A process for the preparation of cyclopentadecanolide from cyclopentadecanone

Abstract

The present application relates to a kind of preparation methods of cyclopentadecanolide, from cyclopentadecanone, under the condition of catalyst, in ozone atmosphere, oxidation preparation cyclopentadecanolide is carried out.Therein, the catalyst used is the composite photocatalyst of inorganic titanium dioxide and organic molecule combination, under the condition of light, the system shows very high activity.In the reaction of the present application, it is not involved in peroxoacetic acid, hydrogen peroxide and other highly dangerous peroxides, process is safer, and product yield can be as high as 97%.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of organic synthesis, in particular to a preparation method of cyclopentadecanolide. BACKGROUND

[0002] Musk is a kind of precious animal perfume with very special delicate fragrance, which is indispensable expensive perfume for blending high-grade perfume. Due to the rarity of the source, it is not easy to obtain, and in the process of studying the synthesis of effective fragrance components, it is found that there is no compound with musk fragrance in natural musk, so in recent years, synthetic method is used to prepare perfume with musk fragrance.

[0003] Macrolide musk has attracted much attention because of almost no toxicity. Macrolide musk has elegant and delicate fragrance, and the content of the fragrance is closer to natural musk and quite stable. Among them, cyclopentadecanolide has elegant and delicate fragrance, and its suitable fragrance can make people feel happy and relaxed, and the addition of cyclopentadecanolide to food and beverage can also improve the palatability of food, so that people's life is improved, thus it is indispensable in people's daily life.

[0004] Cyclopentadecanolide was first synthesized by Ruzicka and his collaborators by chemical method in the middle of last century. At present, the synthesis of cyclopentadecanolide has made great progress, and its industrial production mainly uses cyclododecanone as the starting material, and the main process route is as follows:

[0005] Using cyclododecanone addition alcohol as raw material

[0006]

[0007] Cyclododecanone addition alcohol can be easily prepared by free addition reaction of cyclododecanone and allyl alcohol (for example, see document US3856815).

[0008] German Symrise company patent CN1867556A provides a method for preparing cyclopentadecanolide, which uses cyclododecanone addition alcohol as raw material, and uses 50% hydrogen peroxide aqueous solution to oxidize in propionic acid and trifluoroacetic acid to obtain a peroxide suspension; the suspension is cracked in copper acetate monohydrate under the catalysis of polyethylene glycol to obtain habanolide; and cyclopentadecanolide is obtained after hydrogenation. This method uses a large amount of organic acid and high concentration of hydrogen peroxide, which has greater hidden danger in process safety and environmental protection.

[0009] In summary, it is still necessary to develop a process route for synthesizing cyclopentadecanolide with simple process route, mild reaction conditions and good safety. SUMMARY

[0010] In view of the deficiencies of the prior art in the synthesis of cyclopentadecanolide, the application provides a preparation method of cyclopentadecanolide.

[0011] To achieve the above-mentioned purposes, the technical scheme of the application is as follows:

[0012] A synthesis method of cyclopentadecanolide, which uses cyclopentadecanone as a raw material, and ozone is used to oxidize the cyclopentadecanone in the presence of a composite catalyst to obtain cyclopentadecanolide.

[0013] The reaction route is as follows:

[0014]

[0015] In the application, ozone is used as an oxidizing agent instead of peroxides such as peroxoacetic acid, which greatly improves the safety of the process.

[0016] In the application, the pressure after the addition of ozone in the system is 0.01-0.10 MPa, preferably 0.01-0.05 MPa.

[0017] In the application, the composite catalyst comprises titanium dioxide and organic molecules, and the organic molecules are at least one of quinoline, phenanthridine, acridine and 7,8-benzquinoline; wherein the amount of titanium dioxide is 0.001-1 wt.% of the amount of cyclopentadecanone, and the amount of organic molecules is 0.9-1.2 times the mass of titanium dioxide.

[0018] In the application, the reaction temperature is 20-100 DEG C, preferably 65-80 DEG C.

[0019] In the application, the reaction needs to be carried out under light, and the wavelength of the light required for the reaction is between 400-480 nm, preferably between 420-460 nm.

[0020] In the application, the synthesized cyclopentadecanolide is used in the field of fragrances and spices.

[0021] The application has the following beneficial effects:

[0022] The synthesis route of cyclopentadecanolide provided by the application uses ozone as a catalyst instead of peroxides such as peroxoacetic acid, which greatly improves the safety of the process, reduces the generation of wastewater, is green and environmentally friendly, and improves the economic efficiency of the existing process. The product yield can be as high as 97% or more. DETAILED DESCRIPTION

[0023] In order to further illustrate the application, the following specific examples are given, but the application is not limited to these examples.

