2-(α-Brombenzyliden)-1,1,3,3-tetramethylindan | 75501-28-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: 2-(α-Brombenzyliden)-1,1,3,3-tetramethylindan
• 英文别名: 2-(α-bromobenzylidene)-1,1,3,3-tetramethylindane；2-(α-bromobenzylidene)-1,1,3,3-tetramethylindan；2-[Bromo(phenyl)methylidene]-1,1,3,3-tetramethyl-2,3-dihydro-1H-indene；2-[bromo(phenyl)methylidene]-1,1,3,3-tetramethylindene
• CAS: 75501-28-9
• 化学式: C₂₀H₂₁Br
• 分子量: 341.291
• InChiKey: KWZQKYGNECZVDN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  21
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  2-(α-Brombenzyliden)-1,1,3,3-tetramethylindan 在 [(6)Li]-n-butyllithium 作用下， 以 环戊烷 、 正戊烷 为溶剂， 生成
  参考文献：
  名称：

  Microsolvation and ¹³C−Li NMR Coupling

  摘要：

  The empirical expression (1)J(CLi) = L[n(a + d)](-1) is proposed; it claims a reciprocal dependence of the NMR coupling constant (1)J(C-13, Li) in a C-Li compound on two factors: (i) the number n of lithium nuclei in bonding contact with the observed carbanion center and (ii) the sum (a + d) of the numbers a of anions and d of donor ligands coordinated at the Li nucleus that generates the observed (1)J(CLi) value. The expression was derived from integrations of separate NMR resonances of coordinated and free monodentate donor ligands (t-BuOMe, Et2O or THF) in toluene solutions of dimeric and monomeric 2-(alpha-aryl-alpha-lithiomethylidene)-1,1,3,3-tetramethylindan at moderately low temperatures. This unusually slow ligand interchange is ascribed to steric congestion in these compounds, which is further characterized by measurements of nuclear Overhauser correlations and by solid-state structures of the dimers bearing only one donor per lithium atom (d = 1). Increasing microsolvation numbers dare also accompanied by typical changes of the NMR chemical shifts delta (positive for the carbanionic C-13(alpha), negative for C-para and p-H). The aforementioned empirical expression for (1)J(CLi) appears to be applicable to other cases of solvated monomeric, dimeric, or tetrameric C-Li compounds (alkyl, alkenyl, alkynyl, and aryl) and even to unsolvated (d approximate to trimeric, tetrameric, or hexameric organolithium aggregates, indicating that (1)J(CLi) might serve as a tool for assessing unknown microsolvation numbers. The importance of obtaining evidence about the C-13 NMR C-Li multiplet splitting of both the nonfluxional and fluxional aggregates is emphasized.

  DOI：

  10.1021/ja8026828
• 作为产物：
  描述：

  1,1,3,3-tetramethyl-indan-2-carboxylic acid 在 正丁基锂 、 2,2,2-tribromo-1,3,2-benzodioxaphosphole 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 生成 2-(α-Brombenzyliden)-1,1,3,3-tetramethylindan
  参考文献：
  名称：

  Carbenoid-mediated nucleophilic “hydrolysis” of 2-(dichloromethylidene)-1,1,3,3-tetramethylindane with DMSO participation, affording access to one-sidedly overcrowded ketone and bromoalkene descendants^§

  摘要：

  2-(二氯甲基亚甲基)-1,1,3,3-四甲基茚烷在DMSO作为溶剂的固体KOH存在下，通过最初的氯粒子转移反应形成了Cl,K-卡宾中间体，反应温度≥100°C。这种短暂的中间体通过可逆的质子转移来表明其存在，该过程与DMSO中的氧转移竞争，产生了二甲基硫。推测所得的短暂的酮烯通过与KOH结合形成了1,1,3,3-四甲基茚烷-2-羧酸钾盐（一种形式的水解产物）。该关键酸的锂盐能够酰化芳基锂化合物，产生单面过度拥挤的酮和相应的三级醇。后者是副产物（约10%），与它们的芳基基团的旋转自由度减小相应地形成。作为一个不太麻烦的进一步副产物，上述关键酸的二阴离子通过羧化反应被识别出来，形成了1,1,3,3-四甲基茚烷-2,2-二羧酸。酮的溴化脱氧反应生成了两个单面过度拥挤的溴代烯烃。有关上述Cl,K-卡宾中间体的一些相关性质在支持信息文件1中提供。

  DOI：

  10.3762/bjoc.10.28

文献信息

• Alkenyl Bromides by Brominative Deoxygenation of Ketones in One or Two Steps
  作者：Ulrich Von Roman、Jakob Ruhdorfer、Rudolf Knorr

  DOI：10.1055/s-1993-25986

  日期：——

  The conversion of ketones into alkenyl bromides is accomplished in one or two steps by 2,2,2-tribromo-2,2-dihydro-1,3,2-benzodioxaphosphole or by the dibromomethyl methyl ether prepared therefrom. Investigations of the scope and limitations provide some hints for the preparative planning and improvement.

