as terpineol, and can obtain higher economic benefit.

Description

Method for preparing 3-carenol from 3-carene

Technical Field

The invention relates to deep processing of 3-carene, in particular to a method for preparing 3-carene alcohol for 3-carene.

Background

3-carene is the main component of monoterpene in essential oil, has strong pine-like fragrance, can be mixed with oil, is insoluble in water, is easy to generate oxidation reaction, needs low-temperature airtight preservation, and is easy to rapidly oxidize after being exposed to air. The chemical name of 3-carene is 3, 7-trimethyl bicyclo [4.1.0] -3-heptene, and the molecular formula is C10H16. 3-carene is used as chiral substances which contain three-membered rings in nature, and is mainly used in various essential oils such as turpentine, pepper oil, angelica sinensis oil and the like, for example, the content of the 3-carene in the European red pine oil can reach 40% -45%, and the content of the 3-12% in the angelica sinensis oil, thus the 3-carene belongs to natural equivalent perfume. Can be applied to various edible essence formulas, or can be directly used for medicines, pesticides and cosmetics, can also be used as a synthetic intermediate of the pesticides and the medicines, and can also be used as one of the irreplaceable raw materials in a plurality of valuable chemicals such as plasticizers, non-infectious solvents and the like.

Chinese patent CN02150901.8 discloses a method for preparing epoxypinane from pinene using sodium peroxycarbonate as a reagent. Sodium percarbonate is used as a reagent, acetic anhydride is added during the reaction, a phase transfer catalyst is added when necessary, the reaction is controlled below 60 ℃, and the epoxy pinane can be obtained after the reaction for 1-24 hours.

Disclosure of Invention

The invention aims to provide a method for preparing 3-carene by using 3-carene, which can fully utilize turpentine byproduct 3-carene to successfully prepare 3-carene and increase the application of monoterpene alcohol products.

The invention comprises the following steps:

1) Mixing 3-carene, an oxidant and a solvent, stirring, heating, reacting, adding acetic anhydride, washing and flash evaporating to obtain 3, 4-epoxycarene;

in the step 1), the addition amount of 3-carene and the oxidant can be 1: (1-1.2), the addition amount of the oxidant and the acetic anhydride can be 1: (0.8-1.0), and the addition amount of the solvent and 3-carene can be (2-2.6):1 according to the molar ratio; the oxidizing agent can be selected from sodium peroxycarbonate and the like; the solvent may be selected from 2, 4-dioxane and the like; the temperature of the heating reaction can be 50-60 ℃, and the time of the heating reaction can be 6-10 h.

2) The 3, 4-epoxycarane obtained in the step 1) is hydrogenated and ring-opened by adopting a catalyst, and the 3-carane alcohol product is obtained after rectification and purification.

In step 2), the catalyst may be a Raney-Ni catalyst; the hydrogenation ring opening can be performed under the conditions of the temperature of 120-135 ℃ and the hydrogen pressure of 3-3.5 MPa.

The method converts 3-carene into 3-carene by an epoxidation and hydrogenation ring-opening method, has higher yield, has the prospect of replacing other terpene alcohols such as terpineol, and can obtain higher economic benefit.

Detailed Description

The following examples will illustrate the invention further.

Example 1

180g of 3-carene, 210g of sodium peroxycarbonate and 450g of 2, 4-dioxane are added into a 1000ml three-necked flask, the mixture is heated to 50 ℃ under the condition of rapid stirring, 159g of acetic anhydride is added dropwise, the reaction temperature is kept at 50-55 ℃, stirring is continued for 2 hours after the addition, sampling is carried out and sample introduction tracking is carried out by GC until the 3-carene is basically reacted completely, the required time is 7-9 hours, 400g of water is added after the reaction is finished to dissolve solid inorganic salt, after the separation, an oil layer is firstly washed once by using 200g of 10% sodium hydroxide solution, then is washed once by using 200g of 10% sodium chloride solution, and the pH value is approximately equal to 8. Recovering the solvent, rectifying, and collecting 118-122/20 kPa fractions. The GC content of the 3, 4-epoxycarane is more than 99 percent, and the yield is 80 to 85 percent.

