JPH0769959A - Production of 2-norbornanone - Google Patents
Production of 2-norbornanoneInfo
- Publication number
- JPH0769959A JPH0769959A JP23577393A JP23577393A JPH0769959A JP H0769959 A JPH0769959 A JP H0769959A JP 23577393 A JP23577393 A JP 23577393A JP 23577393 A JP23577393 A JP 23577393A JP H0769959 A JPH0769959 A JP H0769959A
- Authority
- JP
- Japan
- Prior art keywords
- carboxylic acid
- hydroxynorbornane
- norbornanone
- formula
- sodium hypochlorite
- 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.)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、種々の光学活性物質の
合成原料として有用な２−ノルボルナノンの製造方法に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing 2-norbornanone useful as a raw material for synthesizing various optically active substances.
【０００２】[0002]
【従来の技術】血液凝固剤として有用なトロンボキサン
Ａ２受容体アンタゴニストが、光学活性３−アリル−２
−ノルボルナノンから合成できることが報告されている
（Ｎａｒｉｓａｄａ ｅｔ ａｌ．，Ｊ．Ｍｅｄ．Ｃｈ
ｅｍ．，３１，１８４７（１９８８）。A thromboxane A2 receptor antagonist useful as a blood coagulant is an optically active 3-allyl-2.
-It has been reported that it can be synthesized from norbornanone (Narisada et al., J. Med. Ch.
em. , 31 , 1847 (1988).
【０００３】ここで、光学活性３−アリル−２−ノルボ
ルナノンは、通常、光学活性２−ノルボルナノンのカル
ボニル基のα位をアリル化することにより製造されてお
り、従って、トロンボキサンＡ２受容体アンタゴニスト
を製造するに際しては、光学活性２−ノルボルナノンを
入手することが必要となる。Here, the optically active 3-allyl-2-norbornanone is usually produced by allylating the α-position of the carbonyl group of the optically active 2-norbornanone. Therefore, a thromboxane A2 receptor antagonist is obtained. Upon production, it is necessary to obtain optically active 2-norbornanone.
【０００４】ところで、従来、２−ノルボルナノンを製
造する有力な方法として、以下の反応式By the way, conventionally, the following reaction formula has been used as an effective method for producing 2-norbornanone.
【０００５】[0005]
【化３】 に示すように式（２）の２−ヒドロキシノルボルナン−
２−カルボン酸を酸化剤を用いて酸化的に脱炭酸して式
（１）の２−ノルボルナノンを得る方法として以下に示
す３種類の方法が提案されている。[Chemical 3] 2-hydroxynorbornane of the formula (2)
The following three types of methods have been proposed as a method for oxidatively decarboxylating 2-carboxylic acid using an oxidizing agent to obtain 2-norbornanone of the formula (1).
【０００６】即ち、第１方法は、２−ヒドロキシノルボ
ルナン−２−カルボン酸に酸化剤として式（３）That is, the first method uses 2-hydroxynorbornane-2-carboxylic acid as an oxidant of formula (3)
【０００７】[0007]
【化４】 の２−クロロベンゾオキサゾリウム塩を作用させて２−
ノルボルナノンを収率約６６％で得るというものである
（Ｔ．Ｍｕｋａｉｙａｍａ ｅｔ ａｌ．，Ｊ．Ｍｅ
ｄ．Ｃｈｅｍ．Ｓｏｃ．，３１，１８４７（１９８
８））。[Chemical 4] 2-chlorobenzoxazolium salt of
Norbornanone is obtained with a yield of about 66% (T. Mukaiyama et al., J. Me.
d. Chem. Soc. , 31 , 1847 (198
8)).
