JPH0641452B2 - Selective hydrogenation of isoquinolines - Google Patents
Selective hydrogenation of isoquinolinesInfo
- Publication number
- JPH0641452B2 JPH0641452B2 JP61053078A JP5307886A JPH0641452B2 JP H0641452 B2 JPH0641452 B2 JP H0641452B2 JP 61053078 A JP61053078 A JP 61053078A JP 5307886 A JP5307886 A JP 5307886A JP H0641452 B2 JPH0641452 B2 JP H0641452B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- isoquinolines
- hydrogen atom
- alkyl group
- carbon monoxide
- 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.)
- Expired - Lifetime
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Other In-Based Heterocyclic Compounds (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 本発明はイソキノリン類の選択的水素化法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for the selective hydrogenation of isoquinolines.
イソキノリン類は石炭中に多量に含まれ、農薬、医薬、
染料あるいは界面活性剤などの中間体であるが、特にそ
の含窒素環が水素化された１，２，３，４−テトラヒド
ロイソキノリン類は極めて重要な中間体である。Isoquinolines are contained in large amounts in coal, and pesticides, drugs,
It is an intermediate such as a dye or a surfactant, and especially 1,2,3,4-tetrahydroisoquinolines having a hydrogenated nitrogen-containing ring are extremely important intermediates.
従来、かかるイソキノリン類の水素化法としてはたとえ
ばスズと塩酸を用いる方法、ナトリウムとエタノールを
用いる方法あるいはニッケル触媒を用いる方法などが知
られているが、これらの方法はいずれもその操作が煩雑
であったり、収率が低い等の問題があり、工業的に有利
な方法とは言えなかった。Heretofore, as a method for hydrogenating such isoquinolines, for example, a method using tin and hydrochloric acid, a method using sodium and ethanol, a method using a nickel catalyst, or the like has been known. However, there are problems such as low yield and low yield, so it cannot be said to be an industrially advantageous method.
このようなことから、本発明者らはかかる問題を解決
し、容易に、好収率でイソキノリン類の含窒素環を選択
的に水素化する方法について検討の結果、Ｒｈ−ＣＯ系
触媒の存在下、水性ガスシフト条件下でイソキノリン類
の含窒素環が選択的に水素化されることを見出し、本発
明に至った。From the above, the inventors of the present invention have solved the problem and studied the method for selectively hydrogenating the nitrogen-containing ring of isoquinolines easily and in good yield, and as a result, the existence of the Rh-CO-based catalyst was found. Under the present invention, the inventors have found that the nitrogen-containing ring of isoquinolines is selectively hydrogenated under the water gas shift condition, and have reached the present invention.
すなわち、本発明は一般式（１） （式中、Ｒ１およびＲ２はそれぞれ、水素原子、アルキ
ル基、アルコキシ基またはベンジロキシ基を示し、Ｒ３
は、水素原子またはアルキル基を示す。） で示されるイソキノリン類を、一酸化炭素および水の存
在下、Ｒh-ＣＯ系触媒を用いて含窒素環を選択的に水素
化することにより一般式（２） （式中、Ｒ１、Ｒ２およびＲ３は前記と同じ意味を有す
る。） で示される化合物の製造法および該化合物に鉱酸類また
はアルカリ金属の水酸化物を作用させることにより一般
式（３） （式中、Ｒ１、Ｒ２およびＲ３は前記と同じ意味を有す
る。） で示される化合物の製造法を提供するものである。That is, the present invention has the general formula (1) (In the formula, R 1 and R 2 each represent a hydrogen atom, an alkyl group, an alkoxy group or a benzyloxy group, and R 3
Represents a hydrogen atom or an alkyl group. ) Is subjected to selective hydrogenation of a nitrogen-containing ring using a Rh—CO-based catalyst in the presence of carbon monoxide and water to give a compound of the general formula (2) (In the formula, R 1 , R 2 and R 3 have the same meanings as described above.) And a compound of the general formula (3) by reacting the compound with a mineral acid or an alkali metal hydroxide. ) (Wherein R 1 , R 2 and R 3 have the same meanings as described above).
本発明において使用されるＲｈ−ＣＯ系触媒とは通常Ｒ
ｈｎ（ＣＯ）ｍなる式で示され、ｎ，ｍは特に限定され
ず、従来公知のものが使用されるが、代表的にはＲｈ
6(CO)16が挙げられる。The Rh-CO catalyst used in the present invention is usually R
h n (CO) m , where n and m are not particularly limited and conventionally known ones are used, but typically Rh
6 (CO) 16 can be mentioned.
