JPS599551B2 - Method for producing 2,3-homoindole derivative - Google Patents
Method for producing 2,3-homoindole derivativeInfo
- Publication number
- JPS599551B2 JPS599551B2 JP2651774A JP2651774A JPS599551B2 JP S599551 B2 JPS599551 B2 JP S599551B2 JP 2651774 A JP2651774 A JP 2651774A JP 2651774 A JP2651774 A JP 2651774A JP S599551 B2 JPS599551 B2 JP S599551B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- lower alkyl
- cyano
- methyl
- alkyl group
- 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
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002943 quinolinyl group Chemical class N1=C(C=CC2=CC=CC=C12)* 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000004809 thin layer chromatography Methods 0.000 description 4
- MUDSDYNRBDKLGK-UHFFFAOYSA-N 4-methylquinoline Chemical compound C1=CC=C2C(C)=CC=NC2=C1 MUDSDYNRBDKLGK-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- -1 alkyl nitriles Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- HCUARRIEZVDMPT-UHFFFAOYSA-M 1h-indole-2-carboxylate Chemical compound C1=CC=C2NC(C(=O)[O-])=CC2=C1 HCUARRIEZVDMPT-UHFFFAOYSA-M 0.000 description 2
- MBVGYFIYXWVPQY-UHFFFAOYSA-N 6-methoxy-4-methylquinoline Chemical compound N1=CC=C(C)C2=CC(OC)=CC=C21 MBVGYFIYXWVPQY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- STBLNCCBQMHSRC-BATDWUPUSA-N (2s)-n-[(3s,4s)-5-acetyl-7-cyano-4-methyl-1-[(2-methylnaphthalen-1-yl)methyl]-2-oxo-3,4-dihydro-1,5-benzodiazepin-3-yl]-2-(methylamino)propanamide Chemical compound O=C1[C@@H](NC(=O)[C@H](C)NC)[C@H](C)N(C(C)=O)C2=CC(C#N)=CC=C2N1CC1=C(C)C=CC2=CC=CC=C12 STBLNCCBQMHSRC-BATDWUPUSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QOPBEBWGSGFROG-UHFFFAOYSA-N 2-(1h-indol-2-yl)acetic acid Chemical class C1=CC=C2NC(CC(=O)O)=CC2=C1 QOPBEBWGSGFROG-UHFFFAOYSA-N 0.000 description 1
- ZTQNUTNKGQGWCM-UHFFFAOYSA-N 2-methoxyquinoline Chemical compound C1=CC=CC2=NC(OC)=CC=C21 ZTQNUTNKGQGWCM-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229940125878 compound 36 Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- KFSMPSFDAUTTAC-UHFFFAOYSA-N ethyl 2-cyano-4-methyl-2h-quinoline-1-carboxylate Chemical compound C1=CC=C2N(C(=O)OCC)C(C#N)C=C(C)C2=C1 KFSMPSFDAUTTAC-UHFFFAOYSA-N 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- JXDYKVIHCLTXOP-UHFFFAOYSA-N isatin Chemical compound C1=CC=C2C(=O)C(=O)NC2=C1 JXDYKVIHCLTXOP-UHFFFAOYSA-N 0.000 description 1
- PBSJLGYCWCUXLV-UHFFFAOYSA-N methyl 2h-quinoline-1-carboxylate Chemical compound C1=CC=C2N(C(=O)OC)CC=CC2=C1 PBSJLGYCWCUXLV-UHFFFAOYSA-N 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 238000012746 preparative thin layer chromatography Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- APJYDQYYACXCRM-UHFFFAOYSA-N tryptamine Chemical class C1=CC=C2C(CCN)=CNC2=C1 APJYDQYYACXCRM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Indole Compounds (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Description
【発明の詳細な説明】
本発明は一般式
Ｒ、□Ｎ（１）
（式中、Ｒは低級アルキル基を意味し、Ｒ１は水素原子
、低級アルキル基または低級アルコキシ基を意味し、Ｒ
２は低級アルキル基を意味する。Detailed Description of the Invention The present invention is based on the general formula R, □N(1) (wherein, R means a lower alkyl group, R1 means a hydrogen atom, a lower alkyl group or a lower alkoxy group, and R
2 means a lower alkyl group.
