KR970006249B1 - A method for preparation of 6-mono fatty acid ester of l-ascorbic acid - Google Patents
A method for preparation of 6-mono fatty acid ester of l-ascorbic acid Download PDFInfo
- Publication number
- KR970006249B1 KR970006249B1 KR1019940004183A KR19940004183A KR970006249B1 KR 970006249 B1 KR970006249 B1 KR 970006249B1 KR 1019940004183 A KR1019940004183 A KR 1019940004183A KR 19940004183 A KR19940004183 A KR 19940004183A KR 970006249 B1 KR970006249 B1 KR 970006249B1
- Authority
- KR
- South Korea
- Prior art keywords
- acid
- acid ester
- ascorbic acid
- monofatty
- ester
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/62—Three oxygen atoms, e.g. ascorbic acid
Landscapes
- 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
Description
본 발명은 L-아스코르빈산-6-모노지방산 에스테르의 제조방법에 관한 것이다.The present invention relates to a method for preparing L-ascorbic acid-6-monofatty acid ester.
L-아스코르빈산은 강한 항산화 작용을 갖는 생체 활성 물질로서 현재 의약, 화장품, 식품등 여러 분야에 응용되고 있지만, 열, 빛, 공기 중의 산소에 의해 쉽게 산회되어 그 활성을 상실하고 또한 오일류에 용해되지 않아 사용범위가 한계되는 문제점을 갖는다.L-ascorbic acid is a bioactive substance with strong antioxidant activity and is currently applied in various fields such as medicine, cosmetics, and food, but it is easily acidified by oxygen in heat, light, and air, and loses its activity and also dissolves in oils. There is a problem that the use range is limited.
이러한 단점들을 개선하기 위하여 각종 지방산을 이용하여 아스코르빈산 지방산 에스테르 유도체들을 제공하고자 하는 시도가 있었고 이러한 시도는 성공적이었다.In order to remedy these shortcomings, there have been attempts to provide ascorbic acid fatty acid ester derivatives using various fatty acids and this has been successful.
아스코르빈산 지방산 에스테르 유도체의 하나인 L-아스코르빈산-6-모노지방산 에스테르는 미국특허 2350435호, 일본 특허공고 昭 38-21365, 일본 특허공고 소昭42-20052호 및 문헌(J. Am. Oil Chem. Soc., 54, 308(1977)) 등에 황산을 이용하여 제조하는 방법과 지방산 할라이드를 이용하여 제조하는 방법이 EP296483호에 기재되어 있다.L-ascorbic acid-6-monofatty acid ester, which is one of ascorbic acid fatty acid ester derivatives, is described in US Patent No. 2350435, Japanese Patent Publication No. 38-21365, Japanese Patent Publication No. 42-20052, and J. Am. Oil Chem. Soc., 54, 308 (1977) and the like are described in EP296483 by using sulfuric acid and by using fatty acid halides.
상기 공지된 제조방법중 지방산 할라이드를 이용하는 방법은 86%이상의 높은 수율로 L-아스코르빈산-6-모노지방산 에스테르를 얻을 수 있으나, 고가인 N,N-디메틸아세트아미드와 같은 유기 용매와 지방산 클로라이드를 사용하기 때문에 경제적 측면에서 불리하다. 또한 황산을 이용한 방법은 경제적이며 비교적 높은 수율로 L-아스코르빈산-6-모노지방산 에스테르를 얻을 수는 있지만, 상기 지방산 할라이드를 사용한 방법과는 달리 L-아스코르빈산-6-모노지방산 에스테르와 함께 L-아스코르빈산-5-모노지방산 에스테르가 부산물로서 상당량 생성되고 순수한 L-아스코르빈산-6-모노지방산 에스테르를 제조하는데 있어서 순도 문제로 인하여 정제 공정이 번거로울 뿐만 아니라 부생성물인 L-아스코르빈산-5-모노지방산 에스테르의 분리로 인한 수율 감소가 초래된다고 하는 문제점을 갖는다.The fatty acid halide of the above known production method can be obtained in L- ascorbic acid-6- mono fatty acid ester with a high yield of 86% or more, but organic solvents such as expensive N, N- dimethylacetamide and fatty acid chloride It is disadvantageous in terms of economics because it uses. In addition, the method using sulfuric acid is economical and can yield L-ascorbic acid-6-monofatty acid ester in a relatively high yield, but unlike the method using the fatty acid halide, it is different from L-ascorbic acid-6-monofatty acid ester. Together, a significant amount of L-ascorbic acid-5-monofatty acid ester is produced as a by-product, and the purity problem in preparing pure L-ascorbic acid-6-monofatty acid ester is not only cumbersome but also a by-product of L-asth. There is a problem that the yield is reduced due to the separation of the corvinic acid-5-monofatty acid ester.
