JPH0517894B2 - - Google Patents
Info
- Publication number
- JPH0517894B2 JPH0517894B2 JP59174767A JP17476784A JPH0517894B2 JP H0517894 B2 JPH0517894 B2 JP H0517894B2 JP 59174767 A JP59174767 A JP 59174767A JP 17476784 A JP17476784 A JP 17476784A JP H0517894 B2 JPH0517894 B2 JP H0517894B2
- Authority
- JP
- Japan
- Prior art keywords
- aromatic
- metal catalyst
- hydrogen
- reductive
- raney
- 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はトレーサー等として有用な水素同位体
を含有する芳香族化合物を効率良く合成する方法
に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for efficiently synthesizing aromatic compounds containing hydrogen isotopes useful as tracers and the like.
水素同位体すなわち質量数２の重水素原子（以
下Ｄと記す）あるいは質量数３の三重水素原子
（以下Ｔと記す）を含有する有機化合物は、古く
からトレーサー技術に用いられてきたが最近では
化合物そのものの利用価値も光学的性質や薬理活
性の面で注目されてきている。有機化合物に水素
同位体を導入する技術としては一般にD2O、T2O
やD2、T2との交換反応が知られているが、選択
性や収率の点で余り有効な方法とはいえない。高
選択的に水素同位体を有機化合物に導入する方法
としては、芳香族化合物に限定すれば芳香族ハロ
ゲン化物の還元的重水素化が挙げられる。
Hydrogen isotopes, i.e., organic compounds containing deuterium atoms with a mass number of 2 (hereinafter referred to as D) or tritium atoms with a mass number of 3 (hereinafter referred to as T), have been used for tracer technology for a long time, but recently they have been used in tracer technology. The utility value of the compound itself is also attracting attention in terms of optical properties and pharmacological activity. Generally speaking, D 2 O and T 2 O are the techniques for introducing hydrogen isotopes into organic compounds.
Although exchange reactions with D 2 , T 2 , and D 2 are known, these methods are not very effective in terms of selectivity and yield. As a method for highly selectively introducing hydrogen isotopes into organic compounds, limited to aromatic compounds, reductive deuteration of aromatic halides can be mentioned.
この方法は塩基性のD2OまたはT2O中でラネー
金属触媒を用いてハロゲン原子部位に還元的重水
素化を生じさせるものである。 This method uses a Raney metal catalyst in basic D 2 O or T 2 O to cause reductive deuteration of a halogen atom site.
上記従来の還元的水素化方法でも、ハロゲン原
子の結合していない部位でＨ−Ｄ変換やＨ−Ｔ変
換がある程度生じてしまい、選択性が低いという
問題がある。
Even in the conventional reductive hydrogenation method described above, there is a problem in that HD conversion and H-T conversion occur to some extent at sites where halogen atoms are not bonded, resulting in low selectivity.
水素原子として重水素または三重水素のみを含
有した塩基性水溶液に芳香族ハロゲン化物をラネ
ー金属触媒の存在下で接触させる際に超音波照射
を行なう。この超音波照射は機械的撹拌と併用し
てもよいし、あるいは撹拌なしで単独で実施して
もよい。
Ultrasonic irradiation is performed when an aromatic halide is brought into contact with a basic aqueous solution containing only deuterium or tritium as hydrogen atoms in the presence of a Raney metal catalyst. This ultrasonic irradiation may be performed in combination with mechanical stirring or alone without stirring.
本発明で使用する超音波は通常の超音波洗浄器
などで使用されている25KHzあるいは46KHzの波
長のものが良い。 The ultrasonic wave used in the present invention preferably has a wavelength of 25 KHz or 46 KHz, which is used in ordinary ultrasonic cleaners.
一例として、水素同位体原子を導入したい部位
にハロゲン原子を結合させた芳香族化合物をまず
塩基性のD2OまたはT2Oと混合する。D2Oまたは
T2Oを塩基性にするには、D2Oの場合であれば例
えばNaOD、KOD、ND4ODなど、T2Oの場合に
はNaOT、KOT、NT4OTなどを溶解させる。 As an example, an aromatic compound having a halogen atom bonded to a site where a hydrogen isotope atom is desired to be introduced is first mixed with basic D 2 O or T 2 O. D2O or
To make T 2 O basic, for example, NaOD, KOD, ND 4 OD, etc. are dissolved in the case of D 2 O, and NaOT, KOT, NT 4 OT, etc. are dissolved in the case of T 2 O.
次に、D2OまたはT2Oに混合した芳香族化合物
に対し超音波を照射しながらラネー金属触媒に接
触させると、上記芳香族化合物は還元的重素化を
受ける。ラネー金属触媒とは一般にイオン化傾向
の異なる二種類以上の金属の合金の一方を溶出さ
せたもので、本発明で使用するラネー金属触媒と
してはNi−Cl、Cu−Alなどの合金が好適であ
る。 Next, when the aromatic compound mixed in D 2 O or T 2 O is brought into contact with a Raney metal catalyst while being irradiated with ultrasound, the aromatic compound undergoes reductive heavyization. A Raney metal catalyst is generally one obtained by eluting one of two or more metal alloys with different ionization tendencies, and alloys such as Ni-Cl and Cu-Al are suitable as the Raney metal catalyst used in the present invention. .
