JPS6272670A - Production of tetrahydro-4-hydroxyisoquinoline derivative - Google Patents
Production of tetrahydro-4-hydroxyisoquinoline derivativeInfo
- Publication number
- JPS6272670A JPS6272670A JP60211294A JP21129485A JPS6272670A JP S6272670 A JPS6272670 A JP S6272670A JP 60211294 A JP60211294 A JP 60211294A JP 21129485 A JP21129485 A JP 21129485A JP S6272670 A JPS6272670 A JP S6272670A
- Authority
- JP
- Japan
- Prior art keywords
- acetal
- organic sulfonic
- formula
- acid
- sulfonic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- Other In-Based Heterocyclic Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、医薬等の製造中間体として有用なテトラヒド
ロ−弘−ヒドロキシイソキノリン誘導体の製造法に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing tetrahydro-Hiro-hydroxyisoquinoline derivatives useful as intermediates for the production of pharmaceuticals and the like.
ベンジルアミノアセタールを酸の存在下、下記式に示す
ようにして閉環しテトラヒトローダ−ヒドロキシイソキ
ノリンを合成する方法は公知である。A method of ring-closing a benzylaminoacetal in the presence of an acid as shown in the following formula to synthesize a tetrahydroder-hydroxyisoquinoline is known.
（Ａｄｖａｎｃｅｓ ｉｎ Ｈｅｔｅｒｏｃｙｃｌｉ
ｃ Ｃｈｅｍｉｓｔｒｙ 。(Advances in Heterocycle
c Chemistry.
Ｙｏｌ ／！、１０２．／り７３年 Ａｃａｄｅｍｉｃ
Ｐｒｅａａ−Ｎｅｗ Ｙｏｒｋ ａｖｅｌ Ｌｏｎ
ｄｏｎ ）しかし、この方法で用いられる酸はＦｉｓｔ
、 ａ＝ｓｏ。Yol/! , 102. /ri 73 years Academic
Preaa-New York avel Lon
However, the acid used in this method is Fist
, a=so.
のような鉱酸である。It is a mineral acid such as.
しかしながら、この方法による閉環反応は収率が低いと
いう問題点がある。例えば、ｙ、ｏ、ｃ、 。However, the ring-closing reaction by this method has a problem in that the yield is low. For example, y, o, c, .
４ｔ９ 、４ｔ！ｊ！、 ／りｔダ年ではＮ−メチル誘
導体の場合の収率は４ｔｊ％および６３％と低収率であ
る。4t9, 4t! j! In the case of N-methyl derivatives, the yield is as low as 4tj% and 63%.
公知文献等には収率の低下の原因は明確に記載されてい
ないが、本発明者らが詳細に検討を行った結果、閉環反
応の主九る副生成物にテトラヒドロ−弘−アルコキシイ
ソキノリンが存在することを認めた。Although the cause of the decrease in yield is not clearly described in known literature, detailed studies by the present inventors revealed that tetrahydro-Hiro-alkoxyisoquinoline is the main by-product of the ring-closing reaction. acknowledged that it exists.
又、この閉環反応は大過剰の酸を必要とし、牛の結果、
生成物の分離、取９出しが厄介である等の問題点がある
。Also, this ring-closing reaction requires a large excess of acid, resulting in
There are problems such as troublesome separation and extraction of the product.
本発明者らは、収率の向上、すなわち、％ −アルコキ
シ体の生成抑制を目指し、鋭意検討を行ったところ、酸
として、鉱酸の代９に、有機スルホン酸を用いればよい
ことを見出した。The present inventors conducted intensive studies with the aim of improving the yield, that is, suppressing the formation of %-alkoxy compounds, and found that an organic sulfonic acid could be used as the acid in place of the mineral acid. Ta.
さらに、有機スルホン酸は一般に酸性イオン交換樹脂の
ように樹脂状のものも使用でき、その結果、生成物との
分離が容易になることも判明した。Furthermore, it has also been found that organic sulfonic acids can generally be used in resinous forms such as acidic ion exchange resins, and as a result, they can be easily separated from the product.
