JPS6153228A - Method for introducing hydrogen isomer to aromatic compound in high selectivity - Google Patents
Method for introducing hydrogen isomer to aromatic compound in high selectivityInfo
- Publication number
- JPS6153228A JPS6153228A JP59174767A JP17476784A JPS6153228A JP S6153228 A JPS6153228 A JP S6153228A JP 59174767 A JP59174767 A JP 59174767A JP 17476784 A JP17476784 A JP 17476784A JP S6153228 A JPS6153228 A JP S6153228A
- Authority
- JP
- Japan
- Prior art keywords
- aromatic
- aromatic compound
- metal catalyst
- halide
- aqueous solution
- 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.)
- Granted
Links
- 150000001491 aromatic compounds Chemical class 0.000 title claims abstract description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title claims abstract description 5
- 238000000034 method Methods 0.000 title claims description 11
- -1 aromatic halide Chemical class 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 230000002829 reductive effect Effects 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 claims abstract description 5
- 229910052805 deuterium Inorganic materials 0.000 claims abstract description 5
- 229910052722 tritium Inorganic materials 0.000 claims abstract description 5
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000700 radioactive tracer Substances 0.000 abstract description 2
- 229910017767 Cu—Al Inorganic materials 0.000 abstract 1
- HEMHJVSKTPXQMS-DYCDLGHISA-M Sodium hydroxide-d Chemical compound [Na+].[2H][O-] HEMHJVSKTPXQMS-DYCDLGHISA-M 0.000 abstract 1
- 150000004820 halides Chemical class 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 230000005855 radiation Effects 0.000 abstract 1
- 238000005533 tritiation Methods 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001975 deuterium Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical compound ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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)
Abstract
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（以下りと記
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Ｋ Ｄ２
０．Ｔ２ＯやＤ２１ 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。Hydrogen isotope, i.e. deuterium atom with mass number 2 (hereinafter referred to as “T”) or tritium atom with mass number 3 (hereinafter referred to as “T”)
Organic compounds containing ions have long been used in tracer technology, but recently the utility value of the compounds themselves has been attracting attention in terms of their optical properties and pharmacological activity. General KD2 is a technique for introducing hydrogen isotopes into organic compounds.
0. Exchange reactions with T2O and D21T2 are known, but these are not very effective methods in terms of selectivity and yield.
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。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Ｄ２０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 D20 or T2O to cause reductive deuteration of the 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変換がある程度化
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 are degraded 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
照射は機械的攪拌と併用してもよいし、あるいは攪拌な
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２ｊＫＨｚあるいはＩＫＨｚの波長のもの
が良い。The ultrasonic wave used in the present invention preferably has a wavelength of 2jKHz or IKHz, 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Ｄ２０
またはＴ２Ｏと混合する。Ｄ２０またはＴ２Ｏを塩基性
にするには、Ｄ２０の場合であれば例えばＮａ０Ｄ、Ｋ
ＯＤ、ＮＤ４０Ｄなど、Ｔ２Ｏの場合にはＮａ０Ｔ 、
ＫＯＴ 、 ＮＴ４０Ｔ などを溶解させる。As an example, an aromatic compound with a halogen atom bonded to the site where the hydrogen isotope atom is to be introduced is first diluted with basic D20.
Or mixed with T2O. To make D20 or T2O basic, in the case of D20, for example, Na0D, K
OD, ND40D, etc., in the case of T2O, Na0T,
Dissolve KOT, NT40T, etc.
次に、Ｄ２０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前型素化を受ける。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Ｍｉ−Ｃｊｌ 、 Ｃｕ−Ａ／
などの合金が好適である。Next, when the aromatic compound mixed in D20 or T2O is brought into contact with a Raney metal catalyst while being irradiated with ultrasonic waves, the aromatic compound undergoes pre-reduction hydrogenation. A Raney metal catalyst is generally one obtained by eluting one of two or more metal alloys with different ionization tendencies, and the Raney metal catalyst used in the present invention includes Mi-Cjl, Cu-A/
Alloys such as are suitable.