かかる触媒の使用量は原料イソキノリン類に対して通常
0.001〜0.2モル倍、好ましくは0.005〜0.1モル倍、更に
好ましくは0.005〜0.05モル倍である。The amount of such a catalyst used is usually relative to the raw isoquinolines.
The molar ratio is 0.001 to 0.2, preferably 0.005 to 0.1, and more preferably 0.005 to 0.05.
本反応において使用された触媒は、反応終了後、反応液
から回収し、再使用することができる。The catalyst used in this reaction can be recovered from the reaction solution and reused after the completion of the reaction.
この反応において、水は原料イソキノリン類に対して２
当量倍以上使用され、これを大過剰用いて溶媒を兼ねて
もよい。In this reaction, 2 parts of water was added to the starting isoquinolines.
It is used in an equivalent amount or more, and a large excess thereof may be used as a solvent.
反応は、通常一酸化炭素の加圧下で行われ、反応系にお
ける一酸化炭素圧は通常１０〜１００kg／cm2の範囲で
ある。もちろん常圧下でも反応は進行するが、反応の完
結に極めて長時間を要する。The reaction is usually carried out under pressure of carbon monoxide, and the carbon monoxide pressure in the reaction system is usually in the range of 10 to 100 kg / cm 2 . Of course, the reaction proceeds even under normal pressure, but it takes an extremely long time to complete the reaction.
反応は通常溶媒の存在下に行われるが、該溶媒としては
水、脂肪族もしくは脂環式アルコール、アルコキシアル
コール、エーテル等が挙げられ、反応に活性な不飽和化
合物以外であれば特に限定されるものではないが、アル
コール、アルコキシアルコール、エーテルが好ましく使
用される。The reaction is usually carried out in the presence of a solvent, and the solvent includes water, aliphatic or alicyclic alcohols, alkoxy alcohols, ethers, etc., and is not particularly limited as long as it is an unsaturated compound active in the reaction. Alcohols, alkoxy alcohols, and ethers are preferably used, although not limited thereto.
溶媒の使用量は、原料イソキノリンに対して通常１〜５
０重量倍である。The amount of the solvent used is usually 1 to 5 with respect to the raw material isoquinoline.
It is 0 times the weight.
反応温度は原料イソキノリンの種類、使用する溶媒、一
酸化炭素圧などによっても異なるが、通常１００〜２０
０℃である。The reaction temperature varies depending on the type of starting material isoquinoline, the solvent used, the carbon monoxide pressure, etc., but is usually 100 to 20.
It is 0 ° C.
かくして本発明の方法によれば、含窒素環が選択的に水
素化されるが、本方法では水素化されたのちのＮＨ結合
間に一酸化炭素が挿入し、Ｎ−ホルミル−１，２，３，
４−テトラヒドロイソキノリンが得られる。Thus, according to the method of the present invention, the nitrogen-containing ring is selectively hydrogenated, but in this method, carbon monoxide is inserted between the NH bonds after hydrogenation, and N-formyl-1,2, Three
4-Tetrahydroisoquinoline is obtained.
このホルミル化物は、たとえば濃塩酸とメタノールある
いは苛性ソーダとメタノールで処理することにより、容
易に脱ホルミル化され、１，２，３，４−テトラヒドロ
イソキノリンに変換することができる。This formylated product can be easily reformed by treatment with concentrated hydrochloric acid and methanol or caustic soda and methanol to be converted to 1,2,3,4-tetrahydroisoquinoline.
また、通常の接触水素添加では水素化分解されやすいベ
ンジロキシ基をもつイソキノリン類の場合も、本発明の
方法では水素化分解は起こらないという特徴がある。Further, even in the case of isoquinolines having a benzyloxy group which is easily hydrocracked by ordinary catalytic hydrogenation, the method of the present invention is characterized in that hydrocracking does not occur.
以下、実施例により本発明を説明する。Hereinafter, the present invention will be described with reference to examples.
実施例１ 容量１０mlのオートクレープにイソキノリン2.3×10-3
モル、Ｐｈ6(CO)160.019×10-3モル、水28×10-3モルお
よび２−メトキシエタノール２mlを仕込み、一酸化炭素
で56kg／cm2・Ｇに加圧後、150℃に加熱した。Example 1 Isoquinoline 2.3 × 10 −3 in a 10 ml autoclave
Mol, Ph 6 (CO) 16 0.019 × 10 -3 mol, water 28 × 10 -3 mol and 2-methoxyethanol 2 ml were charged, carbon monoxide was applied to 56 kg / cm 2 · G, and then heated to 150 ° C. did.