すなわち、本発明の要旨は、
下記一般式（［）で示されるＮ−メチルベンジルアミノ
アセタール
〔式中 Ｈｌ及びＲＦ、−は同一で・あっても、異って
いてもよい低級アルキル基を示し、又、Ｒ３、Ｒ４゜Ｒ
１及びＲ６は水素原子、低級アルコキシ基または隣シ合
う二つの基が一緒になって、メチレンジオキシ基を示し
、同一であっても異っていてもよい〕を有機スルホン酸
の存在下で閉環することを特徴とする下記一般式（ＩＩ
）で示される〔式中、Ｒ３、Ｒ４、Ｒ５およびＲ・は一
般式（り中で定義し次と同義である〕テトラヒドロ−弘
−ヒドロキシイソキノリン誘導体の製造法に存する。That is, the gist of the present invention is to provide N-methylbenzylaminoacetal represented by the following general formula ([) [wherein Hl and RF, - represent lower alkyl groups which may be the same or different]. , also, R3, R4゜R
1 and R6 represent a hydrogen atom, a lower alkoxy group, or two adjacent groups together represent a methylenedioxy group, which may be the same or different] in the presence of an organic sulfonic acid. The following general formula (II
) [wherein R3, R4, R5 and R. are defined in the general formula and have the same meanings as below].
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明に用いられるＮ−メチルベンジルアミノアセター
ルは一般式（Ｉ）で示され、式中 Ｒ１及びＲ８は同一
であっても、異っていてもよい０１〜Ｃｓの低級アルキ
ル基を示し、又、Ｒ３−Ｒ６は水素原子、０１〜Ｃ３の
低級アルコキシ基または隣り合う二つの基が一緒になっ
てメチレンジオキシ基を示し、同一であっても、異って
いてもよい。The N-methylbenzylaminoacetal used in the present invention is represented by the general formula (I), in which R1 and R8 represent a lower alkyl group of 01 to Cs, which may be the same or different, and , R3-R6 represent a hydrogen atom, a lower alkoxy group of 01 to C3, or two adjacent groups taken together represent a methylenedioxy group, and may be the same or different.
具体的には、
４−メトキシー３，９ｔ−メチレンジオキシ−Ｎ−メチ
ルベンジルアミノジメチルアセタール。Specifically, 4-methoxy-3,9t-methylenedioxy-N-methylbenzylaminodimethyl acetal.
ツーメトキシ−３，弘−メチレンジオキシーＮ −メチ
ルベンジルアミノジエチルアセタール。Twomethoxy-3, Hiro-methylenedioxy-N-methylbenzylaminodiethyl acetal.
ジ−メトキシ−Ｎ−メチルベンジルアミノジメチルアセ
タール。Di-methoxy-N-methylbenzylaminodimethyl acetal.
弘−メトキシ−Ｎ−メチルベンジルアミノジエチルアセ
タール。Hiro-methoxy-N-methylbenzylaminodiethyl acetal.
３−メトキシ−Ｎ−メチルベンジルアミノジメチルアセ
タール。3-methoxy-N-methylbenzylaminodimethyl acetal.
３−メトキシ−Ｎ−メチルベンジルアミノジエチルアセ
タール。3-Methoxy-N-methylbenzylaminodiethyl acetal.
コ、３−ジメトキシーＮ−メチルベンジルアミノジメチ
ルアセタール。3-dimethoxy N-methylbenzylaminodimethyl acetal.
２．３−ジメトキシ−Ｎ−メチルベンジルアミノジエチ
ルアセタール。2.3-Dimethoxy-N-methylbenzylaminodiethyl acetal.
３．９ｔ−ジメトキシ−Ｎ−メチルベンジルアミノジメ
チルアセタール。3.9 t-Dimethoxy-N-methylbenzylaminodimethyl acetal.
３、タージメトキシ−Ｎ−メチルベンジルアミノジエチ
ルアセタール。3. Tadimethoxy-N-methylbenzylaminodiethyl acetal.
３．９Ｌ、ｊ−）ジメトキシ−Ｎ−メチルベンジルアミ
ノジメチルアセタール。3.9L, j-) Dimethoxy-N-methylbenzylaminodimethyl acetal.
ｚ、ａ、ｘ −トリメトキシ−Ｎ−メチルベンジルアミ
ノジエチルアセタール。z,a,x-trimethoxy-N-methylbenzylaminodiethyl acetal.
２．３−メチレンジオキシ−！−メトキシーＮ−メチル
ベンジルアミノジメチルアセタール。2.3-Methylenedioxy-! -Methoxy N-methylbenzylaminodimethyl acetal.
、２．３−メチレンジオキシ−ｊ−メトキシ−Ｎ−メチ
ルベンジルアミノジエチルアセタール等が例示される。, 2,3-methylenedioxy-j-methoxy-N-methylbenzylamino diethyl acetal and the like.
