3-Methylinden-1,1-d2 | 122408-61-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 3-Methylinden-1,1-d2
• 英文别名: 1,1-dideuterio-3-methylindene
• CAS: 122408-61-1
• 化学式: C₁₀H₁₀
• 分子量: 132.174
• InChiKey: COOKKJGOGWACMY-RJSZUWSASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.65
• 重原子数：
  10.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  (R)-(+)-1-methyl-(1,3-₂H2)indene 在 氢化奎尼定 作用下， 以 邻二氯苯 为溶剂， 生成 3-Methylinden-1,1-d2
  参考文献：
  名称：

  Solvent Dependence of Enantioselectivity for a Base-Catalyzed 1,3-Hydron Transfer Reaction. A Kinetic Isotope Effect and NMR Spectroscopic Study

  摘要：

  The base-catalyzed rearrangement of 1-methylindene (1) to 3-methylindene (2) has been studied. The reaction proceeds with substrate enantioselectivity (kinetic resolution) when chiral tertiary amines are used as catalysts. When dihydroquinidine (DHQD) (3) is used to accomplish the 1,3-hydron shift, the enantioselectivity shows a change of sense when the solvent is changed from o-dichlorobenzene (o-DCB) (k(+)/k(-) = 3.70) to dimethyl sulfoxide (DMSO) (k(+)/k(-) = 0.579). The enantiomer-dependent primary deuterium kinetic isotope effects (KIEs) have been determined to (k(H)/k(D))(+) = 5.30 and (k(H)/k(D))(-) = 5.86 in o-DCB and (k(H)/k(D))(+) = 7.76 and (k(H)/k(D))(-) = 8.26 in DMSO, respectively. The enantioselectivity was found to decrease slightly with increasing concentration of the catalyst. Using (p-chlorobenzoyl)dihydroquinidine (p-CIBzDHQD) (4) as catalyst in o-DCB yields the same sense of the enantioselectivity (k(+)/k(-) = 0.502) as dihydroquinidine (3) in DMSO. The conformational properties of the alkaloid DHQD (3) in the solvents acetone, chloroform, DMSO, dioxane, o-DCB, and tetrahydrofuran and of p-ClBzDHQD (4) in o-DCB and chloroform were investigated by means of H-1 NMR spectroscopy. The observed solvent dependence of the enantioselectivity is rationalized in terms of the conformational composition of the cinchona alkaloid catalyst.

  DOI：

  10.1021/jo00110a046

文献信息

• Observation of different primary kinetic isotope effects in a pair of enantioselective reactions
  作者：Olle Matsson、Lennart Meurling、Ulf Obenius、G�ran Bergson

  DOI：10.1039/c39840000043

  日期：——

  The primary deuterium kinetic isotope effect has been determined to be 5.31 and 6.19 for (+)- and (–)-1-methylindene, respectively, in the enantioselective prototropic rearrangement of these compounds to 3-methylindene under the catalytic effect of the chiral base(+)-(8R,9S)-dihydroquinidine in the solvent o-dichlorobenzene at 30 °C.

  在手性碱的催化作用下，这些化合物的对映选择性质子重排成3-甲基茚，主要的氘动力学同位素效应被确定为（+）-和（-）-1-甲基茚的5.31和6.19。在30°C下的邻二氯苯溶剂中的（+）-（8 R，9 S）-二氢奎尼丁。
• 1,3-Hydron transfer in some 5- and 7-substituted 1-methylindenes. Enantioselectivities and enantiomer-dependent kinetic isotope effects
  作者：Marie Aune、G�ran Bergson、Olle Matsson

  DOI：10.1002/poc.610080604

  日期：1995.6

  [5-methoxy- (2), 5-fluoro- (3), 5-nitro- (4) and 7-nitro (5)] and 1-methylindene (1) were employed as substrates. The rate constants, the enantioselectivities and the kinetic isotope effects (KIEs) for the enantioselective reactions [(kH/kD)+ and (kH/kD)−] were determined at 20°C using (+)-(8R, 9S)-dihydroquinidine as chiral catalyst in the solvent o-dichlorobenzene. The rate constants vary according to the

  在茚体系中研究了碱催化的底物-对映选择性的1，3-氢转移（动力学拆分）。在芳香环中取代的一系列1-甲基茚[5-甲氧基-（2），5-氟-（3），5-硝基-（4）和7-硝基（5）]和1-甲基茚（1）被用作底物。对映选择性反应[（k H / k D）+和（k H / k D）- ]的速率常数，对映选择性和动力学同位素效应（KIEs）在20°C下使用（+）-（8 R，9 S）-二氢奎尼丁为溶剂o的手性催化剂-二氯苯。速率常数根据取代基的电子效应而变化。初级氘KIE范围从4·73 [对于（+）-（S）-2]到11·3 [对于（-）-（R）-5]，与速率常数相关，如预期的那样Melander–Westheimer假设。在芳环中引入取代基降低了对映选择性。除了5中的所有化合物显示的对映选择性的同样的意义[ ķ + / ķ - > 1; 使用的所有底物均为（+）-（S）/（-）-（R）]。KIE的对映异构体依赖性在1
• Heesing,A.; Schneeberger,H.-W., Chemische Berichte, 1972, vol. 105, p. 2447 - 2456
  作者：Heesing,A.、Schneeberger,H.-W.

  DOI：——

  日期：——
• MATSSON, O.;MEURLING, L.;OBENIUS, U.;BERGSON, GOERAN, J. CHEM. SOC. CHEM. COMMUN., 1984, N 1, 43-44
  作者：MATSSON, O.、MEURLING, L.、OBENIUS, U.、BERGSON, GOERAN

  DOI：——

  日期：——