Process for making tricyclodecenyl esters

A kind of technology of decenyl ester and dicyclopentadiene, applied in the field of preparing tricyclodecenyl ester, can solve problems such as high price

Inactive Publication Date: 2009-07-22
利安德巴塞尔调味香料和芳香有限责任公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Because distilling this stream is expensive, they are often simply discarded

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Preparation of Tricyclodecenyl Acetate Using Trifluoromethanesulfonic Acid as Catalyst

[0027] Dicyclopentadiene (DCPD, 1048 g, 86% purity) was added dropwise to a stirred mixture of glacial acetic acid (420 g) and trifluoromethanesulfonic acid (1.18 g) at 90-110°C over 5.7 hours. The reaction mixture was then stirred at 120°C for 2.5 hours. Add brine (98g, d 4 20 1.202), water (49 g) and 50% aqueous NaOH (61 g), and the mixture was stirred for 0.5 h. After the layers had settled, the organic phase was separated and washed with brine (2 x 125 g). Distillation of the crude material (1409 g) at 1 Torr gave commercial grade TCDA (888 g, 67% based on DCPD). Major isomer determined by gas chromatography (GC): 92.4%; Isomer A: 1.6%; Isomer B: 4.3%; Isomer C: 0.5%.

[0028] Target range: Major isomer: >90%; Isomer A: <2%; Isomer B: 1-6%; Isomer C: <3%.

Embodiment 3

[0034] Using Crude, Recycled Acetic Acid

[0035] Step A. Hydrolysis of Acetic Anhydride. A by-product stream containing about 80 wt.% acetic acid, acetic anhydride (about 13 wt.%), alpha-pinene, limonene, acetate, and other impurities was mixed with sufficient water (12.3 mL) to hydrolyze the acetic anhydride. Trifluoromethanesulfonic acid (1.36 g) was added and the mixture was heated to 110°C with stirring and maintained at this temperature for 30 minutes. Gas chromatography of the resulting dark brown mixture showed the absence of acetic anhydride, the presence of about 90 wt.% acetic acid, and the remainder a complex mixture of organic compounds.

[0036] Step B. Synthesis of TCDA. DCPD (1048 g, 86% purity) was added dropwise to the mixture obtained in step A at 110-120°C over 5.7 hours. The reaction mixture was stirred at 120°C for an additional 2.5 hours and then cooled to 40°C. Add brine (98g, d 4 20 1.20), water (49 g) and 50% aqueous NaOH (61 g) and the mixture...

Embodiment 4

[0039] Do not gradually join DCPD

[0040] A mixture of DCPD (1048 g, 87-88%), trifluoromethanesulfonic acid (1.19 g) and glacial acetic acid (420 g) was heated to 130° C. with stirring over 55 minutes. The mixture was maintained at 130-135°C for an additional 2.4 hours, then cooled to 40°C. Add brine (104g, d 4 20 1.20), water (52g) and 50% aqueous NaOH (66g) and the mixture was stirred for 30 minutes. The phases were separated and the organic layer was washed with brine (2 x 125 g). The crude material (1284 g) was distilled at 1 Torr to provide commercial grade TCDA (690 g, 51% based on DCPD).

[0041] Examples 1 and 4 show that the yield of commercially acceptable TCDA is increased by gradually adding DCPD to a mixture of acetic acid and trifluoromethanesulfonic acid.

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Abstract

A process for making tricyclodecenyl esters is disclosed. A C2-C4 carboxylic acid and a dicyclopentadiene react in the presence of triflic acid under conditions effective to produce the ester. The process gives tricyclodecenyl esters in good yield while avoiding the need to use a large excess of the carboxylic acid. The process efficiently provides fragrance-quality tricyclodecenyl esters from technical grade dicyclopentadienes and / or recycled carboxylic acids.

Description

field of invention [0001] This invention relates to a process for the preparation of tricyclodecenyl esters. Said esters are derived from dicyclopentadiene compounds and are valuable perfume ingredients. Background of the invention [0002] Tricyclodecenyl esters, especially C derived from dicyclopentadiene 2 -C 4 Esters, are ubiquitous fragrance ingredients in detergents, shampoos, deodorants, hard surface cleaners and other applications. The most common tricyclodecenyl ester, which is prepared by reacting dicyclopentadiene with acetic acid, is tricyclodecenyl acetate or "TCDA". Such products with a sweet, anise-like aroma are sold by several companies, including, for example, International Flavors & Fragrances ( ), Quest( ), Millennium Specialty Chemicals (Navacet TM ) and Symrise ( ). [0003] Tricyclodecenyl esters are typically produced by the acid-catalyzed addition of the corresponding carboxylic acids (acetic, propionic, butyric, isobutyric) to dicyclopent...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C67/04C07C69/013
CPCC07C67/04C07C2103/68C07C2603/68C07C69/013C07C69/145C07C69/24
Inventor M·Y·勒彼德弗
Owner 利安德巴塞尔调味香料和芳香有限责任公司
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