KR0133533B1 - Ascorbic acid derivatives - Google Patents
Ascorbic acid derivativesInfo
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- KR0133533B1 KR0133533B1 KR1019890011206A KR890011206A KR0133533B1 KR 0133533 B1 KR0133533 B1 KR 0133533B1 KR 1019890011206 A KR1019890011206 A KR 1019890011206A KR 890011206 A KR890011206 A KR 890011206A KR 0133533 B1 KR0133533 B1 KR 0133533B1
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- 0 CC(C)(O)OCC(*=C1C)OC1=O Chemical compound CC(C)(O)OCC(*=C1C)OC1=O 0.000 description 1
- ANRKRUGERVXBOQ-UHFFFAOYSA-N CC(C1C(COC(C)(C)O)O2)C1(C)C2=O Chemical compound CC(C1C(COC(C)(C)O)O2)C1(C)C2=O ANRKRUGERVXBOQ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/06—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/20—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen and oxygen
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- Materials Engineering (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
- Furan Compounds (AREA)
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Abstract
요약없음No summary
Description
본 발명은 아스코르브산 유도체, 이것의 제조방법 및 아스코르브산 유도체를 함유하는 항산화제에 관한 것이다.The present invention relates to an ascorbic acid derivative, a method for preparing the same, and an antioxidant containing the ascorbic acid derivative.
아스코르브산은 항산화작용을 하고 이것은 식품의 갈변 방지, 식품의 풍미 또는 신선도 유지 등을 목적으로 사용된다.Ascorbic acid acts as an antioxidant and is used to prevent browning of foods and to maintain the flavor or freshness of foods.
그러나, 아스코르브산은 분해되기 쉬우며 때로는 장시간 동안 상기 효과를 얻기 어렵다.However, ascorbic acid is liable to decompose and sometimes it is difficult to obtain the effect for a long time.
그러므로, 본 발명의 제1의 목적은 아스코르브산의 상기 단점이 해결된 신규의 아스코르브산 유도체를 제공함에 있다. 본 발명의 제2목적은 상기의 신규인 아스코르브산 유도체의 제조방법을 제공함에 있다. 더우기, 본 발명의 제3의 목적은 아스코르브산 유도체를 함유하는 항산화제를 제공함에 있다.Therefore, a first object of the present invention is to provide a novel ascorbic acid derivative in which the above disadvantage of ascorbic acid is solved. It is a second object of the present invention to provide a method for preparing the novel ascorbic acid derivative. Furthermore, a third object of the present invention is to provide an antioxidant containing an ascorbic acid derivative.
본 발명의 제1의 목적은 하기 일반식(Ia)의 아스코르브산 유도체에 의하여 달성된다.A first object of the present invention is achieved by an ascorbic acid derivative of the general formula (Ia).
(식중, R1은 헤테로고리-함유 알킬기, 알킬카르보닐알킬기, 아릴카르보닐알킬기 및 최소한 7탄소원자의 말단알콕시기를 함유하는 알콕시카르보닐알킬기로 이루어지는 군에서 선택되는 기이다.)(Wherein R 1 is a group selected from the group consisting of a heterocyclic-containing alkyl group, an alkylcarbonylalkyl group, an arylcarbonylalkyl group and an alkoxycarbonylalkyl group containing a terminal alkoxy group of at least 7 carbon atoms)
본 발명의 제2의 목적은, 하기 일반식(II)의 화합물을 산으로 처리하여 화합물 중의 디옥솔란 고리를 개환시키고 vic-글리콜기를 제조함을 특징으로 하는, 하기 일반식(Ia)의 아스코르브산 유도체의 제조방법에 의하여 달성된다.A second object of the present invention is ascorbic acid of the general formula (Ia), characterized in that the compound of the general formula (II) is treated with an acid to open the dioxolane ring in the compound to produce a vic-glycol group. It is achieved by a process for the preparation of derivatives.
