KR900006030B1 - Process for preparing L-ascorbyl-2-polyphosphate ester - Google Patents
Process for preparing L-ascorbyl-2-polyphosphate ester Download PDFInfo
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- KR900006030B1 KR900006030B1 KR1019880003878A KR880003878A KR900006030B1 KR 900006030 B1 KR900006030 B1 KR 900006030B1 KR 1019880003878 A KR1019880003878 A KR 1019880003878A KR 880003878 A KR880003878 A KR 880003878A KR 900006030 B1 KR900006030 B1 KR 900006030B1
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- ascorbyl
- acid
- ascorbic acid
- isopropylidine
- polyphosphate ester
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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
-
- 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
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Abstract
내용 없음.No content.
Description
본 발명은 의약품, 식품, 화장품등에 광범위하게 사용되고 있는 L-아스코르빈산(비타민 C)에서 유도되는 L-아스코르빌-2-폴리포스페이트 에스테르의 제조방법에 관한 것이다.The present invention relates to a method for preparing L-ascorbyl-2-polyphosphate ester derived from L-ascorbic acid (vitamin C) which is widely used in medicine, food, cosmetics and the like.
L-아스코르빈산은 공기중에서 빠르게 산파되고 온도, 빛, pH, 금속이온등에 의해 분해되기 때문에 이를 함유하는 상품들의 보존성이 문제가 되며, 그 상품의 상품가치를 떨어뜨리는 원인이 된다.Since L-ascorbic acid is rapidly dispersed in air and decomposed by temperature, light, pH, and metal ions, the preservation of the products containing it becomes a problem and causes a decrease in the product value of the product.
그러나 본 발명에서 제조되는 유도체는 산화 및 분해원인에 대하여 매우 안정(약 20-1,300배)하고(표 1 참고), 생체내에서 용이히게 L-아스코르빈산으로 전환하는 특징을 가지고 있으며, 특히 물을 함유하는 함수성 제품에서의 안정성이 더욱 뛰어난 것으로 알려졌다.However, the derivatives prepared in the present invention are very stable against the causes of oxidation and decomposition (about 20-1,300 times) (see Table 1), and have the characteristics of being easily converted to L-ascorbic acid in vivo, and especially water It is known that the stability is more excellent in the water-containing product containing.
[표 1]TABLE 1
을 합성하기 위한 것이다. 높은 pH에서 구조식(I)로부터 가수분해되어 생성되는 구조식(II),(III)It is to synthesize. Structural formulas (II), (III) produced by hydrolysis from structural formula (I) at high pH
도 소량 포함되는, 통칭 L-아스코르빌-2-폴리포스페이트 에스테르 및 그 염류의 제조에 목적이 있다.It is aimed at the production of the generically known L-ascorbyl-2-polyphosphate esters and salts thereof in small amounts.
본 발명은 구조식(I)을 합성하기 위하여 다음의 구조식(IV)The present invention is to synthesize the following formula (I)
를 먼저 합성한다. 구조식(IV)의 제조방법은 문헌[K. G. A Jackson and J.K.N Jones, Can. J. Chem, 47(1969) 2498]에 잘 나타나 있으며 높은 수율로 얻어진다. 합성된 구조식(IV)를 출발물질로 하여 본 발명은 다음의 합성경로(I)Synthesize first. Methods for the preparation of formula (IV) are described in K. G. A Jackson and J.K.N Jones, Can. J. Chem, 47 (1969) 2498, which is obtained in high yield. Using the synthesized structural formula (IV) as a starting material, the present invention provides the following synthetic route (I)
을 통하여 구조식(V)를 얻는다. 특히 본 발명에서 구조식(IV)를 출발물질로 하는 이유는 L-아스코르빈산의 5,6번 위치를 이소프로필리딘기로 보호함으로써 인산화 반응을 통해 나타날 수 있는 부산물인 다음의 구조식(VI)The structural formula (V) is obtained through Particularly, in the present invention, the structural formula (IV) is used as a starting material because the following structural formula (VI), which is a by-product that can be shown through phosphorylation by protecting the 5,6 position of L-ascorbic acid with isopropylidine group
의 생성이 방지되고 반응효율도 높아지기 때문이다.Is prevented from forming and the reaction efficiency is increased.