）で表わされる２・３−ホモインドール誘導体の製法に
係るものである。さらに詳しくは、本発明は一般式
Ｒ１□ＣＮ〔■〕
（式中、Ｒ、Ｒ１およびＲ２は前掲と同じものを意味す
る。) This relates to a method for producing a 2,3-homindole derivative represented by: More specifically, the present invention relates to the general formula R1□CN[■] (wherein R, R1 and R2 have the same meanings as above).
）で表わされるキノリン誘導体に紫外線を照射すること
によりー般式〔Ｉ〕で表わされる２・３−ホモインドー
ル誘導体を得る製造法に係る。The present invention relates to a production method for obtaining a 2,3-homoindole derivative represented by general formula [I] by irradiating a quinoline derivative represented by () with ultraviolet rays.
本発明方法は、溶媒中に原料化合物〔■〕を適量溶解さ
せ、紫外線を照射すれば反応は進行する。In the method of the present invention, the reaction proceeds by dissolving an appropriate amount of the starting compound [■] in a solvent and irradiating it with ultraviolet rays.
本発明方法で使用される溶媒としては、メタノール、エ
タノール、プロパノールのような低級アルコール類、ジ
エチルエーテル、ジメチルエーテル、ジオキサンのよう
なエーテル類、アセトニトリルのような低級アルキルニ
トリル類、シクロヘキサン、ベンゼンのような炭化水素
類、ジクロルメタンなどが用いられるが、生成物の収量
の点から低級アルコール類が好適である。紫外線照射の
方法としては、適当な光源たとえば水銀灯の光を沢光フ
イルタ一、干渉フイルタ一、回析格子分光器などで分別
選択して照射すればよいが、パイレツクスフイルタ一を
通して１００〜４５０Ｗ高圧水銀灯で照射するのが最も
有効である。本反応は通常室温で行なうことができるが
必ずしもこの温度に限定されるものではない。Solvents used in the method of the present invention include lower alcohols such as methanol, ethanol and propanol, ethers such as diethyl ether, dimethyl ether and dioxane, lower alkyl nitriles such as acetonitrile, cyclohexane and benzene. Although hydrocarbons such as dichloromethane are used, lower alcohols are preferred from the viewpoint of product yield. As a method for irradiating ultraviolet rays, the light from an appropriate light source, such as a mercury lamp, can be selectively irradiated using a glare filter, an interference filter, a diffraction grating spectrometer, etc.; Irradiation with a mercury lamp is most effective. This reaction can usually be carried out at room temperature, but is not necessarily limited to this temperature.
また照射時間は照射光の波長、原料化合物、反応量およ
び反応液の濃度などによつて異なり、通常２〜１０時間
を必要とするが５時間の照射でも十分である。このよう
にして得られる粗目的物を常法により精製、単離して純
粋な形で目的物を得ることができる。Further, the irradiation time varies depending on the wavelength of the irradiation light, the raw material compound, the reaction amount, the concentration of the reaction solution, etc., and usually requires 2 to 10 hours, but 5 hours of irradiation is sufficient. The crude target product thus obtained can be purified and isolated by conventional methods to obtain the target product in pure form.
また実施例に示す通り、本発明によれば異性体であるエ
ンド型とエキソ型が得られる。Furthermore, as shown in the Examples, according to the present invention, endo-type and exo-type isomers can be obtained.
すなわち通常ぱ化合物〔１〕のシアノ基はエンド型とし
て生成するが、これは更に光、熱、三フツ化ホウ素など
で処理することによつて異性体であるエキソ型との混合
物を得、これよりエキソ型を分離することができる。本
発明の目的化合物はこれら両異性体を包含してなるもの
である。That is, the cyano group of compound [1] is usually produced as an endo-type, but this is further treated with light, heat, boron trifluoride, etc. to obtain a mixture with the exo-type, which is an isomer. The exo type can be separated more easily. The target compound of the present invention includes both of these isomers.
