(+/-)-trans-10,11-dihydro-10,11-dihydroxy-5H-dibenzocycloheptene | 118354-09-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 二苯并环庚烯
• 英文名称: (+/-)-trans-10,11-dihydro-10,11-dihydroxy-5H-dibenzocycloheptene
• 英文别名: (9S,10S)-tricyclo[9.4.0.03,8]pentadeca-1(15),3,5,7,11,13-hexaene-9,10-diol
• CAS: 118354-09-9
• 化学式: C₁₅H₁₄O₂
• 分子量: 226.275
• InChiKey: NCRHUZUIKXAFHG-GJZGRUSLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  三甲基乙酸酐 、 (+/-)-trans-10,11-dihydro-10,11-dihydroxy-5H-dibenzocycloheptene 在 vanadyl triflate 作用下， 以 甲苯 为溶剂， 反应 5.0h， 以95%的产率得到trans-11-(2,2-dimethyl-propanoyloxy)-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-10-yl-2,2-dimethylpropanoate
  参考文献：
  名称：

  Catalytic Nucleophilic Acyl Substitution of Anhydrides by Amphoteric Vanadyl Triflate

  摘要：

  [GRAPHICS]Among four vanadyl species examined, vanadyl triflate was the most efficient catalyst to facilitate nucleophilic acyl substitution of anhydrides with a myriad array of alcohols, amines, and thiols in high yields and high chemoselectivity. By using mixed-anhydride technique, one can achieve oleate and peptide syntheses. In marked contrast to common metal triflates, the amphoteric character of the V=O unit in vanadyl species was proven to be responsible for the catalytic profile in this process.

  DOI：

  10.1021/ol016684c
• 作为产物：
  描述：

  5H-二苯并[a,d]环庚烯 在 氢氧化钾 、 碘 、 silver benzoate 作用下， 生成 (+/-)-trans-10,11-dihydro-10,11-dihydroxy-5H-dibenzocycloheptene
  参考文献：
  名称：

  10,11-dihydro-5h-dibenz [b，f] azepine衍生物中的构象过程受限制。DNMR研究

  摘要：

  反式-10-溴-10,11-二氢-11-羟基-5H-二苯并[b，f]氮杂-5-羰基氯的300 MHz可变温度NMR研究表明，存在两种构象受限的异构体，均具有在C（10）和C（11）上有一个抗取向的质子和氢键的gauche取代基，它们通过围绕C（4a）-N（5）-C（5a）键的扭转而通过环反转而相互转换。在21-38°C温度范围内获得的用于环反转过程的活化自由能为ΔG = 16.5±0.2 Kcal mol -1

  DOI：

  10.1016/s0040-4020(01)86190-1

文献信息

• Reactivity and crystal structure of 10,11 -dihdro-10,11-epoxy-5H-dibenzo[a,d]cycloheptene. A comparison with cis-stilbene oxide
  作者：Giuseppe Bellucci、Cinzia Chiappe、F. Marioni、Riccardo Spagna

  DOI：10.1039/p29900002147

  日期：——

  The kinetics and product distributions for the HClO4 catalysed hydrolysis of 10,11-diydro-10,11-epoxy-5H-dibenzo[a,d]cycloheptene1 and of cis-stilbene oxide 6 in tetrahydrofuran–water (8:2), have been investigated by HPLC. The former epoxide gives 9,10-dihydroanthracene-9-carbaldehyde 4 and the trans- and cis-10,11-dihydro-5H-dibenzo[a,d]cycloheptene-10,11-diols, 2 and 3, in he ratio 6:6:1. cis-Stilbene

  为高氯酸的动力学和产品分布4 10,11- diydro -10,11-环氧-5-催化水解ħ -二苯并[一，d ]环庚烯1，并且顺式-茋氧化物6在四氢呋喃-水（8:2 ），已通过HPLC进行了研究。前者环氧化物使9,10-二氢-9-甲醛4和反式-和顺-10,11-二氢-5- ħ -二苯并[一，d ]环庚烯-10,11-二醇，2和3，在他比例6：6：1。顺式-氧化二苯乙烯与速率常数ca反应。低十倍，得到大部分（±）-1,2-二苯乙烷-1,2-二醇。这些差异可以用1的晶体结构来解释，该晶体结构由于C（10）和C（11）处键角的增大而显示出相当大的环应变。这种结构也为1相对于6的微粒体环氧化物水解酶催化的水合速率低得多提供了一种解释。
• Bellucci, Giuseppe; Chiappe, Cinzia; Marioni, Franco, Gazzetta Chimica Italiana, 1993, vol. 123, # 2, p. 87 - 91
  作者：Bellucci, Giuseppe、Chiappe, Cinzia、Marioni, Franco、Cabiddu, Maria Grazia、Cabiddu, Salvatore

  DOI：——

  日期：——
• Catalytic Nucleophilic Acyl Substitution of Anhydrides by Amphoteric Vanadyl Triflate
  作者：Chien-Tien Chen、Jen-Huang Kuo、Chun-Hsin Li、N. B. Barhate、Sang-Wen Hon、Tai-Wei Li、Shi-Deh Chao、Chia-Cheng Liu、Ying-Chieh Li、I-Hsin Chang、Jin-Sheng Lin、Chin-Jing Liu、Y-Chen Chou

  DOI：10.1021/ol016684c

  日期：2001.11.1

  [GRAPHICS]Among four vanadyl species examined, vanadyl triflate was the most efficient catalyst to facilitate nucleophilic acyl substitution of anhydrides with a myriad array of alcohols, amines, and thiols in high yields and high chemoselectivity. By using mixed-anhydride technique, one can achieve oleate and peptide syntheses. In marked contrast to common metal triflates, the amphoteric character of the V=O unit in vanadyl species was proven to be responsible for the catalytic profile in this process.
• Restricted conformational processes in 10,11-dihydro-5h-dibenz [b,f]azepine erivatives. a DNMR study
  作者：G. Bellucci、R. Bianchini、C. Chiappe、F. Marioni、D. Catalano

  DOI：10.1016/s0040-4020(01)86190-1

  日期：1988.1

  11-dihydro-11-hydroxy-5H-dibenz[b,f]azepine-5-carbonyl chloride has shown the presence of two conformationally restricted isomers, both bearing antioriented a protons and hydrogen bonded gauche substituents at C(10) and C(11), which are interconverted through‘ ring inversion by torsion about the C(4a)-N(5)-C(5a) bonds. The free energy of activation for the ring inversion process, obtained in the 21-38°C temperature

  反式-10-溴-10,11-二氢-11-羟基-5H-二苯并[b，f]氮杂-5-羰基氯的300 MHz可变温度NMR研究表明，存在两种构象受限的异构体，均具有在C（10）和C（11）上有一个抗取向的质子和氢键的gauche取代基，它们通过围绕C（4a）-N（5）-C（5a）键的扭转而通过环反转而相互转换。在21-38°C温度范围内获得的用于环反转过程的活化自由能为ΔG = 16.5±0.2 Kcal mol -1