본 발명자들은 이러한 상황하에서 보다 간단한 공정으로 부산물인 L-아스코르빈산-5-모노지방산 에스테르를 함유하지 않는 고순도의 L-아스코르빈산-6-모노지방산 에스테르를 고수율로 제조하는 방법을 제공하고자 예의연구한 결과, 부산물인 L-아스코르빈산-5-모노지방산 에스테르를 목적산물인 L-아스코르빈산-6-모노지방산 에스테르로 전환시킬 수 있음을 발견하고 본 발명을 완성하기에 이르렀다.In this situation, the present inventors provide a method for producing a high-purity L-ascorbic acid-6-monofatty acid ester which does not contain the by-product L-ascorbic acid-5-monofatty acid ester in a simpler process under such a situation. As a result of intensive studies, the present inventors have found that the by-product L-ascorbic acid-5-monofatty acid ester can be converted into the target product L-ascorbic acid-6-monofatty acid ester, thereby completing the present invention.
즉, 본 발명의 목적은 황산 용매중에서 아스코르빈산과 지방산을 반응시켜 L-아스코르빈산-6-모노지방산 에스테르를 제조하는 방법에 있어서, 아스코르빈산과 탄소수 4∼18개의 직쇄 또는 분지 지방산을 반응시켜 L-아스코르빈산-6-모노지방산 에스테르와 L-아스코르빈산-6-모노지방산 에스테르를 함유하는 반응 혼합물을 얻고, 반응 혼합물을 산촉매를 함유하는 무극성 용매에서 35∼90℃로 가온하여 L-아스코르빈산-5-모노지방산 에스테르를 L-아스코르빈산-6-모노지방산 에스테르로 전환시킴을 특징으로 하는 하기 화학식(1)의 L-아스코르빈산-6-모노지방산 에스테르 제조방법을 제공하는 것이다.That is, an object of the present invention is to prepare L-ascorbic acid-6-monofatty acid ester by reacting ascorbic acid with a fatty acid in a sulfuric acid solvent, and ascorbic acid and a straight or branched fatty acid having 4 to 18 carbon atoms. Reaction to obtain a reaction mixture containing L-ascorbic acid-6-monofatty acid ester and L-ascorbic acid-6-monofatty acid ester, and the reaction mixture is warmed to 35-90 ° C. in an apolar solvent containing an acid catalyst. A process for preparing L-ascorbic acid-6-monofatty acid ester of formula (1) characterized by converting L-ascorbic acid-5-monofatty acid ester to L-ascorbic acid-6-monofatty acid ester To provide.
상기 식중, R은 탄소수 4∼18개의 직쇄 또는 분지 지방산을 나타낸다.In the formula, R represents a straight or branched fatty acid having 4 to 18 carbon atoms.