本発明方法は、光照射することによつて目的化合物〔１
〕を得ることができる新規合成法であり、本発明方法で
得られる化合物〔１〕はいずれも新規物質で、有用な薬
理作用を有するインドール酢酸誘導体またはトリプタミ
ン誘導体の合成中間体として有用なものである。In the method of the present invention, the target compound [1
This is a new synthetic method that can obtain the compounds [1], and all of the compounds [1] obtained by the method of the present invention are new substances and are useful as intermediates for the synthesis of indoleacetic acid derivatives or tryptamine derivatives that have useful pharmacological effects. be.
なお、本発明の原料化合物〔〕はたとえば４メチル−６
−メトキシキノリンのジクロルメタン溶液とシアン化カ
リウム溶液の混合物にクロル炭酸エチルを作用させるこ
とによつて得られる。Note that the raw material compound [] of the present invention is, for example, 4-methyl-6
- Obtained by reacting ethyl chlorocarbonate with a mixture of a dichloromethane solution of methoxyquinoline and a potassium cyanide solution.
以下、参考例および実施例をあげてさらに詳しく説明す
る。参考例 １
４−メチルキノリン（５７）のジクロルメタン溶液（５
０７！１１）と、シアン化カリウム（６．８２ｆ）の水
溶液（２０ｍ０との混合物の中にクロル炭酸エチル（７
．６０ｙ）を氷冷攪拌下２時間で滴下する。A more detailed explanation will be given below with reference to reference examples and examples. Reference example 1 Dichloromethane solution of 4-methylquinoline (57) (5
07!11) and an aqueous solution (20m0) of potassium cyanide (6.82f).
．． 60y) was added dropwise over 2 hours while stirring on ice.
その後さらに４時間攪拌後、反応液を希塩酸、水、希水
酸化ナトリウム水溶液で順次洗浄し、硫酸マグネシウム
で乾燥後、ジクロルメタンを留去し、残留物をアルミナ
、ベンゼンで分離精製後エタノールで再結晶すると、エ
チル２−シアノ−４メチル−１・２−ジヒドロキノリン
−１−カルボキシレート（５．０７）を得る。融点８０
〜８１℃
参考例 ２
４−メチル−６−メトキシキノリン（１．４５ｔ）のジ
クロルメタン溶液（１０ｍ１）と、シアン化カリウム（
０．５０７）の水溶液（３ｍ１）の混合物の中にクロル
炭酸エチル（０、５４ｔ）を氷冷攪拌下２時間で滴下す
る。After stirring for another 4 hours, the reaction solution was washed successively with dilute hydrochloric acid, water, and dilute aqueous sodium hydroxide solution, dried over magnesium sulfate, dichloromethane was distilled off, and the residue was separated and purified with alumina and benzene, then recrystallized with ethanol. Then, ethyl 2-cyano-4methyl-1,2-dihydroquinoline-1-carboxylate (5.07) is obtained. Melting point 80
~81℃ Reference Example 2 A dichloromethane solution (10ml) of 4-methyl-6-methoxyquinoline (1.45t) and potassium cyanide (
Ethyl chlorocarbonate (0.54 t) was added dropwise to a mixture of an aqueous solution (3 ml) of 0.507) over 2 hours under ice-cooling and stirring.
その後さらに４時間攪拌後、反応液を希塩酸、水、希水
酸化ナトリウム水溶液で順次洗浄し、硫酸マグネシウム
で乾燥後、ジクロルメタンを留去し、残留物をアルミナ
、ベンゼンで薄層クロマトグラフイ一分離しエタノール
で再結晶すると、エチル ２−シアノ−４−メチル−６
−メトキシ−１・２−ジヒドロキノリン−１−カルボキ
シレート（０，８９ｒ）を得る。融点１２０℃実施例
１
エチル エンド一１−シアノ−６ｂ−メチル１・１ａ・
２・６ｂ−テトラヒドロシクロプロプ〔ｂ〕インドール
−２−カルボキシレートの製法エチル ２−シアノ−４
−メチル−１・２−ジヒドロキノリン−１−カルボキシ
レート５．０ｔをエタノール７００ｍ１に溶解し、３５
０Ｗ高圧水銀灯（英光社ＰＬＨ−３００型）で４時間照
射（反応の終末点は薄層クロマトグラフイ一によつて原
料消失時とする）後、溶媒を留去し、リグロインから再
結晶すると、目的物３，０７を得る。After stirring for another 4 hours, the reaction solution was washed successively with dilute hydrochloric acid, water, and dilute aqueous sodium hydroxide solution, dried over magnesium sulfate, dichloromethane was distilled off, and the residue was subjected to thin layer chromatography using alumina and benzene. When recrystallized from ethanol, ethyl 2-cyano-4-methyl-6
-Methoxy-1,2-dihydroquinoline-1-carboxylate (0,89r) is obtained. Melting point 120℃ Example
1 ethyl endo-1-cyano-6b-methyl 1.1a.
