Amber core synthesis catalyst, preparation method thereof and amber core synthesis method

Abstract

The invention belongs to the technical field of amber core synthesis, and specifically discloses an amber core synthesis catalyst, a preparation method thereof and a synthesis method of amber core, wherein palladium chloride, zinc chloride and nickel chloride are prepared into a mixed solution in a mass ratio of 15-20:5-10:1; glucose is added to the mixed solution, and the reaction is heated at a reaction temperature of 50-78°C and a reaction time of 10-48h; the solid obtained by the reaction is carbonized in an inert atmosphere to obtain a catalyst. After 1-(2-tert-butylphenyloxy)-2-butanol is mixed with the catalyst in a mass ratio of 15-25:1, hydrogen is introduced into the reaction system, the hydrogen pressure is controlled to be 1.5-2.5MPa, and the reaction is heated at a reaction temperature of 140-160°C and a reaction time of 3-15h. When the catalyst is used to prepare the amber core, the yield is increased to more than 90%, the ratio of cis-trans products reaches 75:25, and the reaction temperature is reduced to 150°C for reaction, so that the reaction is milder and safer.

Description

Technical Field

[0001] The invention belongs to the technical field of amber core synthesis, and particularly relates to an amber core synthesis catalyst, a preparation method thereof and a method for synthesizing an amber core. Background Art

[0002] The statements herein merely provide background information related to the present invention and do not necessarily constitute prior art.

[0003] Amber Core is a kind of spice with woody, slightly camphor-like and strong amber aroma. It has excellent fragrance quality, elegant fragrance and long-lasting fragrance. It is a safe and harmless spice widely used in the fields of cosmetics, perfume, etc. Compared with trans-amber core, cis-amber core has better fragrance, softness and fragrance retention, so when preparing amber core, it is necessary to increase the proportion of cis-amber core as much as possible.

[0004] There are several types of amber core cis-isomers:

[0005] , , , .

[0006] Amber core trans isomer:

[0007] , , , .

[0008] The most common synthesis methods at this stage: one is the synthesis process of the original research company Kao Corporation, see CN116615406 fragrance composition for details. In the process, the ratio of cis-trans isomers of the eight isomers of amber core and its preparation method are emphasized. The ratio of cis-trans isomers in the synthesized amber core is 57:43. Then a high distillation column is used to distill the cis body according to the difference in boiling points of cis-trans isomers, and the distilled cis body is added back to increase the ratio of cis, so that the mass ratio of cis-body and trans-body is above 65:35 and below 95:5. Another method is to separate cis-trans isomers by column chromatography.

[0009] In the process of purifying the amber core product to prepare the cis isomer, the separated and removed trans isomer can only be treated as waste. The yield of the cis amber core is low, resulting in a waste of raw materials, and the emission of the trans amber core will also pollute the environment.

[0010] In addition, the reaction temperature of the existing amber core during preparation is about 190°C, which is relatively high in temperature and energy consumption, resulting in high preparation costs. Summary of the invention

[0011] In view of the shortcomings of the prior art, the purpose of the present invention is to provide an amber core synthesis catalyst, a preparation method thereof and a method for synthesizing an amber core.

[0012] In order to achieve the above object, the present invention is implemented through the following technical solutions:

[0013] In a first aspect, the present invention provides a method for preparing an amber core synthetic catalyst, comprising the following steps:

[0014] The palladium chloride, zinc chloride and nickel chloride are uniformly mixed with a solvent and glucose in a mass ratio of 15-20:5-10:1, and heated for reaction at a reaction temperature of 50-78°C and a reaction time of 10-48h; the solid obtained by the reaction is carbonized in an inert atmosphere to obtain a catalyst.

[0015] Glucose forms a complex with a metal salt in the presence of a solvent, and the complex is carbonized at high temperature in an inert atmosphere to obtain a catalyst.

[0016] Glucose has a good coordination effect. Compared with other sugars such as fructose, the prepared catalyst has a high catalytic efficiency. Specifically, the yield of the catalytically prepared amber core can reach 90% or more, and the mass proportion of the cis-isomer in the finished amber core can reach more than 70%.