(식중, R1은 헤테로고리-함유 알킬기, 알킬카르보닐알킬기, 알릴카르보닐알킬기 및 최소한 7탄소원자의 말단알콕시기를 함유하는 알콕시카르보닐알킬기로 이루어지는 군에서 선택되는 기이다.)(Wherein R 1 is a group selected from the group consisting of a heterocyclic-containing alkyl group, an alkylcarbonylalkyl group, an allylcarbonylalkyl group and an alkoxycarbonylalkyl group containing a terminal alkoxy group of at least 7 carbon atoms)
더욱이, 본 발명의 제3의 목적은 하기 일반식(IA)의 아스코르브산 유도체를 함유하는 항산화제에 의하여 달성된다.Furthermore, a third object of the present invention is achieved by an antioxidant containing an ascorbic acid derivative of the general formula (IA).
(식중, R2은 알킬기, 헤테로고리함유 -알킬기, 아르알킬기, 히드록시키르보닐알킬기, 알목시카르보닐알킬기, 알킬카르보닐알킬기, 아릴카르보닐알킬기로 이루어지는 군에서 선택되는 기이다.)(Wherein R 2 is a group selected from the group consisting of an alkyl group, a heterocyclic containing-alkyl group, an aralkyl group, a hydroxykicarbonylalkyl group, an almoxicarbonylalkyl group, an alkylcarbonylalkyl group and an arylcarbonylalkyl group.)
본 발명의 신규인 아스코르브산 유도체를 나타내는 일반식(Ia)중의 R1기는, 본 발명의 항산화제조성-아스코르브산 유도체를 나타내는 일반식(IA)중의 R2기와는 정의되는 치환기의 수가 다르다. R1는 4종류의 치환기를 함유하지만, R2는 이들 4종류를 포함하여 총 7종류의 치환기를 함유한다. 일반식(Ia)의 R1기 중의 알콕시카르보닐알킬기는 최소한 7탄소원자의 말단알콕시기를 함유하는 것으로 한정되는 반면, 이러한 제한은 일반식(IA)의 R2기중의 알콕시카르보닐알킬기에는 해당되지 않는다. 이것은 신규의 아스코르브산 유도체를 정의하는 일반식(Ia)을 제외한 아스코르브산 유도체로 또한 본 발명의 항산화제로서 사용할 수 있음을 뜻한다.The group R 1 in the general formula (Ia) representing the novel ascorbic acid derivative of the present invention is different from the number of substituents defined in the group R 2 in the general formula (IA) representing the antioxidant-ascorbic acid derivative of the present invention. R 1 contains four substituents, but R 2 contains a total of seven substituents including these four. While the alkoxycarbonylalkyl group in the R 1 group of formula (Ia) is limited to containing at least seven carbon atom terminal alkoxy groups, this limitation does not apply to the alkoxycarbonylalkyl group in the R 2 group of formula (IA). . This means that ascorbic acid derivatives except general formula (Ia), which defines novel ascorbic acid derivatives, can also be used as antioxidants of the present invention.
우선 본 발명의 신규인 아스코르브산 유도체를 하기에 설명하겠다.First, the novel ascorbic acid derivative of the present invention will be described below.
본 발명의 신규인 아스코르브산 유도체는 하기 일반식(Ia)로 나타낸다.The novel ascorbic acid derivative of the present invention is represented by the following general formula (Ia).
(식중, R1은 헤테로고리-함유 알킬기, 알킬카르보닐알킬기, 알릴카르보닐알킬기 및 최소한 7탄소원자의 말단알콕시기를 함유하는 알콕시카르보닐알킬기로 이루어지는 군에서 선택되는 기이다.)(Wherein R 1 is a group selected from the group consisting of a heterocyclic-containing alkyl group, an alkylcarbonylalkyl group, an allylcarbonylalkyl group and an alkoxycarbonylalkyl group containing a terminal alkoxy group of at least 7 carbon atoms)
여기에서 헤테로고리-함유 알킬기로서는 고리중에 1내지 3질소원자를 함유하는 헤테로고리-함유알킬기가 바람직하고, 이들의 예는 하기 일반적으로 나타내지는 기를 포함한다.Here, as the heterocyclic-containing alkyl group, a heterocyclic-containing alkyl group containing 1 to 3 nitrogen atoms in the ring is preferable, and examples thereof include the groups generally shown below.
(식중, R3은 임의로 측쇄를 함유할 수 있는 알킬렌기이다.)Wherein R 3 is an alkylene group which may optionally contain a side chain.