[0024] Example 1

[0025] (1) In a glove box, titanium dioxide (0.22 g, 0.1%), quinoline (0.22 g) and cyclopentadecanone (224.38 g, 1.0 mol) were added to a 1 L high-pressure transparent glass reactor, the temperature was raised to 65 °C, the stirring speed was controlled at 400 rpm, and the gas was replaced twice by ozone, and finally the pressure was increased to 0.03 MPa by ozone, then the reaction was irradiated by 450 nm blue light, and the reaction was continued for 2 hours. The reaction was sampled through the bottom tube of the reactor, and the reaction liquid was analyzed by GC. The results showed that the raw material cyclopentadecanone was completely converted, and the product cyclopentadecanolide was obtained. The selectivity of the reaction was 97.0%. Then, pure cyclopentadecanolide 231.97 g was obtained by rectification, and the yield was 96.5%.

[0026] NMR data of cyclopentadecanolide:

[0027] 1 H NMR (400 MHz, CDC13): δ 4.12 (2H, t, J = 5.6 Hz), 2.33 (2H, t, J = 6.4 Hz), 1.62 (4H, m), 1.31 (22H, m). 13 CNMR (100 MHz, CDC13): δ 174.0, 64.3, 34.7, 29.5, 28.7, 28.2, 27.9, 27.8, 27.7, 27.1, 27, 26.9, 26.8, 25.6, 25.0.

[0028] Example 2

[0029] (1) In a glove box, titanium dioxide (1.12 g, 0.5%), phenanthridine (1.23 g) and cyclopentadecanone (224.38 g, 1.0 mol) were added to a 1 L high-pressure transparent glass reactor, the temperature was raised to 80 °C, the stirring speed was controlled at 400 rpm, and the gas was replaced twice by ozone, and finally the pressure was increased to 0.05 MPa by ozone, then the reaction was irradiated by 420 nm blue light, and the reaction was continued for 2 hours. The reaction was sampled through the bottom tube of the reactor, and the reaction liquid was analyzed by GC. The results showed that the raw material cyclopentadecanone was completely converted, and the product cyclopentadecanolide was obtained. The selectivity of the reaction was 98.0%. Then, pure cyclopentadecanolide 233.65 g was obtained by rectification, and the yield was 97.2%.

[0030] Example 3

[0031] (1) In a glove box, titanium dioxide (0.44 g, 0.2%), acridine (0.44 g) and cyclopentadecanone (224.38 g, 1.0 mol) were added into a 1 L high-pressure transparent glass kettle, the temperature was raised to 70 °C, the stirring speed was controlled at 400 rpm, and the gas was replaced twice by ozone, then the pressure was 0.01 MPa by introducing ozone, and then the reaction was carried out by irradiation with 460 nm blue light and continuous stirring for 2 hours. The sample was taken through the bottom tube of the reaction kettle, and the reaction liquid was analyzed by GC detection. The results showed that the raw material cyclopentadecanone was completely converted, and the product cyclopentadecanolide was obtained, and the selectivity of the reaction was 96.5%. Then, pure cyclopentadecanolide 229.08 g was obtained by rectification, and the yield was 95.3%.

Claims

1. A method of synthesizing a cyclopentadecanolide, characterized by: The cyclopentadecanolide is obtained by oxidizing cyclopentadecanone in the presence of a composite catalyst under ozone atmosphere; The composite catalyst comprises titanium dioxide and an organic molecule, and the organic molecule is at least one of quinoline, phenanthridine, acridine and 7,8-benzquinoline.

2. The method of synthesis of claim 1, wherein: The pressure of the system after adding ozone is 0.01-0.10 MPa.

3. The method of synthesis of claim 2, wherein: The pressure of the system after adding ozone is 0.01-0.05 MPa.

4. The method of synthesis of claim 1, wherein: The amount of titanium dioxide is 0.001-1 wt.% of the amount of cyclopentadecanone.

5. The method of synthesis according to claim 1 or 4, wherein: The amount of the organic molecule is 0.9-1.2 times of the mass of titanium dioxide.

6. The method of synthesis of claim 1, wherein: The reaction temperature is 20-100℃.

7. The method of synthesis of claim 6, wherein: The reaction temperature is 65-80℃.

8. The method of synthesis according to any one of claims 1-4, wherein: The reaction is carried out under light, and the wavelength of the light is 400-480 nm.

9. The method of synthesis of claim 8, wherein: The reaction is carried out under light, and the wavelength of the light is 420-460 nm.

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