이하 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명의 방법은 공지 문헌(J. Am. Oil Chem. Soc., 54, 308(1977))에 공지된 황산을 이용한 L-아스코르빈산-6-모노지방산 에스테르의 제조방법을 개량한 것이다. 즉, 본 발명자들의 실험결과 상기 방법에 따라 탄소수 14이하의 지방산을 이용하여 L-아스코르빈산-6-모노지방산 에스테르를 제조하는 경우 부산물로서 L-아스코르빈산-5-모노지방산 에스테르가 약 10-30%정도로 다량 생성되는 것이 발견되었다(참조예 1). 특히 아스코르빈산 분지 지방산 에스테르의 경우 5-모노 에스테르가 약 30% 생성되며, 이를 6-모노 에스테르로부터 분리하기 위해서는 재결정 등의 별도의 분리방법이 요구된다(참조예 2). 순수한 5-모노 에스테르와 6-모노 에스테르 각각을 1.5M 농도로 황산에 용해시켜 하룻밤동안 교반한 후 황산 용액을 얼음물에 넣고 에테르로 추출하여 HPLC분석한 결과, 5-모노 에스테르와 6-모노 에스테르의 비는 3 : 7로 동일하게 존재하는 것을 발견하였다. 이러한 결과는 반응 생성물중에 5-모노 에스테르와 6-모노 에스테르가 평형 존재하는 것을 의미한다. 따라서 아스코르빈산 6-모노지방산 에스테르의 생성률이 상대적으로 적어지기 때문에 L-아스코르빈산-6-모노지방산 에스테르의 수율이 탄소수 14 이하의 지방산일수록 낮아지고, L-아스코르빈산-5-모노지방산 에스테르가 같이 존재함으로써 L-아스코르빈산-6-모노지방산 에스테르의 결정화가 어려우며 이를 고순도로 얻기 위해서는 수 회의 재결정 공정을 거쳐야 하기 때문에 정제방법이 복잡하게 된다.The method of the present invention is an improvement of the method for preparing L-ascorbic acid-6-monofatty acid ester using sulfuric acid known from the known literature (J. Am. Oil Chem. Soc., 54, 308 (1977)). That is, according to the experiments of the present inventors, when L-ascorbic acid-6-monofatty acid ester is produced using fatty acids having 14 or less carbon atoms according to the above method, L-ascorbic acid-5-monofatty acid ester is about 10 as a by-product. It was found that a large amount was generated at about -30% (Reference Example 1). In particular, ascorbic acid branched fatty acid esters produce about 30% of 5-mono esters, and in order to separate them from 6-mono esters, a separate separation method such as recrystallization is required (Reference Example 2). Pure 5-mono esters and 6-mono esters were dissolved in sulfuric acid at a concentration of 1.5 M, stirred overnight, and the sulfuric acid solution was poured into iced water, extracted with ether, and analyzed by HPLC. The ratio was found to be the same at 3: 7. This result means that the 5-mono ester and the 6-mono ester are in equilibrium in the reaction product. Therefore, since the production rate of ascorbic acid 6-monofatty acid ester is relatively low, the yield of L-ascorbic acid-6-monofatty acid ester is lower for fatty acids having 14 or less carbon atoms, and L-ascorbic acid-5-monofatty acid The presence of the esters together makes crystallization of the L-ascorbic acid-6-monofatty acid ester difficult, and the purification method is complicated because several recrystallization steps are required to obtain the high purity.
그러나 본 발명자는 부산물인 L-아스코르빈산-5-모노지방산 에스테르가 무극성 용매에서 산촉매에 의하여 L-아스코르빈산-6-모노지방산 에스테르로 전이되는 것을 발견하였다. 즉, 황산을 이용한 공지의 방법으로 생성된 L-아스코르빈산-5-모노지방산 에스테르와 L-아스코르빈산-6-모노지방산 에스테르의 혼합물을 무극성 용매에 용해하고 여기에 촉매량의 산을 가하여 처리하므로써 L-아스코르빈산-5-모노지방산 에스테르를 열역학적으로 안정한 L-아스코르빈산-6-모노 지방산 에스테르로 거의 전이시킬 수 있었다.However, the inventors have found that the by-product L-ascorbic acid-5-monofatty acid ester is transferred to L-ascorbic acid-6-monofatty acid ester by an acid catalyst in a nonpolar solvent. That is, a mixture of L-ascorbic acid-5-monofatty acid ester and L-ascorbic acid-6-monofatty acid ester produced by a known method using sulfuric acid is dissolved in a nonpolar solvent and treated by adding a catalytic amount of acid thereto. As a result, the L-ascorbic acid-5-monofatty acid ester can be almost transferred to the thermodynamically stable L-ascorbic acid-6-mono fatty acid ester.
