JPH0229059B2 - - Google Patents
Info
- Publication number
- JPH0229059B2 JPH0229059B2 JP59119154A JP11915484A JPH0229059B2 JP H0229059 B2 JPH0229059 B2 JP H0229059B2 JP 59119154 A JP59119154 A JP 59119154A JP 11915484 A JP11915484 A JP 11915484A JP H0229059 B2 JPH0229059 B2 JP H0229059B2
- Authority
- JP
- Japan
- Prior art keywords
- present
- tetralone
- reaction
- phenacyl
- producing
- 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
- XHLHPRDBBAGVEG-UHFFFAOYSA-N 1-tetralone Chemical class C1=CC=C2C(=O)CCCC2=C1 XHLHPRDBBAGVEG-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 4
- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical compound ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 claims description 4
- LIGACIXOYTUXAW-UHFFFAOYSA-N phenacyl bromide Chemical compound BrCC(=O)C1=CC=CC=C1 LIGACIXOYTUXAW-UHFFFAOYSA-N 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- -1 phenacyl group Chemical group 0.000 description 3
- 239000005297 pyrex Substances 0.000 description 3
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- QRUBYZBWAOOHSV-UHFFFAOYSA-M silver trifluoromethanesulfonate Chemical compound [Ag+].[O-]S(=O)(=O)C(F)(F)F QRUBYZBWAOOHSV-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OWWIWYDDISJUMY-UHFFFAOYSA-N 2,3-dimethylbut-1-ene Chemical compound CC(C)C(C)=C OWWIWYDDISJUMY-UHFFFAOYSA-N 0.000 description 1
- IRUDSQHLKGNCGF-UHFFFAOYSA-N 2-methylhex-1-ene Chemical compound CCCCC(C)=C IRUDSQHLKGNCGF-UHFFFAOYSA-N 0.000 description 1
- JMMZCWZIJXAGKW-UHFFFAOYSA-N 2-methylpent-2-ene Chemical compound CCC=C(C)C JMMZCWZIJXAGKW-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N dimethylbutene Natural products CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007858 starting material Substances 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)
Description
【発明の詳細な説明】
本発明は光反応によつてα―テトラロン誘導体
を製造する新規な製造方法に関する。
α―テトラロン誘導体の製法として知られてい
るJ.Am.Chem.Soc.，73，786（1951）に記載され
ている方法では例えば下記の反応式におけるシス
体(2)を合成するためにはシス配置をもつた(1)を出
発原料として用いなければならず、合成経路が複
雑であり
また、J.Org.Chem.，37 487（1972）に記載さ
れている方法では下記のように(3)と(4)の混合物し
か得られなかつた。
ところで、本発明者らは種々の金属塩存在下の
光反応について研究していたところトリフルオロ
メタンスルホン酸銀（銀トリフラート）の存在下
塩化フエナシル又は臭化フエナシルと各種のオレ
フインのアセトニトリル溶液にガラス（登録商標
パイレツクス）透過光を１時間〜６時間照射した
ところフエナシル基にオレフインが付加かつ閉環
してα―テトラロン誘導体が得られることを見出
し本発明を完成するに至つた。
すなわち、本発明は銀トリフラートの存在下塩
化フエナシル又は臭化フエナシルとオレフインの
アセトニトリル溶液にガラス（登録商標パイレツ
クス）透過光を照射してα―テトラロン誘導体を
製造する方法であつて、その反応機構としては下
記の反応式によつて示すように銀イオンの影響に
より塩化フエナシルの電子受容能が高められ、オ
レフインから塩化フエナシルへの１電子移動によ
り進行するものと考えられ、この機構は臭化フエ
ナシルの場合と全く同様である。
本発明の上記反応は熱反応では全く進行せず原
料が回収され、また、このように１段階で２つの
Ｃ―Ｃ結合を生成する点で合成反応としても特徴
的である。
本発明で使用するオレフインとしては炭素数３
以上の鎖状オレフイン、脂環式オレフイン等いず
れでもよいが、特に、１―オクテン、３―メチル
―２―ブテン、２，３―ジメチルブテン、ジメチ
ルブテン、シクロヘキセン、シクロオクテン、メ
チルヘキセン等が好適である。
ところで、本発明の光反応による特徴は先に述
べた従来法に比して高い位置選択性と立体選択性
とを有し、例えば非対称オレフインの場合テトラ
ロン誘導体としては２つの位置異性体が考えられ
るが、本発明にあつては高い位置選択性を示し、
４位置換のα―テトラロン誘導体のみが得られ、
また、本発明の反応途中で折出する塩化銀又は臭
化銀は沈澱し反応管の底部に凝固して反応物の光
吸収を妨げることなく反応はスムースに進行する
等の効果を奏する。
以下、実施例をもつて本発明を具体的に説明す
る。
実施例 １
塩化フエナシル0.310ｇ（2m mol）、１―オク
テン0.337ｇ（3m mol）、銀トリフラート0.514ｇ
（2m mol）を20mlのアセトニトリルにとかし、
耐熱ガラス管（登録商標「パイレツクス」管）に
入れ450W高圧水銀灯で1.7時間照射する。析出し
た固体を別し、減圧で溶媒を除去した後、クロ
ロホルムにとかし、重曹水、チオ硫酸ナトリウム
水溶液で洗滌し、有機層を無水硫酸ナトリウムで
乾燥した後、溶媒を減圧で除去する。残渣をシリ
カゲルカラムクロマトにより精製し４―ヘキシル
―α―テトラロン0.164ｇを得た。確認手段はス
ペクトルデータによる。収率は36％である。
同様の操作により各種オレフインに対して得ら
れたα―テトラロン誘導体を示すと第１表のとお
りであつた。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing α-tetralone derivatives by photoreaction. In the method described in J.Am.Chem.Soc., 73 , 786 (1951), which is known as a method for producing α-tetralone derivatives, for example, in order to synthesize the cis isomer (2) in the following reaction formula, (1) with a cis configuration must be used as a starting material, and the synthetic route is complicated. Furthermore, the method described in J.Org.Chem., 37 487 (1972) could only yield a mixture of (3) and (4) as shown below. By the way, the present inventors were researching photoreactions in the presence of various metal salts, and found that glass ( The present inventors discovered that upon irradiation with transmitted light (Pyrex (registered trademark)) for 1 to 6 hours, an olefin was added to the phenacyl group and the ring was closed, yielding an α-tetralone derivative, leading to the completion of the present invention. That is, the present invention is a method for producing α-tetralone derivatives by irradiating an acetonitrile solution of phenacyl chloride or