[0017] In the process of preparing the catalyst, the inventors tried to use one or two of palladium chloride, zinc chloride and nickel chloride as raw materials to prepare the catalyst. The yield of amber core was significantly reduced, and the mass fraction of cis-isomer in the amber core product was low, making it difficult to simultaneously achieve an increase in the yield of amber core and the proportion of cis-isomer.

[0018] In some embodiments, the mass ratio of palladium chloride, zinc chloride and nickel chloride is 15:5:1.

[0019] In some embodiments, the mass ratio of palladium chloride to glucose is 1:45-55, preferably 1:50.

[0020] In some embodiments, the solvent of the mixed solution is methanol, ethanol or isopropanol.

[0021] Preferably, the solvent of the mixed solution is ethanol.

[0022] In some embodiments, the reaction temperature is 65-75° C., and the reaction time is 15-30 h.

[0023] Preferably, the reaction time is 19-21 hours.

[0024] In some embodiments, the carbonization temperature is 700-900°C.

[0025] In a second aspect, the present invention provides an amber core synthetic catalyst prepared by the preparation method.

[0026] In a third aspect, the present invention provides a method for synthesizing an amber core, comprising the following steps:

[0027] After mixing 1-(2-tert-butylphenyloxy)-2-butanol and the catalyst at a mass ratio of 15-25:1, hydrogen is introduced into the reaction system, the hydrogen pressure is controlled to be 1.5-2.5 MPa, and the reaction is heated at a reaction temperature of 140-160° C. and a reaction time of 3-15 hours.

[0028] In some embodiments, the mass ratio of 1-(2-tert-butylphenyloxy)-2-butanol to the catalyst is 20:1.

[0029] In some embodiments, the mass ratio of 1-(2-tert-butylphenyloxy)-2-butanol to the catalyst is 8-12:1.

[0030] In some embodiments, the reaction temperature is 145-155° C., and the reaction time is 6-9 h.

[0031] The beneficial effects achieved by one or more embodiments of the present invention are as follows:

[0032] The content of amber core in the reaction solution prepared by the synthesis method of amber core of the present invention reaches about 95%, and the yield of amber core is increased from the original 76% to 95%, thereby effectively improving the utilization rate of raw materials.

[0033] In the reaction liquid, the mass ratio of the cis-isomer and the trans-isomer of the amber core is 70-80:30-20, which effectively increases the ratio of the cis-isomer of the amber core and the selectivity of the cis-isomer. The qualified product (satisfying the mass ratio of the cis-isomer and the trans-isomer required in the original research literature (see CN116615406 flavor composition) to be above 65:35 and below 95:5) can be produced by directly distilling the reaction liquid. There is no need to use high-tower distillation or column chromatography, and steps such as column chromatography or high-tower distillation for separating cis- and trans-isomers can be omitted. The preparation steps are simpler, the utilization rate of raw materials is higher, and the production efficiency is effectively improved.

[0034] The catalyst provided by the invention has a relatively good catalytic effect, can not only increase the proportion of the cis isomer of the amber core, but also reduce the reaction temperature from the traditional 190° C. to 150° C. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] The accompanying drawings in the specification, which constitute a part of the present invention, are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute improper limitations on the present invention.

[0036] Figure 1This is the hydrogen spectrum of the amber core in Example 1 of the present invention. DETAILED DESCRIPTION

[0037] It should be noted that the following detailed descriptions are illustrative and intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used in the present invention have the same meanings as those commonly understood by those skilled in the art to which the present invention belongs.

[0038] The present invention will be further described below in conjunction with the embodiments.

[0039] Example 1

[0040] The method for preparing the catalyst comprises the following steps:

[0041] In a flask, add 3g palladium chloride, 1g zinc chloride, 0.2g nickel chloride, 200mL anhydrous ethanol solvent, slowly add 150g glucose, heat the system to 70℃, and react for 20h. Cool to room temperature, filter to remove ethanol, rinse the filter cake with ethanol once, and put the washed solid into a vacuum drying oven at 60℃ for 12h. Put the dried solid into a crucible, heat at a rate of 25℃ / min under argon protection, and carbonize at 800℃ for 12h to obtain 60g of catalyst.