따라서 본 발명의 방법에 의하면 L-아스코르빈산-5-모노지방산 에스테르가 L-아스코르빈산-6-모노지방산 에스테르로 전이되므로 수율 증대는 물론 정제공정도 단순하여지기 때문에 경제적으로 L-아스코르빈산-6-모노지방산 에스테르를 제조할 수 있다. 특히 이 방법은 탄소수 4∼14, 특히 8∼12개의 지방산의 L-아스코르빈산-6-모노지방산 에스테르 제조에 유용하다.Therefore, according to the method of the present invention, since L-ascorbic acid-5-monofatty acid ester is transferred to L-ascorbic acid-6-monofatty acid ester, the yield process is simplified and the purification process is simplified. Vinic acid-6-monofatty acid esters can be prepared. This method is particularly useful for the production of L-ascorbic acid-6-monofatty acid esters of 4 to 14 carbon atoms, in particular 8 to 12 fatty acids.
본 발명의 제조공정을 상세히 설명하면, 황산을 이용하는 공지의 방법(J. Am. Oil Chem. Soc., 54, 308(1977))으로 제조한 L-아스코르빈산-5-모노지방산 에스테르와 L-아스코르빈산-6-모노지방산 에스테르의 혼합물을 무극성 용매에 5∼50중량% 농도로 용해하고 촉매량의 산을 첨가하여 약 10∼90℃에서 약 10분 내지 60분간 가열 교반하여 L-아스코르빈산-5-모노지방산 에스테르가 L-아스코르빈산-6-모노지방산 에스테르로 전이된다. 본 발명의 공정에서 사용될 수 있는 무극성 용매로는 디클로로메탄, 클로로포름, 사염화탄소, 벤젠, 톨루엔을 예시할 수 있다. 그 중에서 할로카본류, 특히 클로로로포름이 적당하다. 벤젠류의 용매는 L-아스코르빈산-5-모노지방산 에스테르를 단독으로 용해시키는 경우 그의 용해도가 낮아 전이 반응시 반응물이 탄화되는 문제가 있으나 L-아스코르빈산-6-모노지방산 에스테르가 혼합된 경우에는 탄화가 거의 일어나지 않아 사용 가능하며, 특히 탄소수 12개 이상의 고급지방산 에스테르의 전이에 적당하다.When explaining the manufacturing process of the present invention in detail, L- ascorbic acid-5- mono fatty acid ester and L prepared by a known method using sulfuric acid (J. Am. Oil Chem. Soc., 54, 308 (1977)) -A mixture of ascorbic acid-6-monofatty acid ester is dissolved in a nonpolar solvent at a concentration of 5 to 50% by weight, a catalytic amount of acid is added, and the mixture is heated and stirred at about 10 to 90 ° C for about 10 to 60 minutes to give L-ascor Vinic acid-5-monofatty acid ester is converted to L-ascorbic acid-6-monofatty acid ester. Nonpolar solvents that can be used in the process of the present invention include dichloromethane, chloroform, carbon tetrachloride, benzene, toluene. Among them, halocarbons, particularly chloroform, are suitable. The solvent of benzene has a low solubility in case of dissolving L-ascorbic acid-5-monofatty acid ester alone, but the reaction product is carbonized during the transition reaction, but L-ascorbic acid-6-monofatty acid ester is mixed. In this case, carbonization hardly occurs and can be used, and is particularly suitable for the transition of higher fatty acid esters having 12 or more carbon atoms.
반응 온도는 10∼90℃의 범위내에 있을 수 있지만, 저온에서는 전이 속도가 느리고, 고온에서는 변색의 문제가 있어 35∼75℃의 범위, 특히 56∼60℃범위의 온도가 바람직하다.Although the reaction temperature may be in the range of 10 to 90 ° C, the transition rate is low at low temperatures, and there is a problem of discoloration at high temperatures, and a temperature in the range of 35 to 75 ° C, particularly 56 to 60 ° C is preferable.
무극성 용매에 용해되는 L-아스코르빈산-5-모노지방산 에스테르와 L-아스코르빈산-6-모노지방산 에스테르의 혼합물의 농도는 5-50중량%까지 가능하나 10중량%가 가장 적당하다.The concentration of the mixture of L-ascorbic acid-5-monofatty acid ester and L-ascorbic acid-6-monofatty acid ester dissolved in a non-polar solvent can be up to 5-50% by weight, but 10% by weight is most suitable.
