3,8-divinylchlorin e8 trimethyl ester | 33745-56-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四吡咯及其衍生物
• 英文名称: 3,8-divinylchlorin e8 trimethyl ester
• 英文别名: 3,8-divinylchlorin e₈ trimethyl ester；18-(2-methoxycarbonyl-ethyl)-20-methoxycarbonylmethyl-3,8,13,17-tetramethyl-7,12-divinyl-17,18-dihydro-21H,23H-porphine-2-carboxylic acid methyl ester
• CAS: 33745-56-1
• 化学式: C₃₇H₄₀N₄O₆
• 分子量: 636.748
• InChiKey: ZHOWPEROMYNKRP-MIUGAMJUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.03
• 重原子数：
  47.0
• 可旋转键数：
  8.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  136.26
• 氢给体数：
  2.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  3,8-divinylchlorin e8 trimethyl ester 在 sodium hexamethyldisilazane 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 以84%的产率得到pheophorbide a methyl ester
  参考文献：
  名称：

  Novel Synthetic Routes to 8-Vinyl Chlorophyll Derivatives

  摘要：

  New methodology was developed toward the synthesis of 8-de-ethyl-8-vinylchlorophyll-a 1. Such 8-de-ethyl-8-vinyl derivatives of the green plant pigment chlorophyll-a 2 have been proposed to be intermediates during biosynthesis of chlorophylls and bacteriochlorophylls. Transformation of the 8-ethyl group to an 8-vinyl group was studied on derivatives (e.g. 5) of chlorin-e(6) trimethyl ester 9. The reported methodology involves regioselective osmylation on ring-B, followed by dehydration of the resulting 7,8-diol (e.g. 7). Based on a model synthesis, three partial synthetic approaches starting from 2 have been developed, using different protective groups for the 3-vinyl group. Several 8-de-ethyl-8-vinyl derivatives of 9 (e.g. 8 and its C-13-labeled analogue 22) have been synthesized. A new, mild recyclization method for fabrication of the isocyclic ring-E in chlorophylls was discovered which permits conversion of 8-de-ethyl-8-vinylchlorin-e(6) analogues 6 and 8 into the corresponding 8-de-ethyl-8-vinylpheophorbides 10 and 11. A change from vinyl to ethyl at the 3-position in chlorophylls causes a hypsochromic shift of 10 nm or more in the optical spectrum, whereas the identity of the 8-substituent (ethyl or vinyl) appears not to affect the wavelength of the band at about 660 nm. Hence, transformation from 8-vinyl to 8-ethyl during chloroplast biogenesis is a step which does not affect the light absorption/harvesting properties of the final isolated chlorophyll chromophores.

  DOI：

  10.1021/jo9721608
• 作为产物：
  描述：

  (5Z,10Z,14Z,19Z)-(17S,18S)-18-(2-Methoxycarbonyl-ethyl)-20-methoxycarbonylmethyl-3,8,13,17-tetramethyl-12-[2-(2-nitro-phenylselanyl)-ethyl]-7-vinyl-17,18,21,23-tetrahydro-porphine-2-carboxylic acid methyl ester 在 1 双氧水 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以73%的产率得到3,8-divinylchlorin e8 trimethyl ester
  参考文献：
  名称：

  Novel Synthetic Routes to 8-Vinyl Chlorophyll Derivatives

  摘要：

  New methodology was developed toward the synthesis of 8-de-ethyl-8-vinylchlorophyll-a 1. Such 8-de-ethyl-8-vinyl derivatives of the green plant pigment chlorophyll-a 2 have been proposed to be intermediates during biosynthesis of chlorophylls and bacteriochlorophylls. Transformation of the 8-ethyl group to an 8-vinyl group was studied on derivatives (e.g. 5) of chlorin-e(6) trimethyl ester 9. The reported methodology involves regioselective osmylation on ring-B, followed by dehydration of the resulting 7,8-diol (e.g. 7). Based on a model synthesis, three partial synthetic approaches starting from 2 have been developed, using different protective groups for the 3-vinyl group. Several 8-de-ethyl-8-vinyl derivatives of 9 (e.g. 8 and its C-13-labeled analogue 22) have been synthesized. A new, mild recyclization method for fabrication of the isocyclic ring-E in chlorophylls was discovered which permits conversion of 8-de-ethyl-8-vinylchlorin-e(6) analogues 6 and 8 into the corresponding 8-de-ethyl-8-vinylpheophorbides 10 and 11. A change from vinyl to ethyl at the 3-position in chlorophylls causes a hypsochromic shift of 10 nm or more in the optical spectrum, whereas the identity of the 8-substituent (ethyl or vinyl) appears not to affect the wavelength of the band at about 660 nm. Hence, transformation from 8-vinyl to 8-ethyl during chloroplast biogenesis is a step which does not affect the light absorption/harvesting properties of the final isolated chlorophyll chromophores.

  DOI：

  10.1021/jo9721608

文献信息

• A convenient synthetic approach to 8-vinyl-chlorophyll derivatives
  作者：Benjamin Gerlach、Kevin M. Smith

  DOI：10.1016/0040-4039(96)01143-4

  日期：1996.7

  Partial syntheses of two 8-vinyl-derivatives (3 and 6) of chlorin-e6 trimethyl ester 5 are reported; in certain organisms, 8-de-ethyl-8-vinylchlorophyll-a 3 has been proposed to be a biosynthetic precursor of the plant chlorophylls and of the bacteriochlorophylls.

  报导了二氢卟酚-e 6三甲酯5的两个8-乙烯基衍生物（3和6）的部分合成。在某些生物中，有人提出8-去乙基-8-乙烯基叶绿素-a 3是植物叶绿素和细菌叶绿素的生物合成前体。
• A Simple and Short Synthesis of Divinyl Chlorophyll Derivatives
  作者：Gang Zheng、Thomas J. Dougherty、Ravindra K. Pandey

  DOI：10.1021/jo982431u

  日期：1999.5.1