【０００８】第２の方法は、２−ヒドロキシノルボルナ
ン−２−カルボン酸に酸化剤として過ヨウ素酸ナトリウ
ム（ＮａＩＯ４）を作用させて２−ノルボルナノンを収
率約８０〜９０％で得るというものである（Ｇ．Ｈｅｌ
ｍｃｈｅｎ ｅｔ ａｌ．，Ｔｅｔｒａｈｅｄｒｏｎ
Ａｓｙｍｍｅｔｒｙ，１，３５７（１９９０））。The second method is to react 2-hydroxynorbornane-2-carboxylic acid with sodium periodate (NaIO 4 ) as an oxidant to obtain 2-norbornanone with a yield of about 80 to 90%. Yes (G. Hel
mchen et al. , Tetrahedron
Asymmetry, 1 , 357 (1990)).
【０００９】第３の方法は、２−ヒドロキシノルボルナ
ン−２−カルボン酸に酸化剤としてビスマス酸ナトリウ
ム−リン酸（ＮａＢｉＯ３−Ｈ３ＰＯ４）を作用させて
２−ノルボルナノンを収率約５５％で得るというもので
ある（特開平５−５１３４５号公報）。In the third method, 2-hydroxynorbornane-2-carboxylic acid is reacted with sodium bismuthate-phosphoric acid (NaBiO 3 -H 3 PO 4 ) as an oxidant to give 2-norbornanone in a yield of about 55%. (Japanese Patent Application Laid-Open No. 5-51345).
【００１０】[0010]
【発明が解決しようとする課題】しかしながら、上述の
第１の方法の場合には、使用する酸化剤が入手しにく
く、また高価であるために、工業的に実施するには問題
があった。However, in the case of the above-mentioned first method, the oxidizing agent to be used is difficult to obtain and expensive, so that there is a problem in industrial implementation.
【００１１】また、第２の方法の場合は、使用する酸化
剤が高価であるために、工業的に実施するには問題があ
った。Further, in the case of the second method, since the oxidizing agent used is expensive, there is a problem in carrying it out industrially.
【００１２】第３の方法の場合には、使用する酸化剤が
重金属のビスマスを含む化合物を使用しているので環境
に悪影響を与える可能性が大きく、また、収率も低いの
で大量処理に不向きであり、やはり工業的に実施するに
は問題があった。In the case of the third method, since the oxidizing agent used is a compound containing a heavy metal bismuth, there is a large possibility of adversely affecting the environment, and the yield is low, so that it is not suitable for large-scale processing. However, there was still a problem in implementing it industrially.
【００１３】本発明は、上述したような従来技術の課題
を解決しようとするものであり、血液凝固剤として有用
なトロンボキサンＡ２受容体アンタゴニストをはじめと
する、種々の生理活性物質の合成原料として有用な２−
ノルボルナノンを、２−ヒドロキシノルボルナン−２−
カルボン酸を効率的且つ工業的に簡便に酸化的脱炭酸し
て製造できるようにすることを目的とする。The present invention is intended to solve the above-mentioned problems of the prior art, and is used as a synthetic raw material for various physiologically active substances including thromboxane A2 receptor antagonists useful as blood coagulants. Useful 2-
Norbornanone, 2-hydroxynorbornane-2-
An object of the present invention is to make it possible to produce a carboxylic acid by oxidative decarboxylation efficiently and industrially and easily.
【００１４】[0014]
【課題を解決するための手段】本発明者らは、入手しや
すく廉価な次亜塩素酸ナトリウムが予想外にも２−ヒド
ロキシノルボルナン−２−カルボン酸を効率的に酸化的
脱炭酸させることができること、及びこの反応を利用す
ることにより上述の目的が達成できることを見出し、本
発明を完成させるに至った。The inventors of the present invention unexpectedly found that sodium hypochlorite, which is easily available and inexpensive, can efficiently oxidatively decarboxylate 2-hydroxynorbornane-2-carboxylic acid. It was found that the above-mentioned object can be achieved by utilizing this reaction, and has completed the present invention.
