Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Patent
1997-06-16
1999-06-29
Geist, Gary
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C07C 3523
Patent
active
059170964
DESCRIPTION:
BRIEF SUMMARY
FIELD OF THE INVENTION
The present invention relates to a new process for the preparation of .beta.-Caryophyllene alcohol.
BACKGROUND OF THE INVENTION
.beta.-Caryophyllene alcohol is an important tricyclic sesquiterpenol, which can be widely used in perfumery and pharmaceutical industries. At present, .beta.-caryophyllene alcohol is prepared through the hydration of .beta.-caryophyllene. As disclosed in JP 01, 268, 657, .beta.-caryophyllene alcohol is prepared by utilizing the .beta.-caryophyllene as presented in mint oil. In addition, .beta.-caryophyllene alcohol can also be prepared from a small amount of .beta.-caryophyllene separated from cloveoil, copaihaoil, lavenderoil and bluinea oil, vitex cannabifolia oil from Chinese Compositae plants.
The sesquiterpene composition in Chinese pinus massoniana oleoresin contains longifolene, .beta.-caryophyllene , cyclo-longifolene and longipinene. Among them, the .beta.-caryophyllene content accounts for 13-17% of the composition. However, since its chemical configuration is very similar to the others and their differences in boiling points are only within 2.degree. C., it is very difficult to conduct the separation process for obtaining .beta.-caryophyllene alcohol in commercial practice.
The object of the present invention is to provide a new process for the preparation of .beta.-caryophyllene alcohol from the .beta.-caryophyllene contained in sesquiterpene composition in Chinese pinus massoniana oleoresin without the need of said separation.
SUMMARY OF THE INVENTION
The object of the present invention is achieved by the following technical solution. The sesquiterpene fraction at 110-120.degree. C./6 mmHg from Chinese pinus massoniana oleoresin composition undergoes isomerization in the presence of sulfuric acid as catalyst to prepare isolongifolene. After the rectification of the isolongifolene has been completed, there remains a residue in the amount of higher than 15% presented at the bottom of the rectification vessel, which is usually discarded or burned as an industrial waste. According to the present invention, the said residue is separated, re-crystallized and purified to prepare .beta.-caryophyllene alcohol. It has been verified via structure analysis and reaction mechanism studies that the .beta.-caryophyllene as presented in said sesquiterpene fraction, at the presence of catalytic sulfuric acid, has been converted into .beta.-caryophyllene alcohol via rearrangement, transannulation and hydration reactions of .beta.-caryophyllene. The process for the preparation of .beta.-caryophyllene alcohol in accordance with this invention has the advantages of simplified process and higher quality of product, which is a new process for the preparation of .beta.-caryophyllene alcohol.
BEST MODES FOR CARRYING OUT THE INVENTION
EXAMPLE 1
Separation
1245 g of the residue obtained from the bottom of the rectification vessel for the rectification of isolongifolene was added into a 2000 ml three-neck flask. The flask was heated to 160-220.degree. C. under 10 mmHg and the fraction of 150-200.degree. C. was collected. The distillate was kept still for crystallization and then filtered via a Buchner filter after the crystals had been crystallized out from the solution to obtain 879.3 g crystalline .beta.-caryophyllene alcohol (mp. 92.8.degree. C. without thermometer correction).
EXAMPLE 2
Re-crystallization
500 ml of n-hexane was added into 500 g crystalline .beta.-caryophyllene alcohol as obtained in Example 1. The crystalline .beta.-caryophyllene alcohol was dissolved into n-hexane under the condition of being warmed in a 50.degree. C. water bath and then, the solution was filtered under the condition of keeping the temperature. The filtrate was kept still for crystallization and then, the solution was filtered after the crystal had been crystallized out to obtain 440 g of crystalline .beta.-caryophyllene alcohol (mp. 94.2-94.8.degree. C. without thermometer correction). The various spectral data were as follows: 1330, 1100, 1059, 1019 (s, C--OH).
REFERENCES:
patent: 4229599 (1980-10-01), Mussinan et al.
patent: 4267076 (1981-05-01), Mookherjee et al.
March Textbook of Advanced Organic Chemistry Reactions Mechanisms and Structure. pp. 581-582 -(1968).
CA 116. 524 "Pharmacologic Studies on .beta. Caryophyllene Alcohol, Tang" Zhongguo Yaolixue Tonglao (1991) 7(12), 145-8.
CA 121 129933 "Chemical Characteristics of Oleoresins of Some Exotic Pines", Song Linchan Huaxire Yu Gongyl (1993) 13(14), 277-87.
CA 120, 265848 "Chemical Constitiuants of Oleoresin From Main Chinese Pine Species" Su, Linchen Huaxule Yu Gongup 1993 13(Zengkan) pp. 33-40.
CA 109:129325 "Aromate Chemicals from Ingifolene" Kichukna, Pollena, Tluszcze, Srodki Procace, Kramet.
Geist Gary
Research Institute of Chemical Processing and Utilization of For
Vollano Jean F
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