[0042] Preparation of amber core:

[0043] Add 200g of 1-(2-tert-butylphenyloxy)-2-butanol and 10g of catalyst to the autoclave, heat to 150°C, hydrogen pressure to 2.0MPa, stir and react for 8h, filter the resulting reaction liquid, remove the catalyst, and obtain a reaction liquid. The mass ratio of the cis-trans isomers of the amber core in the reaction liquid is 76:24.

[0044] The reaction solution was distilled, and the fraction at 100-115°C was collected under a pressure of 100 Pa to obtain 185 g of amber core product. The hydrogen spectrum was as follows: Figure 1 As shown, the yield of amber core is 90%, and the mass ratio of cis-trans isomers in the finished amber core is 77:23.

[0045] Example 2

[0046] The method for preparing the catalyst comprises the following steps:

[0047] In a flask, add 1.5kg palladium chloride, 0.5kg zinc chloride, 0.1kg nickel chloride, 100L anhydrous ethanol solvent, slowly add 80kg glucose, heat the system to 75℃, and react for 25h. Cool to room temperature, filter to remove ethanol, rinse the filter cake with ethanol once, and put the washed solid into a vacuum drying oven at 60℃ for 12h. Put the dried solid into a crucible, heat at a rate of 25℃ / min under argon protection, and carbonize at 850℃ for 10h to obtain 30kg of catalyst.

[0048] Preparation of amber core: Add 500 kg of 1-(2-tert-butylphenyloxy)-2-butanol and 25 kg of catalyst into an autoclave, slowly heat to 150°C, hydrogen pressure of 2.0 MPa, stir and react for 8 hours, filter the obtained reaction liquid, remove the catalyst, and obtain a reaction liquid.

[0049] The reaction liquid was distilled, and the fraction at 100-115° C. was collected under a pressure of 100 Pa to obtain 467 kg of amber core finished product with a yield of 91% and a mass ratio of cis-to-trans isomers of 75:25.

[0050] Comparative Example 1

[0051] The difference from Example 1 is that in the preparation method of the catalyst, zinc chloride is replaced by palladium chloride, and the rest is the same as Example 1.

[0052] The preparation method of the amber core is the same as that of Example 1.

[0053] The reaction liquid was distilled, and the fraction at 100-115° C. was collected under a pressure of 100 Pa to obtain 165 g of amber core finished product. The yield of amber core was 80%, and the mass ratio of cis-trans isomers in the amber core finished product was 70:30.

[0054] Comparative Example 2

[0055] The difference from Example 1 is that in the preparation method of the catalyst, nickel chloride is replaced by palladium chloride, and the rest is the same as Example 1.

[0056] The preparation method of the amber core is the same as that of Example 1.

[0057] The reaction liquid was distilled, and the fraction at 100-115° C. was collected under a pressure of 100 Pa to obtain 152 g of amber core product. The yield of amber core was 74%, and the mass ratio of cis-trans isomers in the amber core product was 68:32.

[0058] Comparative Example 3

[0059] The difference from Example 1 is that in the preparation method of the catalyst, palladium chloride is replaced by zinc chloride, and the rest is the same as Example 1.

[0060] The preparation method of the amber core is the same as that of Example 1.

[0061] The reaction solution was distilled, and the fraction at 100-115° C. was collected under a pressure of 100 Pa to obtain 103 g of amber core finished product. The yield of amber core was 50%, and the mass ratio of cis-trans isomers in the amber core finished product was 60:40.

[0062] Comparative Example 4

[0063] The difference from Example 1 is that in the preparation method of the catalyst, palladium chloride is replaced by nickel chloride, and the rest is the same as Example 1.

[0064] The preparation method of the amber core is the same as that of Example 1.

[0065] The reaction liquid was distilled, and the fraction at 100-115° C. was collected under a pressure of 100 Pa to obtain 123 g of amber core product. The yield of amber core was 60%, and the mass ratio of cis-trans isomers in the amber core product was 58:42.