그러나 구저식(V)를 높은 수율로 얻기 위해서는 반응액중에 존재하는 구조식(IV)의 산화요인(온도, pH, 산화효소)을 방지해야 한다.However, in order to obtain V (V) in high yield, the oxidizing factors (temperature, pH, oxidase) of structural formula (IV) present in the reaction solution should be prevented.
따라서, 본 발명은 이를 위해 5,6-이소프로필리딘-L-아스코르빈산을 출발물질로 하여 항산화제(시스테인, H2S, 티오아세트산, 티오글리콜산, 프로필갈레이트 등)를 소량 첨가하고 인산화 반응 효율이 높은 트리메타포스페이트(Na3P3O9)를 사용함으로써 구조식(V)를 높은 수율로 얻을 수 있다. 얻어진 구조식(V)은 산에 의해 쉽게 구조식(I)로 되는 성질이 있으므로 pH 조정 또는 강산성 양이온교환수지(H+형)를 통과시킴으로서 목적하는 구조식(I)로 전환된다.Therefore, the present invention is to add a small amount of antioxidants (cysteine, H 2 S, thioacetic acid, thioglycolic acid, propylgallate, etc.) starting from 5,6-isopropylidine-L- ascorbic acid for this purpose Structural formula (V) can be obtained in high yield by using a trimethaphosphate (Na 3 P 3 O 9 ) having high phosphorylation reaction efficiency. The obtained structural formula (V) has the property of easily becoming the structural formula (I) by an acid, and is converted into the desired structural formula (I) by passing pH adjustment or strong acid cation exchange resin (H + type).
본 발명의 화합물의 제조는 아래의 실시예에 따라서 설명하며, 이는 설명을 위한 것으로서 본 발명을 제한하는 것은 아니다.The preparation of the compounds of the present invention is described according to the following examples, which are intended to be illustrative and not limiting of the present invention.
[실시예 1]Example 1
L-아스코르빈산 30g(0.17몰), 아세톤 135㎖를 혼합교반하며 아세틸 클로라이드 3.75㎖를 서서히 첨가하였다. 25-30℃에서 2시간 강하게 교반하면 결정형이 변하게 된다. 생성된 결정을 여과하면서 차가운 아세톤-헥산(4 : 7) 용액 110㎖로 세척하였다. 세척한 결정은 수산화 칼륨을 넣은 데시케이터속에서 진공 건조하였다. 얻어진 5,6-O-이소프로필리딘-L-아스코르빈산은 35.6g(수율 96.7%)이 었다.30 g (0.17 mol) of L-ascorbic acid and 135 ml of acetone were mixed and stirred, and 3.75 ml of acetyl chloride was slowly added. Strong stirring at 25-30 ° C. for 2 hours will change the crystal form. The resulting crystals were washed with 110 ml of cold acetone-hexane (4: 7) solution while filtering. The washed crystals were vacuum dried in a desiccator containing potassium hydroxide. The obtained 5,6-O-isopropylidine-L-ascorbic acid was 35.6 g (yield 96.7%).