本発明方法によれば超音波照射によってミクロな攪拌が
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, micro-agitation is generated in the liquid by ultrasonic irradiation, which promotes thermal diffusion throughout and suppresses heat generation that inhibits the selective introduction of hydrogen isotopes. It is thought that a very high selectivity effect of the isotope binding position can be obtained as shown in the figure.
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（Ｉ）で示すダークロロアセトフェノンを１
０％Ｎａ０Ｄ重水溶液に混合してマグネチックスターラ
ーで攪拌しながらラネーＮ１−Ａｐ金合金添加し、５ｏ
−ｔｏ℃に維持しつつ超音波照射は行なわずｌＣ攪拌を
続け、得られた反応生成物を分析したところ、第１図に
（ＩＩ）、（ｉｌｌ）、（ｌｖ）で示した構造をもつ生
成物がそれぞれ１９％、２９％、Ｊ／％の比率で存在し
ていた。Dark chloroacetophenone shown as (I) in Figure 1 is
Raney N1-Ap gold alloy was added to the 0% Na0D heavy water solution while stirring with a magnetic stirrer, and 5o
When maintaining the temperature at -to℃ and continuing 1C stirring without ultrasonic irradiation, the resulting reaction product was analyzed and found to have the structures shown in (II), (ill), and (lv) in Figure 1. The products were present in proportions of 19%, 29%, and J/%, respectively.
一方、上記の７０％Ｎａ０Ｄ重水溶液に混合したダーク
ロロアセトフェノン（Ｉ）に本発明に従って超音波を照
射しながらラネーＮｉ−Ａ１合金を添加し、ｊＯ〜６０
℃に保温して超音波を郊射し続け、得られた反応生成物
を分析したところ生成物（１１）が１３％を占めていた
。Meanwhile, Raney Ni-A1 alloy was added to darkchloroacetophenone (I) mixed in the above 70% Na0D heavy aqueous solution while irradiating ultrasonic waves according to the present invention, and jO ~ 60
The reaction product was analyzed by keeping it warm at ℃ and continuing to irradiate it with ultrasonic waves, and it was found that product (11) accounted for 13% of the reaction product.
第１図は水素同位体を含む塩基性水溶液に芳香族ハロゲ
ン化物を接触させて還元的重水素化を行なうプロ七スを
模式的に示す図である。FIG. 1 is a diagram schematically showing a process in which reductive deuteration is carried out by bringing an aromatic halide into contact with a basic aqueous solution containing a hydrogen isotope.
Claims (1)
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。In the method for reductive deuteration or tritiumation of an aromatic halide, the aromatic halide is contacted 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 hydrogen isotopes into aromatic compounds, characterized by applying ultrasonic irradiation during contact.
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 true JPS6153228A (en) | 1986-03-17 |
| JPH0517894B2 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) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0486242A (en) * | 1990-07-30 | 1992-03-18 | Sekisui Chem Co Ltd | Manufacture of laminated molding |
| JP2009137911A (en) * | 2007-12-10 | 2009-06-25 | National Institute Of Advanced Industrial & Technology | Method for regioselective deuteration of aromatic rings of aromatic compounds |
| JP2013508360A (en) * | 2009-10-26 | 2013-03-07 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Process for preparing deuterated aromatic compounds |
-
1984
- 1984-08-22 JP JP59174767A patent/JPS6153228A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0486242A (en) * | 1990-07-30 | 1992-03-18 | Sekisui Chem Co Ltd | Manufacture of laminated molding |
| JP2009137911A (en) * | 2007-12-10 | 2009-06-25 | National Institute Of Advanced Industrial & Technology | Method for regioselective deuteration of aromatic rings of aromatic compounds |
| JP2013508360A (en) * | 2009-10-26 | 2013-03-07 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Process for preparing deuterated aromatic compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0517894B2 (en) | 1993-03-10 |
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