  通过使用2,2,2-三溴-2,2-二氢-1,3,2-苯并二氧磷杂环己烯或由此制备的二溴甲基甲醚，可以将酮转化为烯基溴，这一过程在一到两步内完成。对范畴和限制条件的研究为制备规划和改进提供了一些线索。
• Knorr, Rudolf; Lattke, Ernst; Raepple, Edith, Liebigs Annalen der Chemie, 1980, # 8, p. 1207 - 1215
  作者：Knorr, Rudolf、Lattke, Ernst、Raepple, Edith

  DOI：——

  日期：——
• KNORR R.; LATTKE E.; RAEPPLE E., LIEBIGS ANN. CHEM., 1980, NO 8, 1207-1215
  作者：KNORR R.、 LATTKE E.、 RAEPPLE E.

  DOI：——

  日期：——
• Microsolvation and ¹³C−Li NMR Coupling
  作者：Rudolf Knorr、Thomas Menke、Kathrin Ferchland、Johann Mehlstäubl、David S. Stephenson

  DOI：10.1021/ja8026828

  日期：2008.10.29

  The empirical expression (1)J(CLi) = L[n(a + d)](-1) is proposed; it claims a reciprocal dependence of the NMR coupling constant (1)J(C-13, Li) in a C-Li compound on two factors: (i) the number n of lithium nuclei in bonding contact with the observed carbanion center and (ii) the sum (a + d) of the numbers a of anions and d of donor ligands coordinated at the Li nucleus that generates the observed (1)J(CLi) value. The expression was derived from integrations of separate NMR resonances of coordinated and free monodentate donor ligands (t-BuOMe, Et2O or THF) in toluene solutions of dimeric and monomeric 2-(alpha-aryl-alpha-lithiomethylidene)-1,1,3,3-tetramethylindan at moderately low temperatures. This unusually slow ligand interchange is ascribed to steric congestion in these compounds, which is further characterized by measurements of nuclear Overhauser correlations and by solid-state structures of the dimers bearing only one donor per lithium atom (d = 1). Increasing microsolvation numbers dare also accompanied by typical changes of the NMR chemical shifts delta (positive for the carbanionic C-13(alpha), negative for C-para and p-H). The aforementioned empirical expression for (1)J(CLi) appears to be applicable to other cases of solvated monomeric, dimeric, or tetrameric C-Li compounds (alkyl, alkenyl, alkynyl, and aryl) and even to unsolvated (d approximate to trimeric, tetrameric, or hexameric organolithium aggregates, indicating that (1)J(CLi) might serve as a tool for assessing unknown microsolvation numbers. The importance of obtaining evidence about the C-13 NMR C-Li multiplet splitting of both the nonfluxional and fluxional aggregates is emphasized.
• Carbenoid-mediated nucleophilic “hydrolysis” of 2-(dichloromethylidene)-1,1,3,3-tetramethylindane with DMSO participation, affording access to one-sidedly overcrowded ketone and bromoalkene descendants^§
  作者：Rudolf Knorr、Thomas Menke、Johannes Freudenreich、Claudio Pires

  DOI：10.3762/bjoc.10.28

  日期：——

  2-(Dichloromethylidene)-1,1,3,3-tetramethylindane was “hydrolyzed” by solid KOH in DMSO as the solvent at ≥100 °C through an initial chlorine particle transfer to give a Cl,K-carbenoid. This short-lived intermediate disclosed its occurrence through a reversible proton transfer which competed with an oxygen transfer from DMSO that created dimethyl sulfide. The presumably resultant transitory ketene incorporated KOH to afford the potassium salt of 1,1,3,3-tetramethylindan-2-carboxylic acid (the product of a formal hydrolysis). The lithium salt of this key acid is able to acylate aryllithium compounds, furnishing one-sidedly overcrowded ketones along with the corresponding tertiary alcohols. The latter side-products (ca. 10%) were formed against a substantially increasing repulsive resistance, as testified through the diminished rotational mobility of their aryl groups. As a less troublesome further side-product, the dianion of the above key acid was recognized through carboxylation which afforded 1,1,3,3-tetramethylindan-2,2-dicarboxylic acid. Brominative deoxygenation of the ketones furnished two one-sidedly overcrowded bromoalkenes. Some presently relevant properties of the above Cl,K-carbenoid are provided in Supporting Information File 1.

  2-(二氯甲基亚甲基)-1,1,3,3-四甲基茚烷在DMSO作为溶剂的固体KOH存在下，通过最初的氯粒子转移反应形成了Cl,K-卡宾中间体，反应温度≥100°C。这种短暂的中间体通过可逆的质子转移来表明其存在，该过程与DMSO中的氧转移竞争，产生了二甲基硫。推测所得的短暂的酮烯通过与KOH结合形成了1,1,3,3-四甲基茚烷-2-羧酸钾盐（一种形式的水解产物）。该关键酸的锂盐能够酰化芳基锂化合物，产生单面过度拥挤的酮和相应的三级醇。后者是副产物（约10%），与它们的芳基基团的旋转自由度减小相应地形成。作为一个不太麻烦的进一步副产物，上述关键酸的二阴离子通过羧化反应被识别出来，形成了1,1,3,3-四甲基茚烷-2,2-二羧酸。酮的溴化脱氧反应生成了两个单面过度拥挤的溴代烯烃。有关上述Cl,K-卡宾中间体的一些相关性质在支持信息文件1中提供。