阅读说明：本技术 一种化妆品用香料中间体β-紫罗兰酮的制备方法 (Preparation method of perfume intermediate beta-ionone for cosmetics ) 是由 李金国 于 2020-08-04 设计创作，主要内容包括：本发明公开了一种化妆品用香料中间体β-紫罗兰酮的制备方法,向三口烧瓶中加入催化剂和邻二甲苯,置于10~20℃的条件下,然后向其中逐滴加假紫罗兰酮,反应40~80min后,离心分离出催化剂,再将液体产物进行精馏操作分离出目标产物β-紫罗兰酮；催化剂是通过介孔SnO<Sub>2</Sub>-ZrO<Sub>2</Sub>复合氧化物的制备、固体超强酸WO<Sub>3</Sub>/SnO<Sub>2</Sub>-ZrO<Sub>2</Sub>的制备、离子液体前驱体NMMPS的制备、锡基杂多酸型离子液体在WO<Sub>3</Sub>/SnO<Sub>2</Sub>-ZrO<Sub>2</Sub>上的原位负载而成的。本发明所制备的催化剂呈固体状态,其在循环利用过程中很容易从反应体系中分离；该催化剂酸性较强并同时具有B-L双重酸性位点,在反应过程中酸性不易流失进而强化反应活性。(The invention discloses a preparation method of a perfume intermediate beta-ionone for cosmetics, which comprises the steps of adding a catalyst and o-xylene into a three-neck flask, placing the three-neck flask at the temperature of 10-20 ℃, then dropwise adding pseudo-ionone into the three-neck flask, reacting for 40-80 min, centrifugally separating out the catalyst, and rectifying a liquid product to separate out a target product beta-ionone; the catalyst is prepared by mesoporous SnO 2 ‑ZrO 2 Preparation of composite oxide and solid super acidic WO 3 /SnO 2 ‑ZrO 2 Preparation of the ionic liquid precursor NMMPS, preparation of the tin-based heteropoly acid type ionic liquid in WO 3 /SnO 2 ‑ZrO 2 In situ. The catalyst prepared by the method is in a solid state, and can be easily separated from a reaction system in the recycling process; the catalyst has strong acidity and has B-L dual acid sites, and the acidity is not easy to lose in the reaction process so as to strengthen the reaction activity.)

1. A method for preparing a perfume intermediate beta-ionone for cosmetics is characterized by comprising the following steps: adding a catalyst and o-xylene into a three-neck flask, placing at 10-20 ℃, then dropwise adding pseudo-ionone into the three-neck flask, reacting for 40-80 min, centrifugally separating out the catalyst, and rectifying a liquid product to separate out a target product beta-ionone; the catalyst is prepared from WO₃/SnO₂-ZrO₂Super acid is combined with tin-based heteropoly acid type solid ionic liquid.

2. The process for preparing beta-ionone as a fragrance intermediate for cosmetics according to claim 1, wherein the catalyst is obtained by the following steps:

mesoporous SnO₂-ZrO₂Preparation of composite oxides

Dissolving tin tetrachloride and zirconyl nitrate into deionized water, adding CTAC (cetyltrimethyl ammonium chloride), continuing stirring for 10min, dropwise adding 0.1mol/L sodium hydroxide solution to keep the pH value of the mixed solution between 10 and 12, transferring the mixed solution into a hydrothermal reaction kettle, keeping the temperature of the hydrothermal reaction kettle at 130 to 180 ℃ for 10 to 20 h, cooling the reaction kettle to room temperature, filtering and washing the obtained product, drying the product at 110 to 130 ℃ for 6 to 12 h, and roasting the obtained product at 450 to 650 ℃ for 4 to 8h to obtain the SnO with the mesoporous structure₂-ZrO₂；

(2) Solid super acid WO₃/SnO₂-ZrO₂Preparation of

Adding equal amount of ammonium paratungstate and oxalic acid into deionized water, and then adding SnO into the deionized water₂-ZrO₂Evaporating the obtained mixed solution to dryness at 75 ℃, and then roasting the obtained product at 550 ℃ for 5 hours to obtain solid super acidic WO₃/SnO₂-ZrO₂In which WO₃The content of (A) is 25-40 wt%;