20g of 3, 4-epoxycarene, 15g of absolute ethyl alcohol, 1g of Raney-Ni catalyst and 0.04g of sodium hydroxide are taken and added into a hydrogenation kettle, after the gas trisome in the kettle is replaced by nitrogen, the pressure of hydrogen in the kettle is kept at 2.5-3.0 mPa, the reaction temperature is 120 ℃ for 10-15 hours, the catalyst is filtered after the reaction is finished, the ethanol solvent is removed, and the 3-carane alcohol is obtained by flash evaporation. The 3-carane alcohol content is more than 90 percent, and the yield is 78 to 83 percent.

Example 2

90g of 3-carene, 105g of sodium peroxycarbonate and 225g of 2, 4-dioxane are added into a 500ml three-necked flask, the mixture is heated to 50 ℃ under the condition of rapid stirring, 80g of acetic anhydride is dropwise added, the reaction temperature is kept at 50-55 ℃, stirring is continued for 2 hours after the addition, sampling is carried out and sample introduction tracking is carried out by GC until the 3-carene is basically reacted completely, the required time is 7-9 hours, 200g of water is added after the reaction is finished to dissolve solid inorganic salt, an oil layer is firstly washed once by 10% sodium hydroxide solution 100g after liquid separation, and then is washed once by 10% sodium chloride solution 100g, so that the pH value is approximately equal to 8 is measured. Recovering the solvent, rectifying, and collecting 118-122/20 kPa fractions. The GC content of the 3, 4-epoxycarane is more than 99 percent, and the yield is 80 to 85 percent. The 3, 4-epoxycarane is hydrogenated and ring-opened according to the embodiment 1, the 3-carane alcohol content is more than 90 percent, and the yield is 78 to 83 percent.

Example 3

45g of 3-carene, 52.5g of sodium peroxycarbonate and 112.5g of 2, 4-dioxane are added into a 250ml three-necked flask, the mixture is heated to 50 ℃ under the condition of rapid stirring, 40g of acetic anhydride is dripped, the reaction temperature is kept at 50-55 ℃, stirring is continued for 2 hours after the addition, sampling is carried out and sample introduction tracking is carried out by GC until the 3-carene is completely reacted, the required time is 7-9 hours, 100g of water is added after the reaction is finished to dissolve solid inorganic salt, after the liquid separation, an oil layer is firstly washed once by 10% of sodium hydroxide solution, then is washed once by 50g of 10% of sodium chloride solution, and the pH value is approximately equal to 8 is measured. Recovering the solvent, rectifying, and collecting 118-122/20 kPa fractions. The GC content of the 3, 4-epoxycarane is more than 99 percent, and the yield is 80 to 85 percent. The 3, 4-epoxycarane is hydrogenated and ring-opened according to the embodiment 1, the 3-carane alcohol content 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 present invention. All equivalent changes and modifications within the scope of the present invention are intended to be covered by the present invention.

Claims

1. A method for preparing 3-carene from 3-carene, which is characterized by comprising the following steps:

1) Mixing 3-carene, an oxidant and a solvent, stirring, heating, reacting, adding acetic anhydride, washing and flash evaporating to obtain 3, 4-epoxycarene; the addition amount of the 3-carene and the oxidant is 1: (1-1.2) according to the mol ratio; the addition amount of the oxidant and the acetic anhydride is 1: (0.8-1.0) according to the mol ratio; the addition amount of the solvent and 3-carene is (2.0-2.6):1 according to the mol ratio;

the oxidant is selected from sodium peroxycarbonate; the solvent is selected from 2, 4-dioxane; the temperature of the heating reaction is 50-60 ℃, and the heating reaction time is 6-10 h;

2) Adding sodium hydroxide into the 3, 4-epoxycarane obtained in the step 1), carrying out hydrogenation ring opening by using a catalyst, and rectifying and purifying to obtain a product 3-carane alcohol; the catalyst is a Raney-Ni catalyst; the hydrogenation ring opening is hydrogenation ring opening under the conditions of the temperature of 120-135 ℃ and the hydrogen pressure of 3-3.5 MPa.