Preparation of 2,6b-tetrahydrocycloprop[b]indole-2-carboxylate Ethyl 2-cyano-4
-Dissolve 5.0 t of methyl-1,2-dihydroquinoline-1-carboxylate in 700 ml of ethanol,
After 4 hours of irradiation with a 0W high-pressure mercury lamp (Eikosha PLH-300 model) (the end point of the reaction is when the raw material disappears according to thin layer chromatography), the solvent is distilled off and recrystallized from ligroin. Obtain objective 3,07.
融点１０４〜１０５℃元素分析値 Ｃｌ４Ｈｌ４Ｎ２Ｏ
２
理論値 Ｃ６９．４ＯＨ５．８３Ｎｌｌ．５６実験値
Ｃ６９．４４Ｈ５．８６Ｎｌｌ，３Ｏ実施例 ２エチル
エンド一１−シアノ−５−メトキシ６ｂ−メチル−１
・１ａ・２・６ｂ−テトラヒドロシクロプロプ〔ｂ〕イ
ンドール−２−カルボキシレートの製法エチル ２−シ
アノ−４−メチル−６−メトキシ−１・２−ジヒドロキ
ノリン−１−カルボキシレート７０即をエタノール１０
ｍ１に溶解し、３５０ｗ高圧水銀灯（英光社ＰＬＨ−３
００型）で４時間照射後、溶媒を留去し、残留物をアル
ミナ、ベンゼンで薄層クロマトグラフイ一で分離し、石
油ベンジンから再結晶すると、目的物３６▼を得る。Melting point 104-105℃ Elemental analysis value Cl4Hl4N2O
2 Theoretical value C69.4OH5.83Nll. 56 experimental value
C69.44H5.86Nll,3OExample 2ethyl endo-1-cyano-5-methoxy6b-methyl-1
・Preparation of 1a, 2, 6b-tetrahydrocycloprop[b]indole-2-carboxylate 70 parts of ethyl 2-cyano-4-methyl-6-methoxy-1,2-dihydroquinoline-1-carboxylate and 10 parts of ethanol
m1, and a 350W high-pressure mercury lamp (Eikosha PLH-3
After 4 hours of irradiation with 00 type), the solvent is distilled off, the residue is separated by thin layer chromatography using alumina and benzene, and recrystallized from petroleum benzine to obtain the target compound 36▼.
融点１２４〜１２５すＣ元素分哲値 Ｃｌ５Ｈｌ６Ｎ２
Ｏ３
理論値 Ｃ６６．ｌ５Ｈ５．９２ＮｌＯ．２９実験値
Ｃ６６．Ｏ５Ｈ５．９３ＮｌＯ．２７実施例 ３エチル
エキソ一１−シアノ−６ｂ−メチル−１・１ａ・２・
６ｂ−テトラヒドロシクロプロプ〔ｂ〕インドール−２
−カルボキシレートの生成エチル エンド一１−シアノ
−６−メチル−１・１ａ・２・６ｂ−テトラヒドロシク
ロプロプ〔ｂ〕インドール−２−カルボキシレート３１
０〜を無水ベンゼン５ｍ１に溶解し、それと三フツ化ホ
ウ素−エーテル１００Ｗ１９の混合物を２．５時間還流
する。Melting point 124-125 C element fractional value Cl5Hl6N2
O3 theoretical value C66. l5H5.92NlO. 29 experimental value
C66. O5H5.93NlO. 27 Example 3 Ethyl exo-1-cyano-6b-methyl-1.1a.2.
