Development of new synthetic method based on the substitution on the nitrogen atom oximes

基于氮原子肟取代的新合成方法的开发

• 批准号: 08454195
• 负责人: NARASAKA Koichi
• 金额: $ 4.61万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08454195/
• 关键词: oxime; imine; amination; 過レニウム酸テトラブチルアンモニウム; キノリン; アミノ化反応

New synthetic methods have been developed for the synthesis of various amino compounds based on the substitution reaction on the sp2 nitrogen atom of oximes.1) Preparation of anilines by the direct amination of aromatic compoundsElectron rich aromatic compounds react with 1-indanone 0-methylsulfonyloxime in the presence of SnCl_4 and CF_3SO_3H,giving the corresponding imines. The imines thus formed are converted to aniline derivative by hydrolysis.2) Preparation of dihydro pyrroles and tetrahydropyridinesIntramolecular substitution reaction of ketone 0-methylsulfonyloxime having active methylene group at the gamma- or delta-position proceeds in the presence of DBU to afford 3,4-dihydro-2H-pyrrole or 2,3,4,5-tetrahydropyridine, respectively.3) Preparation of primary amines by coupling reactions of organometallics with 0-sulfonyloximesPrimary amines are synthesized by the coupling reaction between organometallic reagents and 0-sulfonyloximes. That is, in the presence of CuCN as a catalys … More t, alkyl Grignard reagents react with 4,4'-bis (trifluoromethyl) benzophenone to give N-alkylimines, the hydrolysis of which yields primaray, secondary, and tertiary-alkylamines in high yield. By employing 3,3', 5,5'-tetrakis-(trifluoromethyl) benzophenone 0-p-toluenesulfonyloxime, the reaction with Grignard reagents proceeds without the copper catalyst, and anilines and alkylamines are obtained after hydrolysis of the resulted imines.4) Preparation of the nitrogen containing heterocyclic compounds via alkylideneaminyl radicalsIntramolecular cyclization of m-hydroxyphenethylketone 0-2,4-dinitrophenyloximes proceeds by the treatment with NaH and DDQ,affording 8-hydroxyquinolines. The reaction of m-hydroxyphenethylketone 0-2,4-dinitrophenyloximes with NaH and NaBH_3CN gives 8-hydroxy-tetrahydroquinolines. It was found that these reactions proceed via an alkylideneaminyl radical intermediate generated by one electron transfer between the two phenyl groups. This electron transfer method for the generation of alkylideneaminyl radicals is further utilized for the synthesis of 3,4-dihydro-2H-pyrrole derivatives by the intramolecular radical addition to an olefinic moiety. Less

通过肟的sp2位氮原子上的取代反应，发展了合成各种氨基化合物的新方法。1）芳香族化合物直接胺化制备苯胺富电子芳香族化合物在SnCl_4和CF_3SO_3H存在下与1-茚满酮-O-甲磺酰肟反应，得到相应的亚胺。2）二氢吡咯和四氢吡啶的制备在DBU存在下，γ-或δ-位上具有活性亚甲基的酮O-甲磺酰肟进行分子内取代反应，得到3，4-二氢-2H-吡咯或2，3，4，5-四氢吡啶，3）通过有机金属试剂与O-磺酰肟的偶联反应制备伯胺通过有机金属试剂与O-磺酰肟之间的偶联反应合成伯胺。也就是说，在CuCN作为催化剂的存在下， ...更多信息 叔烷基格氏试剂与4，4 ′-二（三氟甲基）二苯甲酮反应生成N-烷基亚胺，再水解得到伯、仲、叔烷基胺，产率较高。通过使用3，3 '，5，5'-四-（三氟甲基）二苯甲酮0-对甲苯磺酰肟，与格氏试剂的反应在没有铜催化剂的情况下进行，并且在所得亚胺水解后得到苯胺和烷基胺。4）通过亚烷基氨基自由基制备含氮杂环化合物将间羟基苯乙基酮0-2，4-二硝基苯肟通过用NaH和DDQ处理来进行，得到8-羟基喹啉。间羟基苯乙酮O-2，4-二硝基苯肟与NaH和NaBH_3CN反应生成8-羟基四氢喹啉。发现这些反应通过两个苯基之间的单电子转移产生的亚烷基氨基自由基中间体进行。这种产生亚烷基氨基的电子转移方法进一步用于通过分子内自由基加成到烯烃部分上来合成3，4-二氢-2H-吡咯衍生物。少

项目成果

H.Kusama, Y.Yamashita, K.Uchiyama, and K.Narasaka: "Transformation of Oximes of Phenethyl Ketone derivation to Quinolines and Azaspirotrienones Catalyzed by Tetrabutylammonium Perrhenate and Trifluoromethanesulfonic Acid." Bull.Chem Soc.Jpn.70.

H.Kusama、Y.Yamashita、K.Uchiyama 和 K.Narasaka：“高铼酸四丁基铵和三氟甲磺酸催化苯乙基酮衍生物肟转化为喹啉和氮杂螺三酮。”

S.Mori, K.Uchiyama, Y.Hayashi, K.Narasaka, and E.Nakamura: "SN^2 Substitution on sp^2 Nitrogen of Protonated Oxime." Chem.Lett.111. (1988)

S.Mori、K.Uchiyama、Y.Hayashi、K.Narasaka 和 E.Nakamura：“质子化肟的 sp^2 氮上的 SN^2 取代。”

965 (1997)

965 (1997)

Katuya Uchiyama: "Synthesis of 8-Hydroxyquinolines by the Cyclization of m-Hydroxyphenyl Ketone Ο-2,4-Dinitrophenyloximes" Synlett. 445-446 (1997)

Katuya Uchiyama：“通过间羟基苯基酮 Ο-2,4-二硝基苯肟的环化合成 8-羟基喹啉”Synlett 445-446 (1997)。

Seiji Mori: "S_N2 Substitution on sp2 Nitrogen of Protonated Oxime" Chemistry Letters. 111-112 (1998)

Seiji Mori：“质子化肟的 sp2 氮上的 S_N2 取代”化学快报。