(3) preparation of ionic liquid precursor NMMPS

Adding o-xylene and 1, 3-propane sultone into a three-neck flask, transferring the three-neck flask into a water bath, dropwise adding N-methylmorpholine, keeping the temperature at 60-80 ℃, stirring and reacting for 6-12 hours, carrying out reduced pressure suction filtration on the obtained reaction solution, washing the obtained precipitate with o-xylene, and finally drying the obtained precipitate at 80-100 ℃ for 5-10 hours to obtain a solid as an ionic liquid precursor, wherein the solid is marked as NMMPS;

(4) tin-based heteropolyacid ionic liquids in WO₃/SnO₂-ZrO₂In situ loading of

Silicotungstic acid, stannous sulfate, NMMPS and solid superacid WO₃/SnO₂-ZrO₂Adding deionized water into the flask, stirring at room temperature for 30min, transferring to an oil bath at 100-120 ℃ for reflux treatment for 6-10 h, and filtering, washing and drying the product to obtain WO₃/SnO₂-ZrO₂A composite catalyst of solid superacid and tin-based heteropoly acid type ionic liquid; sn is prepared from silicotungstic acid, stannous sulfate and NMMPS in the reaction process_0.5[NMMPS]₂SiW₁₂O₄₀、Sn[NMMPS]SiW₁₂O₄₀、Sn_0.5[NMMPS]HSiW₁₂O₄₀One kind of (1).

3. The process for producing beta-ionone, which is a cosmetic perfume intermediate, according to claim 1, characterized in that: the mass ratio of the catalyst to the pseudo ionone is 1 (4-6); the mass-volume ratio of the catalyst to the o-xylene is (3-6) g/100 mL.

4. The process for producing beta-ionone, which is a cosmetic perfume intermediate, according to claim 2, characterized in that: in the step (1), the CTAC is added in an amount of 2-5 wt% of the mass of the stannic chloride and the zirconyl nitrate; the molar ratio of the stannic chloride to the zirconyl nitrate is (0.6-1): 1, and the molar concentration of the zirconyl nitrate in the mixed solution is 0.1 mol/L.

5. The process for producing beta-ionone, which is a cosmetic perfume intermediate, according to claim 2, characterized in that: in the step (3), the mass ratio of the N-methylmorpholine to the 1, 3-propane sultone is 1:1, and the molar concentration of the 1, 3-propane sultone in the o-xylene is 0.1 mol/L.

6. The process for producing beta-ionone, which is a cosmetic perfume intermediate, according to claim 2, characterized in that: in the step (4), the quantity ratio of NMMPS to silicotungstic acid is (1-2): 1, the quantity ratio of stannous sulfate to silicotungstic acid is (0.5-1.0): 1, and WO is contained in the composite catalyst₃/SnO₂-ZrO₂The mass fraction of the solid super acid is 30-60 wt%.

Technical Field

The invention belongs to the technical field of cosmetics, and particularly relates to a preparation method of a perfume intermediate beta-ionone for cosmetics.

Background

Ionone, also known as vanillin, has a flavor similar to that of cymbidium at room temperature, is an important perfume, and can be used in cosmetics, foods and beverages. The ionone mainly has two isomers of alpha and beta, wherein the alpha-ionone is mainly used in spice essence, and the beta-ionone can be added into food, cigarettes, toothpaste, soap, perfume and cosmetics for use, and is also a common medical intermediate in industry for synthesizing vitamin A, carotenoid, beta-carotene and the like.

The natural beta-ionone product is difficult to purify and low in efficiency, so that the purification is rare and few. The beta-ionone used in industrial application is mostly synthesized by cyclization by using pseudoionone as a raw material. The pseudoionone can be obtained in different products due to different cyclization conditions. Under the condition of strong acid, the product mainly contains beta-ionone; under weak acid condition, the product mainly contains alpha-ionone; under other conditions, the product is mainly gamma-ionone.

