KR790001645B1 - Process for the preparation of 2,3-dihydropyrane derivatives - Google Patents

Process for the preparation of 2,3-dihydropyrane derivatives Download PDF

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KR790001645B1
KR790001645B1 KR7502337A KR750002337A KR790001645B1 KR 790001645 B1 KR790001645 B1 KR 790001645B1 KR 7502337 A KR7502337 A KR 7502337A KR 750002337 A KR750002337 A KR 750002337A KR 790001645 B1 KR790001645 B1 KR 790001645B1
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piperidine
benzyl
preparation
room temperature
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히로시 무라이
신고 마쓰무라
다가시 오오구보
신이찌 다다
나베 오사무 다
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모리시다 히로시
닛뽄 신야쿠 가부시기가이샤
오오미야 다가시
다가라 슈조오 가부시기가이샤
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member

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  • Organic Chemistry (AREA)
  • Hydrogenated Pyridines (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

Title comds. [I; R1 = alkyl group, benzyl group or (alkyl group, halogen, alkoxy group, or nitrogen group substitued) benzyl group; R2 = piperidine group were prepd. by reaction of enamine compds (II) with methylvinylketone. Thus, 134.2g -phenylpropionaldehyde was reacted with 111g piperidine and 130g potassium carbonate at room temp. for 30 min and the product mixed with 75g met- hlvinylketone followed by mixing for 30 min to give 3-benzyl-6-methyl-2-(1-piperidine)-3,4-dihy- dro-2H-pyrane

Description

2, 3-디하이드로피란 유도체의 제조법Preparation method of 2, 3-dihydropyran derivatives

본 발명은, 일반식 R1-CH=CH-R2(식중 R1은 알킬기, 벤질기 또는 알킬기, 할로겐, 알콕실기 니트로기 중 어느 것으로든 치환된 벤질기를 나타내며, R2는 피페리딘기를 나타냄)으로 표시된 엔아민과 메틸비닐켄톤을 반응시켜 다음 일반식(I)In the present invention, the general formula R 1 -CH = CH-R 2 wherein R 1 represents an alkyl group, a benzyl group or a benzyl group substituted with any of an alkyl group, a halogen, an alkoxyl group nitro group, and R 2 represents a piperidine group. By reacting the enamine and methylvinylkentone represented by the following general formula (I)

Figure kpo00001
Figure kpo00001

(식중 R1, R2는 전술한 바와 동일함)Wherein R 1 and R 2 are the same as described above.

로 나타낸 신규 화합물인 2,3-디하이드로피란 유도체를 얻는 방법에 관한 것이다.It is related with the method of obtaining the 2, 3- dihydropyran derivative which is a novel compound shown by.

본 발명을 더욱 상세히 설명하면, 본 발명은 다음 일반식In more detail, the present invention provides the following general formula

R1-CH=CH-R2 R 1 -CH = CH-R 2

(식중 R1, R2는 전술한 바와 동일함).Wherein R 1 and R 2 are the same as described above.

로 표시한 엔아민과 메틸비닐케톤과를 무용매 또는 반응 불활성 용매(예를 들면, 에테르)중에서 냉각하 또는 실온에서 수십분 혹은 수시간 반응시킴으로서 일반식(I)로 표시된 화합물을 좋은 수율로 얻는 방법을 제공하는데 있다.A method of obtaining the compound represented by the general formula (I) in good yield by reacting an enamine represented by the above with methyl vinyl ketone in a solvent-free or reaction inert solvent (e.g., ether) or by reacting for several minutes or several hours at room temperature. To provide.

이 일반식(I)로 표시된 2,3-디하이드로피란 유도체는 신규한 화합물이며, 또한 혈압 강하작용, 소염작용, 항균 작용을 가지는 의료상 극히 유용한 화합물이다. 더우기 본원 화합물을 원료로서, 현저한 약효를 나타낼뿐 아니라 2,5-디 치환 피리딘 유도체 합성에서 중간물질로서도 사용할 수 있다.The 2,3-dihydropyran derivative represented by the general formula (I) is a novel compound and is a very useful compound for medical use having a blood pressure lowering action, an anti-inflammatory action and an antibacterial action. Furthermore, the compound of the present invention can be used as a raw material, as well as exhibiting significant efficacy, and can also be used as an intermediate in the synthesis of 2,5-di-substituted pyridine derivatives.