특히, 바람직한 헤테로고리-함유 알킬기는 피리딜매틸기, 피리미딜매틸기, 트리아질매틸기 등이다.In particular, preferred heterocyclic-containing alkyl groups are pyridylmethyl group, pyrimidylmethyl group, triazylmethyl group and the like.
알킬카르보닐알킬기의 예는 하기 일반식으로 나타내지는 기를 포함한다.Examples of the alkylcarbonylalkyl group include a group represented by the following general formula.
(식중, R4은 임의로 측쇄를 함유할 수 없는 알킬렌기이고 ; R5은 임의로 측쇄를 함유할 수 있는 알킬기이다.)(Wherein R 4 is an alkylene group which may not optionally contain a side chain; R 5 is an alkyl group which may optionally contain a side chain.)
특히 바람직한 알킬카르보닐알킬기는 -CH2-CO-CH3, -CH2-CO-C2H5등이다.Particularly preferred alkylcarbonylalkyl groups are -CH 2 -CO-CH 3 , -CH 2 -CO-C 2 H 5, and the like.
더욱이, 아릴카르보닐알킬기의 예는 하기 일반식으로 나타내지는 기를 포함한다.Moreover, examples of the arylcarbonylalkyl group include a group represented by the following general formula.
(식중, R6은 임의로 측쇄를 함유할 수 있는 알킬렌기이고 ; Ar은 임의로 고리에 치환기를 함유할 수 있는 아릴기이다.)(Wherein R 6 is an alkylene group which may optionally contain a side chain; Ar is an aryl group which may optionally contain a substituent on the ring.)
특히 바람직한 아릴카르보닐알킬기는-CH2-CO-C6H5등이다.Particularly preferred arylcarbonylalkyl groups are -CH 2 -CO-C 6 H 5 and the like.
최소한 7탄소원자의 말단알콕시기를 함유하는 알콕시카르보닐알킬기의 예는 하기 일반식으로 나타내지는 기를 포함한다.Examples of the alkoxycarbonylalkyl group containing at least seven carbon atom terminal alkoxy groups include groups represented by the following general formula.
(식중, R7은 임의로 측쇄를 함유할 수 있는 알킬렌기이고 R8은 임의로 측쇄를 함유할 수 있는 7이상 탄소원자의 알킬기이다.)(Wherein R 7 is an alkylene group which may optionally contain a side chain and R 8 is an alkyl group of 7 or more carbon atoms which may optionally contain a side chain.)
특히 바람직한 알콕시카르보닐알킬기는 -CH2-CO-O-n-C10H21등이다.Particularly preferred alkoxycarbonylalkyl groups are -CH 2 -CO-OnC 10 H 21 and the like.
본 발명의 신규인 아스코르브산 유도체는 우수한 항산화작용을 하고 바람직하게는 식품의 항산화제 또는 미용 및 미백화장품으로서 사용할 수 있다.The novel ascorbic acid derivatives of the present invention have excellent antioxidant activity and can preferably be used as antioxidants in foods or cosmetic and whitening cosmetics.
본 발명의 상기한 일반식(Ia)의 신규인 아스코르브산 유도체의 제조방법을 하기에 설명하겠다.The method for producing a novel ascorbic acid derivative of general formula (Ia) described above will be described below.
본 발명의 제조에 있어서, 하기 일반식(II)의 화합물을 출발물질로서 사용한다.In the preparation of the present invention, the compound of the following general formula (II) is used as starting material.