phenacyl bromide and olefin with glass (registered trademark Pyrex) transmitted light in the presence of silver triflate, and the reaction mechanism thereof is as follows: As shown in the reaction formula below, the electron-accepting ability of phenacyl chloride is increased by the influence of silver ions, and it is thought that the process proceeds by the transfer of one electron from olefin to phenacyl bromide. The case is exactly the same. The above reaction of the present invention is characterized as a synthetic reaction in that the raw material is recovered without any thermal reaction proceeding, and two C--C bonds are produced in one step. The olefin used in the present invention has 3 carbon atoms.
Any of the above chain olefins, alicyclic olefins, etc. may be used, but 1-octene, 3-methyl-2-butene, 2,3-dimethylbutene, dimethylbutene, cyclohexene, cyclooctene, methylhexene, etc. are particularly preferred. It is. By the way, the feature of the photoreaction of the present invention is that it has higher regioselectivity and stereoselectivity than the conventional methods mentioned above. For example, in the case of an asymmetric olefin, two regioisomers can be considered as a tetralone derivative. However, in the present invention, it shows high regioselectivity,
Only α-tetralone derivatives substituted at the 4-position were obtained,
In addition, silver chloride or silver bromide precipitated during the reaction of the present invention precipitates and solidifies at the bottom of the reaction tube, so that the reaction proceeds smoothly without interfering with light absorption of the reactants. The present invention will be specifically described below with reference to Examples. Example 1 Phenacyl chloride 0.310g (2m mol), 1-octene 0.337g (3m mol), silver triflate 0.514g
(2m mol) was dissolved in 20ml of acetonitrile,
Place it in a heat-resistant glass tube (registered trademark "Pyrex" tube) and irradiate it with a 450W high-pressure mercury lamp for 1.7 hours. After separating the precipitated solid and removing the solvent under reduced pressure, it is dissolved in chloroform, washed with an aqueous sodium bicarbonate solution and an aqueous sodium thiosulfate solution, the organic layer is dried over anhydrous sodium sulfate, and the solvent is removed under reduced pressure. The residue was purified by silica gel column chromatography to obtain 0.164 g of 4-hexyl-α-tetralone. Confirmation method is based on spectral data. Yield is 36%. Table 1 shows α-tetralone derivatives obtained for various olefins by similar operations. 【table】
Claims (1)
塩化フエナシル又は臭化フエナシルと各種オレフ
インのアセトニトリル溶液にガラス透過光を照射
することによりα―テトラロン誘導体を製造する
ことを特徴とするα―テトラロン誘導体の製造方
法。1 In the presence of trifluoromethanesulfonate,
1. A method for producing an α-tetralone derivative, which comprises producing an α-tetralone derivative by irradiating an acetonitrile solution of phenacyl chloride or phenacyl bromide and various olefins with glass-transmitted light.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59119154A JPS6140A (en) | 1984-06-12 | 1984-06-12 | Production of alpha-tetralone derivative through photoreaction process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59119154A JPS6140A (en) | 1984-06-12 | 1984-06-12 | Production of alpha-tetralone derivative through photoreaction process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6140A JPS6140A (en) | 1986-01-06 |
| JPH0229059B2 true JPH0229059B2 (en) | 1990-06-27 |
Family
ID=14754255
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59119154A Granted JPS6140A (en) | 1984-06-12 | 1984-06-12 | Production of alpha-tetralone derivative through photoreaction process |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6140A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6046022A (en) * | 1983-08-23 | 1985-03-12 | Sumitomo Electric Ind Ltd | Pretreating method of ion implanted substrate |
| JP2567230B2 (en) * | 1986-12-15 | 1996-12-25 | セイコープレシジョン株式会社 | Program shutter |
| JP5263754B2 (en) * | 2007-12-27 | 2013-08-14 | 独立行政法人産業技術総合研究所 | Method for producing cyclic ketone |
| EP2768895B1 (en) | 2011-10-18 | 2015-12-30 | Covestro Deutschland AG | Polymer compound with heat absorbing characteristics |
-
1984
- 1984-06-12 JP JP59119154A patent/JPS6140A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6140A (en) | 1986-01-06 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |