CN113480498B

CN113480498B - Biomass-based gamma-octadecanolide synthesis method

Info

Publication number: CN113480498B
Application number: CN202110844784.6A
Authority: CN
Inventors: 王天义; 范一义; 汪洋; 张政; 吴旭; 何云飞; 汪炎
Original assignee: Anhui Hyea Aromas Co ltd
Current assignee: Anhui Hyea Aromas Co ltd
Priority date: 2021-07-26
Filing date: 2021-07-26
Publication date: 2022-11-29
Anticipated expiration: 2041-07-26
Also published as: CN113480498A

Abstract

The invention relates to a synthetic method based on biomass-based gamma-octadecanolactone, which belongs to the technical field of perfume synthesis and specifically comprises the following steps: firstly, mixing a solvent and oleic acid, adding a catalyst and an additive at the temperature of 0-5 ℃, and heating and refluxing for 8-10 hours at the temperature of 70-85 ℃; and step two, after the reaction is finished, filtering, extracting the filtrate by using deionized water and diethyl ether, concentrating the obtained organic phase under reduced pressure, and drying to obtain the gamma-octadecanolactone. The invention also prepares an additive in the synthesis process, the additive takes the diatomite as a raw material, the micropore structure of the diatomite is more uniform after roasting, the peculiar smell generated in the reaction process can be better absorbed, and the product quality is improved.

Description

Biomass-based gamma-octadecanolide synthesis method

Technical Field

The invention belongs to the technical field of spice synthesis, and particularly relates to a biomass-based gamma-octadecanolide-based synthesis method.

Background

Saturated gamma-lactone compounds naturally exist in various fruits, are a very important edible flavor, and are widely used in various beverages, baked goods and desserts. The gamma-octadecanoic lactone is a common spice substance in the daily chemical industry field, has fruit fragrance, and has the characteristics of lasting fragrance, soft fragrance, aroma enhancement and the like, so the gamma-octadecanoic lactone is widely applied to the fields of foods, daily cosmetics, tobacco spices and the like.

The gamma-octadecanolide prepared in the existing synthesis process has obvious plastic odor or sour taste, which affects the quality of the gamma-octadecanolide.

Disclosure of Invention

The invention aims to provide a synthetic method based on biomass-based gamma-octadecanolide.

The purpose of the invention can be realized by the following technical scheme:

a synthetic method based on biomass-based gamma-octadecanolide comprises the following steps:

firstly, mixing a solvent and oleic acid, adding a catalyst and an additive at the temperature of 0-5 ℃, and heating and refluxing for 8-10h at the temperature of 70-85 ℃;

and step two, after the reaction is finished, filtering, extracting the filtrate by using deionized water and diethyl ether, concentrating the obtained organic phase under reduced pressure, and drying to obtain the gamma-octadecanolactone. In the reaction process, double bonds in oleic acid molecules firstly migrate, and under the action of a catalyst, carbon cations are quickly shifted from delta 9 to delta 4, and carbon chains are cyclized to generate gamma-octadecanolactone.

The reaction process is as follows:

further, the catalyst is one of concentrated sulfuric acid with a mass fraction of 98% and perchloric acid with a mass fraction of 70%.

Further, the solvent is one of n-hexane and chloroform.

Further, the temperature at the time of drying is 30 to 40 ℃.

Further, the additive is prepared by the following steps:

step S11, mixing diatomite and deionized water, stirring and mixing for 30-50min at 50-75 ℃, then sieving with a 100-mesh sieve, drying at 40 ℃ to constant weight, roasting at 700-800 ℃ for 2h, and cooling to obtain solid A;

and S12, mixing the solid A and an alkali solution, reacting for 1h at the temperature of 50-60 ℃, washing the reacted solution with distilled water after the reaction is finished until the washing liquid is neutral, and drying to constant weight at the temperature of 40 ℃ after the washing is finished to obtain the additive.

Further, in the step S11, the mass ratio of the diatomite to the deionized water is 1:20.

further, the alkaline solution in the step S12 is one of a sodium hydroxide aqueous solution and ammonia water, and the mass fraction of the alkaline solution is 15%; the dosage ratio of the solid A to the alkali solution is 1g:3mL.

The invention has the beneficial effects that:

the method takes biomass-based oleic acid as a raw material to prepare the gamma-octadecalactone, double bonds in oleic acid molecules are firstly transferred in the reaction process, and carbon chains are cyclized to generate the gamma-octadecalactone when carbocation is rapidly shifted from delta 9 to delta 4 under the action of a catalyst. The additive is prepared in the synthesis process, diatomite is used as a raw material, the micropore structure of the diatomite is more uniform after roasting, peculiar smell generated in the reaction process can be better absorbed, the product quality is improved, the synthesis procedures are reduced, on the other hand, alkali solution can react with metal oxide in the diatomite, the content of the metal oxide is reduced, the content of silicon dioxide is increased, the silicon dioxide has a certain catalytic effect on the isomerization reaction of olefin, and the product yield is improved.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

Preparing an additive:

step S11, mixing diatomite and deionized water, stirring and mixing for 30min at 50 ℃, then sieving with a 100-mesh sieve, drying at 40 ℃ to constant weight, roasting at 700 ℃ for 2h, and cooling to room temperature to obtain solid A; wherein the mass ratio of the diatomite to the deionized water is 1:20;

and S12, mixing the solid A and an alkali solution, reacting for 1h at the temperature of 50 ℃, washing the reacted solution with distilled water after the reaction is finished until the washing liquid is neutral, and drying to constant weight at the temperature of 40 ℃ after the washing is finished to obtain the additive. The aqueous alkali is sodium hydroxide aqueous solution, and the mass fraction of the aqueous alkali is 15%; the dosage ratio of the solid A to the alkali solution is 1g:3mL.

