Preparation method of cyclospice
By using a metallic Ni precursor and an organophosphorus ligand to catalyze the reaction of cyclooctene and ketene under light irradiation, the problems of high equipment corrosion and poor selectivity in existing technologies have been solved, achieving highly selective synthesis of cyclooctene and improving product purity and yield.
Patent Information
- Application Number
- CN202510927346.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-07
- Publication Date
- 2025-11-07
AI Technical Summary
Existing methods for synthesizing cyclooctyl flavorings require the use of strong Lewis acid catalysts, which result in high equipment corrosion, poor yield and selectivity, and difficulty in controlling the acetylation position and avoiding over-acylation.
Using metallic Ni as a catalyst, combined with organophosphorus ligands, cyclooctene and ketene are reacted under light conditions, avoiding the use of strong Lewis acids, thus synthesizing cyclooctene with high selectivity.
This method enables the synthesis of cyclospicates with low corrosivity and high selectivity, avoiding the formation of byproducts and improving product purity and yield.
Smart Images
Figure BDA0005485145590000011 
Figure BDA0005485145590000031
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the field of organic synthesis, in particular to a preparation method of a cyclooctane spice. BACKGROUND
[0002] Cyclooctene and its derivatives as a new type of spice raw material, due to its unique chemical properties (such as high volatility, stability and compatibility with biological molecules) in the spice industry show potential. The aroma characteristics of such compounds include: with woody, green and light fruit-like flavor notes, which can be compounded with other spices (such as rose ether, citronellal), enhance the stereo sense of aroma. Such compounds can be used in perfumes, cosmetics, food flavor, air freshener and other fields, provide unique aromatic properties; also has good chemical stability, can ensure the stability of the aroma.
[0003] In recent years, with the growth of consumer demand for personalized fragrance, the development of new, stable and unique aroma of spice molecules has become a hot industry.
[0004] The currently reported patents mainly use cyclooctene as raw material to synthesize cyclooctane spice through acylation reaction. Such method needs to use about 10% Lewis acid catalyst, acid anhydride or acyl chloride as acylation raw material, and equivalent of organic acid or hydrogen halide as by-product, which has strong corrosive property, high equipment requirement, and the disadvantages of poor yield and selectivity; using the mechanism of Friedel-Crafts acylation, it is difficult to control the position of acetyl and double bond in the acetylation process, and it is easy to over-acylate and add multiple acyl functional groups.
[0005] Therefore, it has strong potential commercial value to develop a new synthesis process of cyclooctane spice. SUMMARY
[0006] The purpose of the present application is to overcome the deficiencies in the prior art, and provide a preparation method for synthesizing cyclooctane spice with high selectivity.
[0007] To achieve the above-mentioned purpose of the application, the technical scheme of the present application is as follows:
[0008] A synthesis method of cyclooctane spice, comprising: using cyclooctene and ethenone as raw materials, under light conditions, using metal Ni precursor as catalyst, and under the synergistic action of organic phosphine ligand, high-selectivity synthesis of cyclooctane spice.
[0009] The reaction route is as follows:
[0010]
[0011] In the present application, the amount of ethenone is 1.0-1.5 times, preferably 1.0-1.2 times, the amount (molar amount) of cyclooctene.
[0012] In the present application, the metal Ni precursor mainly includes one or more of nickel chloride, nickel bromide, nickel acetate, Ni(COD)2, and methyl nickel chloride dimer;
[0013] Preferably, the amount is 0.01-0.5 mol% of cyclooctene.
[0014] In the present application, the organic phosphine ligand mainly includes one or more of tributylphosphine, tri-tert-butylphosphine, triphenylphosphine, tricyclohexylphosphine, tris(1-naphthyl)phosphine, diphenylphosphine methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,5-bis(diphenylphosphino)pentane, and 1,6-bis(diphenylphosphino)hexane.
[0015] Preferably, the amount of the organic phosphine ligand (calculated as monophosphine) is 0.8-2.5 times, preferably 1.0-2.0 times, the molar amount of the metal Ni precursor.
