exo-dimethyl tricyclo<3.2.2.0^2,4>nona-6,8-diene-6,7-dicarboxylate | 5932-77-4

• 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: exo-dimethyl tricyclo<3.2.2.0^2,4>nona-6,8-diene-6,7-dicarboxylate
• 英文别名: 2,3-di(methoxycarbonyl)tricyclo<3.2.4.0^2,4>nona-6,9-diene；(1rC⁸,2tH,4tH)-tricyclo[3.2.2.0^2,4]nona-6,8-diene-6,7-dicarboxylic acid dimethyl ester；(1rC⁸,2tH,4tH)-Tricyclo[3.2.2.0^2,4]nona-6,8-dien-6,7-dicarbonsaeure-dimethylester；dimethyl (1S,2S,4R,5R)-tricyclo[3.2.2.02,4]nona-6,8-diene-6,7-dicarboxylate
• CAS: 5932-77-4
• 化学式: C₁₃H₁₄O₄
• 分子量: 234.252
• InChiKey: IKEMREZHYYEGDB-OJOKCITNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.54
• 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：

  exo-dimethyl tricyclo<3.2.2.0^2,4>nona-6,8-diene-6,7-dicarboxylate 在 氢氧化钾 作用下， 生成 (1rC⁸,2tH,4tH)-tricyclo[3.2.2.0^2,4]nona-6,8-diene-6,7-dicarboxylic acid
  参考文献：
  名称：

  Alder; Jacobs, Chemische Berichte, 1953, vol. 86, p. 1528,1535

  摘要：

  DOI：
• 作为产物：
  描述：

  环庚三烯 、 丁炔二酸二甲酯 在 六羰基铬 作用下， 以 二丁醚 为溶剂， 反应 72.0h， 以40%的产率得到exo-dimethyl tricyclo<3.2.2.0^2,4>nona-6,8-diene-6,7-dicarboxylate
  参考文献：
  名称：

  Metal-Mediated [6 + 2] Cycloadditions of Alkynes to Cycloheptatriene and N-Carbethoxyazepine

  摘要：

  UV photolysis of [(eta(6)-C(7)H(7)R)Cr(Co)(3)] (1, R = H, Ph, CH(CO(2)Me)(2)) and R'C = CR' (R' = Ph, Tol, SiMe(3), Et) in toluene or n-hexane gives the [6 + 2] cycloadducts [(eta(2:4)-C9H7(R)R'(2))Cr(CO)(3)] (2). Heating 2 in toluene releases the 7,8-disubstituted bicyclo[4.2.1]nona-2,4,7-trienes 3 and [(eta(6)-C(6)H(5)Me)Cr(CO)(3)]. Irradiation of solutions of 1 and dimethyl acetylenedicarboxylate at 0 degrees C yields the bicyclotriene as the major product but no organometallic complex. The diphenyl derivative 2a undergoes a reversible intramolecular metal migration to the eta(6)-aryl species 4. Irradiation of the azepine complex [(eta(6)-C6H6N(CO(2)Et))Cr(CO)(3)] (5) and R'C = CR' (R' = Ph, SiMe(3)) in toluene also forms [6 + 2] cycloadducts [(eta(2:4)-C8H6N(CO2Er)R'(2))Cr(CO)(3)] (6). The heterobicyclotrienes 7 are isolated from 6 by treatment with iodine (R' = SiMe(3)) or by hearing in toluene (R' = Ph). X-ray crystal structures are reported for 6b (R' = SiMe(3)) [orthorhombic, P2(1)2(1)2(1), a = 8.871(1), b = 10.148(1), and c = 26.017(4) Angstrom, R = 0.041 for 2500 independent reflections] and a byproduct (8) that results from the endo [6 + 4] cycloaddition of N-carbethoxyazepine to 5; monoclinic, P2(1)/c, a = 10.665(9), b = 14.976(7), and c = 13.004(7) Angstrom, beta = 100.05(7)degrees, R = 0.047 for 1044 independent reflections. Heating cycloheptatriene and alkynes R'C = CR' (R' = SiMe(3), Me, Et) in dibutyl ether with a catalytic amount of Cr(CO)(6) or Fe-2(CO)(9) also gives good yields of the [6 + 2] cycloadducts 3, whereas the thermal reaction with dimethyl acetylenedicarboxylate in the presence of Cr(CO)(6) gives the known norcaradiene [4 + 2] adduct 9.

  DOI：

  10.1021/ja00112a005

文献信息

• Reaction of Strained Homoconjugated Compounds with Benzene in the Presence of Palladium(II) Acetate
  作者：Katsuhiro Saito、Masatoshi Kozaki、Akira Imai、Yasushi Hara、Kensuke Takahashi

  DOI：10.1246/cl.1994.1769

  日期：1994.9

  Reaction of tricyclo[3.2.2.02,4]nona-6,9-diene derivatives with benzene in the presence of palladium(II) acetate afforded pentacyclic benzo derivatives through successive repeated substitutions accompanied by formation of cyclopropane rings. A bicyclo[2.2.2]octa-2,5-diene derivative also underwent a similar reaction.

  在乙酸钯 (II) 存在下，三环 [3.2.2.02,4]nona-6,9-二烯衍生物与苯反应，通过连续重复取代并伴随形成环丙烷环，得到五环苯并衍生物。双环[2.2.2]octa-2,5-二烯衍生物也经历了类似的反应。
• ortho-Disubstitution reactions of aromatic rings with homo-conjugated bicyclo[2.2.2]octa-2,5-diene derivatives in the presence of palladium(II) acetate
  作者：Katsuhiro Saito、Katsuhiko Ono、Toshifumi Takeda、Shingo Kiso、Kazuya Uenishi、Masatoshi Kozaki

  DOI：10.1016/s0040-4020(02)01126-2

  日期：2002.10

  Bicyclo[2.2.2]octa-2,5-diene derivatives 5 and 7 reacted with aromatic compounds such as benzene, naphthalene, anthracene, phenanthrene, and tropone in the presence of Pd(OAc)(2) to afford ortho-disubstituted aromatics 6 and 8-12. Since the yields and regioselectivity were generally low, the reaction conditions were optimized by using iodoarenes as reagents to provide sufficient yields and regioselectivity. In order to investigate reactivities of diene moieties, several kinds of homo-conjugated dienes were surveyed for the reaction. Only dienes containing a bicyclo[2.2.2]octa-2,5-diene skeleton gave the ortho-disubstituted aromatics. (C) 2002 Elsevier Science Ltd. All rights reserved.
• High-pressure addition reactions involving cycloheptatriene-norcaradiene equilibrium
  作者：Gerard Jenner、Mihail Papadopoulos

  DOI：10.1021/jo00355a002

  日期：1986.3
• Stereospecificity of dienophile addition to cycloheptatrienes
  作者：M.J. Goldstein、A.H. Gevirtz

  DOI：10.1016/s0040-4039(00)71680-7

  日期：——
• Prinzbach et al., Chemische Berichte, 1974, vol. 107, p. 1971,1985
  作者：Prinzbach et al.

  DOI：——

  日期：——