CN1130170A - Synthetic method for methyl cedrone - Google Patents
Synthetic method for methyl cedrone Download PDFInfo
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- CN1130170A CN1130170A CN 95101865 CN95101865A CN1130170A CN 1130170 A CN1130170 A CN 1130170A CN 95101865 CN95101865 CN 95101865 CN 95101865 A CN95101865 A CN 95101865A CN 1130170 A CN1130170 A CN 1130170A
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- acid
- synthetic method
- reaction
- vertofix coeur
- hydrocarbon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invented synthesis uses the Chinese volatile oil distilled from cedar wood as starting material, and the cedar wood ketone is made by using acetic anhydride acetylation under the existance of prototropic acid, which is the formic acid or acetic acid or phosphoric acid or polyphosphoric acid or sulfuric acid, the isomenization and acetylation are undergone simultaneously. Said invention selects the suitable prototropic acid as catalyst and the high yield of methyl cedar wood ketone is obtained by controlling the reaction temperature and time.
Description
The present invention relates to field of perfumery, relate to the synthetic technology of vertofix coeur.
Vertofix coeur is a kind of banksia rose spices with Moschus, grane ambra, and its fragrance is lasting strongly, has good modification, coordination, fixation effect in blending.Be widely used in the daily chemical essences such as perfumed soap, makeup, shampoo.The method for making of vertofix coeur is after cedar(wood)oil fractionation isomerization, and carries out acetylization reaction with aceticanhydride, obtains through rectifying then.Prior art is because the catalyzer of selecting for use in isomerization reaction is improper and there is defective in operation steps, and therefore, the finished product fragrance that makes is impure, and yield is low.
The objective of the invention is to select suitable protonic acid is catalyzer, grasps reaction conditionss such as temperature of reaction and reaction times, to obtain the synthetic method of the high vertofix coeur of yield.
The technical scheme of vertofix coeur synthetic method of the present invention is: with Chinese cedar(wood)oil is starting raw material; in the presence of protonic acid; make with the aceticanhydride acetylize; its so-called protonic acid is formic acid or acetate or phosphoric acid or polyphosphoric acid or sulfuric acid etc., and the isomerization and the acetylization reaction of the major ingredient ene of cedar(wood)oil, β-chamene, thujopsene carried out simultaneously.
The synthetic method of vertofix coeur of the present invention, the mol ratio that it is characterized in that protonic acid and hydrocarbon is 0.5-5: 1.
The synthetic method of vertofix coeur of the present invention, the mol ratio of its acetylizing agent aceticanhydride and hydrocarbon is 1.0-8.0: 1.
The synthetic method of vertofix coeur of the present invention, the acetylization reaction temperature is 10-100 ℃, 5-12 hours reaction times.
The present invention relates to the synthetic method of vertofix coeur, its reaction formula is as follows:
In above reaction, cedar wood oil alcohol is sloughed a part water and is generated ene (I) under the protonic acid effect, and β-chamene (II) isomery under the protonic acid effect turns to ene (I), carries out acetylization reaction again.
Reaction A:
Thujopsene (III) obtains different isomerized products under different conditions.Under mild acid conditions, (III) first isomery turns to 1,4, and 11,11-tetramethyl-dicyclo [5,4,0]-11-3,7-diene (VII), (L, E, Friedrich, Dissertation, 1966, University Microfilms, Lnc., Ann Arbor, Michigan, No.67-8559, P128), further isomerization then obtains 2,2,3,7-tetramethyl-three rings [5,2,2,0
1,6]-11-3-alkene (VIII), (L, E, Friedrich, Dissertation, 1966, University Microfilms, Ann Arbor, Michigan, No.67-8559, P51,110-112) and other C
15H
24Tricyclic hydrocarbon.
Reaction B:
+other?C
15H
24
tricyclic?hydrocarbons
Under strong acid condition, thujopsene (III) isomery turns to β-chamigrene (IX) and α-chami9rene (X), and further isomery turns to 6,8a-ethylene-1,1,6-trimethylammonium-1,2,3,5,6,7,8,8a-octahydro naphthalene (XI) and other C again
15H
24Tricyclic hydrocarbon (US Pat, 3,681,470).
Reaction C:
The fragrance of vertofix coeur depends primarily on acetyl cedrene (IV) and 4-ethanoyl-6,8a-ethylene-1,1, and 6-trimethylammonium-1,2,3,5,6,7,8,8a-octahydro naphthalene (VI), and (VI) can make (US Pat, 3,754,037) by IX, X, XI acetylize.