本発明に用いられる有機スルホン酸としては、可溶性有
機スルホン酸と不溶性有機スルホン酸とがある。可溶性
有機スルホン酸の例としては、ベンゼンスルホン酸、ｏ
−２ｍ−及びｐ−トルエンスルホンＭ、ｏ−、ｍ−及ヒ
ｐ−キシレンスルホン酸等の芳香族スルホン酸：メタン
スルホン酸、エタンスルホン酸等の脂肪族スルホン酸が
挙げられる。不溶性有機スルホン酸の例としては、酸性
陽イオン交換樹脂が挙げられ、市販のものが用いられる
。例えば、ゲル型酸性陽イオン交換樹脂としてはダイア
イオン（登録商標）８に／Ｂ、ポーラス型酸性陽イオン
交換樹脂としてはダイアイオン（登録商伸）ＰＫコθｔ
。The organic sulfonic acids used in the present invention include soluble organic sulfonic acids and insoluble organic sulfonic acids. Examples of soluble organic sulfonic acids include benzenesulfonic acid, o
Aromatic sulfonic acids such as -2m- and p-toluenesulfonic acid M, o-, m- and hypoxylene sulfonic acid; aliphatic sulfonic acids such as methanesulfonic acid and ethanesulfonic acid. Examples of insoluble organic sulfonic acids include acidic cation exchange resins, and commercially available ones are used. For example, a gel type acidic cation exchange resin is Diaion (registered trademark) 8/B, and a porous type acidic cation exchange resin is Diaion (registered trade name) PK Coθt.
.
ＰＫ２／ｌ 、ＥＸ／９ｔｔＨ，ｐｘＪｊ♂Ｌが、ハイ
ポーラス型酸性陽イオン交換樹脂としてダイアイオン（
登録商標）ＨＰＫｊｊ等が挙げられる。PK2/l, EX/9ttH, pxJj♂L are used as highly porous acidic cation exchange resins such as Diaion (
(registered trademark) HPKjj, etc.
有機スルホン酸の使用量はＮ−メチルベンジルアミノア
セタールに対して、通常、／、θ〜１００当量、好まし
くは／、θ〜コθ当量である。The amount of organic sulfonic acid used is usually /, θ to 100 equivalents, preferably /, θ to coθ equivalents, based on N-methylbenzylaminoacetal.
本発明に用いられる溶媒には特に制限はないが、水溶媒
が好ましい。溶媒量は酸１モルに対して通常、／ ０〜
／ ００００ ｗｅ 、好ましくはＩＯθ〜１０００１
ｄである。Although there are no particular limitations on the solvent used in the present invention, an aqueous solvent is preferred. The amount of solvent is usually / 0 to 1 mole of acid.
/ 0000 we, preferably IOθ~10001
It is d.
本発明の反応温度は、θ℃〜／６０℃、好ましくは！’
０℃〜７．２０℃である。The reaction temperature of the present invention is θ°C to /60°C, preferably! '
It is 0°C to 7.20°C.
次に、本発明の反応方法であるが、有機スルホン酸とし
て可溶性有機スルホン酸を用いる場合は、攪拌しながら
反応を行い、反応終了後、アルカリで中和し、その後、
抽出、溶媒留去を行うことによって、目的物を得ること
ができる。Next, in the reaction method of the present invention, when a soluble organic sulfonic acid is used as the organic sulfonic acid, the reaction is carried out with stirring, and after the reaction is completed, it is neutralized with an alkali, and then,
The desired product can be obtained by extraction and solvent distillation.
又、不溶性有機スルホン酸を用いる場合は、懸濁系での
悄拌反応もしくは流通方式のいずれの方法を用いてもよ
く、反応終了後、アルカリ交換および／または有機溶媒
による抽出、溶媒留去を行うことによって、目的物を得
ることができる。In addition, when using an insoluble organic sulfonic acid, either a stirring reaction in a suspension system or a flow method may be used, and after the reaction is completed, alkali exchange and/or extraction with an organic solvent and solvent distillation are performed. By doing this, you can obtain the desired object.
（実施例）
以下、実施例により本発明を更に詳細に説明するが、本
発明はその要旨を超えない限り以下の実施例に限定され
るものではない。(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.