이하, 실시예에 의해 상세히 설명한다.Hereinafter, it demonstrates in detail by an Example.

[실시예 1]Example 1

3-벤질-6-메틸-2-(1-피페리딘)-3,4-디하이드로-2H-피란의 제조법Preparation of 3-benzyl-6-methyl-2- (1-piperidine) -3,4-dihydro-2H-pyran

β-페닐 프로피온 알데하이드 134.2g을 500ml의 에테르에 용해하고, 피페리딘 111g과 탄산칼륨 130g을 가하여 실온에서 30분간 교반한 후, 여과하고, 용매를 유거하여 얻은 황색유상물(189.5g)을 실온에서 교반하면서, 메틸 비닐 케톤 75g을 가하여 1시간 후 석유에테르를 가하여 석출한 결정을 여취한다. 융점 58-60℃의 무색결정 152g을 얻는다.134.2 g of β-phenyl propionaldehyde was dissolved in 500 ml of ether, 111 g of piperidine and 130 g of potassium carbonate were added, stirred at room temperature for 30 minutes, filtered, and the yellow oil (189.5 g) obtained by distilling off the solvent was washed with room temperature. 75 g of methyl vinyl ketone is added while stirring at, and after 1 hour, petroleum ether is added to precipitate the precipitated crystals. 152 g of colorless crystals having a melting point of 58-60 占 폚 are obtained.

[실시예 2]Example 2

3-(4-메톡시 벤질)-6-메틸-2-(1-피페리딘)-3,4-디하이드로-2H-피란의 제조법.Preparation of 3- (4-methoxy benzyl) -6-methyl-2- (1-piperidine) -3,4-dihydro-2H-pyran.

β-(4-아니실) 프로피온 알데하이드 5.0g을 에테르 50ml에 용해하고, 피페리딘 3.0g과 탄산 칼륨 5.0g을 가하여, 실온에서 30분간 교반한후, 여과하고, 용매를 유거하여 얻은 황색 유상물(7.0g)을 실온에서 교반하면서, 메틸 비닐 케톤 2.4g을 가하여 30분간 교반을 계속한 다음, 석유 에테르로 재결정을 행하면, 융점 68-70℃의 무색결정 5.3g을 얻는다.5.0 g of β- (4-anisyl) propion aldehyde was dissolved in 50 ml of ether, 3.0 g of piperidine and 5.0 g of potassium carbonate were added thereto, stirred at room temperature for 30 minutes, filtered and the yellow oily phase obtained by distilling off the solvent. 2.4 g of methyl vinyl ketone was added while stirring water (7.0 g) at room temperature, stirring was continued for 30 minutes, and recrystallization with petroleum ether gave 5.3 g of colorless crystals having a melting point of 68-70 ° C.

[실시예 3]Example 3

3-(4-에톡시벤질)-6-메틸-2-(1-피페리딘)-3,4-디하이드로-2H-피란의 제조법.Preparation of 3- (4-ethoxybenzyl) -6-methyl-2- (1-piperidine) -3,4-dihydro-2H-pyran.

β-(4-에톡시 페닐)-프로피온 알데하이드 43.4g을 에테르 200ml에 용해하고, 탄산 칼륨 35g과 피페딘 22.8g을 가하여 실온에서 30분간 교반한후 여과하고 에테르를 유거하여 얻은 황색유상물(63.9g)을 교반하면서 냉각하에 메틸 비닐 케톤 18.9g을 가하여, 실온에서 3시간 방치한 후 감압 유거하면, 비점 170-204℃/4mmHg의 유분 41.5g을 얻는다.A yellow oil obtained by dissolving 43.4 g of β- (4-ethoxy phenyl) -propion aldehyde in 200 ml of ether, 35 g of potassium carbonate and 22.8 g of pipene, stirred at room temperature for 30 minutes, filtered, and distilling off ether (63.9). 18.9g of methyl vinyl ketones are added under cooling, stirring g), and it is left to stand at room temperature for 3 hours, and when distilled under reduced pressure, the oil content 41.5g of boiling point 170-204 degreeC / 4mmHg is obtained.

[실시예 4]Example 4

3-(3,4-디메톡시벤질)-6-메틸-2-(1-피페리딘)-3,4-디하이드로-2H-피란의 제조법.Preparation of 3- (3,4-dimethoxybenzyl) -6-methyl-2- (1-piperidine) -3,4-dihydro-2H-pyran.

3,4-디메톡시 하이드로 신나뭄 알데하이드 37.0g을 에테르 200ml에 용해하고, 피페리딘 21g과 탄산칼륨 37g을 가하고, 실온에서 30분간 교반하고, 여과하여, 에테르를 유거하여 얻은 황색유상물(48.5g)을 실온에서 교반하면서 메틸 비닐 케톤 14.7g을 가한다. 1시간후 n-헥산을 가하여 석출하는 결정을 여취한다. 융점 62-64℃의 무색결정 29g을 얻는다.37.0 g of 3,4-dimethoxy hydrocinnamum aldehyde was dissolved in 200 ml of ether, 21 g of piperidine and 37 g of potassium carbonate were added, stirred at room temperature for 30 minutes, filtered and the yellow oil obtained by distilling off the ether (48.5). 14.7 g of methyl vinyl ketone are added while stirring g) at room temperature. After 1 hour, n-hexane is added to precipitate crystals. 29 g of colorless crystals having a melting point of 62-64 占 폚 are obtained.

[실시예 5]Example 5

3-n-부틸-6-메틸-2-(1-피페리디노)-3,4-디하이드로-2H-피란의 제조법.Preparation of 3-n-butyl-6-methyl-2- (1-piperidino) -3,4-dihydro-2H-pyran.

카프로익 알데하이드 10g을 n-헥산 40ml에 용해하고, 피페리딘 9,2g과 탄산 칼륨 10g을 가하여 실온에서 30분간 교반하고, 여과후, n-헥산을 유거하여 얻은 무색 유상물(13.7g)을 실온에서 교반하면서 메틸비닐 케톤 6.0g을 가하여 실온에서 1시간 방치한 후, 감압 증류하여, 비점 99-106℃/4mmHg의 유분 9.4g을 얻는다.Dissolve 10 g of caproic aldehyde in 40 ml of n-hexane, add 9,2 g of piperidine and 10 g of potassium carbonate, stir at room temperature for 30 minutes, filter, and colorless oil (13.7 g) obtained by distilling n-hexane. 6.0g of methyl vinyl ketones are added, stirring at room temperature, and it is left to stand at room temperature for 1 hour, and it distills under reduced pressure, and 9.4g of oils of boiling point 99-106 degreeC / 4mmHg are obtained.

동일하게 하여 이하의 화합물을 얻었다.In the same manner, the following compounds were obtained.

Figure kpo00002
Figure kpo00002

Claims (1)

다음 일반식(Ⅱ)의 엔아민 화합물을 메틸비닐 케톤과 반응시킴을 특징으로 하는 다음 일반식(I)와 2,3-디하이드로피란 유도체의 제조방법.A process for preparing the following general formula (I) and 2,3-dihydropyran derivatives, characterized by reacting an enamine compound of general formula (II) with methylvinyl ketone.
Figure kpo00003
Figure kpo00003
 식중 R1은 알킬기, 벤질기 또는 알킬기, 할로겐, 알콕실기 혹은 니트로기 중 어느 것으로 치환된 벤질이고;Wherein R 1 is benzyl substituted with alkyl, benzyl or alkyl, halogen, alkoxyl or nitro group; R2는 1-피페리딘기 임.R 2 is a 1-piperidine group.
KR7502337A 1975-10-29 1975-10-29 Process for the preparation of 2,3-dihydropyrane derivatives KR790001645B1 (en)

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