In the process of preparing ionone by pseudo ionone cyclization, H is often adopted₂SO₄、H₃PO₄And the like, but the high-concentration acid adopted in the reaction is used for catalysis, so that the operation is inconvenient, certain dangerousness is caused, the corrosion to equipment is large, the liquid acid consumption is large, the treatment after the reaction is complicated, and the environment is polluted. In addition, the cyclization reaction of the pseudo ionone under the catalysis of concentrated sulfuric acid enables a rapid reaction with violent heat release, the viscosity of a reaction system is high, the concentrated sulfuric acid is easy to stay at the bottommost layer of the system, the mixing state is difficult to control, the local overheating phenomenon is serious, and the product yield is influenced. At present, a heterogeneous system taking solid super acid as a catalyst and a homogeneous system taking acidic ionic liquid as a representative have been developed to a certain extent. The solid super acid is easy to separate from the product, can be repeatedly used, and is economical and environment-friendly; the acidic ionic liquid has the technical advantages of high catalytic efficiency and the like.

In patent CN106496006B, modified acidic functionalized ionic liquid is used for preparing beta-ionone in a catalytic manner, the conversion rate of pseudo-ionone can reach more than 99%, and the yield of beta-ionone reaches 94%; wherein the acidic functionalized ionic liquid is [ C₃SO₃HMim]HSO₄、[C₃SO₃HNhp]HSO₄[C₃SO₃HPy]HS₄One or more of; the modifier is one or more of alkaline earth metal chloride and rare earth metal chloride. But the ionic liquid is still present in liquid form, which isThe loss is severe during the circulation.

Therefore, a novel efficient, economic and environment-friendly green catalyst is developed to replace the traditional liquid acid catalyst for synthesizing ionone, so that the environment is protected and a green chemical concept is developed.

Disclosure of Invention

In order to solve the problems in the prior art, the invention discloses a preparation method of a perfume intermediate beta-ionone for cosmetics, which is prepared by mixing WO₃/SnO₂-ZrO₂The super acid is combined with the tin-based heteropoly acid type solid ionic liquid and applied to the conversion of pseudo ionone into beta ionone.

The invention is realized by the following technical scheme:

the invention discloses a preparation method of a perfume intermediate beta-ionone for cosmetics, which comprises the steps of adding a catalyst and o-xylene into a three-neck flask, placing the three-neck flask at 10-20 ℃, dropwise adding pseudo-ionone into the three-neck flask, reacting for 40-80 min, centrifugally separating out the catalyst, and rectifying a liquid product to separate out a target product beta-ionone; the catalyst is prepared from WO₃/SnO₂-ZrO₂Super acid is combined with tin-based heteropoly acid type solid ionic liquid. Preferably, the mass ratio of the catalyst to the pseudo-ionone is 1 (4-6); the mass-volume ratio of the catalyst to the o-xylene is (3-6) g/100 mL.

Wherein, the catalyst is realized by the following specific steps:

(1) mesoporous SnO₂-ZrO₂Preparation of composite oxides

Dissolving tin tetrachloride and zirconyl nitrate into deionized water, adding CTAC (cetyltrimethyl ammonium chloride), continuing stirring for 10min, dropwise adding 0.1mol/L sodium hydroxide solution to keep the pH value of the mixed solution between 10 and 12, transferring the mixed solution into a hydrothermal reaction kettle, keeping the temperature of the hydrothermal reaction kettle at 130 to 180 ℃ for 10 to 20 h, cooling the reaction kettle to room temperature, filtering and washing the obtained product, drying the product at 110 to 130 ℃ for 6 to 12 h, and roasting the obtained product at 450 to 650 ℃ for 4 to 8h to obtain the SnO with the mesoporous structure₂-ZrO₂；

(2) Solid super acid WO₃/SnO₂-ZrO₂Preparation of

Adding equal amount of ammonium paratungstate and oxalic acid into deionized water, and then adding SnO into the deionized water₂-ZrO₂Evaporating the obtained mixed solution to dryness at 75 ℃, and then roasting the obtained product at 550 ℃ for 5 hours to obtain solid super acidic WO₃/SnO₂-ZrO₂In which WO₃The content of (A) is 25-40 wt%;