Example 2

Preparing an additive:

step S11, mixing diatomite and deionized water, stirring and mixing for 50min at 75 ℃, then sieving with a 100-mesh sieve, drying at 40 ℃ to constant weight, roasting at 800 ℃ for 2h, and cooling to room temperature to obtain solid A; wherein the mass ratio of the diatomite to the deionized water is 1:20;

and S12, mixing the solid A and an alkali solution, reacting for 1h at the temperature of 60 ℃, washing the reacted solution with distilled water after the reaction is finished until the washing liquid is neutral, and drying to constant weight at the temperature of 40 ℃ after the washing is finished to obtain the additive. The aqueous alkali is ammonia, and the mass fraction of the aqueous alkali is 15%; the dosage ratio of the solid A to the alkali solution is 1g:3mL.

Example 3

The synthetic method based on biomass-based gamma-octadecanolide comprises the following steps:

firstly, mixing a solvent and oleic acid, adding a catalyst and an additive at the temperature of 0 ℃, and heating and refluxing for 8 hours at the temperature of 70 ℃;

and step two, after the reaction is finished, filtering, extracting the filtrate by using deionized water and diethyl ether, concentrating the obtained organic phase under reduced pressure, and drying to obtain the gamma-octadecalactone.

Wherein the catalyst is concentrated sulfuric acid with the mass fraction of 98%; the solvent is n-hexane. The temperature during drying was 30 ℃. The additive was prepared as in example 1.

Example 4

firstly, mixing a solvent and oleic acid, adding a catalyst and an additive at the temperature of 0 ℃, and heating and refluxing for 9 hours at the temperature of 80 ℃;

and step two, after the reaction is finished, filtering, extracting the filtrate by using deionized water and diethyl ether, concentrating the obtained organic phase under reduced pressure, and drying to obtain the gamma-octadecanolactone.

Wherein the catalyst is concentrated sulfuric acid with the mass fraction of 98%. The solvent is n-hexane. The temperature during drying was 30 ℃. The additive was prepared as in example 1.

Example 5

A synthetic method based on biomass-based gamma-octadecalactone comprises the following steps:

firstly, mixing a solvent and oleic acid, adding a catalyst and an additive at the temperature of 5 ℃, and heating and refluxing for 10 hours at the temperature of 85 ℃;

Wherein the catalyst is perchloric acid with the mass fraction of 70%. The solvent is chloroform. The temperature during drying was 40 ℃. The additive was prepared as in example 1.

Comparative example 1

Preparing an additive:

step S11, mixing diatomite and deionized water, stirring and mixing for 30min at 50 ℃, then sieving with a 100-mesh sieve, drying at 40 ℃ to constant weight, roasting for 2h at 700 ℃, and cooling to room temperature to obtain solid A; wherein the mass ratio of the diatomite to the deionized water is 1:20;

comparative example 2

The additive of example 4 was replaced with solid a prepared in comparative example 1, and the remaining raw materials and preparation process were kept unchanged.

Comparative example 3

The additive of example 4 was not added, and the remaining raw materials and preparation process remained unchanged.

The yields of the samples prepared in examples 3 to 5 and comparative examples 2 to 3, and the odors of the samples were measured; the results are shown in table 1 below:

TABLE 1

	Example 3	Example 4	Example 5	Comparative example 2	Comparative example 3
						Smell(s)	No plastic smell	No plastic smell	No plastic smell	No plastic smell	Has plastic smell
Yield/%	78.2	78.9	78.4	68.8	68.2

As can be seen from Table 1 above, the odor of the product obtained in the present invention is superior, and the yield of the product obtained by the method is higher.

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.

Claims

1. A synthetic method based on biomass-based gamma-octadecanolide is characterized by comprising the following steps:

firstly, mixing a solvent and oleic acid, adding a catalyst and an additive at the temperature of 0-5 ℃, and heating and refluxing for 8-10 hours at the temperature of 70-85 ℃;

step two, after the reaction is finished, filtering, extracting the filtrate by using deionized water and diethyl ether, concentrating the obtained organic phase under reduced pressure, and drying to obtain gamma-octadecanolactone;

the additive is prepared by the following steps:

step S11, mixing diatomite and deionized water, stirring and mixing for 30-50min at 50-75 ℃, then sieving with a 100-mesh sieve, drying at 40 ℃ to constant weight, roasting at 700-800 ℃ for 2h, and cooling to obtain solid A; the mass ratio of the diatomite to the deionized water is 1:20;

s12, mixing the solid A and an alkali solution, reacting for 1h at the temperature of 50-60 ℃, washing the reacted solution with distilled water after the reaction is finished until the washing solution is neutral, and drying to constant weight at the temperature of 40 ℃ after the washing is finished to obtain an additive; the alkali solution is one of a sodium hydroxide aqueous solution and ammonia water, and the mass fraction of the alkali solution is 15%; the dosage ratio of the solid A to the alkali solution is 1g:3mL.

2. The method for synthesizing gamma-octadecalactone based on biomass according to claim 1, wherein the catalyst is one of concentrated sulfuric acid with a mass fraction of 98% and perchloric acid with a mass fraction of 70%.

3. The method for synthesizing gamma-octadecalactone based on biomass according to claim 1, wherein the solvent is one of n-hexane and chloroform.

4. The method for synthesizing gamma-octadecalactone based on biomass according to claim 1, wherein the temperature for drying is 30-40 ℃.