diethyl 2-methyl-1,1-cyclopentanedicarboxylate | 5222-64-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: diethyl 2-methyl-1,1-cyclopentanedicarboxylate
• 英文别名: methyl-2 cyclopentanedicarboxylate-1,1 de diethyle；2-Methyl-cyclopentan-1,1-dicarbonsaeure-diaethylester；2-Methyl-1.1-bis-ethoxycarbonyl-cyclopentan；1,1-Diethoxycarbonyl-2-methyl-cyclopentan；2-methyl-cyclopentane-1,1-dicarboxylic acid diethyl ester；diethyl 2-methylcyclopentane-1,1-dicarboxylate；1,1-Bis-aethoxycarbonyl-2-methyl-cyclopentan
• CAS: 5222-64-0
• 化学式: C₁₂H₂₀O₄
• 分子量: 228.288
• InChiKey: YHPVVTHYYHNUEG-UHFFFAOYSA-N

物化性质

• 沸点：
  99 °C(Press: 4 Torr)
• 密度：
  1.0323 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  diethyl 2-methyl-1,1-cyclopentanedicarboxylate 在 氢氧化钾 作用下， 以 乙醇 为溶剂， 反应 1.0h， 生成 methyl trans-2-methylcyclopentanecarboxylate
  参考文献：
  名称：

  Canonne, P.; Plamondon, J., Canadian Journal of Chemistry, 1989, vol. 67, p. 555 - 564

  摘要：

  DOI：
• 作为产物：
  描述：

  1,4-戊二醇 在 氢溴酸 、 sodium 作用下， 以 乙醇 为溶剂， 生成 diethyl 2-methyl-1,1-cyclopentanedicarboxylate
  参考文献：
  名称：

  Julia,M.; Maumy,M., Bulletin de la Societe Chimique de France, 1969, p. 2415 - 2427

  摘要：

  DOI：

文献信息

• Treasures from the Free Radical Renaissance Period – Miscellaneous hexenyl radical kinetic data
  作者：Athelstan L. J. Beckwith、Carl H. Schiesser

  DOI：10.1039/c0ob00708k

  日期：——

  Rate constant data and Arrhenius parameters have been determined for a series of substituted hexenyl radicals of differing electronic and steric demand. Electron-withdrawing groups (CF3, CO2Et) directly attached to the radical centre slighly accelerate 5-exo ring-closure (kcis + ktrans ∼ 2.1 × 105 s−1 at 25°) relative to donating groups (OMe; 1.6 × 105 s−1 at 25°). Sterically demanding groups (tert-Bu)

  已针对一系列具有不同电子和空间需求的取代己烯基确定了速率常数数据和Arrhenius参数。相对于捐赠基团（OMe ），直接连接至自由基中心的吸电子基团（CF 3，CO 2 Et）缓慢促进5- exo闭环（25°时k cis + k trans〜2.1 ×10 5 s -1） ；在25°时为1.6×10 5 s -1）。如预期的那样，对空间要求较高的组（叔-Bu ）减慢环化过程（1×10 5 s -1）。这些观察结果与5 - exo闭环的活化能的细微变化是一致的。有趣的是，溶剂的性质似乎对该化学有重大影响，随着溶剂极性的增加，顺式/反式立体选择性有时会提高。除了包含CF 3（吸电子）基团的系统显示出环化/捕获速率常数（k c / k H）增加外，k c / k H普遍下降。记录随着溶剂极性增加的比率；据推测，这些变化主要是由于所用各种溶剂中k H的变化引起的。
• Oxidative deprotonation of carbonyl compounds by Fe(III) salts
  作者：Attilio Citterio、Anna Cerati、Roberto Sebastiano、Claudia Finzi、Roberto Santi

  DOI：10.1016/s0040-4039(00)72739-0

  日期：1989.1

  Iron (III) salts (perchlorate and nitrate nonahydrate) in acetonitrile or acetic anhydride at 0–50°C oxidize the ∝-position of malonic esters efficiently via the corresponding radicals. In the presence of olefins and aromatics, inter- and intramolecular free radical chain or oxidative additions are observed.