(3) preparation of ionic liquid precursor NMMPS

Adding o-xylene and 1, 3-propane sultone into a three-neck flask, transferring the three-neck flask into a water bath, dropwise adding N-methylmorpholine, keeping the temperature at 60-80 ℃, stirring and reacting for 6-12 hours, carrying out reduced pressure suction filtration on the obtained reaction solution, washing the obtained precipitate with o-xylene, and finally drying the obtained precipitate at 80-100 ℃ for 5-10 hours to obtain a solid as an ionic liquid precursor, wherein the solid is marked as NMMPS;

(4) tin-based heteropolyacid ionic liquids in WO₃/SnO₂-ZrO₂In situ loading of

Silicotungstic acid, stannous sulfate, NMMPS and solid superacid WO₃/SnO₂-ZrO₂Adding deionized water into the flask, stirring at room temperature for 30min, transferring to an oil bath at 100-120 ℃ for reflux treatment for 6-10 h, and filtering, washing and drying the product to obtain WO₃/SnO₂-ZrO₂A composite catalyst of solid superacid and tin-based heteropoly acid type ionic liquid; sn is prepared from silicotungstic acid, stannous sulfate and NMMPS in the reaction process_0.5[NMMPS]₂SiW₁₂O₄₀、Sn[NMMPS]SiW₁₂O₄₀、Sn_0.5[NMMPS]HSiW₁₂O₄₀One kind of (1).

In a preferable embodiment, in the step (1), the CTAC is added in an amount of 2-5 wt% of the mass of the stannic chloride and the zirconyl nitrate; the molar ratio of the stannic chloride to the zirconyl nitrate is (0.6-1): 1, and the molar concentration of the zirconyl nitrate in the mixed solution is 0.1 mol/L.

As a preferred embodiment, in the step (3), the mass ratio of N-methylmorpholine to 1, 3-propane sultone is 1:1, and the molar concentration of 1, 3-propane sultone in o-xylene is 0.1 mol/L.

In a preferred embodiment, in the step (4), the ratio of the amount of NMMPS to the amount of silicotungstic acid is (1-2): 1, the ratio of the amount of stannous sulfate to the amount of silicotungstic acid is (0.5-1.0): 1, and WO is contained in the composite catalyst₃/SnO₂-ZrO₂The mass fraction of the solid super acid is 30-60 wt%.

Compared with the prior art, the invention has the following beneficial effects.

1) The tin-based solid ionic liquid exists in a solid state, and heteropoly acid radicals with multi-charge characteristics are used as anions, and organic cations, metal cations and protons are simultaneously used as counter ions to construct a heteropoly acid functional ionic liquid organic-inorganic hybrid material with a cation part having B-L dual acidity. The strong acid functional group, the organic cation and the metal cation are introduced into the organic cation to replace the counter-charged proton to form the acid salt, so that the acid strength of the organic cation reaches the level of super acid, and the high catalytic activity and reaction stability are further embodied in the reaction process.

2) The tin-based solid ionic liquid and WO in the composite catalyst₃/SnO₂-ZrO₂The solid super acid has various types of acid sites, so that the reaction performance of the catalyst can be prevented from being reduced after the deactivation of the catalytic active sites of the same type. In addition, the synergistic effect between the solid ionic liquid and the super acid can further strengthen the surface acidity of the catalyst, thereby improving the yield of the beta-ionone.

3) The prepared catalyst combining the solid super acid and the solid ionic liquid is in a solid state, overcomes the defects of the traditional inorganic acid catalyst, and is easy to separate from a reaction system in the recycling process; in addition, the catalyst has strong acidity and has B-L dual acidic sites, so that the acidity is not easy to lose in the reaction process to further strengthen the reaction activity, and a good new thought is provided for a green and clean route for converting pseudo-ionone into beta-ionone.

Detailed Description

The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.