[0016] In the present application, the reaction temperature is 20-80℃, preferably 30-60℃.
[0017] In the present application, the wavelength range of the light source used for the reaction is 200-800 nm, preferably 300-500 nm.
[0018] In the present application, the solvent used for the reaction is one or more of hexane, pentane, heptane, octane, cyclohexane, toluene, xylene, trichloromethane (chloroform), 1,2-dichloroethane, methanol, ethanol, isopropanol, n-butanol, ethylene glycol, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, diethyl ether, and tetrahydrofuran.
[0019] Preferably, the amount is 0.2-4.0 times the mass of cyclooctene.
[0020] As a preferred embodiment, the reaction mode of the present application is as follows: the metal nickel precursor, the phosphine ligand, and the solvent are first added to the reactor, stirred for 15-30 min. to complex, then cyclooctene and ethyl ketone are added, and the light source is turned on to stir the reaction.
[0021] The perfume prepared by the present application has rustic, natural, floral, green, and woody fragrance, and can be applied to the field of high-end perfumes and fragrance.
[0022] The present application has the following beneficial effects:
[0023] The present application avoids the use of strong Lewis acid, uses ethyl ketone as the raw material, avoids the generation of equivalent organic acid or hydrogen halide by-product, greatly reduces the corrosion of the system, reduces the equipment cost, can obtain a product with a double bond position with high selectivity, and no over-acylation occurs. DETAILED DESCRIPTION
[0024] For the purposes of the present invention, further embodiments will be described in the following with reference to examples. It is understood that the following examples are merely intended to provide a better understanding of the present invention and are not meant in any way to restrict the present invention to the following examples.
[0025] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The term "and / or" as used herein refers to and encompasses any and all combinations of one or more of the associated listed items.
[0026] Example 1
[0027] In a glove box, metal Ni precursor, nickel chloride (0.06 g, 0.05 mol%) and ligand, triphenylphosphine (0.12 g, 0.05 mol%) were added to 1 L clear glass reactor, the complex was stirred for 15 min at room temperature (25 °C), then cyclooctene (110.20 g, 1.0 mol) was added to the reactor, finally ketene (46.2 g, 1.1 mol) was introduced, the light source was turned on with wavelength set at 360 nm, the stirring was started, the temperature was raised to 40 °C, and the reaction was continued for about 3 h. The reaction was stopped by sampling through the bottom tube of the reactor, and the reaction liquid was analyzed by GC. The raw material cyclooctene was completely converted, and acetylcyclooctene was obtained by removing the solvent. The selectivity of the reaction was 90.0%. The pure acetylcyclooctene was separated by column chromatography to obtain 135.46 g of pure acetylcyclooctene with a purity of 99.0%.
[0028] NMR data of acetylcyclooctene spice:
[0029]
[0030] 1 HNMR (400 MHz, CDC13): δ 5.80 (dd, J = 6.5, 10.8 Hz, 1H), 5.62 (dt, J = 6.5, 10.8 Hz, 1H), 3.15-3.26 (m, 1H), 2.35-2.43 (m, 2H), 2.12 (s, 3H), 2.06-2.18 (m, 2H), 1.40-1.85 (m, 6H). 13 CNMR (100 MHz, CDC13): δ 203.2, 132.5, 130.1, 48.9, 47.1, 30.2, 28.0, 27.9, 25.8, 24.2.
[0031] Example 2
[0032] In a glove box, metal Ni precursor nickel acetate (0.18 g, 0.10 mol%) and ligand tributylphosphine (0.22 g, 0.11 mol%) were added to cyclohexane (60 g) in a 1 L clear glass reactor, complexation was carried out at room temperature (25 °C) for 20 min, then cyclooctene (110.20 g, 1.0 mol) was added to the reactor, finally ketene (42.0 g, 1.0 mol) was introduced, the light source was turned on, the wavelength was set to 300 nm, the stirring was started, the temperature was raised to 30 °C, and the reaction was continued for about 3 h. The reaction was stopped, and the sample was taken through the bottom tube of the reactor, and the reaction liquid was analyzed by GC. The conversion rate of cyclooctene was 95%, then the solvent was removed to obtain acetylcyclooctene, and the selectivity of the reaction was 88.0%. The pure acetylcyclooctene 127.07 g was separated by column chromatography, and the purity was 99.0%.
