KR810001047B1 - Method for preparing cyclic acetal derivative of sterylglucoside - Google Patents

Abstract

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Description

Method for preparing cyclic acetal derivative of sterylglucoside

The present invention is the following general formula (I)

-시토스테릴기, 캄페스테릴기, 스티그마스테릴기 혹은 이들의 혼합물을 표시하거나, 또는 코레스테릴기를 표시한다.(Where R is

-Represent a cytosteryl group, a camphorsteryl group, a stigmasteryl group or a mixture thereof, or a cholesteryl group.

-D-글루코피라노시드 유도체의 제조방법에 관한 것이다. 본 화합물은 문헌에 미재인 신규물질로서, 우수한 혈관보강작용, 지혈작용, 항염증작용을 나타내고, 독성도 또 지극히 약하여 의약품으로서 유용하다. 본 발명의 화합물(I)은 여러가지 방법으로 합성할 수 있으나 특히 다음 방법이 바람직하다.R ¹ represents H or a methyl group), 2,3-oxide alkylidene-4,6-alkylidene-

A method for producing a -D-glucopyranoside derivative. This compound is a novel substance which is unknown in the literature, and has excellent vascular reinforcement, hemostatic action, and anti-inflammatory action, and its toxicity is extremely weak, so it is useful as a medicine. The compound (I) of the present invention can be synthesized by various methods, but the following method is particularly preferable.

That is, the following general formula (II)

(Wherein R is as defined above) as a compound represented by the general formula (II)

(R ¹ CHO) n (II)

The target (I) is synthesized by reacting aldehydes such as paraformaldehyde and paraaldehyde in which R ¹ represents H or a methyl group and n represents an integer of 3 or more in the presence of an acid catalyst. .

In this method, the excess aldehydes used in the reaction may be used as a solvent, but if necessary, it may be performed by adding an organic solvent such as benzene. Sulfuric acid is usually used as the acid catalyst. If necessary, a dehydrating agent may be added.

The present invention will be described in detail with reference to the following Examples, but the present invention is not limited to these Examples.

Example 1

-D-글루코피라노시드, 스테릴-

-D-글루코피라노시드(대두레시틴으로부터 추출제조한 스테릴-

-D-글루코피라노시드로서, 그 스테롤의 조정은

-시토스테롤 60%, 스티그마스테롤 20%, 캄페스테롤 20%이다) 10.0g을 300㎖의 프라스코에 넣어서 파라알데히드 100㎖를 첨가하여 현탁액으로 한다. 농황산 한 방울을 첨가하여 실온으로 24시간 교반한다. 벤젠 200㎖를 첨가하고 이어서 무수 탄산칼륨 10.0g을 첨가하고 실온으로 3시간 교반한후 여과한다. 감압하에서 벤젠 및 과잉된 파라알데히드를 유거한다. 잔류물에 에탄올을 첨가하면 결정화된다.Steryl-2,3-oxidoethylidene-4,6-ethylidene-

D-glucopyranoside, sterilyl

-D-glucopyranoside (steryl- extracted from soy lecithin)

As -D-glucopyranoside, the sterol adjustment is

10.0 g of 60% cytosterol, 20% stigmasterol, and 20% camphorol) is added to 300 ml of fresco and 100 ml of paraaldehyde is added to give a suspension. Add one drop of concentrated sulfuric acid and stir to room temperature for 24 hours. 200 ml of benzene is added, followed by 10.0 g of anhydrous potassium carbonate, which is stirred for 3 hours at room temperature and then filtered. Benzene and excess paraaldehyde are distilled off under reduced pressure. The addition of ethanol to the residue crystallizes.

When recrystallized from ethanol, 7.5g of colorless crystals of the desired compound having a melting point of 184-186 占 폚 were obtained (yield 64.4%).

Elemental Analysis C ₄₁ H ₆₈ O ₇ As

Calculated C: 73.17 H: 10.19

Found C: 72.90 H: 10.10

MS m / e 672, 670,658 (M ⁺ )

Example 2

-D-글루코피라노시드Coresteryl-2,3-oxideethylidene-4,6-ethylidene-

-D-glucopyranoside

-D-글루코피라노시드 4.0g을 200㎖의 나스콜에 넣어, 파라알데히드 50㎖로 현탁시키고, 농황산 한 방울을 첨가하여 실온으로 24시감 교반한다. 이어서 실시예 1의 경우와 같이 후처리를 하고 조제의 결정 4.8g을 얻은다. 이것을 에탄올에서 재결정한바 융점 177-178℃의 목적한 화합물의 3.1g이 무색침전상결정으로서 얻어졌다(수율 66.0%).Coresteryl

4.0 g of -D-glucopyranoside was added to 200 ml of nascol, suspended with 50 ml of paraaldehyde, and a drop of concentrated sulfuric acid was added and stirred for 24 hours at room temperature. Subsequently, the same treatment as in Example 1 was carried out to obtain 4.8 g of the prepared crystal. When recrystallized from ethanol, 3.1 g of the target compound having a melting point of 177 to 178 ° C was obtained as colorless precipitated phase crystals (yield 66.0%).

Elemental Analysis C ₃₉ H ₆₄ O ₇ As

Calculation C: 72.63 H: 10.00

Found C: 72.53 H: 10.17

Example 3

-시토스테릴-2,3-옥시드에틸리덴-4,6-

-D-에릴리덴 글루코피라노시드

-Cytosteryl-2,3-oxideethylidene-4,6-

-D-Elylidene glucopyranoside

-시토스테릴-

-D-글루코피라노시드 3.0g을 200㎖의 프라스코에 넣어서, 파라알데히드 50㎖로 현탁시키고, 농황산 한 방울을 첨가하여 실온으로 12시감 교반한다. 이어서 실시예 1의 경우와 같이 후처리를 하고, 조결정 3.0g을 얻는다. 이것을 에탄올에서 재결정한바 융점 184~186℃의 목적한 화합물 2.6g이 무색침상 결정으로 얻어졌다(수율 74.3%).

-Sitosteryl-

3.0 g of -D-glucopyranoside was placed in 200 ml of fresco, suspended with 50 ml of paraaldehyde, and a drop of concentrated sulfuric acid was added and stirred at room temperature for 12 hours. Subsequently, post-treatment is performed as in the case of Example 1 to obtain 3.0 g of crude crystals. The crystals were recrystallized from ethanol to give 2.6 g of the target compound having a melting point of 184 to 186 캜 as colorless needles (yield 74.3%).

Elemental Analysis C ₄₁ H ₆₈ O ₇ As

Calculated C: 73.17 H: 10.19

Found C: 73.04 H: 10.16

Example 4

-D-글루코피라노시드. 스테릴-

-D-글루코시드(실시예 1의 경우와 같음) 10.0g을 300㎖의 프라스코에 넣어서, 파라포름 알데히드 10.0g과 벤젠 200㎖를 첨가하여 서현탁액으로 한다. 농황산 한 방울을 첨가하여 실온으로 24시간 교반한다. 그후 유거관을 붙여서 천천히 가온한다. 벤젠 유거에 따라서 반응이 진행된다. 균일한 용액으로 되었을 때 가열을 정지하고, 냉각시킨후 무수탄산칼륨 3.0g을 첨가하고 30분간 교반한다. 여과 후 감압으로 농축 건조시킨다. 벤젠에 용해시키고 칼람클로마토그래피(와코(和光)겔 C-200로 분리 정제한다. (벤젠/에테르 4 : 1 혼액으로 용출). 얻어진 미황색 분말을 에탄올에서 재결정하여 융점 160~162℃의 목적한 화합물 4.8g이 무색침상 결정으로서 얻어졌다(수율 43.9%)Steyl-2,3-oxidemethylidene-4,6-methylidene-

-D-glucopyranoside. Steril

10.0 g of -D-glucoside (as in Example 1) is placed in 300 ml of fresco, and 10.0 g of paraformaldehyde and 200 ml of benzene are added to prepare a suspension. Add one drop of concentrated sulfuric acid and stir to room temperature for 24 hours. After that, attach the canister and warm it up slowly. The reaction proceeds with benzene distillation. When it became a uniform solution, heating was stopped, and after cooling, 3.0 g of anhydrous potassium carbonate was added and stirred for 30 minutes. After filtration, concentrated to dryness under reduced pressure. It is dissolved in benzene and separated and purified by column chromatography (Wako gel C-200., Eluted with benzene / ether 4: 1 mixture). 4.8 g of compound was obtained as colorless needles (yield 43.9%)

Elemental Analysis As C ₃₈ H ₆₂ O ₇

Calculated C: 72.34 H: 9.91

Found C: 72.21 H: 10.02

Claims (1)

The compound represented by the following general formula (II) and the aldehydes such as paraformaldehyde and paraaldehyde represented by the following general formula (III) are reacted in the presence of an acid catalyst, and 4,6- represented by the following general formula (I) Oxidealkylidene-4,6-alkylidene-

Method for preparing a -D-glucopyranoside derivative

General formula (III) (R ¹ CHO) n (III) In the above formula R is

-Represent a cytosteryl group, camphorsteryl group, stigmasteryl group or a mixture thereof or a cholesteryl group, R ¹ represents H or a methyl group and n represents an integer of 3 or more.