dimethyl 8,12-diphenylbenzo[a]heptalene-6,7-dicarboxylate | 169527-53-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: dimethyl 8,12-diphenylbenzo[a]heptalene-6,7-dicarboxylate
• 英文别名: dimethyl (7aPM,12aMP)-8,12-diphenylbenzoheptalene-6,7-dicarboxylate
• CAS: 169527-53-1
• 化学式: C₃₂H₂₄O₄
• 分子量: 472.54
• InChiKey: LMHMIDPHUSHWSC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  36
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.06
• 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：

  dimethyl 8,12-diphenylbenzo[a]heptalene-6,7-dicarboxylate 在 五氯化磷 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 正己烷 、 氯仿 为溶剂， 反应 4.5h， 生成 8,12-diphenyl-6,7-bis[(diphenylphosphinoyl)methyl]benzo[a]heptalene
  参考文献：
  名称：

  Synthesis of (P)- and (M)-6,7-Bis[(diphenylphosphanyl)methyl]-8,12-diphenylbenzo[a]heptalenes - Potential Ligands for Homogeneous Asymmetric Catalysis

  摘要：

  The title bis(phosphane) ligands have been prepared starting from optically pure diisopropyl (P)- and (M)-8,22-diphenylbenzo[a]heptalene-6,7-dicarboxylaes ((P)-1b and (M)-1b) that had been obtained by HPLC separation of rac-1b on a semi-preparative Chiralcel OD column. Reduction of (P)-1b and (M)-1b with diisobutylaluminum hydride (DIBAH) gave optically pure (P)- and (M)-dimethanols 3 (Scheme 6 and Fig. 5). Unfortunately, the almost quantitative chlorination of rac-3 with PCl5 in CHCl3 at - 60 degrees led with (M)-3 to nearly complete loss of optical integrity However, mesylate formation of (P)-3. followed by phosphanylation with LiP(BH3)Ph-2 gave (P)-6 with only a small loss of optical activity. Optically pure (P)-6 was obtained by crystallization from Et2O/hexane, which removed the nearly insoluble rac-6. The pure bis(phosphane) ligands (P)-2 and (M)-2 can be liberated quantitatively from 6 by warming 6 in toluene in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO). First Rh'-catalyzed asymmetric hydrogenation reactions of (Z)-alpha-(acetamido)cinnamic acid ((Z)-14) in the presence of (P)-2 led to (R)-N-acetylphenylalanin ((R)-15) in optical purities up to 77% (see Table 1).

  DOI：

  10.1002/(sici)1522-2675(20000119)83:1<258::aid-hlca258>3.0.co;2-a
• 作为产物：
  描述：

  dimethyl 4b,10-etheno-5,9-diphenyl-10H-benz[a]azulene-11,12-dicarboxylate 以 N,N-二甲基甲酰胺 为溶剂， 反应 19.0h， 生成 dimethyl 8,12-diphenylbenzo[a]heptalene-6,7-dicarboxylate
  参考文献：
  名称：

  二甲基-8,12-二苯基[合成和手性光学属性d ]庚搭烯-6,7-二羧酸二乙酯†

  摘要：

  在2摩尔％[RuH 2（PPh 3）4 ]的存在下，于100°在MeCN中使6,10-二苯基苯并[ a ] azulene（3）与乙酰二羧酸二甲酯（ADM）反应，得到7：1混合物2,6-二苯基-9,10-苯并三环[6.2.2.0 1,7 ] dodeca-2,4,6,9,11-戊烯-11,12-二羧酸酯（4）和二甲基8,12-二苯基苯甲酸酯的合成[ d ]庚二烯-6，7-二羧酸酯（5；方案2）。当在DMF中于150°加热1小时时，三轮车4导致形成81.5％的庚烯-6,7-二羧酸酯5和15％的起始氮杂3。。当在假异丙苯中将三轮车4加热到高达180°的温度时，未观察到三轮车4的重排。庚烯-6,7-二羧酸酯5在Chiracel色谱柱上很容易分离成其对映体（PM）和（MP）-5（参见图2）。在150°加热1小时后，（MP）-5完全没有消旋。苯并[ a ] azulene（6）与ADM的Ru催化反应导致形成二甲基9

  DOI：

  10.1002/hlca.19930760814

文献信息

• Thermal Reaction of Azulenes with Dimethyl Acetylenedicarboxylate in Supercritical Carbon Dioxide
  作者：Richard Hunziker、David Sperandio、Hans-J�rgen Hansen

  DOI：10.1002/hlca.19950780322

  日期：1995.5.10

  (cf. Scheme 2) was not observed. Similarly, benz[a]azulene (25) yielded in supercritical CO2 (150°/170 bar) in the presence of 4 equiv. of ADM dimethyl benzo[d]heptalene-6,7-dicarboxylate (29; 30%) and dimethyl benzo[a]cyclopent[cd]azulene-1,2-dicarboxylate (28; 22%; Scheme 5). The reaction of 5,9-diphenylbenz[a]azulene (26) and ADM in supercritical CO2 (100°/150 bar) gave the corresponding benzo[d]heptalene-6