원소분석치 (C9H12O6)Elemental Analysis (C 9 H 1 2O 6 )
계산치(%) : C ; 50.00, H ; 5.55, O ; 44.41Calculated (%): C; 50.00, H; 5.55, O; 44.41
실측치(%) : C ; 49.97, H ; 5.56, O ; 44.38Found (%): C; 49.97, H; 5.56, O; 44.38
[실시예 2]Example 2
밀페된 용기내에 5,6-O-이소프로필리딘-L-아스코르빈산 21.62g(0.1몰)을 산소를 제거한 물에 녹인후 질소 가스를 주입시켰다. 10N-NaOH로 pH를 10.3-10.9로 조정하면서 액량을 100㎖로 하였다. 항산화제로 시스테인 0.05g을 첨가한 후 소듐트리메타포스페이트 39,77g(0.13몰)을 서서히 가하면서 pH를10,3-10.9로 계속 조정하였고 32-36℃의 온도를 유지하며 24시간 교반하였다. 반응 종료후 HPLC 분석에 의하면 5.6-O-이소프로필리딘-L-아스코르빈산 잔존율은 2.5%(즉, 미반응물 0.54g)로 나타났다. 반응 종료액을 강산성 양이온 교환수지(SKIB-H+형)에 S.V 1.0으로 통과시켜 탈염시키고 유출되는 액은 농축하여 아세톤을 날린후 물을 첨가하여 액량을 200㎖가 되도록 하였다. 이액에 산화마그네슘을 가하여 pH를 10,9로 조정한 후 생성되는 무기물 침전은 여과 제거하였다. 활성탄 4g을 첨가하여 30℃에서 1시간 탈색시키고 이를 여과 제거하였다. 여과한 여액에 메탄을 300㎖를 서서히 가하여 결정을 석출시키고 냉장보관(4시간)하여 결정을 숙성시켰다. 결정물 여과하여 건조한 결과 L-아스코르빌-2-폴리포스페이트 마그네슘 41.0g이 얻어 졌다.21.62 g (0.1 mol) of 5,6-O-isopropylidine-L-ascorbic acid was dissolved in deoxygenated water and nitrogen gas was introduced into a sealed container. The liquid amount was 100 ml, adjusting the pH to 10.3-10.9 with 10N-NaOH. After adding 0.05 g of cysteine as an antioxidant, 39,77 g (0.13 mol) of sodium trimetaphosphate was slowly added thereto, and the pH was continuously adjusted to 10,3-10.9 and stirred for 24 hours while maintaining a temperature of 32-36 ° C. HPLC analysis after the completion of the reaction showed that the 5.6-O-isopropylidine-L-ascorbic acid residual ratio was 2.5% (ie, 0.54 g of unreacted material). The reaction solution was passed through a strongly acidic cation exchange resin (SKIB-H + type) as SV 1.0 to desalinate, and the solution was concentrated, blowing acetone, and adding water to make the liquid 200 ml. Magnesium oxide was added to the solution to adjust the pH to 10,9, and the inorganic precipitates formed were filtered off. 4 g of activated carbon was added to decolorize at 30 ° C. for 1 hour, and the resultant was filtered off. 300 ml of methane was slowly added to the filtrate to precipitate crystals and refrigerated (4 hours) to mature the crystals. Crystals filtered off and dried to give 41.0 g of magnesium L-ascorbyl-2-polyphosphate.
이것을 HPLC로 분석한 결과 건조물로 환산 99.5%였다. 페이퍼 크로마토그래프에 의하면 (24시간 전개, 전개용매 , n-프로파놀-물-트리클로로 아세트산(75 : 20 ; 5), 발색시약 ; 1% 염화철(95% 메탄올)용액)This was analyzed by HPLC and found 99.5% in terms of dry matter. According to the paper chromatograph (24 hours development, developing solvent, n-propanol-water-trichloro acetic acid (75: 20; 5), coloring reagent; 1% iron chloride (95% methanol) solution)
L-아스코르빌-2-트리포스페이트 89%L-ascorbyl-2-triphosphate 89%
L-아스코르빌-2-디포스페이트 6%L-ascorbyl-2-diphosphate 6%
L-아스코르빌-2-모노포스페이트 1%L-ascorbyl-2-monophosphate 1%
L-아스코르빌-2-테트라포스페이트 4%L-ascorbyl-2-tetraphosphate 4%
의 혼합물로 나타났다.Appeared to be a mixture of.