本発明方法によれば、超音波照射によつてミク
ロな撹拌が液中に生じ、このため熱拡散が全体に
促進されて水素同位体の選択的導入を阻害する発
熱が抑制され、後述の実施例に示されるように非
常に高い同位体結合位置の選択性効果が得られる
ものと考えられる。
According to the method of the present invention, ultrasonic irradiation causes microscopic agitation in the liquid, which promotes thermal diffusion throughout and suppresses heat generation that inhibits selective introduction of hydrogen isotopes. As shown in the example, it is believed that a very high selectivity effect of the isotope binding position can be obtained.
本発明によれば、芳香族ハロゲン化物の還元的
重水素化あるいは三重水素化反応における選択性
が高まり、より効果的に、特定の位置に水素同位
体原子の結合した芳香族化合物を製造することが
できる。
According to the present invention, selectivity in the reductive deuteration or tritiumation reaction of aromatic halides is increased, and aromatic compounds having hydrogen isotope atoms bonded to specific positions can be produced more effectively. I can do it.
第１図中に（）で示す４−クロロアセトフエ
ノンを10％NaOD重水溶液に混合してマグネチツ
クスターラーで撹拌しながらラネーNi−Al合金
を添加し、50〜60℃に維持しつつ超音波照射は行
なわずに撹拌を続け、得られた反応生成物を分析
したところ、第１図に，，で示した構造を
もつ生成物がそれぞれ19％、29％、31％の比率で
存在していた。
4-chloroacetophenone shown in parentheses in Figure 1 was mixed with a 10% NaOD heavy aqueous solution, and Raney Ni-Al alloy was added while stirring with a magnetic stirrer. When stirring was continued without sonic irradiation and the resulting reaction products were analyzed, products with the structures shown in Figure 1 were present at a ratio of 19%, 29%, and 31%, respectively. was.
一方、上記の10％NaOD重水溶液に混合した４
−クロロアセトフエノン（）に本発明に従つて
超音波を照射しながらラネーNi−Al合金を添加
し、50〜60℃に保温して超音波を照射し続け、得
られた反応生成物を分析したところ生成物が83
％を占めていた。 On the other hand, 4 mixed with the above 10% NaOD heavy water solution
- Raney Ni-Al alloy is added to chloroacetophenone () while irradiating it with ultrasound according to the present invention, the temperature is kept at 50-60°C and the irradiation with ultrasound is continued, and the resulting reaction product is Analysis revealed that the product was 83
It accounted for %.
第１図は水素同位体を含む塩基性水溶性に芳香
族ハロゲン化物を接触させて還元的重水素化を行
なうプロセスを模式的に示す図である。
FIG. 1 is a diagram schematically showing a process of bringing an aromatic halide into contact with a basic aqueous solution containing a hydrogen isotope to perform reductive deuteration.
Claims (1)
含有した塩基性水溶液に芳香族ハロゲン化物をラ
ネー金属触媒の存在下で接触させる芳香族ハロゲ
ン化物の還元的重水素化または三重水素化を行な
う方法において、前記接触時に超音波照射を行な
うことを特徴とする芳香族化合物に高選択的に水
素同位体を導入する方法。1. A method for reductive deuteration or tritiumation of an aromatic halide in which the aromatic halide is brought into contact with a basic aqueous solution containing only deuterium or tritium as hydrogen atoms in the presence of a Raney metal catalyst, A method for highly selectively introducing a hydrogen isotope into an aromatic compound, the method comprising performing ultrasonic irradiation during the contacting.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59174767A JPS6153228A (en) | 1984-08-22 | 1984-08-22 | Method for introducing hydrogen isomer to aromatic compound in high selectivity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59174767A JPS6153228A (en) | 1984-08-22 | 1984-08-22 | Method for introducing hydrogen isomer to aromatic compound in high selectivity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6153228A JPS6153228A (en) | 1986-03-17 |
| JPH0517894B2 true JPH0517894B2 (en) | 1993-03-10 |
Family
ID=15984314
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59174767A Granted JPS6153228A (en) | 1984-08-22 | 1984-08-22 | Method for introducing hydrogen isomer to aromatic compound in high selectivity |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6153228A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0749218B2 (en) * | 1990-07-30 | 1995-05-31 | 積水化学工業株式会社 | Manufacturing method of laminated molded product |
| JP5071796B2 (en) * | 2007-12-10 | 2012-11-14 | 独立行政法人産業技術総合研究所 | Method for regioselective deuteration of aromatic rings of aromatic compounds |
| JP5662461B2 (en) * | 2009-10-26 | 2015-01-28 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Process for preparing deuterated aromatic compounds |
-
1984
- 1984-08-22 JP JP59174767A patent/JPS6153228A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6153228A (en) | 1986-03-17 |
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