【００１５】即ち、本発明は、 式（１）That is, the present invention is based on the formula (1)
【００１６】[0016]
【化５】 で表わされる２−ノルボルナノンを製造する方法におい
て：式（２）[Chemical 5] In the method for producing 2-norbornanone represented by the formula: Formula (2)
【００１７】[0017]
【化６】 で表わされる２−ヒドロキシノルボルナン−２−カルボ
ン酸に次亜塩素酸ナトリウムを作用させて酸化的に脱炭
酸させることにより式（１）の２−ノルボルナノンを得
ることを特徴とする製造方法を提供する。[Chemical 6] A 2-norbornane-2-carboxylic acid represented by the formula (2) is treated with sodium hypochlorite to oxidatively decarboxylate it to obtain 2-norbornanone of the formula (1). .
【００１８】以下、本発明を詳細に説明する。The present invention will be described in detail below.
【００１９】本発明の製造方法においては、上述したよ
うに２−ヒドロキシノルボルナン−２−カルボン酸に次
亜塩素酸ナトリウムを作用させて酸化的脱炭酸させる
が、この場合、２−ヒドロキシノルボルナン−２−カル
ボン酸と次亜塩素酸ナトリウムとを、−１０〜４０℃、
好ましくは０〜２０℃の温度で混合撹拌することにより
酸化的脱炭酸を実現することができる。In the production method of the present invention, as described above, 2-hydroxynorbornane-2-carboxylic acid is reacted with sodium hypochlorite to oxidatively decarboxylate. In this case, 2-hydroxynorbornane-2 is used. -Carboxylic acid and sodium hypochlorite, -10 ~ 40 ℃,
Oxidative decarboxylation can be achieved by mixing and stirring, preferably at a temperature of 0 to 20 ° C.
【００２０】なお、本発明において、２−ヒドロキシノ
ルボルナン−２−カルボン酸として光学活性なものを使
用した場合、酸化的脱炭酸反応の前後でラセミ化しな
い。従って、本発明は光学活性な２−ノルボルナノンを
製造する場合に適している。In the present invention, when 2-hydroxynorbornane-2-carboxylic acid which is optically active is used, it is not racemized before and after the oxidative decarboxylation reaction. Therefore, the present invention is suitable for producing optically active 2-norbornanone.
【００２１】次亜塩素酸ナトリウムの使用量は、２−ヒ
ドロキシノルボルナン−２−カルボン酸に対して好まし
くは１．００〜１．５０当量、より好ましくは１．０５
〜１．１０当量とする。The amount of sodium hypochlorite used is preferably 1.00 to 1.50 equivalents, more preferably 1.05 equivalent to 2-hydroxynorbornane-2-carboxylic acid.
~ 1.10 equivalents.
【００２２】この酸化的脱炭酸時には溶媒を使用しなく
てもよいが、必要に応じて水、あるいは水とベンゼン、
トルエン等の芳香族炭化水素類、ペンタン、ヘキサン、
ヘプタン等の脂肪族炭化水素類との二相系の反応溶媒を
使用することができる。また、酸化的脱炭酸時には、必
要に応じて、塩酸などの鉱酸、酢酸などの有機酸、ある
いは酢酸系緩衝液などを添加してもよい。A solvent may not be used during this oxidative decarboxylation, but if necessary, water or water and benzene,
Aromatic hydrocarbons such as toluene, pentane, hexane,
A two-phase reaction solvent with an aliphatic hydrocarbon such as heptane can be used. Further, at the time of oxidative decarboxylation, a mineral acid such as hydrochloric acid, an organic acid such as acetic acid, or an acetic acid-based buffer solution may be added, if necessary.
【００２３】なお、次亜塩素酸ナトリウムとしては、通
常、１２％水溶液として市販されているのものを好まし
く使用することができる。As sodium hypochlorite, it is possible to preferably use a commercially available 12% aqueous solution.
【００２４】反応終了後、常法により反応液から２−ノ
ルボルナノンを得ることができる。例えば、反応液をヘ
キサンなどの溶媒で抽出し、得られた有機層をチオ硫酸
ナトリウム水溶液、飽和炭酸水素ナトリウム水溶液、飽
和食塩水で順次洗浄した後、溶媒を減圧留去し、得られ
た残渣を減圧蒸留することにより２−ノルボルナノンを
得ることができる。After completion of the reaction, 2-norbornanone can be obtained from the reaction solution by a conventional method. For example, the reaction solution was extracted with a solvent such as hexane, and the obtained organic layer was washed successively with an aqueous solution of sodium thiosulfate, an aqueous solution of saturated sodium hydrogencarbonate and a saturated saline solution, and the solvent was evaporated under reduced pressure to obtain a residue. 2-norbornanone can be obtained by distillation under reduced pressure.
【００２５】本発明において使用する２−ヒドロキシノ
ルボルナン−２−カルボン酸は、種々の方法により入手
することができる。例えば、特開平５−５１３４５号公
報などに開示された方法により製造したものを使用する
ことができる。The 2-hydroxynorbornane-2-carboxylic acid used in the present invention can be obtained by various methods. For example, those manufactured by the method disclosed in Japanese Patent Laid-Open No. 5-51345 can be used.
【００２６】[0026]
【作用】本発明においては、２−ヒドロキシノルボルナ
ン−２−カルボン酸を酸化的に脱炭酸させて２−ノルボ
ルナノンを製造する。このとき酸化剤として、入手容易
で非常に廉価な次亜塩素酸ナトリウムを使用する。この
次亜塩素酸ナトリウムは、非常に効率よく２−ヒドロキ
シノルボルナン−２−カルボン酸を酸化的脱炭酸するこ
とができる。従って、本発明によれば、２−ヒドロキシ
ノルボルナン−２−カルボン酸を効率的且つ工業的に簡
便に酸化的脱炭酸することが可能となる。In the present invention, 2-hydroxynorbornane-2-carboxylic acid is oxidatively decarboxylated to produce 2-norbornanone. At this time, sodium hypochlorite, which is easily available and is very inexpensive, is used as the oxidizing agent. This sodium hypochlorite can very efficiently oxidatively decarboxylate 2-hydroxynorbornane-2-carboxylic acid. Therefore, according to the present invention, oxidative decarboxylation of 2-hydroxynorbornane-2-carboxylic acid can be carried out efficiently and industrially and easily.
【００２７】[0027]
【実施例】以下に、本発明を実施例により具体的に説明
する。EXAMPLES The present invention will be specifically described below with reference to examples.
【００２８】実施例１ ２−ヒドロキシ−５−ノルボルナン−２−カルボン酸１
５．６ｇを氷冷により１０〜１５℃に保持し撹拌しなが
ら、それに１２％次亜塩素酸ナトリウム水溶液６５．１
ｇを徐々に滴下した。滴下終了後１０〜１５℃で１時間
撹拌して反応を熟成させた。反応終了後、反応液をヘキ
サンで抽出し、得られた有機層を１０％チオ硫酸ナトリ
ウム水溶液、飽和炭酸水素ナトリウム水溶液、飽和食塩
水で順次洗浄した。洗浄した有機層からヘキサンを減圧
留去し、得られた残渣を減圧蒸留して２−ノルボルナノ
ンを１０．３ｇ（収率９３％）得た。得られた２−ノル
ボルナノンの物性データを以下に示す。Example 1 2-Hydroxy-5-norbornane-2-carboxylic acid 1
5.6 g of ice-cooled solution was maintained at 10 to 15 ° C. with stirring, and while stirring, a 12% sodium hypochlorite aqueous solution 65.1 was added thereto.
g was gradually added dropwise. After completion of dropping, the reaction was aged by stirring at 10 to 15 ° C for 1 hour. After completion of the reaction, the reaction solution was extracted with hexane, and the obtained organic layer was washed successively with a 10% sodium thiosulfate aqueous solution, a saturated sodium hydrogen carbonate aqueous solution, and a saturated saline solution. Hexane was distilled off from the washed organic layer under reduced pressure, and the obtained residue was distilled under reduced pressure to obtain 10.3 g (yield 93%) of 2-norbornanone. The physical property data of the obtained 2-norbornanone are shown below.
【００２９】融点：９６〜９７℃１ Ｈ−ＮＭＲ（３００ＭＨｚ，ＣＤＣｌ３，δ）：１．
３８〜１．６０（３Ｈ，ｍ），１．７０〜１．９０（４
Ｈ，ｍ），２．５０〜２．１１（１Ｈ，ｍ），２．５９
（１Ｈ，ｂｒ．ｓ），２．６７（１Ｈ，ｂｒ．ｓ）１３ Ｃ−ＮＭＲ（７５．５ＭＨｚ，ＣＤＣｌ３，δ）：
２４．１，２７．１，３５．２，３７．６，４５．２，
４９．８，２１８．２。Melting point: 96 to 97 ° C. 1 H-NMR (300 MHz, CDCl 3 , δ): 1.
38-1.60 (3H, m), 1.70-1.90 (4
H, m), 2.50 to 2.11 (1H, m), 2.59
(1H, br.s), 2.67 (1H, br.s) 13 C-NMR (75.5 MHz, CDCl 3 , δ):
24.1, 271, 35.2, 37.6, 45.2
49.8, 218.2.
【００３０】実施例２ ２−ヒドロキシノルボルナン−２−カルボン酸１５．６
ｇを水１００ｍｌに溶解し、その溶液にヘキサン１００
ｍｌを加えて２相系反応液とした。この反応液に１２％
次亜塩素酸ナトリウム６５．１ｇを徐々に滴下した。滴
下終了後１０〜１５℃で１時間撹拌して反応を熟成させ
た。反応終了後、反応液から水層を除き、有機層を１０
％チオ硫酸ナトリウム水溶液、飽和炭酸水素ナトリウム
水溶液、飽和食塩水で順次洗浄した。洗浄した有機層か
らヘキサンを減圧留去し、得られた残渣を減圧蒸留して
２−ノルボルナノンを９．９ｇ（収率９０％）得た。Example 2 2-Hydroxynorbornane-2-carboxylic acid 15.6
g in 100 ml of water and add 100 parts of hexane to the solution.
ml was added to make a two-phase reaction solution. 12% in this reaction solution
65.1 g of sodium hypochlorite was gradually added dropwise. After completion of dropping, the reaction was aged by stirring at 10 to 15 ° C for 1 hour. After the reaction was completed, the aqueous layer was removed from the reaction solution and the organic layer was washed with 10
% Sodium thiosulfate aqueous solution, saturated sodium hydrogen carbonate aqueous solution, and saturated saline solution in that order. Hexane was distilled off under reduced pressure from the washed organic layer, and the obtained residue was distilled under reduced pressure to obtain 9.9 g of 2-norbornanone (yield 90%).
【００３１】実施例３ ２−ヒドロキシノルボルナン−２−カルボン酸１５．６
ｇを酢酸緩衝液（ｐＨ５．０）に溶解し、その溶液を氷
冷により１０〜１５℃に保持し撹拌しながら、それに１
２％次亜塩素酸ナトリウム水溶液６５．１ｇを徐々に滴
下した。滴下終了後１０〜１５℃で１時間撹拌して反応
を熟成させた。反応終了後、反応液をヘキサンで抽出
し、得られた有機層を１０％チオ硫酸ナトリウム水溶
液、飽和炭酸水素ナトリウム水溶液、飽和食塩水で順次
洗浄した。洗浄した有機層からヘキサンを減圧留去し、
得られた残渣を減圧蒸留して２−ノルボルナノンを８．
８ｇ（収率８０％）得た。Example 3 2-Hydroxynorbornane-2-carboxylic acid 15.6
g was dissolved in acetate buffer (pH 5.0), and the solution was kept at 10 to 15 ° C. by ice cooling and stirred to 1
65.1 g of a 2% sodium hypochlorite aqueous solution was gradually added dropwise. After completion of dropping, the reaction was aged by stirring at 10 to 15 ° C for 1 hour. After completion of the reaction, the reaction solution was extracted with hexane, and the obtained organic layer was washed successively with a 10% sodium thiosulfate aqueous solution, a saturated sodium hydrogen carbonate aqueous solution, and a saturated saline solution. Hexane was distilled off under reduced pressure from the washed organic layer,
The resulting residue was distilled under reduced pressure to give 2-norbornanone 8.