사용 촉매로는 건조 염산가스, 황산, p-톨루엔설폰산이 있으나 황산이 가장 적당하다.The catalysts used are dry hydrochloric acid gas, sulfuric acid and p-toluenesulfonic acid, but sulfuric acid is most suitable.
이하 실시예를 통하여 본 발명의 방법을 보다 상세히 설명한다. 참조예 1에서는 황산을 이용한 공지된 방법을 제조한 아스코르빈산 모노지방산 에스테르들의 HPLC 분석결과를, 참조예 2에서는 아스코르빈산-5-모노에틸엑산산 에스테르의 제조방법을, 실시예 1에서는 본 발명의 방법에 따라 아스코르빈산-6-모노에틸헥산 에스테르를 제조하는 방법을 기술한다.The following describes the method of the present invention in more detail. In Reference Example 1, HPLC analysis results of ascorbic acid monofatty acid esters prepared by a known method using sulfuric acid are shown. In Reference Example 2, a method of preparing ascorbic acid-5-monoethyl acid ester is shown in Example 1. According to the method of the invention, a process for preparing ascorbic acid-6-monoethylhexane ester is described.
[참조예 1]Reference Example 1
공지된 방법[(J. Am. Oil Chem. Soc., 54, 308(1977))]에 의하여 각종 지방산을 이용하여 제조한 아스코르빈산 모노지방산 에스테르 혼합물을 초산에틸에 적당한 농도로 희석하여 HPLC를 행하고, 결과를 표 1에 나타내었다.HPLC was obtained by diluting the ascorbic acid monofatty acid ester mixture prepared using various fatty acids to an appropriate concentration in ethyl acetate by a known method (J. Am. Oil Chem. Soc., 54, 308 (1977)). The results are shown in Table 1.
칼럼 : μBondapak Phenyl(3.9mm×300mm, 10μm)Column: μBondapak Phenyl (3.9mm × 300mm, 10μm)
이동상 : 메탄올; 0.05N 초산나트륨=3 : 7Mobile phase: methanol; 0.05N sodium acetate = 3: 7
주사량 : 15μlInjection volume: 15μl
[참조예 2]Reference Example 2
L-아스코르빈산-5-모노에틸헥산산 에스테르의 제조Preparation of L-ascorbic acid-5-monoethylhexanoic acid ester
L-아스코르빈산 30g(70.34mmol)을 97% 황산 300ml에 녹였다. 2-에틸헥산산 38.4ml(240.45mmol)을 가하고 상온에서 36시간 교반하였다. 반응액을 각빙 1700g에 가하고 초산에틸 250ml로 2회 추출하였다. 추출액을 포화소금수로 3회 세척하고 황산마그네슘을 가하여 건조하였다. 추출액을 포화소금수로 3회 세척하고 황산마그네슘을 가하여 건조하였다. 여과하고 감압 농축한 후 n-헥산을 가하여 결정화된 L-아스코르빈산-6-모노에틸헥산산 에스테르를 여과하였다. 여액을 다시 감압 농축하고 초산에틸-n-헥산에서 L-아스코르빈산-6-모노에틸헥산산 에스테르를 결정화하여 제거하였다. 이 공정을 3회 더 실시한 여액을 농축하고 잔사를 톨루엔으로 결정화하여 표제 화합물을 3,6g(7%)의 백색 고체로 얻었다.30 g (70.34 mmol) of L-ascorbic acid were dissolved in 300 ml of 97% sulfuric acid. 38.4 ml (240.45 mmol) of 2-ethylhexanoic acid were added and stirred at room temperature for 36 hours. The reaction solution was added to 1700 g of ice cubes, and extracted twice with 250 ml of ethyl acetate. The extract was washed three times with saturated brine, and dried over magnesium sulfate. The extract was washed three times with saturated brine, and dried over magnesium sulfate. After filtration and concentration under reduced pressure, n-hexane was added to the crystallized L-ascorbic acid-6-monoethylhexanoic acid ester. The filtrate was concentrated under reduced pressure again and removed by crystallization of L-ascorbic acid-6-monoethylhexanoic acid ester in ethyl acetate-n-hexane. The filtrate, which was subjected to this process three more times, was concentrated and the residue was crystallized with toluene to give 3,6 g (7%) of the title compound as a white solid.