Reaction D:
The starting raw material that vertofix coeur of the present invention is selected for use is Chinese cedar(wood)oil; its major ingredient is ene (I), β-chamene (II), thujopsene (III) and cedar wood oil alcohol; these four kinds of component content are respectively: (1) 18-30%; (2) 5-10%; (3) 30-40%; (4) 20-30%; because the difference in the place of production---as Guizhou or Sichuan product---is all had any different by the content of various components; so the vertofix coeur that makes after the acetylize also has difference on fragrance, must just can become the commodity vertofix coeur behind the adjustment component.
Characteristics of the present invention are that the isomerization and the acetylization reaction of ene (I), β chamene (II) and thujopsene (III) carries out simultaneously.Select suitable reaction conditionss such as bronsted acid catalyst, acid concentration, reaction solvent, temperature of reaction and reaction times, can obtain the vertofix coeur of better yield.
As previously mentioned, to the isomerization of thujopsene (III), we wish not carry out with reaction B, and carry out with reaction C, so just need to select stronger bronsted acid catalyst.For the present invention, formic acid, acetate, phosphoric acid, polyphosphoric acid or sulfuric acid are more suitable.For the mole number of the required acid of every mole of hydrocarbon, we think more suitable with 0.5-5mol.As sour consumption very little, unfavorable to isomerization; And sour consumption is too many, can cause again to pay reaction, causes yield to descend.Higher acid concentration is favourable to our the desired reaction that obtains, and requires usually that water content is less than 20% in the concentrated acid, and the result that acid concentration is not high is that isomerization is not thorough, and by product is increased.
Acetylizing agent aceticanhydride among the present invention there is no much requirements for every mole of employed aceticanhydride of hydrocarbon, can in very large range change, and is generally 1.0-8.0mol, preferably 1.5-3.5mol.
Acetylization reaction of the present invention, can use also can be without solvent, and solvent can be selected acetate, ethylene dichloride, hexanaphthene, benzene or toluene etc. for use.If use solvent, its amount can be 0.5-1 times of hydrocarbon.
Temperature of reaction is chosen in 10-100 ℃.Temperature is too low, and reaction mixture viscosity is big, is difficult for stirring, and reaction is slow.Temperature is too high, and it is many then to pay product, and yield is low.We think that more suitable temperature is 65-80 ℃, 5-12 hours reaction times.
The following describes one embodiment of the present of invention.
The Sichuan cedar(wood)oil is removed cedar wood oil alcohol through fractionation, gets the raw material chamene.
In the 100L reactor, add aceticanhydride 18Kg, polyphosphoric acid (105%) 20Kg is heated with stirring to 75 ℃, adds the solution of 20Kg raw material chamene in 10Kg benzene.Reaction mixture after 7 hours, adds water 30Kg at 75 ℃ of stirring reactions, decomposes polyphosphoric acid.Oil reservoir is put into washing pot, and water layer extracts with benzene, and extraction liquid is also incorporated washing pot into.The neutralization that adds dilute alkali is washed to neutrality then.Get the vertofix coeur crude product after reclaiming benzene, 120-168 ℃/70Pa cut is collected in rectifying, gets faint yellow vertofix coeur finished product, and yield 60% contains the ketone amount greater than 80%, the banksia rose musky odor that tool is strong.
Claims (4)
1, the synthetic method of vertofix coeur; with Chinese cedar(wood)oil is starting raw material, in the presence of protonic acid, makes with the aceticanhydride acetylize; it is characterized in that so-called protonic acid is formic acid or acetate or phosphoric acid or polyphosphoric acid or sulfuric acid, isomerization and acetylization reaction carry out simultaneously.
2, the synthetic method of vertofix coeur as claimed in claim 1, the mol ratio that it is characterized in that protonic acid and hydrocarbon is 0.5-5: 1.
3, the synthetic method of vertofix coeur as claimed in claim 1, the mol ratio that it is characterized in that acetylizing agent aceticanhydride and hydrocarbon is 1.0-8.0: 1.