  1,3,4,6,8-五甲基az（9），当在4当量存在下于150 bar的超临界CO 2中于100°加热时。炔二羧酸二甲酯（ADM）的形成导致16％的3,5,6,8,10-五甲基庚二烯-1,2-二羧酸二甲酯12a和其双键转移异构体12b的1：1混合物的形成以及4％的相应的氮杂1,2-二羧酸13（方案4）。没有观察到[1 + 2]加合物11的形成（参见方案2）。同样，在超临界CO 2中生成苯并[ a ] azulene（25）（150°/ 170 bar）在4当量的情况下 制备ADM二甲基苯并[ d ]庚烯-6，7-二羧酸酯（29； 30％）和二甲基苯并[ a ]环戊[ cd ]]并1,2-二羧酸二甲酯（28； 22％；方案5）。5,9-二苯基苯并[ a ] azulene（26）和ADM在超临界CO 2（100°/ 150 bar）中的反应得到相应的苯并[ d ]庚二烯-6,7-二羧酸31（22％）和二甲基5
• Formation of Heptaleno[1,2-c]furans and Heptaleno[1,2-c]furanones
  作者：Peter Uebelhart、Peter Mohler、Reza-Ali Fallahpour、Hans-J�rgen Hansen

  DOI：10.1002/hlca.19950780605

  日期：1995.9.20

  into their antipodes on a Chiralcel OD column. The (P)-configuration is assigned to the heptaleno[1,2-c]furans showing a negative Cotton effect at ca. 320 nm in the CD spectrum in hexane (cf. Figs. 3–5 as well as Table 7). The (P)-configuration of (–)-6a is correlated with the established (P)-configuration of the dimethanol (–)-5avia dehydrogenation with MnO2. The degree of twisting of the heptalene

  庚烷-4,5-二甲醇4a和4d的脱氢反应在室温下与碱性MnO 2在室温下的CH 2 Cl 2中不经历双键转移（DBS）过程，导致分别形成相应的庚二酮[1,2- c ]呋喃6a和6d，以及分别形成相应的庚二酮[1,2 - c ]呋喃-3-酮7a和7d（参见方案2和8）。两种产品类型的形成必然涉及DBS流程（请参阅方案7）。的DBS异构体的脱氢反应4a中，即，图5a，具有的MnO 2在CH 2氯2在室温下的结果，除了图6A和7A，在heptaleno [1,2的形成Ç ] -furan- 1-酮8a和少量的庚烯-4,5-二甲醛9a（参见方案3）。在CH 2 Cl中用MnO 2脱氢时，具有庚烯骨架CC键固定位置的苯并[ a ]庚二烯-6,7-二甲醇4c在图2中，仅给出相应的呋喃酮11b（方案4）。由[ 2 ħ 2 ]在C（7）的甲醇函数的-labelling，它可以表明，呋喃酮的形成发生在相应的乳醇的阶段[3-
• A Detailed Investigation of the Reaction of 5,9-Diphenylbenz[a]azulene with Dialkyl Acetylenedicarboxylates Leading to Dialkyl 8,12-Diphenylbenzo[a]heptalene-6,7-dicarboxylates
  作者：Anthony Linden、Markus Meyer、Peter Mohler、Andreas J. Rippert、Hans-Jürgen Hansen

