dimethyl 6,8,10-trimethyl-1-<(E)-2-phenylethenyl>heptalene-4,5-dicarboxylate | 167258-91-5

• 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 6,8,10-trimethyl-1-<(E)-2-phenylethenyl>heptalene-4,5-dicarboxylate
• 英文别名: dimethyl 6,8,10-trimethyl-5-<(E)-2-phenylethenyl>heptalene-1,2-dicarboxylate；[(E)-2-[4,5-bis(methoxycarbonyl)-6,8,10-trimethylheptalen-1-yl]ethenyl]benzene；dimethyl 6,8,10-trimethyl-1-[(E)-2-phenylethenyl]heptalene-4,5-dicarboxylate；dimethyl 6,8,10-Trimethyl-1-[(E)-2-phenylethenyl]-heptalene-4,5-dicarboxylate；dimethyl 6,8,10-trimethyl-5-[(E)-2-phenylethenyl]heptalene-1,2-dicarboxylate
• CAS: 167258-91-5
• 化学式: C₂₇H₂₆O₄
• 分子量: 414.501
• InChiKey: YEJMVNRHOHAPCD-VAWYXSNFSA-N

物化性质

• 沸点：
  610.3±48.0 °C(Predicted)
• 密度：
  1.17±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  31
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.19
• 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：

  三羰基三吡啶铬(0) 、 dimethyl 6,8,10-trimethyl-1-<(E)-2-phenylethenyl>heptalene-4,5-dicarboxylate 在 BF₃*OEt₂ 作用下， 以 乙醚 为溶剂， 以39%的产率得到tricarbonyl(η(6)-[(E)-2-[4,5-bis(methoxycarbonyl)-6,8,10-trimethylheptalen-1-yl]ethenyl]benzene)chromium
  参考文献：
  名称：

  新型(三羰基)(庚烯)铬配合物的合成与性能

  摘要：

  A number of novel (tricarbonyl)chromium complexes of heptalenes 10-13, 16-20 and 23-25 have been prepared by reaction of the heptalenes with [Cr(CO)(3)L-3] (L=NH3, Py; cf. Schemes 3- 6). Surprisingly, the off-state complexes 17 and 19, in which the Cr(CO)(3) group Complexes on the diester ring, have been obtained with excellent regioselectivity. The directing effect of ester C=O groups on the regioselectivity of the Cr(CO)(3) coordination to heptalene rings has been discussed. These complexes undergo thermal rearrangements via 1,2-intra-ring shift and inter-ring migration of the Cr(CO)(3) fragment to give the thermodynamically more stable on-state complexes 16 and 27, respectively (cf Schemes 8 and 9). The analogous thermal behavior of other prepared complexes has also been investigated. A new procedure for the selective preparation of complexes 10 and 13, in which the Cr(CO)(3) group is coordinated to the phenyl ring of the styryl substituent has also been developed (Scheme 7). The attachment of the Cr(CO)(3) fragment to the phenyl group has a visible influence on the UV/VIS behavior of the on-state complexes 10 and 13a. as well as on the photochemical behavior of the DBS isomers 13a/13b (cf Scheme 10).

  DOI：

  10.1002/1522-2675(200204)85:4<1166::aid-hlca1166>3.0.co;2-u
• 作为产物：
  描述：

  dimethyl 5,6,8,10-tetramethylheptalene-1,2-dicarboxylate 、 苯甲醛 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 以34%的产率得到dimethyl 6,8,10-trimethyl-1-<(E)-2-phenylethenyl>heptalene-4,5-dicarboxylate
  参考文献：
  名称：

  供体-受体-取代庚烯的光谱研究

  摘要：

  It is shown that the heptalene-4.5-dicarboxylates 5 react with their Me group at C(1) with N,N-dimethylformamide dimethyl acetal or other acetals of this type in N,N-dimethylformamide (DMF) to give the corresponding 1-[(E)-2-(N,N-dialkylamino)ethenyl]-substituted heptalene-4,5-dicarboxylates 8a-8e as well as 8k and 8i in good yields (Table 1). In a similar manner, the 1-[(E)-2-pyrrolidinoethenyl]-substituted heptalene-5-carboxylates 8f-h were synthesized from the corresponding heptalene-carboxylates 10-12, carrying a CHO, CN. or (E)-2-(methoxycarbonyl)ethenyl group at C(4) (Table 1). All new heptalenes with the pi -donor and pi -acceptor groups at C(1) and C(4), respectively, exhibit a strongly enhanced heptalene band I in the spectral region of 450-500 nm in MeCN (Table 7 and Figs. 4-7), whereby the specific position is dependent on the pi -donor quality of the N,N-dialkylamino substituent at C(2') and the pi -acceptor property of the group at C(4). The position of heptalene band I is also strongly solvent-dependent as is demonstrated in the case of heptalene 8i (Table 9). A good linear correlation with the CT band of 1-(diethylamino)-4-nitrobenzene or (E)-4-(dimethylamino)-beta -nitrostyrene (Figs. 11 and 12) characterizes the heptalene band I also as an electronic CT transition. Irradiation into this band of 8i leads, as observed in other cases (cf. [I I), to a double-bond shift in the heptalene moiety (--> 8'i: Figs. 8-10). On warming in solution, 8'i is converted quantitatively to 8i.