4, the synthetic method of vertofix coeur as claimed in claim 1 is characterized in that the acetylization reaction temperature is 10-100 ℃, 5-12 hours reaction times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95101865A CN1037342C (en) | 1995-03-02 | 1995-03-02 | Synthetic method for methyl cedrone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95101865A CN1037342C (en) | 1995-03-02 | 1995-03-02 | Synthetic method for methyl cedrone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1130170A true CN1130170A (en) | 1996-09-04 |
| CN1037342C CN1037342C (en) | 1998-02-11 |
Family
ID=5074109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95101865A Expired - Lifetime CN1037342C (en) | 1995-03-02 | 1995-03-02 | Synthetic method for methyl cedrone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1037342C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265170B (en) * | 2008-04-22 | 2010-06-02 | 杭州格林香料化学有限公司 | Method for synthesizing methylcedrenone by using solid super-strong acid |
| CN104045538A (en) * | 2014-06-16 | 2014-09-17 | 江西华宇香料化工有限公司 | Method for preparing methyl cedryl ketone from Chinese fir wood oil |
| CN111646888A (en) * | 2020-08-04 | 2020-09-11 | 李金国 | Method for producing cosmetic perfume cedryl ketone |
| CN111792989A (en) * | 2020-08-04 | 2020-10-20 | 李金国 | Method for producing methyl cedryl ketone for cosmetics |
| CN114369004A (en) * | 2021-12-31 | 2022-04-19 | 水木海清生物科技(福建)有限公司 | Cypress isomerization method with low acid consumption and low acid consumption |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3754037A (en) * | 1971-01-18 | 1973-08-21 | Givaudan Corp | Process for the acetylation of chamigrenes |
| US3681470A (en) * | 1971-01-18 | 1972-08-01 | Givaudan Corp | Acid isomerization of thujopsene and novel tricyclic olerinic c15 h24 hydrocarbons formed thereby |
| NL8104273A (en) * | 1981-09-16 | 1983-04-18 | Naarden International Nv | PERFUME COMPOSITIONS AND PERFUMED PRODUCTS CONTAINING ONE OR MORE TETRAMETHYL-TRI-CYCLOUNDECYL METHYL KETONES AS PERFUME RAW. |
-
1995
- 1995-03-02 CN CN95101865A patent/CN1037342C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265170B (en) * | 2008-04-22 | 2010-06-02 | 杭州格林香料化学有限公司 | Method for synthesizing methylcedrenone by using solid super-strong acid |
| CN104045538A (en) * | 2014-06-16 | 2014-09-17 | 江西华宇香料化工有限公司 | Method for preparing methyl cedryl ketone from Chinese fir wood oil |
| CN104045538B (en) * | 2014-06-16 | 2015-08-19 | 江西华宇香料化工有限公司 | A kind of oleum Cunninghamiae lanceolatae prepares the method for vertofix coeur |
| CN111646888A (en) * | 2020-08-04 | 2020-09-11 | 李金国 | Method for producing cosmetic perfume cedryl ketone |
| CN111792989A (en) * | 2020-08-04 | 2020-10-20 | 李金国 | Method for producing methyl cedryl ketone for cosmetics |
| CN114369004A (en) * | 2021-12-31 | 2022-04-19 | 水木海清生物科技(福建)有限公司 | Cypress isomerization method with low acid consumption and low acid consumption |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1037342C (en) | 1998-02-11 |
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Owner name: HUANGYAN PERFUMERY Free format text: FORMER OWNER: BRANCH NO.1 OF HUANGYAN ESSENCES FACTORY Effective date: 20050128 |
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Owner name: ZHEJIANG HUANGYAN SPICES LTD. Free format text: FORMER NAME OR ADDRESS: HUANGYAN PERFUMERY |
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Address after: 318020, No. 1 Jiangkou Road, Huangyan District, Zhejiang, Taizhou Patentee after: Huangyan Zhejiang spice Co.,Ltd. Address before: 318020, No. 1 Jiangkou Road, Huangyan District, Zhejiang, Taizhou Patentee before: Huangyan Perfumery |
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Effective date of registration: 20050128 Address after: 318020, No. 1 Jiangkou Road, Huangyan District, Zhejiang, Taizhou Patentee after: HUANGYAN PERFUMERY Address before: 317400 No. 152 East Ring Road, Zhejiang, Huangyan Patentee before: BRANCH NO 1 OF HUANGYAN ESSENC |
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Owner name: INTERNATIONAL SPICE XIANGJING( HANGZHOU ) CO., LTD Free format text: FORMER OWNER: ZHEJIANG HUANGYAN PERFUMERY CO., LTD. Effective date: 20090508 |
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Effective date of registration: 20090508 Address after: No. 88, Xiang Xiang Road, Yangxi street, Jiande, Zhejiang Patentee after: INTERNATIONAL FLAVORS & FRAGRANCE (HANGZHOU) Co.,Ltd. Address before: No. 1, Jiangkou Road, Huangyan District, Zhejiang, Taizhou Patentee before: Huangyan Zhejiang spice Co.,Ltd. |
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Expiration termination date: 20150302 Granted publication date: 19980211 |