  乙腈或乙酸酐中的铁（III）盐（高氯酸盐和硝酸盐九水合物）在0–50°C下可通过相应的自由基有效氧化丙二酸酯的α-位。在烯烃和芳族化合物的存在下，观察到分子间和分子内的自由基链或氧化加成。
• Perkin–Markovnikov Type Reaction Initiated with Electrogenerated Superoxide Ion
  作者：Fumihiro Ojima、Tetsuo Osa

  DOI：10.1246/bcsj.62.3187

  日期：1989.10

  The cyclic condensation of active methylene compounds such as diethyl malonate, dimethyl malonate, ethyl acetoacetate, or acetylacetone and dibromoalkanes such as 1,2-dibromoethane, 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane, 1,6-dibromohexane, 1,3-dibromobutane, or 1,4-dibromopentane with electrogenerated superoxide ion was studied electrochemically in N,N-dimethylformamide (DMF) using cyclic voltammetry (CV) and controlled potential macro-electrolysis. The CV shows that electrogenerated superoxide ion reacts with both active methylene compounds and dibromoalkanes in the dissolved oxygen medium. Controlled potential macro-electrolysis of the above components generally yielded cycloalkanes as the main products. In comparison, the chemical method using sodium ethoxide was also carried out. Two reaction mechanisms via the proton abstraction of active methylene compounds with electrogenerated superoxide ion and via the nucleophilic attack of the superoxide ion on dibromoalkanes are presented.

  活性亚甲基化合物，如二乙基马来酸酯、二甲基马来酸酯、乙酰乙酸乙酯或乙酰乙酮，与二溴烷烃，如1,2-二溴乙烷、1,3-二溴丙烷、1,4-二溴丁烷、1,5-二溴戊烷、1,6-二溴己烷、1,3-二溴丁烷或1,4-二溴戊烷的循环缩合反应，采用循环伏安法（CV）和控制电位宏电解法在N,N-二甲基甲酰胺（DMF）中进行了电化学研究。CV结果表明，电生超氧阴离子在溶解氧介质中与活性亚甲基化合物和二溴烷烃均发生反应。上述组分的控制电位宏电解通常以环烷烃作为主要产物。相比之下，使用乙醇钠的化学方法也进行了研究。提出了两种反应机理：一种是活性亚甲基化合物与电生超氧阴离子的质子抽取反应，另一种是超氧阴离子对二溴烷烃的亲核攻击反应。
• .alpha.-Spirocyclopentyl- and .alpha.-spirocyclopropyl-.gamma.-butyrolactones: conformationally constrained derivatives of anticonvulsant and convulsant .alpha.,.alpha.-disubstituted .gamma.-butyrolactones
  作者：Eileen M. Peterson、Kun Xu、Katherine D. Holland、Ann C. McKeon、Steven M. Rothman、James A. Ferrendelli、Douglas F. Covey

  DOI：10.1021/jm00028a011

  日期：1994.1

  To further study the putative gamma-butyrolactone site of the GABA(A)/chloride channel complex, constrained derivatives of convulsant and anticonvulsant alpha,alpha-disubstituted gamma-butyrolactones (alpha-spirocyclopropyl- and alpha-spirocyclopentyl-gamma-butyrolactones) were synthesized and evaluated biologically. Most of the spirocyclopropyl agents were anticonvulsants when tested against pentylenetetrazole-induced seizures in mice. These agents effectively displaced (35)[S]-tert-butylbicyclophosphorothionate ((35)[S] -TBPS), a ligand for the picrotoxin binding site of the GABA(A)/chloride channel, from rat neuronal membranes and affected the GABA-mediated current in hippocampal neurons. The monomethyl-substituted spirocyclopropyl agent with a methyl group cis to the carbonyl (15) potentiates GABA-induced current whereas the trans derivative (16) blocks the current. The only anticonvulsant in the spirocyclopentyl series was the unsubstituted spirocyclopentyl compound 2. All the other substituted spirocyclopentyl targets were inactive in vivo at the highest dose tested except for convulsant 9, which has a trans 2,5-dimethyl-substituted cyclopentyl ring. All the spirocyclopentyl derivatives displaced (35)[S]-TBPS from rat neuronal membranes very effectively, and they also all potentiated GABA-induced chloride current except for convulsant 9 which blocked the current. From the data obtained in this investigation, it appears that when the volume occupied above and below the lactone ring is as large as that occupied by spirocyclopentyl agent 9, convulsant activity is observed. Groups with less volume in these areas either are inactive in the behavioral test or have anticonvulsant activity. When bound to the GABA(A)/chloride channel, the larger molecules may stabilize the closed state of the channel whereas the smaller molecules may stabilize the open state.
• Colman; Perkin, Journal of the Chemical Society, 1888, vol. 53, p. 201
  作者：Colman、Perkin

  DOI：——

  日期：——