実施例／
ノーメトキシ−３，ｐ′−メチレンジオキシ−Ｎ−メチ
ルベンジルアミノジメチルアセタールＯ６♂！ ｔ （
Ｊ ミＩＪモル）オよヒｐ−）ルエンスルポン酸ｊ、７
／ ｆ （３０ミリモル）を水４ｍ／に混合し、油浴
？θ℃にて３時間攪拌した。反応液は室温まで冷却後、
希Ｎａ ＯＨ溶液でｐＨ〜／弘とし、塩化メチレンで抽
出した。この抽出液を液体クロマトグラフィーで分析し
たところ、目的物であるテトラヒトローダ−ヒドロキシ
インキノリン誘導体の収量は０．６−２４ Ｆであった
。Example/Nomethoxy-3,p'-methylenedioxy-N-methylbenzylaminodimethyl acetal O6♂! t (
J miIJmol)oyohyp-)luenesulfonic acidj, 7
/ f (30 mmol) was mixed with 4 m/f of water and placed in an oil bath. The mixture was stirred at θ°C for 3 hours. After cooling the reaction solution to room temperature,
The pH was brought to ~/Hiroshi with dilute NaOH solution and extracted with methylene chloride. When this extract was analyzed by liquid chromatography, the yield of the target tetrahydroder-hydroxyin quinoline derivative was 0.6-24F.
（収率ｌ／％）
また、副生成物であるテトラヒトローダ−メトキシイソ
キノリン誘導体の収量はθ、Ｏｊ ７ ｔであった。（
収率？％）
実施例２
λ−メトキシー３−−メチレンジオキシーＨ−メチルベ
ンジルアミノジメチルアセタールＯＪ！ｔ （７ミリモ
ル）および陽イオン交換樹脂ダイアイオンＰＫ２０？（
官能基量が／、２ｍｅｑ／ｗｔｉ−Ｒのものを、あらか
じめ、２ＮＨＣｔにて前処理したもの）２ｓ肩１を水／
２−に混合し、油浴♂Ｏ℃にて３時間加熱攪拌した。反
応混合物を室温まで冷却後、希ＮａＯＨ溶液にてｐＨ−
／４ｔとし、室温にて２時間攪拌した。次に、塩化メチ
レンを加え、抽出および濾過を行ない塩化メチレン層を
液体クロマトグラフィーで定量した。その結果、目的物
であるテトラヒトローダ−ヒドロキシイソキノリン誘導
体の収量は０、！ ／ ７ ｔであり、これは収率７３
％に相当する。また、副生成物であるテトラヒドローダ
−メトキシイソキノリン誘導体の収量は０．０ ／ ／
りｔであり、これは収率コチに相当する。(Yield 1/%) Moreover, the yield of the tetrahydroder-methoxyisoquinoline derivative, which is a by-product, was θ, Oj 7 t. (
yield? %) Example 2 λ-Methoxy-3-methylenedioxy-H-methylbenzylaminodimethyl acetal OJ! t (7 mmol) and the cation exchange resin Diaion PK20? (
Those with a functional group content of /, 2 meq/wti-R were pretreated with 2NHCt) 2s shoulder 1 was treated with water/
2-, and heated and stirred in an oil bath at 0°C for 3 hours. After cooling the reaction mixture to room temperature, the pH was adjusted to -
/4t, and stirred at room temperature for 2 hours. Next, methylene chloride was added, extraction and filtration were performed, and the methylene chloride layer was quantified by liquid chromatography. As a result, the yield of the desired tetrahydroder-hydroxyisoquinoline derivative was 0! /7 t, which is a yield of 73
Corresponds to %. In addition, the yield of the by-product tetrahydroder-methoxyisoquinoline derivative was 0.0//
t, which corresponds to the yield flathead.
比較例
コーメトキシー３−−メチレンジオキシーＮ−メチルベ
ンジルアミノジメチルアセタールθ、／ ｊ ｊ’ （
ｊミリモル）を４ Ｎ Ｈｏｔイゴに混合し、油浴≦θ
℃にて３時間攪拌した。反応液を室温まで冷却後、希Ｍ
ａ ＯＨ溶液でｐＨ−Ｌ／％とし塩化メチレンで抽出し
た。この塩化メチレン層を液体クロマトグラフィーで分
析したところ、目的物であるテトラヒトローダ−ヒドロ
キシイソキノリン誘導体の収量は０．６４７ ｔであり
、これは収率ｔ０優に相当する。また、副生成物である
テトラヒトローダ−メトキシイソキノリン誘導体の収量
はθ、θ２ダ？であり、これは収率／θ％に相当する。Comparative Example Comethoxy 3--methylenedioxy-N-methylbenzylaminodimethyl acetal θ, / j j' (
j mmol) in 4 N Hot Igo, oil bath ≦θ
The mixture was stirred at ℃ for 3 hours. After cooling the reaction solution to room temperature, dilute M
a Adjusted to pH-L/% with OH solution and extracted with methylene chloride. When this methylene chloride layer was analyzed by liquid chromatography, the yield of the target tetrahydroder-hydroxyisoquinoline derivative was 0.647 t, which corresponds to an excellent yield of t0. Also, the yield of the by-product tetrahydroder-methoxyisoquinoline derivative is θ, θ2 da? , which corresponds to yield/θ%.