6b-tetrahydrocycloprop[b]indole-2
-Production of carboxylate Ethyl endo-1-cyano-6-methyl-1,1a,2,6b-tetrahydrocycloprop[b]indole-2-carboxylate 31
0~ is dissolved in 5 ml of anhydrous benzene, and a mixture of it and boron trifluoride-ether 100W19 is refluxed for 2.5 hours.
ベンゼンを留去後、残留物を分取薄層クロマトグラフイ
ーベンゼン一ｎ−ヘキサン（１：１）で分離しエンド型
とエキソ型をそれぞれ得る。エキソ型のそれを石油ベン
ジンから再結晶すると、精製目的物１２８Ｔｎ９を得る
。融点９８〜９９℃
元素分析値 Ｃｌ４Ｈｌ４Ｎ２Ｏ２
理論値 Ｃ６９．４ＯＨ５．８３Ｎｌｌ．５６実験値
Ｃ６９．５８Ｈ５．７９Ｎｌｌ．５３実施例 ４エチル
エキソ一１−シアノ−５−メトキシ６ｂ−メチル−１
・１ａ・２・６ｂ−テトラヒドロシクロプロプ〔ｂ〕イ
ンドール−２−カルボキシレートの生成エチル エンド
一１−シアノ−６ｂ−メチル１・１ａ・２・６ｂ−テト
ラヒドロシクロプロプ〔ｂ〕インドール−２−カルボキ
シレート３６Ｔ１９をアセトン４ｍ１に溶かした溶液を
出発物質がそれ以上消失しなくなるまで２時間３５０Ｗ
Ｗｊ圧水銀灯（英光社ＰＬＨ−３００型）で光照射（反
応の終末点は薄層クロマトグラフイ一により判断した。After distilling off the benzene, the residue was separated by preparative thin layer chromatography using benzene and n-hexane (1:1) to obtain endo-type and exo-type, respectively. When the exo form is recrystallized from petroleum benzine, the purified target product 128Tn9 is obtained. Melting point 98-99°C Elemental analysis value Cl4Hl4N2O2 Theoretical value C69.4OH5.83Nll. 56 experimental value
C69.58H5.79Nll. 53 Example 4 Ethyl exo-1-cyano-5-methoxy6b-methyl-1
・Production of 1a, 2, 6b-tetrahydrocycloprop [b] indole-2-carboxylate Ethyl endo-1-cyano-6b-methyl 1, 1a, 2, 6b-tetrahydrocycloprop [b] indole-2-carboxylate A solution of Rate 36T19 in 4 ml of acetone was heated at 350 W for 2 hours until no more starting material disappeared.
Light irradiation was performed using a Wj pressure mercury lamp (Eikosha PLH-300 model) (the end point of the reaction was determined by thin layer chromatography).
Claims (1)
子、低級アルキル基または低級アルコキシ基を意味し、
Ｒ＿２は低級アルキル基を意味する。 ）で表わされるキノリン誘導体に紫外線を照射すること
を特徴とする一般式▲数式、化学式、表等があります▼ （式中、Ｒ、Ｒ＿１およびＲ＿２は前掲と同じものを意
味する。 ）で表わされる２・３−ホモインドール誘導体の製造法
。[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R means a lower alkyl group, R_1 means a hydrogen atom, a lower alkyl group or a lower alkoxy group,
R_2 means a lower alkyl group. ) A general formula characterized by irradiating ultraviolet rays to a quinoline derivative represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R, R_1 and R_2 have the same meanings as above.) Method for producing a 2,3-homindole derivative.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2651774A JPS599551B2 (en) | 1974-03-06 | 1974-03-06 | Method for producing 2,3-homoindole derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2651774A JPS599551B2 (en) | 1974-03-06 | 1974-03-06 | Method for producing 2,3-homoindole derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS50117770A JPS50117770A (en) | 1975-09-16 |
| JPS599551B2 true JPS599551B2 (en) | 1984-03-03 |
Family
ID=12195657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2651774A Expired JPS599551B2 (en) | 1974-03-06 | 1974-03-06 | Method for producing 2,3-homoindole derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS599551B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5881815B2 (en) | 2012-04-12 | 2016-03-09 | 株式会社東芝 | X-ray tube |
-
1974
- 1974-03-06 JP JP2651774A patent/JPS599551B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS50117770A (en) | 1975-09-16 |
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