KR0181713B1 - L-menthyl-oxyaldehyde and method of them - Google Patents

L-menthyl-oxyaldehyde and method of them Download PDF

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KR0181713B1
KR0181713B1 KR1019960054794A KR19960054794A KR0181713B1 KR 0181713 B1 KR0181713 B1 KR 0181713B1 KR 1019960054794 A KR1019960054794 A KR 1019960054794A KR 19960054794 A KR19960054794 A KR 19960054794A KR 0181713 B1 KR0181713 B1 KR 0181713B1
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menthol
oxyaldehyde
mentyl
formula
catalyst
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KR1019960054794A
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Korean (ko)
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KR19980036247A (en
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김근수
이정일
박준영
최영현
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박명규
재단법인한국인삼연초연구원
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
    • 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
    • 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
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/86—Use of additives, e.g. for stabilisation

Abstract

이 발명은 멘톨향을 보통때도 발산하고 열분해시에도 발산하는 신규 물질인 다음 구조식(Ⅰ)의 ℓ-멘틸-옥시알데히드에 관한 것임. 이 구조식(Ⅰ)의 화합물은 ℓ-멘톨과 트리메틸 오르도포메이트를 유기 용매와 촉매의 존재하에 반응시켜 제조함. 구조식(Ⅰ)의 화합물은 멘톨향을 보통때도 발산하고 열분해시에도 발산하며, 식품, 담배, 의약품, 향료에 유용하게 사용될 수 있음.The present invention relates to l-mentyl-oxyaldehyde of the following structural formula (I), which is a novel substance which emits menthol flavor as usual and also during pyrolysis. The compound of formula (I) was prepared by reacting l-menthol and trimethyl orthoformate in the presence of an organic solvent and a catalyst. The compound of formula (I) emits menthol fragrance normally and also during pyrolysis, and can be useful for food, tobacco, medicine and fragrance.

Description

[발명의 명칭][Name of invention]

ℓ-멘틸-옥시알데히드 및 그 제조방법l-mentyl-oxyaldehyde and preparation method thereof

[발명의 상세한 설명]Detailed description of the invention

[발명의 목적][Purpose of invention]

본 발명의 목적은 식품, 담배, 의약품, 향수 등에 멘톨향을 부여하는 신규물질을 제공하기 위한 것이다.An object of the present invention is to provide a novel substance for imparting menthol flavor to food, tobacco, pharmaceuticals, perfumes, and the like.

[발명이 속하는 기술분야 및 그 분야의 종래기술][Technical field to which the invention belongs and the prior art in that field]

본 발명은 멘톨향을 발현하는 새로운 물질인 다음 구조식(Ⅰ)의 ℓ-멘틸-옥시알데히드에 관한 것이다.The present invention relates to l-mentyl-oxyaldehyde of the following structural formula (I), which is a new substance expressing menthol flavor.

위 구조식(Ⅰ)으로 표시되는 화합물은 담배, 식품, 의약품, 향수 등에 멘톨향을 부여하기 위하여 유용하게 사용될 수 있다.The compound represented by the above structural formula (I) may be usefully used to impart menthol flavor to tobacco, food, medicine, perfume, and the like.

가수분해나 열분해되어 멘톨향을 발산시키는 화합물로는 ℓ-멘틸 리나룰 카보네이트(미국특허 3312226호), 멘틸 디카보네이트 에스테르(미국특허 4532944호), 글리콜 사카라이드 멘틸 카보네이트 에스테르(미국특허 3332428, 3419543호)등이 이미 알려져 있다. 전술한 화합물들은 가수분해되거나 열분해될 때 멘톨향을 발생하는 것으로 알려져 있다.Compounds that give hydrolysis or pyrolysis to give off menthol flavor include l-mentyl linarul carbonate (US Pat. No. 3,312,226), menthyl dicarbonate ester (US Pat. No. 4,532,944), glycol saccharide menthyl carbonate (US Pat. No. 3,332,428,41 19543). Is already known. The aforementioned compounds are known to generate menthol flavor when hydrolyzed or pyrolyzed.

[발명이 이루고자 하는 기술적 과제][Technical problem to be achieved]

본 발명자들은 담배, 식품, 의약품, 향료 등에 사용하기 위한 가향료, 특히 멘톨향을 발산하는 가향료를 개발하기 위하여 연구한 결과, 상기 구조식(Ⅰ)의 ℓ-멘틸-옥시알데히드를 발명하였고, 이 구조식(Ⅰ)의 화합물은 가수분해나 열분해되어 멘톨향을 낼 수 있는 전술한 공지의 화합물들과는 달리 보통상태에서도 멘톨향을 발생하며 열분해시에도 멘톨향을 발산시킴을 알게 되었다.The inventors of the present invention have studied to develop a flavoring agent for use in tobacco, food, medicine, flavoring, etc., in particular, a menthol-releasing flavoring agent, and invented the l-mentyl-oxyaldehyde of the formula (I). The compounds of formula (I) have been found to generate menthol flavours under normal conditions and to give off menthol flavours even when thermally decomposed, unlike the above known compounds which can be hydrolyzed or pyrolyzed to give menthol flavor.

상기 구조식(Ⅰ)의 ℓ-멘틸-옥시알데히드는 현재까지 알려지지 않은 새로운 물질이다.The l-menthyl-oxyaldehyde of the above formula (I) is a new substance which is unknown to date.

[발명의 구성 및 작용][Configuration and Function of Invention]

본 발명은 새로운 물질인 구조식(Ⅰ)의 ℓ-멘틸-옥시알데히드에 관계된다.The present invention relates to l-mentyl-oxyaldehyde of the formula (I) which is a new substance.

상기 구조식(Ⅰ)의 ℓ-멘틸-옥시알데히드는 ℓ-멘톨과 트리메틸 오르도포메이트를 반응시켜 제조한다. 따라서 본 발명은 ℓ-멘톨과 트리메틸 오르도포메이트를 반응시켜 ℓ-멘틸-옥시알데히드를 제조하는 방법에도 관계된다.The l-menthyl-oxyaldehyde of formula (I) is prepared by reacting l-menthol with trimethyl orthoformate. Therefore, the present invention also relates to a method of producing l-mentyl-oxyaldehyde by reacting l-menthol with trimethyl orthoformate.

전술한 ℓ-멘톨과 트리메틸 오르도포메이트를 반을시킬때는 ℓ-멘톨과 촉매를 유기용매에 녹여 트리메틸오르도포메이트와 반응시키는 것이 좋다.When half the aforementioned l-menthol and trimethyl orthoformate, it is preferable to dissolve the l-menthol and catalyst in an organic solvent and react with trimethylordoformate.

본 발명의 방법에 사용되는 용매로는 디클로로메탄, 클로로포름, 테트라히드로 퓨란, 벤젠, 톨루엔등이 있으며, 그 중에서도 가장 바람직한 것은 디클로로메탄이다. 본 발명의 방법에 사용되는 촉매로는 파라톨루엔 술폰산, 캄퍼술폰산, 황산, 암버라이트, 실리카겔 및 ZnCl2, AlCl3, TiCl4등의 루이스산이 있으며, 그 중에서도 가장 바람직한 것은 컴퍼술폰산이다.Solvents used in the method of the present invention include dichloromethane, chloroform, tetrahydrofuran, benzene, toluene and the like, and most preferred is dichloromethane. Catalysts used in the process of the present invention include paratoluene sulfonic acid, camphorsulfonic acid, sulfuric acid, amberlite, silica gel, and Lewis acids such as ZnCl 2 , AlCl 3 , TiCl 4 , and the most preferable one is compass sulfonic acid.

[발명의 효과][Effects of the Invention]

본 발명에 의하면 멘톨향이 보통때도 발산되고 열분해시에도 발산되어 담배, 식품, 의약품, 향료 등의 가향료로 유용하게 이용되는 신규 화합물이 얻어진다.According to the present invention, the menthol flavor is usually released and is also released during pyrolysis, thereby obtaining a novel compound which is usefully used as a flavoring agent for tobacco, food, medicine, perfume, and the like.

이하 본 발명을 실시예에 의하여 구체적으로 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail with reference to Examples.

[실시예]EXAMPLE

[실시예 1]Example 1

ℓ-멘틸-옥시알데히드의 제조Preparation of l-Mentyl-oxyaldehyde

5g의 ℓ-멘톨과 7g의 트리메틸 오르도포메이트를 60ml의 디클로로메탄에 녹이고 0.37g의 컴퍼술폰산을 첨가하여 실온에서 3시간 교반한 뒤 14g의 트리메틸 오르도포메이트를 더 첨가하고 실온에서 3시간 동안 더 교반시킨다. 10% NaHCO3용액으로 씻은 다음 탈수하여 농축하면 불순물이 포함된 무색의 액체가 얻어진다.Dissolve 5 g of l-menthol and 7 g of trimethyl orthoformate in 60 ml of dichloromethane, add 0.37 g of Compsulfonic Acid and stir for 3 hours at room temperature, then add 14 g of trimethyl orthoformate and further for 3 hours at room temperature. Stir. Washing with 10% NaHCO 3 solution, dehydrating and concentrating gives a colorless liquid containing impurities.

이 액체를 칼럼크로마토그라피하여 3.6g(61.1%수율)의 순수한 ℓ-멘틸 옥시알데히드를 얻었다.This liquid was chromatographed to give 3.6 g (61.1% yield) of pure l-mentyl oxyaldehyde.

최종 생성물의 NMR 분석결과는 다음과 같다.The NMR analysis of the final product is as follows.

400MHz,1H-NMR(CDCl3, δ) ; 0.76(d, 3H), 0.92(t, 6H), 1.02-2.07(m, 9H), 4.81(ddd, 1H), 8.08(s, 1H),13C-NMR(100MHz, CDCl3, ppm) ; 16.66, 21.36, 22.58, 23.88, 26.59, 32.02, 34.74, 41.50, 47.44, 74.69, 161.43,400 MHz, 1 H-NMR (CDCl 3 , δ); 0.76 (d, 3H), 0.92 (t, 6H), 1.02-2.07 (m, 9H), 4.81 (ddd, 1H), 8.08 (s, 1H), 13 C-NMR (100 MHz, CDCl 3 , ppm); 16.66, 21.36, 22.58, 23.88, 26.59, 32.02, 34.74, 41.50, 47.44, 74.69, 161.43,

Claims (5)

다음 구조식(Ⅰ)로 표시되는 ℓ-멘틸-옥시알데히드.L-mentyl-oxyaldehyde represented by the following structural formula (I). ℓ-멘톨과 트리메틸 오르도포메이트를 반응시켜 ℓ-멘틸 옥시알데히드를 제조하는 방법.A process for producing l-mentyl oxyaldehyde by reacting l-menthol with trimethyl orthoformate. 제2항에서, ℓ-멘톨과 트리메틸 오르도포메이트간의 반응이 유기용매중에서 촉매의 존재하에 진행됨을 특징으로 하는 방법.3. A process according to claim 2, wherein the reaction between l-menthol and trimethyl ordoformate proceeds in the presence of a catalyst in an organic solvent. 제3항에서, 용매가 디클로로메탄, 벤젠, 톨루엔, 클로로포름, 테트라히드로 퓨란 중에서 선택된 것임을 특징으로 하는 방법.4. The process of claim 3 wherein the solvent is selected from dichloromethane, benzene, toluene, chloroform, tetrahydrofuran. 제3항에서, 촉매가 ZnCl2, AlCl3, TiCl4, 실리카겔, 암버라이트, 파라톨루엔 술폰산, 캄퍼술폰산중에서 선택된 것임을 특징으로 하는 방법.4. The process of claim 3 wherein the catalyst is selected from ZnCl 2 , AlCl 3 , TiCl 4 , silica gel, amberlite, paratoluene sulfonic acid, camphorsulfonic acid.
KR1019960054794A 1996-11-18 1996-11-18 L-menthyl-oxyaldehyde and method of them KR0181713B1 (en)

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