8 g (yield 80%) was obtained.
【００３２】[0032]
【発明の効果】本発明によれば、種々の生理活性物質の
合成原料として有用な２−ノルボルナノンを、２−ヒド
ロキシノルボルナン−２−カルボン酸から効率的且つ工
業的に簡便に製造することができる。INDUSTRIAL APPLICABILITY According to the present invention, 2-norbornanone, which is useful as a raw material for the synthesis of various physiologically active substances, can be efficiently and industrially produced from 2-hydroxynorbornane-2-carboxylic acid. .
Claims (1)
て：式（２） 【化２】 で表わされる２−ヒドロキシノルボルナン−２−カルボ
ン酸に次亜塩素酸ナトリウムを作用させて酸化的に脱炭
酸させることにより式（１）の２−ノルボルナノンを得
ることを特徴とする製造方法。1. Formula (1): In the method for producing 2-norbornanone represented by the formula: Formula (2) A method for producing 2-norbornanone of the formula (1), which comprises reacting 2-hydroxynorbornane-2-carboxylic acid represented by the formula (1) with sodium hypochlorite to oxidatively decarboxylate it.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23577393A JP2864490B2 (en) | 1993-08-26 | 1993-08-26 | Method for producing 2-norbornanone |
| DE69409733T DE69409733T2 (en) | 1993-08-26 | 1994-08-19 | Process for the production of optically active 2-norbornanons |
| EP94113001A EP0640579B1 (en) | 1993-08-26 | 1994-08-19 | Process for producing optically active 2-norbornanone |
| US08/293,215 US5498799A (en) | 1993-08-26 | 1994-08-19 | Process for producing optically active 2-norbornanone |
| KR1019940020779A KR100334844B1 (en) | 1993-08-26 | 1994-08-23 | Method for preparing optically active 2-norbornane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23577393A JP2864490B2 (en) | 1993-08-26 | 1993-08-26 | Method for producing 2-norbornanone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0769959A true JPH0769959A (en) | 1995-03-14 |
| JP2864490B2 JP2864490B2 (en) | 1999-03-03 |
Family
ID=16991030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23577393A Expired - Fee Related JP2864490B2 (en) | 1993-08-26 | 1993-08-26 | Method for producing 2-norbornanone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2864490B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005102972A1 (en) * | 2004-04-19 | 2005-11-03 | Daikin Industries, Ltd. | Method for producing hydrate of fluoroalkyl ketone |
| JP2006522463A (en) * | 2002-11-01 | 2006-09-28 | クーリギー インコーポレイテッド | Optimal spreader system, apparatus and method for micro heat exchange cooled by fluid |
-
1993
- 1993-08-26 JP JP23577393A patent/JP2864490B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006522463A (en) * | 2002-11-01 | 2006-09-28 | クーリギー インコーポレイテッド | Optimal spreader system, apparatus and method for micro heat exchange cooled by fluid |
| WO2005102972A1 (en) * | 2004-04-19 | 2005-11-03 | Daikin Industries, Ltd. | Method for producing hydrate of fluoroalkyl ketone |
| US7598425B2 (en) | 2004-04-19 | 2009-10-06 | Daikin Industries, Ltd. | Method for producing hydrate of fluoroalkyl ketone |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2864490B2 (en) | 1999-03-03 |
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