[0033] Example 3
[0034] In a glove box, metal Ni precursor Ni(COD)2(0.03 g, 0.01 mol%) and ligand 1,3-bis(diphenylphosphino)propane (0.02 g, the amount of organic phosphine ligand is 1 times the molar amount of metal Ni precursor, calculated as monophosphine) were added to butyl acetate (100 g) in a 1 L clear glass reactor, complexation was carried out at room temperature (25 °C) for 30 min, then cyclooctene (110.20 g, 1.0 mol) was added to the reactor, finally ketene (50.4 g, 1.2 mol) was introduced, the light source was turned on, the wavelength was set to 360 nm, the stirring was started, the temperature was raised to 60 °C, and the reaction was continued for about 3 h. The reaction was stopped, and the sample was taken through the bottom tube of the reactor, and the reaction liquid was analyzed by GC. The conversion rate of cyclooctene was 98%, then the solvent was removed to obtain acetylcyclooctene, and the selectivity of the reaction was 92.0%. The pure acetylcyclooctene 135.64 g was separated by column chromatography, and the purity was 99.0%.
[0035] Comparative Example 1
[0036] Cyclooctene (110.20 g, 1.0 mol) and acetic anhydride (204.18 g, 2.0 mol) were added to a glass bottle, zinc chloride (11 g, 10 wt%) was added, the stirring was started, the temperature was raised to 90-95 °C, and the reaction was continued for about 8 h. Then water washing, alkali washing, water washing, phase separation by extraction were carried out, and finally acetylcyclooctene 51.68 g was separated, the yield was 34%, and it contained multiple isomers.
[0037] It is readily understood that the above-described embodiments are only illustrative of the application and not intended to limit the scope of the application. Other variations and modifications can be made to the embodiments described and illustrated herein, without departing from the spirit of the application, the scope of which is defined by the appended claims.
Claims
1. A method of synthesizing a cyclic octane flavor, characterized by: The synthesis of cyclooctane spice is carried out under light condition by using cyclooctene and ethenone as raw materials, metal Ni precursor as catalyst and organic phosphine ligand.
2. The method of synthesis of claim 1, wherein: The metal Ni precursor is selected from one or more of nickel chloride, nickel bromide, nickel acetate, Ni(COD)2, methyl nickel chloride dimer.
3. The method of synthesis of claim 2, wherein: The amount of metal Ni precursor is 0.01-0.5 mol% of cyclooctene.
4. The method of synthesis of claim 1, wherein: The organic phosphine ligand includes one or more of tributylphosphine, tri-tert-butylphosphine, triphenylphosphine, tricyclohexylphosphine, tris(1-naphthyl)phosphine, diphenylphosphine methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,5-bis(diphenylphosphino)pentane, 1,6-bis(diphenylphosphino)hexane.
5. The method of synthesis of claim 4, wherein: The amount of organic phosphine ligand is 0.8-2.5 times, preferably 1.0-2.0 times of the molar amount of metal Ni precursor.
6. The method of synthesis of claim 1, wherein: The reaction temperature is 20-80℃, preferably 30-60℃.
7. The method of synthesis of claim 1, wherein: The wavelength of light source used in the reaction is 200-800nm, preferably 300-500nm.
8. The method of synthesis of claim 1, wherein: The solvent used in the reaction is one or more of hexane, pentane, heptane, octane, cyclohexane, toluene, xylene, trichloromethane (chloroform), 1,2-dichloroethane, methanol, ethanol, isopropyl alcohol, n-butyl alcohol, ethylene glycol, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, diethyl ether, tetrahydrofuran.
9. The method of synthesis of claim 8, wherein: The amount of solvent is 0.2-4.0 times of the amount of cyclooctene.