(식중, R1은 헤테로고리-함유 알킬기, 알킬카르보닐알킬기, 아릴카르보닐알킬기 및 최소한 7탄소원자의 말단알콕시기를 함유하는 알콕시카르보닐알킬기로 이루어지는 군에서 선택되는 기이다.)(Wherein R 1 is a group selected from the group consisting of a heterocyclic-containing alkyl group, an alkylcarbonylalkyl group, an arylcarbonylalkyl group and an alkoxycarbonylalkyl group containing a terminal alkoxy group of at least 7 carbon atoms)
일반식 (II)의 화합물은, 종래의 방법에 의하여 아스코르브산을 캐탈화시키므로써 하기 일반식(III)의 5,6-O-이소프로필리덴아스코르브산을 제조하고, 다시 제조된 화합물(III)을 일반식 R1X(식중, R1은 일반식 (II)의 R1과 동일하고, X는 할로겐원자이다.)의 유기할로겐화물과 반응시켜서 화합물 (III)의 3위치에서 수산기를 에테르화시키므로써 수득된다. 이러한 할로겐화수소이탈반응은 Williamson반응에 의해서 행하여지거나 또는 상이동촉매를 사용하는 유기상-수성상게 내에서 행하여질 수 있다.Compound of formula (II) catalyzes ascorbic acid by a conventional method to prepare 5,6-O-isopropylidene ascorbic acid of the following formula (III), and then to prepare compound (III) Is reacted with an organic halide of formula R 1 X (wherein R 1 is the same as R 1 in formula (II) and X is a halogen atom) to etherify the hydroxyl group at position 3 of compound (III). Obtained by. This dehydrohalation reaction can be carried out by the Williamson reaction or in an organic phase-aqueous phase using a phase transfer catalyst.
본 발명의 제조방법에 의햐면, 출발물질인 화합물(II)를 산처리하여 상기 화합물의 디옥솔란고리를 개환시키므로써 vic-글리콜기를 제조한다. 이와같이하여 일반식(Ia)로 나타내지는 목적의 아스코르브산 유도체를 수득한다.According to the production method of the present invention, a vic-glycol group is prepared by subjecting compound (II) as a starting material to ring-open the dioxolane ring of the compound. Thus, the ascorbic acid derivative of the objective represented by general formula (Ia) is obtained.
반응에 사용하는 산의 예로는 염산, 아세트산, 황산, p-톨루엔술폰산, 메탄술폰산, 캄파술폰산 등을 들 수 있다. 본 반응은 바람직하게는 메탄올, 에탄올, 디옥산, 테트라히드로푸란 및 1,2-디메톡시에탄중에서 선택되는 최소한 하나의 유기용매에서 행한다.Examples of the acid used for the reaction include hydrochloric acid, acetic acid, sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, camphorsulfonic acid and the like. The reaction is preferably carried out in at least one organic solvent selected from methanol, ethanol, dioxane, tetrahydrofuran and 1,2-dimethoxyethane.
본 발명의 항산화제를 하기에 설명하겠다.The antioxidant of the present invention will be described below.
상술한 바와 같이, 본 발명의 항산화제는 하기 일반식(IA)의 아스코르브산 유도체를 함유한다.As mentioned above, the antioxidant of the present invention contains an ascorbic acid derivative of the general formula (IA).
일반식(IA)중의 R2기는 상수한 바와 같은 신규의 아스코르브산 유도체를 나타내는 일반식(Ia)중의 R1기보다 넓은 범위이내이고, 따라서 일반식(IA)의 아스코르브산 유도체는 또한 공지된 화합물을 포함하기도 한다.The R 2 group in formula (IA) is within a broader range than the R 1 group in formula (Ia), which represents a novel ascorbic acid derivative as constant, so ascorbic acid derivatives of formula (IA) are also known compounds It may also include.
즉, R2기는 R1기와 유사한 4종류의 치환기(헤테로고리-함유 알킬기, 알킬카르보닐알킬기, 아릴카르보닐알킬기 및 알콕시카르보닐알킬기)를 함유하고, 더욱이 이들외에 알킬기, 아르알킬기 및 히드록시카르보닐알킬기의 3종류의 치환기를 함유한다. 상기한 치환기중의 알킬이란 용어는 직쇄 또는 측쇄알킬기를 뜻한다. 일반식(Ia)의 R1기중의 알콕시카르보닐알킬기는 최소한 7탄소원자의 말단알콕시기를 함유하는 것에 한정되지만, 일반식(IA)의 R2기는 이러한 제한없이 광범위한 알콕시카르보닐알킬기를 포함한다.That is, the R 2 group contains four kinds of substituents (heterocyclic-containing alkyl group, alkylcarbonylalkyl group, arylcarbonylalkyl group and alkoxycarbonylalkyl group) similar to the R 1 group, and in addition to these, an alkyl group, an aralkyl group and a hydroxycar It contains three types of substituents of a carbonylalkyl group. The term alkyl in the above substituents refers to a straight or branched chain alkyl group. Although the alkoxycarbonylalkyl group in the R 1 group of formula (Ia) is limited to containing at least 7 carbon atom terminal alkoxy groups, the R 2 group of formula (IA) includes a wide range of alkoxycarbonylalkyl groups without such limitation.
일반식(IA)에 의하여 나타내지는 아스코르브산 유도체는 라디칼제거능력이 없고, 아스코르브산 및 종래의 아스코르브산 유도체보다 안정성이 우수하다는 장점이 있으므로 항산화제로서 바람직하게 사용된다.Ascorbic acid derivatives represented by the general formula (IA) are preferably used as antioxidants because they do not have radical scavenging ability and are superior in stability to ascorbic acid and conventional ascorbic acid derivatives.
본 발명의 실시예를 하기에 설명하겠다.Examples of the present invention will be described below.
제조예 1 [신규인 아스코르브산 유도체(Ia)의 제조]Preparation Example 1 [Preparation of New Ascorbic Acid Derivative (Ia)]
(1) L-5,6-O-이소프로필리덴아스코르브산의 합성(1) Synthesis of L-5,6-O-isopropylidene ascorbic acid
180g의 아스코르브산을 아세톤 750ml중에서 교반하고 40℃로 가온시킨다. 20ml부피의 아세틸클로라이드를 가하고, 연속적으로 교반하면서 현탁액층을 형성시킨다.180 g of ascorbic acid is stirred in 750 ml of acetone and warmed to 40 ° C. 20 ml volume of acetylchloride is added and a suspension layer is formed with continuous stirring.
3시간 후에, 현탁액층을 빙냉시키고 여과에 의하여 침전물을 수집한다. 수득한 침전물을 깔대기상에서 아세톤-n-헥산냉혼합물(3 : 7)로 세척하고 감압하에서 실리카겔로 건조시킨다.After 3 hours, the suspension layer is ice cooled and the precipitate is collected by filtration. The precipitate obtained is washed with acetone-n-hexane cold mixture (3: 7) on a funnel and dried over silica gel under reduced pressure.
그후, 아세톤으로 재결정하여 190g의 L-5,6-O-이소프로필리덴아스코르브산(융점 : 206~208℃)을 수득한다.After recrystallization with acetone, 190 g of L-5,6-O-isopropylidene ascorbic acid (melting point: 206-208 DEG C) is obtained.
(2) L-5,6-O-이소프로필리덴-3-O-벤조일메틸아스코르브산의 합성(2) Synthesis of L-5,6-O-isopropylidene-3-O-benzoylmethyl ascorbic acid
(1)에서 수득한 화합물 4.32g을 30ml의 DMSO에 용해시킨다. 1.78g의 NaHCO3를 가한 후, 생성용액을 실온에서 30분동안 교반한다. 이 용액에 4.37g의 페나실브로마이드를 가하고, 수득되는 용액을 40℃로 가온하고 18시간동안 교반한다. 냉각시킨후에 80ml의 H2O를 가하고, 4N염산에 의하여 pH를 5로 조정한다. pH-조정용액을 에틸아세테이트(100ml×2)와 진탕한다. 유기층을 물 및 염화나트륨포화수용액으로 배합, 세척하고, 황산나트륨으로 건조시키고 감압하에 농축시킨다. 수득한 유상물질에 실리카겔컬럼크로마토그래피를 행하고 벤젠-에틸아세테이트의 혼합물로 응출시켜 L-5,6-O-이소프로필리덴-3-O-벤조일메틸아스코르브산을 수득한다.4.32 g of the compound obtained in (1) is dissolved in 30 ml of DMSO. After adding 1.78 g of NaHCO 3 , the resulting solution is stirred at room temperature for 30 minutes. To this solution is added 4.37 g of phenacylbromide and the resulting solution is warmed to 40 ° C. and stirred for 18 hours. After cooling, 80 ml of H 2 O was added and the pH was adjusted to 5 with 4N hydrochloric acid. The pH-adjusted solution is shaken with ethyl acetate (100 ml x 2). The organic layer is combined with water and saturated aqueous sodium chloride solution, washed, dried over sodium sulfate and concentrated under reduced pressure. The obtained oily substance is subjected to silica gel column chromatography and coagulated with a mixture of benzene-ethyl acetate to give L-5,6-O-isopropylidene-3-O-benzoylmethylascorbic acid.
(3)L-3-O-벤조일메틸아스코르브산의 합성(3) Synthesis of L-3-O-benzoylmethyl ascorbic acid
40ml의 테트라히드로푸란-메탄올 혼합물(3 : 1)에 (2)에서 수득한 3.3g의 화합물을 용해시키고 10ml의 2N염산을 가하여 실온에서 20시간동안 생성용액을 교반한다. 반응용액을 감압하에 농축시키고 잔류물을 에틸아세테이트-석유에테르로 재결정하여 L-3-O-벤조일메틸아스코르브산(표 1의 화합물번호 112에 해당)을 수득한다.Dissolve 3.3 g of the compound obtained in (2) in 40 ml of tetrahydrofuran-methanol mixture (3: 1), add 10 ml of 2N hydrochloric acid, and stir the resulting solution for 20 hours at room temperature. The reaction solution is concentrated under reduced pressure and the residue is recrystallized from ethyl acetate-petroleum ether to give L-3-O-benzoylmethyl ascorbic acid (corresponding to compound number 112 of Table 1).
본 발명의 수득되는 화합물(번호 112)은 하기에 서술되는 항산화시험에 사용된다.The obtained compound (No. 112) of the present invention is used in the antioxidant test described below.
제조예 2 [신규인 아스코르브산 유도체(Ia)의 제조]Preparation Example 2 [Preparation of New Ascorbic Acid Derivative (Ia)]
제조예 1에서와 동일한 방법으로 공정을 행하여 하기 표 1에 나타낸 신규의 화합물(번호 110 및 115)을 수득한다.The process was carried out in the same manner as in Preparation Example 1 to obtain novel compounds (No. 110 and 115) shown in Table 1 below.
이러한 화합물을 하기에 서술한 항산화시험에 사용한다.These compounds are used in the antioxidant tests described below.
제조예 3 [신규인 아스코르브산 유도체(Ia)의 제조]Preparation Example 3 [Preparation of New Ascorbic Acid Derivative (Ia)]
(1) L-5,6-이소프로필리덴-3-O-(3-피코일)아스코르브산의 합성(1) Synthesis of L-5,6-isopropylidene-3-O- (3-phycoyl) ascorbic acid
40ml의 증류수에 1.66g의 NaHCO3를 용해시키고 80ml의 메틸에틸캐톤을 가한다. 생성용액에 제조예 1의 (1)에서 수득한 4.32g의 L-5,6-O-이소프로필리덴아스코르브산을 가한다. 수득되는 혼합물을 교반하고, 여기에 3.26g의 3-피코일클로라이드, 1.66g의 NaHCO3및 1.60g의 테트라부틸암모늄 브로마이드를 가한다. 생성혼합물을 70℃로 가열하고 10시간동안 격렬히 교반한다. 유기층을 분리하고 수성층을 4NB염산에 의하여 pH를 4로 조정하고 100ml의 에틸아세테이트와 함께 진탕한다. 유기층을 물로 배합, 세척하고 황산나트륨으로 건조시키고 감압하에 농축시킨다. 수득되는 잔류물에 실리카겔컬럼크로마토그래피를 행하여 벤젠-에틸아세테이트 혼합물로 용출시키므로써 L-5,6-이소프로필리덴-3-O-(3-피코일)아스코르브산을 수득한다.Dissolve 1.66 g of NaHCO 3 in 40 ml of distilled water and add 80 ml of methylethylcatone. 4.32 g of L-5,6-O-isopropylidene ascorbic acid obtained in Preparation Example 1 (1) was added to the resulting solution. The resulting mixture is stirred and 3.26 g of 3-phycoylchloride, 1.66 g of NaHCO 3 and 1.60 g of tetrabutylammonium bromide are added thereto. The resulting mixture is heated to 70 ° C. and stirred vigorously for 10 hours. The organic layer was separated and the aqueous layer was adjusted to pH 4 with 4NB hydrochloric acid and shaken with 100 ml of ethyl acetate. The organic layer is combined with water, washed, dried over sodium sulfate and concentrated under reduced pressure. The obtained residue is subjected to silica gel column chromatography to elute with a benzene-ethyl acetate mixture to give L-5,6-isopropylidene-3-O- (3- picoyl) ascorbic acid.