  DOI：10.1002/(sici)1522-2675(19991215)82:12<2274::aid-hlca2274>3.0.co;2-9

  日期：1999.12.15

  The synthesis of 5,9-dipbenylbenz[a]azulene (1) from 1,3-diphenylcyclopent[a]indene-2,8-dione (4) and cyclopropene has been re-investigated. The reduction of the decarbonylated cycloadduct 5 with LiAlH4/AlCl3 in Et2O leads not only to the expected 7,10-dihydrobenz[a]azulene 6, but also to small amounts of the cyclopropa[b]fluorenes exo-7 and endo-7 (cf Scheme 2), the structures of which have been determined by X-ray crystal-structure analysis (cf. Fig. 1). The reaction of 1 with dialkyl acetylenedicarboxylates (ADR) in MeCN at 100 degrees in the presence of 2 mol-% of catalysts such as [RuH2(PPh3)(4)] results mainly in the formation of the expected 8,12-diphenylbenzo[a]heptalene-6,7-dicarboxylates 3. A thorough investigation of the reaction mixture of 1 and dimethyl acetylenedicarboxylate (ADM) revealed the presence of a number of intermediates and side products (Scheme 5). Most important was the isolation and identification of the cyclobutene intermediate 9a (cf. Fig. 4), which is formed by a zwitterionic rearrangement of the primary adduct 2a of 1 and ADM and represents the direct precursor of the heptalene-diester 3a. Compounds of type 9a have so far only been postulated as necessary intermediates in the thermal reaction of azulenes and ADR to give corresponding heptalenedicarboxylates. Compound 9a is photochemically unstable and undergoes rearrangement even under the influence of normal laboratory light into a mixture of trans-10a and cis-10a (Scheme 8). Both diastereoisomers are also found in the original reaction mixture of 1 and ADM, but not when the reaction is performed under exclusion of light. On heating in MeCN at 100 degrees, or better in DMF at 150 degrees, trans-10a and cis-10a undergo rearrangement to the fluoranthene-1,2-dicarboxylate 11a (Scheme 9), which is also present in the original reaction mixture of 1 and ADM. The catalysts do not accelerate the reaction of 1 and ADR, but they lead to better yields of the benzo[a]heptalene-6,7-dicarboxylates 3, especially in the reaction of 1 with diisopropyl acetylenedicarboxylate (ADiP) (cf. Tables 1 and 2).
• Synthesis of (P)- and (M)-6,7-Bis[(diphenylphosphanyl)methyl]-8,12-diphenylbenzo[a]heptalenes - Potential Ligands for Homogeneous Asymmetric Catalysis
  作者：Peter Mohler、Andreas Johannes Rippert、Hans-Jürgen Hansen

  DOI：10.1002/(sici)1522-2675(20000119)83:1<258::aid-hlca258>3.0.co;2-a

  日期：2000.1.19

  The title bis(phosphane) ligands have been prepared starting from optically pure diisopropyl (P)- and (M)-8,22-diphenylbenzo[a]heptalene-6,7-dicarboxylaes ((P)-1b and (M)-1b) that had been obtained by HPLC separation of rac-1b on a semi-preparative Chiralcel OD column. Reduction of (P)-1b and (M)-1b with diisobutylaluminum hydride (DIBAH) gave optically pure (P)- and (M)-dimethanols 3 (Scheme 6 and Fig. 5). Unfortunately, the almost quantitative chlorination of rac-3 with PCl5 in CHCl3 at - 60 degrees led with (M)-3 to nearly complete loss of optical integrity However, mesylate formation of (P)-3. followed by phosphanylation with LiP(BH3)Ph-2 gave (P)-6 with only a small loss of optical activity. Optically pure (P)-6 was obtained by crystallization from Et2O/hexane, which removed the nearly insoluble rac-6. The pure bis(phosphane) ligands (P)-2 and (M)-2 can be liberated quantitatively from 6 by warming 6 in toluene in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO). First Rh'-catalyzed asymmetric hydrogenation reactions of (Z)-alpha-(acetamido)cinnamic acid ((Z)-14) in the presence of (P)-2 led to (R)-N-acetylphenylalanin ((R)-15) in optical purities up to 77% (see Table 1).
• Synthesis and Chiroptical Properties of Dimethyl 8,12-Diphenylbenzo[d]heptalene-6,7-dicarboxylate
  作者：Andreas J. Rippert、Hans-J�rgen Hansen

  DOI：10.1002/hlca.19930760814

  日期：1993.12.15

  6,10-Diphenylbenz[a]azulene (3) was reacted with dimethyl acetylenedicarboxylate (ADM) in the presence of 2 mol-% of [RuH2(PPh3)4] in MeCN at 100° to yield a 7:1 mixture of dimethyl 2,6-diphenyl-9,10-benzotricyclo[6.2.2.01,7]dodeca-2,4,6,9,11-pentaene-11,12-dicarboxylate (4) and dimethyl 8,12-diphenylbenzo[d]heptalene-6,7-dicarboxylate (5; Scheme 2). The tricycle 4, when heated in DMF at 150° for 1

  在2摩尔％[RuH 2（PPh 3）4 ]的存在下，于100°在MeCN中使6,10-二苯基苯并[ a ] azulene（3）与乙酰二羧酸二甲酯（ADM）反应，得到7：1混合物2,6-二苯基-9,10-苯并三环[6.2.2.0 1,7 ] dodeca-2,4,6,9,11-戊烯-11,12-二羧酸酯（4）和二甲基8,12-二苯基苯甲酸酯的合成[ d ]庚二烯-6，7-二羧酸酯（5；方案2）。当在DMF中于150°加热1小时时，三轮车4导致形成81.5％的庚烯-6,7-二羧酸酯5和15％的起始氮杂3。。当在假异丙苯中将三轮车4加热到高达180°的温度时，未观察到三轮车4的重排。庚烯-6,7-二羧酸酯5在Chiracel色谱柱上很容易分离成其对映体（PM）和（MP）-5（参见图2）。在150°加热1小时后，（MP）-5完全没有消旋。苯并[ a ] azulene（6）与ADM的Ru催化反应导致形成二甲基9