mp : 61∼62℃mp: 61-62 degreeC
TLC(디에틸에테르 : 초산=30 : 1)Rf0.78TLC (diethyl ether: acetic acid = 30: 1) R f 0.78
NMR(CDCl3+DMSO-d6,200MHz,δ)0.8∼1.62(m,14H),2.23(m,1H),3.76(d,1H)j, 4.99(d,1H), 5.56(m,1H)NMR (CDCl 3 + DMSO-d 6 , 200 MHz, δ) 0.8 to 1.62 (m, 14H), 2.23 (m, 1H), 3.76 (d, 1H) j, 4.99 (d, 1H), 5.56 (m, 1H )
[실시예 1]Example 1
L-아스코르빈산-6-모노에틸헥산산 에스테르의 제조Preparation of L-ascorbic acid-6-monoethylhexanoic acid ester
L-아스코르빈산 30g(170.34mmol)을 97% 황산 300ml에 녹였다. 2-에틸헥산산 38.4ml(240.45mmol)을 가하고 상온에서 36시간 교반하였다. 반응액을 각빙 1700g에 가하고 초산에틸 250ml로 2회 추출하였다. 추출액을 포화 소금수로 3회 세척하고 감압 농축하였다. 잔사에 틀루엔 300ml와 황산 0.1ml를 가하고 50℃에서 20분간 교반하였다. 톨루엔 감압 농축하고 잔사를 초산에틸 300ml에 녹였다. 포화 소금수로 2회 세척한 황산마그네슘을 가하여 건조하였다. 여과하고 가압 농축한 후 n-헥산을 가하여 결장화하여 45g(87.4%)의 백색 고체를 얻었다.30 g (170.34 mmol) of L-ascorbic acid were dissolved in 300 ml of 97% sulfuric acid. 38.4 ml (240.45 mmol) of 2-ethylhexanoic acid were added and stirred at room temperature for 36 hours. The reaction solution was added to 1700 g of ice cubes, and extracted twice with 250 ml of ethyl acetate. The extract was washed three times with saturated brine and concentrated under reduced pressure. 300 ml of toluene and 0.1 ml of sulfuric acid were added to the residue, which was stirred for 20 minutes at 50 ° C. Toluene was concentrated under reduced pressure, and the residue was dissolved in 300 ml of ethyl acetate. Magnesium sulfate washed twice with saturated brine was added and dried. Filtration and concentration under pressure were followed by colonization by addition of n-hexane to give 45 g (87.4%) of a white solid.
mp : 82∼85℃mp: 82-85 degreeC
TLC(디에틸에테르 : 초산=30 : 1)Rf0.64TLC (diethyl ether: acetic acid = 30: 1) R f 0.64
NMR(CDCl3+200MHz,δ)0.8∼1.68(m,14H), 2.3(m,1H), 4.28(d,1H), 4.43(broad,1H), 4.76(s,1H), 4.84(broad,1H), 7.07(broad,1H), 9.95(broad,1H).NMR (CDCl 3 +200 MHz, δ) 0.8 to 1.68 (m, 14H), 2.3 (m, 1H), 4.28 (d, 1H), 4.43 (broad, 1H), 4.76 (s, 1H), 4.84 (broad, 1H), 7.07 (broad, 1H), 9.95 (broad, 1H).
[실시예 2]Example 2
L-아스코르빈산-6-모노이소발레린산 에스테르의 제조Preparation of L-ascorbic acid-6-monoisovaleric acid ester
실시예 1과 동일하게 실시하되, 에틸헥산산 대신에 이소발레린산을 사용하여 표제 화합물 47g(89.4%)을 백색 고체로 얻었다.In the same manner as in Example 1, 47 g (89.4%) of the title compound was obtained as a white solid using isovaleric acid instead of ethylhexanoic acid.
[실시예 3]Example 3
L-아스코르빈산-6-모노에틸헥산 에스테르의 제조Preparation of L-ascorbic acid-6-monoethylhexane ester
실시예 1과 동일하게 실시하되, 무극성 용매로서 톨루엔 대신에 클로로포름을 사용하여 표제 화합물 46g(88.6%)을 백색 고체로 얻었다.In the same manner as in Example 1, 46 g (88.6%) of the title compound was obtained as a white solid using chloroform instead of toluene as a nonpolar solvent.