24時間後、冷却し、触媒除去後、蒸留によりＮ−ホルミ
ル−１，２，３，４−テトラヒドロイソキノリンを収率
６９％で得た。After 24 hours, the mixture was cooled, the catalyst was removed, and N-formyl-1,2,3,4-tetrahydroisoquinoline was obtained by distillation in a yield of 69%.
実施例２ イソキノリンに代えて６−ベンジロキシ−７−メトキシ
イソキノリンを用いる以外は実施例１と同様に反応、後
処理してＮ−ホルミル−６−ベンジロキシ−７−メトキ
シ−1,2,3,4−テトラヒドロイソキノリンを収率６６％
で得た。Example 2 N-formyl-6-benzyloxy-7-methoxy-1,2,3,4 was reacted and worked up in the same manner as in Example 1 except that 6-benzyloxy-7-methoxyisoquinoline was used instead of isoquinoline. -Tetrahydroisoquinoline yield 66%
Got with.
Claims (2)
ル基、アルコキシ基またはベンジロキシ基を示し、Ｒ３
は、水素原子またはアルキル基を示す。） で示されるイソキノリン類を、一酸化炭素および水の存
在下、Ｒh-ＣＯ系触媒を用いて含窒素環を選択的に水素
化することを特徴とする一般式（２） （式中、Ｒ１、Ｒ２およびＲ３は前記と同じ意味を有す
る。） で示される化合物の製造法。1. A general formula (1) (In the formula, R 1 and R 2 each represent a hydrogen atom, an alkyl group, an alkoxy group or a benzyloxy group, and R 3
Represents a hydrogen atom or an alkyl group. ) The isoquinoline represented by the formula (2) is characterized in that the nitrogen-containing ring is selectively hydrogenated using a Rh-CO catalyst in the presence of carbon monoxide and water. (In the formula, R 1 , R 2 and R 3 have the same meanings as described above.)
ル基、アルコキシ基またはベンジロキシ基を示し、Ｒ３
は、水素原子またはアルキル基を示す。） で示されるイソキノリン類を、一酸化炭素および水の存
在下、Ｒh-ＣＯ系触媒を用いて含窒素環を選択的に水素
化することにより一般式（２） （式中、Ｒ１、Ｒ２およびＲ３は前記と同じ意味を有す
る。） で示される化合物を得、これに鉱酸類またはアルカリ金
属の水酸化物を作用させることを特徴とする一般式
（３） （式中、Ｒ１、Ｒ２およびＲ３は前記と同じ意味を有す
る。） で示される化合物の製造法。2. General formula (1) (In the formula, R 1 and R 2 each represent a hydrogen atom, an alkyl group, an alkoxy group or a benzyloxy group, and R 3
Represents a hydrogen atom or an alkyl group. ) Is subjected to selective hydrogenation of a nitrogen-containing ring using a Rh—CO-based catalyst in the presence of carbon monoxide and water to give a compound of the general formula (2) (Wherein R 1 , R 2 and R 3 have the same meaning as described above), and a mineral acid or a hydroxide of an alkali metal is allowed to act on the compound. 3) (In the formula, R 1 , R 2 and R 3 have the same meanings as described above.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61053078A JPH0641452B2 (en) | 1986-03-11 | 1986-03-11 | Selective hydrogenation of isoquinolines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61053078A JPH0641452B2 (en) | 1986-03-11 | 1986-03-11 | Selective hydrogenation of isoquinolines |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62212371A JPS62212371A (en) | 1987-09-18 |
| JPH0641452B2 true JPH0641452B2 (en) | 1994-06-01 |
Family
ID=12932766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61053078A Expired - Lifetime JPH0641452B2 (en) | 1986-03-11 | 1986-03-11 | Selective hydrogenation of isoquinolines |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0641452B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114130389B (en) * | 2021-08-31 | 2023-11-17 | 浙江工业大学 | Supported catalyst, preparation thereof and application thereof in selective hydrogenation of nitrogen-containing heterocyclic compound |
-
1986
- 1986-03-11 JP JP61053078A patent/JPH0641452B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62212371A (en) | 1987-09-18 |
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