本発明方法によれば、医薬等の製造中間体として有用な
テトラヒドロ−Ｚ−ヒドロキシイソキノリン誘導体を高
収率で製造することができる。According to the method of the present invention, a tetrahydro-Z-hydroxyisoquinoline derivative useful as an intermediate in the production of pharmaceuticals and the like can be produced in high yield.
出 願 人 三菱化成工業株式会社 代 理 人 弁理士 要否用 −ほか／名Sender: Mitsubishi Chemical Industries, Ltd. Representative Patent attorney (if necessary) - Others/Name
Claims (1)
ルアミノアセタール ▲数式、化学式、表等があります▼（ I ） 〔式中、Ｒ＾１及びＲ＾２は同一であつても、異つてい
てもよい低級アルキル基を示し、又、 Ｒ＾３、Ｒ＾４、Ｒ＾５及びＲ＾６は水素原子、低級ア
ルコキシ基または隣り合う二つの基が一緒になつてメチ
レンジオキシ基を示し、同一であつても異つていてもよ
い〕を有機スルホン酸の存在下で閉環することを特徴と
する下記一般式 （II）で示される ▲数式、化学式、表等があります▼（II） 〔式中、Ｒ＾３、Ｒ＾４、Ｒ＾５およびＲ＾６は一般式
（ I ）中で定義したと同義である〕テトラヒドロ−４
−ヒドロキシイソキノリン誘導体の製造法。(1) N-methylbenzylaminoacetal represented by the following general formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, R^1 and R^2 may be the same but different. R^3, R^4, R^5 and R^6 are hydrogen atoms, lower alkoxy groups, or two adjacent groups taken together to form a methylenedioxy group. There are ▲mathematical formulas, chemical formulas, tables, etc. shown by the following general formula (II), which is characterized by ring-closing the compounds (which may be the same or different) in the presence of an organic sulfonic acid. II) [In the formula, R^3, R^4, R^5 and R^6 have the same meanings as defined in general formula (I)] Tetrahydro-4
-Production method of hydroxyisoquinoline derivative.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60211294A JPS6272670A (en) | 1985-09-25 | 1985-09-25 | Production of tetrahydro-4-hydroxyisoquinoline derivative |
| US06/901,388 US4760145A (en) | 1985-09-04 | 1986-08-28 | Certain 6,7-methylene dioxydihydro or tetrahydro-isoquinoline derivatives |
| EP86401912A EP0214905A3 (en) | 1985-09-04 | 1986-08-29 | Tetrahydroisoquinoline derivatives |
| KR1019860007411A KR900004835B1 (en) | 1985-09-04 | 1986-09-04 | Process for the preparation of tetrahydro-isoquino isoqinoline derivatives |
| CA000517489A CA1300147C (en) | 1985-09-04 | 1986-09-04 | 8-hydroxy-2-methyl-6,7-methylenedioxy-1,2,3,4- tetrahydroisoquinoline compounds |
| KR1019900007731A KR920001564B1 (en) | 1985-09-04 | 1990-05-25 | Tetrahydro isoquinoline derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60211294A JPS6272670A (en) | 1985-09-25 | 1985-09-25 | Production of tetrahydro-4-hydroxyisoquinoline derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6272670A true JPS6272670A (en) | 1987-04-03 |
Family
ID=16603551
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60211294A Pending JPS6272670A (en) | 1985-09-04 | 1985-09-25 | Production of tetrahydro-4-hydroxyisoquinoline derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6272670A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02217611A (en) * | 1989-02-15 | 1990-08-30 | Canon Inc | Dynamic pressure bearing device |
| US7445564B2 (en) | 2004-03-30 | 2008-11-04 | Daiwa Seiko, Inc. | Golf club head |
-
1985
- 1985-09-25 JP JP60211294A patent/JPS6272670A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02217611A (en) * | 1989-02-15 | 1990-08-30 | Canon Inc | Dynamic pressure bearing device |
| US7445564B2 (en) | 2004-03-30 | 2008-11-04 | Daiwa Seiko, Inc. | Golf club head |
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