[0066] Comparative Example 5

[0067] The difference from Example 1 is that in the preparation method of the catalyst, "3g palladium chloride, 1g zinc chloride, 0.2g nickel chloride" is replaced by "4.2g palladium chloride", and the rest is the same as Example 1.

[0068] The preparation method of the amber core is the same as that of Example 1.

[0069] The reaction liquid was distilled, and the fraction at 100-115° C. was collected under a pressure of 100 Pa to obtain 135 g of amber core product. The yield of amber core was 66%, and the mass ratio of cis-trans isomers in the amber core product was 55:45.

[0070] Comparative Example 6

[0071] The difference from Example 1 is that in the preparation method of the catalyst, "3g palladium chloride, 1g zinc chloride, 0.2g nickel chloride" is replaced by "4.2g zinc chloride", and the rest is the same as Example 1.

[0072] The preparation method of the amber core is the same as that of Example 1.

[0073] The reaction solution was distilled, and the fraction at 100-115° C. was collected under a pressure of 100 Pa to obtain 82 g of amber core finished product. The yield of amber core was 40%, and the mass ratio of cis and trans isomers in the amber core finished product was 50:50.

[0074] Comparative Example 7

[0075] The difference from Example 1 is that in the preparation method of the catalyst, "3g palladium chloride, 1g zinc chloride, 0.2g nickel chloride" is replaced by "4.2g nickel chloride", and the rest is the same as Example 1.

[0076] The preparation method of the amber core is the same as that of Example 1.

[0077] The reaction liquid was distilled, and the fraction at 100-115° C. was collected under a pressure of 100 Pa to obtain 92.5 g of amber core finished product. The yield of amber core was 45%, and the mass ratio of cis-trans isomers in the amber core finished product was 53:47.

[0078] Comparative Example 8

[0079] The difference from Example 1 is that in the preparation method of the catalyst, glucose is replaced by fructose, and the rest is the same as Example 1.

[0080] The preparation method of the amber core is the same as that of Example 1.

[0081] The reaction liquid was distilled, and the fraction at 100-115° C. was collected under a pressure of 100 Pa to obtain 165 g of amber core finished product. The yield of amber core was 80%, and the mass ratio of cis-trans isomers in the amber core finished product was 70:30.

[0082] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing an amber core synthetic catalyst, characterized in that: The steps include: The palladium chloride, zinc chloride and nickel chloride are uniformly mixed with the solvent and glucose in a mass ratio of 15-20:5-10:1, the reaction temperature is 50-78°C, and the reaction time is 10-48h; the solid obtained by the reaction is carbonized in an inert atmosphere to obtain a catalyst; The mass ratio of palladium chloride to glucose is 1:45-55; The carbonization temperature is 700-900°C.

2. The method for preparing an amber core synthetic catalyst according to claim 1, wherein: The mass ratio of palladium chloride, zinc chloride and nickel chloride is 15-18:5-8:

1.

3. The method for preparing an amber core synthetic catalyst according to claim 1, wherein: The solvent is methanol, ethanol or isopropanol.

4. The method for preparing an amber core synthetic catalyst according to claim 3, wherein: The solvent is ethanol.

5. The method for preparing an amber core synthetic catalyst according to claim 1, wherein: The reaction temperature is 65-75°C and the reaction time is 15-30h.

6. An amber core synthetic catalyst, characterized in that: Prepared by the preparation method described in any one of claims 1 to 5.

7. A method for synthesizing an amber core, characterized in that: The steps include: After mixing 1-(2-tert-butylphenyloxy)-2-butanol and the catalyst according to claim 6 at a mass ratio of 15-25:1, hydrogen is introduced into the reaction system, the hydrogen pressure is controlled to be 1.5-2.5MPa, the reaction temperature is 140-160°C, and the reaction time is 3-15h.

8. The method for synthesizing an amber core according to claim 7, characterized in that: The reaction temperature is 145-155°C and the reaction time is 6-9h.

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