2-(dibenzylamino)ethyl acetoacetate | 71784-32-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-(dibenzylamino)ethyl acetoacetate
• 英文别名: 2-(dibenzylamino)ethyl 3-oxobutanoate
• CAS: 71784-32-2
• 化学式: C₂₀H₂₃NO₃
• 分子量: 325.408
• InChiKey: NXDLEHIXALCKCB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  24
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-(dibenzylamino)ethyl acetoacetate 在 铜 四氢吡咯 、 三乙胺 、 甲烷磺酰基叠氮化物 作用下， 以 水 、 甲苯 、 乙腈 为溶剂， 反应 38.0h， 生成 (E)-Bis(2-(N,N-dibenzylamino)ethyl) fumarate
  参考文献：
  名称：

  Applications of Stevens [1,2]-Shifts of Cyclic Ammonium Ylides. A Route to Morpholin-2-ones

  摘要：

  2-(N,N-Dialkylamino)ethyl diazoacetoacetates 2 were prepared in two steps from readily available ethanolamines 1. When heated in the presence of catalytic Cu, the substrates cleanly formed morpholinones 3, presumably via the intermediacy of copper carbenoids and cyclic ammonium ylides. In most cases involving benzylic or allylic migrating groups, ylide [1,2]-shift occurred in good yield (55-80%). In the case of benzhydryl containing substrate 2g, only dimer 4 was isolated. Simple alkyl groups failed to undergo the rearrangement, with the exception of tert-butyl case 2i, which furnished morpholinone 3i in low yield. Substituted allylic case 2l gave only [1,2]-shift product 3l, with no evidence for competing [2,3]-shift to give 3l'. Diazoacetates 2n-p also underwent conversion to morpholinones 3n-p in 19-64% yield with Cu(acac)(2) catalysis.

  DOI：

  10.1021/jo00099a041
• 作为产物：
  描述：

  双乙烯酮 、 N,N-二苄基乙醇胺 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成 2-(dibenzylamino)ethyl acetoacetate
  参考文献：
  名称：

  Applications of Stevens [1,2]-Shifts of Cyclic Ammonium Ylides. A Route to Morpholin-2-ones

  摘要：

  2-(N,N-Dialkylamino)ethyl diazoacetoacetates 2 were prepared in two steps from readily available ethanolamines 1. When heated in the presence of catalytic Cu, the substrates cleanly formed morpholinones 3, presumably via the intermediacy of copper carbenoids and cyclic ammonium ylides. In most cases involving benzylic or allylic migrating groups, ylide [1,2]-shift occurred in good yield (55-80%). In the case of benzhydryl containing substrate 2g, only dimer 4 was isolated. Simple alkyl groups failed to undergo the rearrangement, with the exception of tert-butyl case 2i, which furnished morpholinone 3i in low yield. Substituted allylic case 2l gave only [1,2]-shift product 3l, with no evidence for competing [2,3]-shift to give 3l'. Diazoacetates 2n-p also underwent conversion to morpholinones 3n-p in 19-64% yield with Cu(acac)(2) catalysis.

  DOI：

  10.1021/jo00099a041

文献信息

• Synthesis of new water-soluble dihydropyridine vasodilators.
  作者：MASARU IWANAMI、TADAO SHIBANUMA、MASAHARU FUJIMOTO、RYUTARO KAWAI、KAZUHARU TAMAZAWA、TOICHI TAKENAKA、KOZO TAKAHASHI、MASUO MURAKAMI

  DOI：10.1248/cpb.27.1426

  日期：——

  Several kinds of water-soluble dihydropyridine vasodilators were prepared and their vasodilating activities were evaluated. Among them, 2-(N-benzyl-N-methylamino)-ethyl methyl 2, 6-dimethyl-4-(m-nitrophenyl)-1, 4-dihydropyridine-3, 5-dicarboxylate hydrochloride (YC-93) was found to have outstanding activity and bioavailability. Various synthetic routes for this compound were examined.

  制备了几种水溶性二氢吡啶血管扩张剂，并评估了它们的血管扩张活性。其中，2-（N-苯基-N-甲基氨基）-乙基-甲基-2, 6-二甲基-4-（m-硝基苯基）-1, 4-二氢吡啶-3, 5-二羧酸盐盐酸盐（YC-93）被发现具有出色的活性和生物利用度。对该化合物的各种合成路线进行了研究。
• Photocyclization of 2-(dialkylamino)ethyl acetoacetates: Remote proton transfer and Stern-Volmer quenching kinetics in the system involving two reactive excited states
  作者：Tadashi Hasegawa、Naoko Yasuda、Michikazu Yoshioka

  DOI：10.1002/(sici)1099-1395(199604)9:4<221::aid-poc773>3.0.co;2-i

  日期：1996.4

  Upon irradiation, 2-(dibenzylamino)ethyl and 2-(N-benzyl-N-methylamino)ethyl acetoacetate (1a and 1b) undergo photocyclization via remote proton transfer from the benzyl group to the acetyl carbonyl oxygen to give eight-membered azalactones. Irradiation of the corresponding (diisopropylamino)- and (dimethylamino)ethyl esters gave no azalactones. Introduction of the methyl group on C-2 of 1a brought about a complicated photoreaction, probably due to competition of alpha-cleavage, The Stern-Volmer plots for the photoreaction of la did not show the linear relationship, indicating that the photoreaction proceeds from two reactive excited states, The Stern-Volmer quenching equation for the system was obtained by applying the steady-state approximation and was used for the analysis of the photoreaction of 1a. The triplet lifetime was determined to be 1.6 x 10(-8) s.
• IWANAMI M.; SHIBANUMA T.; FUJIMOTO M.; KAWAI R.; TAMAZAWA K.; TAKENAKA T.+, CHEM. AND PHARM. BULL., 1979, 27, NO 6, 1426-1440
  作者：IWANAMI M.、 SHIBANUMA T.、 FUJIMOTO M.、 KAWAI R.、 TAMAZAWA K.、 TAKENAKA T.+

  DOI：——

  日期：——
• Applications of Stevens [1,2]-Shifts of Cyclic Ammonium Ylides. A Route to Morpholin-2-ones
  作者：F. G. West、B. N. Naidu

  DOI：10.1021/jo00099a041

  日期：1994.10

  2-(N,N-Dialkylamino)ethyl diazoacetoacetates 2 were prepared in two steps from readily available ethanolamines 1. When heated in the presence of catalytic Cu, the substrates cleanly formed morpholinones 3, presumably via the intermediacy of copper carbenoids and cyclic ammonium ylides. In most cases involving benzylic or allylic migrating groups, ylide [1,2]-shift occurred in good yield (55-80%). In the case of benzhydryl containing substrate 2g, only dimer 4 was isolated. Simple alkyl groups failed to undergo the rearrangement, with the exception of tert-butyl case 2i, which furnished morpholinone 3i in low yield. Substituted allylic case 2l gave only [1,2]-shift product 3l, with no evidence for competing [2,3]-shift to give 3l'. Diazoacetates 2n-p also underwent conversion to morpholinones 3n-p in 19-64% yield with Cu(acac)(2) catalysis.