(2)L-3-O-(3-피코일)아스코르브산의 합성(2) Synthesis of L-3-O- (3-Picoyl) Ascorbic Acid
(1)에서 수득한 화합물을 사용하는 것을 제외하고는 제조예 1의 (3)에서와 동일한 방법으로 조작을 행한다. 벤젠-석유에테르로 재결정하여 L-3-O-(3-피코일)아스코르브산(표 1의 화합물번호 113에 해당)을 수득한다.The same procedure as in (3) of Production Example 1 was carried out except that the compound obtained in (1) was used. Recrystallization with benzene-petroleum ether yields L-3-O- (3-phycoyl) ascorbic acid (corresponding to compound number 113 in Table 1).
수득한 본 발명의 화합물(번호 113)을 하기에 설명하는 항산화시험에 사용한다.The obtained compound (No. 113) of the present invention is used in the antioxidant test described below.
참고예 1 [아스코르브산 유도체(IA)에 포함되는 기타 아스코르브산 유도체의 제조]Reference Example 1 Preparation of Other Ascorbic Acid Derivatives Contained in Ascorbic Acid Derivative (IA)
제조예 1에서와 동일한 방법으로 공정을 행하여 하기 표 1의 화합물들(번호 1,1, 102, 103, 104,105, 106, 107,108,109,111 및 114)을 수득한다.The process is carried out in the same manner as in Preparation Example 1 to obtain the compounds shown in Table 1 (Nos. 1,1, 102, 103, 104,105, 106, 107,108,109,111, and 114).
수득되는 화합물들도 또한 하기에 설명되는 항산화시험에 사용한다.The compounds obtained are also used in the antioxidant test described below.
[표 1]TABLE 1
시험예 1 [안정된 라디칼을 사용하여 시험된 항산화작용]Test Example 1 [Antioxidation Tested Using Stable Radicals]
안정된 유리기인 α,α-디페닐-β-피크릴히드라질(DPPH)의 환원활성을 M.S.Blois법(Nature, vol. 181, 페이지 1199, 1958)에 의하여 시험하고 이것을 항산화작용에 대한 지수로서 사용한다. 이와같이 하여, 샘플을 에탄올중의 0.1mM-DPPH용액 3ml에 가하고, 20분 후에 분광광도계를 사용하여 517nm파장에서의 흡광도를 측정한다. 용매콘트롤[0.5% 이하의 디메틸포름아미드(DMF)]과의 흡광도차를 환원활성으로 한다.The reducing activity of the stable free group α, α-diphenyl-β-picrylhydrazyl (DPPH) was tested by MSBlois method (Nature, vol. 181, page 1199, 1958) and used as an index for antioxidant activity. do. In this way, the sample is added to 3 ml of 0.1 mM-DPPH solution in ethanol, and after 20 minutes, the absorbance at 517 nm wavelength is measured using a spectrophotometer. The absorbance difference with the solvent control [0.5% or less of dimethylformamide (DMF)] is set as the reducing activity.
시험화합물에 대한 50% 라디칼 제거농도를 표 2에 나타낸다.The 50% radical removal concentration for the test compound is shown in Table 2.
표 2에서 알 수 있듯이, 본 발명의 시험화합물은 항산화작용이 개량되었다. 또한 번호 102내지 115의 기타 화합물은 R1이 긴사슬-알킬기인 번호 101의 화합물보다 항산화력이 우수함이 명백해졌다.As can be seen from Table 2, the test compound of the present invention has improved antioxidant activity. It was also clarified that other compounds of Nos. 102 to 115 were superior in antioxidant power to those of No. 101 wherein R 1 is a long chain alkyl group.
[표 2]TABLE 2
상기한 바와같이, 본 발명은 항산화작용이 우수한 신규의 아스코르브산 유도체 및 이것의 제조방법을 제공한다. 더욱이, 본 발명은 또한 상기한 아스코르브산 유도체 또는 기타 공지된 아스코르브산 유도체를 함유하는 신규의 항산화제도 제공한다.As described above, the present invention provides a novel ascorbic acid derivative having excellent antioxidant activity and a method for producing the same. Moreover, the present invention also provides novel antioxidants containing the ascorbic acid derivatives described above or other known ascorbic acid derivatives.
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