[실시예 3]Example 3
5,6-O-이소프로필리딘-L-아스코르빈산 21.62g(0.1몰)에 항 산화제로 티오글리롤산 0.05g을 첨가한 후 실시예 2의 방법으로 반응시켰다. 반응 종료후 HPLC 분석에 의해 5,6-O-이소프로괼리딘-L-아스코르빈산의 잔존률은 2.8%(즉, 미반응물 0.61g)로 나타났다. 최종 생성물은 실시예 2와 같이 탈염처리한 후 수산화 칼슘으로 pH 10.9로 조정하였다. 이때 침전되는 무기물은 여과 제거하였고 활성탄으로 여액을 탈색시켰다. 여기서 나온 탈색액에 메탄을 300㎖를 서서히 첨가하여 결정을 석출시켰다. 냉장보관(4시간)하여 숙성시킨 결정을 여과하고 건조한 결과 L-아스코르빌-2-폴리포스페이트 칼슘 42.5g이 얻어졌다. 이것을 HPLC로 분석한 결과 건조물로 환산 99.3%였다.To 21.62 g (0.1 mole) of 5,6-O-isopropylidine-L-ascorbic acid, 0.05 g of thioglyrrolic acid was added as an antioxidant, followed by reaction according to the method of Example 2. HPLC analysis after the completion of the reaction showed that the residual ratio of 5,6-O-isopropyridine-L-ascorbic acid was 2.8% (ie, 0.61 g of unreacted material). The final product was desalted as in Example 2 and then adjusted to pH 10.9 with calcium hydroxide. At this time, the precipitated inorganic material was filtered off and the filtrate was decolorized with activated carbon. 300 ml of methane was slowly added to the decolorizing solution obtained to precipitate crystals. Refrigerated (4 hours), aged crystals were filtered and dried to give 42.5 g of L-ascorbyl-2-polyphosphate calcium. This was analyzed by HPLC and found 99.3% in terms of dry matter.
페이퍼 크로마토그래피에 의하면According to paper chromatography
L-아스코르빌-2-트리포스페이트 89.4%L-ascorbyl-2-triphosphate 89.4%
L-아스코르빌-2-디포스페이트 7.5%L-ascorbyl-2-diphosphate 7.5%
L-아스코르빌-2-모노포스페이트 1.1%L-ascorbyl-2-monophosphate 1.1%
L-아스코르빌-2-테트라포스페이트 2.0%L-ascorbyl-2-tetraphosphate 2.0%
의 혼합물로 나타났다.Appeared to be a mixture of.
[실시예 4]Example 4
실시예 2와 같이 처리하면서 항산화제 프로필 갈레이트 0.05g을 사용하였다. 반응 종료후 5,6-O-이소프로필리딘-L-아스코르빈산 잔존율은 3.2%(즉, 미반응 0.69g)로 실시예 2와 같이 처리하면서 L-아스코르빈산-2-폴리포스페이트 바륨 50.4g을 얻었다. 이것을 HPLC로 분석한 결과 건조물로 환산 99.7%로 나타났다.0.05 g of antioxidant propyl gallate was used in the same manner as in Example 2. After completion of the reaction, the 5,6-O-isopropylidine-L-ascorbic acid residual ratio was 3.2% (i.e., unreacted 0.69 g) with L-ascorbic acid-2-polyphosphate barium treatment as in Example 2 50.4 g was obtained. This was analyzed by HPLC and found to be 99.7% in terms of dry matter.
페이퍼 크로마토그래피에 의하면,According to paper chromatography,
L-아스코르빌-2-트리포스페이트 91.5%L-ascorbyl-2-triphosphate 91.5%
L-아스코르빌-2-디포스페이트 5.2%L-ascorbyl-2-diphosphate 5.2%
L-아스코르빌-2-모노포스페이트 0.3%L-ascorbyl-2-monophosphate 0.3%
L-아스코르빌-2-테트라포스페이트 3.0%L-ascorbyl-2-tetraphosphate 3.0%
의 혼합물로 나타났다.Appeared to be a mixture of.
Claims (1)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019880003878A KR900006030B1 (en) | 1988-04-07 | 1988-04-07 | Process for preparing L-ascorbyl-2-polyphosphate ester |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019880003878A KR900006030B1 (en) | 1988-04-07 | 1988-04-07 | Process for preparing L-ascorbyl-2-polyphosphate ester |
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| Publication Number | Publication Date |
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| KR890016035A KR890016035A (en) | 1989-11-28 |
| KR900006030B1 true KR900006030B1 (en) | 1990-08-20 |
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- 1988-04-07 KR KR1019880003878A patent/KR900006030B1/en not_active Expired
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