[실시예 4]Example 4
L-아스코르빈산-6-모노에틸헥산산 에스테르의 제조Preparation of L-ascorbic acid-6-monoethylhexanoic acid ester
실시예 1과 동일하게 실시하되, 산 촉매제로서 황산 대신에 건조 염산 가스를 사용하여 표제 화합물 44.5g(85.5%)을 백색 고체로 얻었다.In the same manner as in Example 1, 44.5 g (85.5%) of the title compound was obtained as a white solid using dry hydrochloric acid gas instead of sulfuric acid as the acid catalyst.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019940004183A KR970006249B1 (en) | 1994-03-04 | 1994-03-04 | A method for preparation of 6-mono fatty acid ester of l-ascorbic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019940004183A KR970006249B1 (en) | 1994-03-04 | 1994-03-04 | A method for preparation of 6-mono fatty acid ester of l-ascorbic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR950026867A KR950026867A (en) | 1995-10-16 |
| KR970006249B1 true KR970006249B1 (en) | 1997-04-25 |
Family
ID=19378334
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019940004183A KR970006249B1 (en) | 1994-03-04 | 1994-03-04 | A method for preparation of 6-mono fatty acid ester of l-ascorbic acid |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR970006249B1 (en) |
-
1994
- 1994-03-04 KR KR1019940004183A patent/KR970006249B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR950026867A (en) | 1995-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2566826C1 (en) | Method of producing 1-palmitoyl-3-acetylglycerine and method of producing 1-palmitoyl-2-linoleoyl-3-acetylglycerine using said compound | |
| ES2413480T3 (en) | Method to produce L-biopterin | |
| KR100346672B1 (en) | Method for preparing 3-O-substituted ascorbic acid | |
| DE60202483T2 (en) | PROCESS FOR THE PREPARATION OF L-RIBAVIRIN | |
| JPH0378394B2 (en) | ||
| CA1325423C (en) | Process for the synthesis of azido-3'-deoxy-3'-thiamidine and analogs | |
| FR2852012A1 (en) | PROCESS FOR THE PREPARATION OF O-ACYLATED GLUCOSE DERIVATIVES | |
| JP2507543B2 (en) | Method for producing derivative of ascorbic acid | |
| KR20080027368A (en) | Method for producing nebivolol | |
| KR970006249B1 (en) | A method for preparation of 6-mono fatty acid ester of l-ascorbic acid | |
| JPS5835992B2 (en) | Method for purifying natural prostaglandins and synthetic analogs of prostaglandins | |
| WO2002022618A1 (en) | Method for preparing camptothecin and its derivatives | |
| EP0685473B1 (en) | Benzoheterocyclic compounds, as antioxidants | |
| CN110950836A (en) | Preparation method of benzodithiol heterocyclic alkene skeleton compound | |
| CN111333513B (en) | Preparation method of 2,4-difluoro-3-nitrobenzoic acid | |
| KR0157422B1 (en) | Process for production of 6-(3-dimethylamino-propionyl)forskolin | |
| EP0220822B1 (en) | Ascorbic acid or erythorbic acid derivatives and process for producing same | |
| JPH03279348A (en) | Production of 2,4,5-trifluoro-3-alkoxybenzoic acid | |
| JPS6053039B2 (en) | N-Acetyl/Iramic acid derivative and method for producing the same | |
| CS9692A3 (en) | Process for preparing 3-fluoropyrimidine nucleosides | |
| FR2479192A1 (en) | PROCESS FOR THE PREPARATION OF TETRA-SUBSTITUTED CYCLOPROPANIC DERIVATIVES | |
| JP4121044B2 (en) | Method for producing sialic acid derivative | |
| JP2000510486A (en) | α-Tocopherol-4-aminobenzoic acid ester compound and method for producing the same | |
| FR2580644A1 (en) | Derivatives of ascorbic acid | |
| KR0176327B1 (en) | Preparation process of 7,8-difluoro-benzoxazine derivatives |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| G160 | Decision to publish patent application | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20070316 Year of fee payment: 11 |
|
| LAPS | Lapse due to unpaid annual fee |