  DOI：

  10.1002/1522-2675(20010919)84:9<2670::aid-hlca2670>3.0.co;2-p

文献信息

• Thermal and Ru-catalyzed Reactions of Styryl-Substituted Azulenes with Dimethyl Acetylenedicarboxylate
  作者：Anne Andr�e Sophie Briquet、Hans-J�rgen Hansen

  DOI：10.1002/hlca.19940770723

  日期：1994.11.2

  are formed, the corresponding benzanellated azulene trans-29 ist found to be the second main product (21 and 10%, respectively) under both reaction conditions. The thermal reaction yields also the benzanellated azulene 28 which is not found in the catalyzed variant of the reaction. Heptalene-1,2-dicarboxylates are also formed from 4-[(E)-styryl]azulenes (e.g. (E)-33 and (E)-34; Scheme 14) and ADM at

  1-[（E）-苯乙烯基] azulenes与十氢化萘中的乙炔二羧酸二甲酯（ADM）在190-200°的热反应不会导致相应的庚烯1,2-二羧酸酯的形成（方案2）。主要产物是相应的薁基-1,2-二羧酸酯（见4和9），并伴有benzanellated薁反式- 10A和反式- 11分别。后者的化合物通过起始天青烯和ADM的Diels - Alder反应，然后与ADM进行烯反应形成（参见方案3）。[RuH 2（PPh 3）4 ]在ACN中于110°催化4,6,8-三甲基-1-[[（E）-4-R-苯乙烯基] azulenes（R = H，MeO，Cl;流程4）与ADM的反应主要成分为1,2-二氮杂ul。但是，在这种情况下，也会少量生成相应的庚烯1,2-二羧酸酯（3-5％；方案4）。所述benzanellated薁反式- 10A和反式-图10b是在反应混合物中少量（2-3％）也有发现。还观察到了少量的（
• New Syntheses of Di-π-Substituted Heptalenes
  作者：Jianfeng Song、Hans-Jürgen Hansen

  DOI：10.1002/(sici)1522-2675(19991215)82:12<2260::aid-hlca2260>3.0.co;2-z

  日期：1999.12.15

  To study the effect of double-bond shifts (DBS) in different type of heptalenes linked to extended pi- systems, several di-pi-substituted heptalenes were synthesized. 6-[(E)-Styryl]heptalene-dicarboxylate 4 was smoothly converted to 1-(chloromethyl)heptalene-dicarboxylate 5 by treatment with t-BuOK and C2Cl6 in THF at -78 degrees. The one-pot reaction of 5 and P(OEt)(3) in the presence of NaI, followed by Wittig-Horner reaction, afforded the 1,6-di-pi-substitute heptalene 6. The reaction of 6-[(1E,3E)-4-phenylbuta-1,3-dienyl]heptalenes 7 or 15 with t-BuOK and benzaldehyde in THF led to the formation of the 1,6-di-pi-substituted heptalenes 13 or 16, together with transesterification products 14 or 17. The transformation of the MeOCO group at C(4) of 6-[(E)-styryl]heptalene-dicarboxylate 4 to a phenylbuta-1,3-dienyl substituent afforded the 3,6-di-pi-substituted heptalene 21a, which is in thermal equilibrium with its DBS isomer 21b in solution. Oxidation of heptalene 22 with SeO2 in dioxane gave carbaldehyde 23, which was then subjected to a Wittig reaction to give the 6,9-di-pi-substituted heptalene-dicarboxylate 24.
• DOUBLE-BOND SHIFTS OF SUBSTITUTED (4N)-ANNULENES FOR INFORMATION STORAGE AND DATA PROCESSING
  申请人：Ciba Specialty Chemicals Holding Inc.

  公开号：EP0944899B1

  公开（公告）日：2002-08-07
• Briquet Anne Andree Sophie, Hansen HansJuergen, Helv. chim. acta, 77 (1994) N 7, S 1940- 1968
  作者：Briquet Anne Andree Sophie, Hansen HansJuergen

  DOI：——

  日期：——
• Synthesis and Properties of Novel (Tricarbonyl)(heptalene)chromium Complexes
  作者：Ekaterina A. Ochertyanova、Hans-Jürgen Hansen、Yuri A. Ustynyuk

  DOI：10.1002/1522-2675(200204)85:4<1166::aid-hlca1166>3.0.co;2-u

  日期：2002.4

  A number of novel (tricarbonyl)chromium complexes of heptalenes 10-13, 16-20 and 23-25 have been prepared by reaction of the heptalenes with [Cr(CO)(3)L-3] (L=NH3, Py; cf. Schemes 3- 6). Surprisingly, the off-state complexes 17 and 19, in which the Cr(CO)(3) group Complexes on the diester ring, have been obtained with excellent regioselectivity. The directing effect of ester C=O groups on the regioselectivity of the Cr(CO)(3) coordination to heptalene rings has been discussed. These complexes undergo thermal rearrangements via 1,2-intra-ring shift and inter-ring migration of the Cr(CO)(3) fragment to give the thermodynamically more stable on-state complexes 16 and 27, respectively (cf Schemes 8 and 9). The analogous thermal behavior of other prepared complexes has also been investigated. A new procedure for the selective preparation of complexes 10 and 13, in which the Cr(CO)(3) group is coordinated to the phenyl ring of the styryl substituent has also been developed (Scheme 7). The attachment of the Cr(CO)(3) fragment to the phenyl group has a visible influence on the UV/VIS behavior of the on-state complexes 10 and 13a. as well as on the photochemical behavior of the DBS isomers 13a/13b (cf Scheme 10).