Isopropylidenebenzocyclobutene | 84007-72-7

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: Isopropylidenebenzocyclobutene
• 英文别名: 1-isopropylidenebenzocyclobutene；7-propan-2-ylidenebicyclo[4.2.0]octa-1,3,5-triene
• CAS: 84007-72-7
• 化学式: C₁₁H₁₂
• 分子量: 144.216
• InChiKey: OMKSZNNWQKSPAK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  Isopropylidenebenzocyclobutene 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 以38%的产率得到1,1'-Epoxy-1-(1'-methylethylidene)benzocyclobutene
  参考文献：
  名称：

  Preparation and Photosensitized Oxidation of Isopropylidenecyclobutanes and -cyclobutenes

  摘要：

  Isopropylidenecyclobutanes 2-5 underwent facile ene reaction with singlet dioxygen, yielding (upon Ph(3)P reduction) the corresponding pairs of epimeric allylic alcohols 9 and 10, 11 and 12, 13 and 14, and 15 and 16, respectively. A combination of spectral evidence and molecular modeling studies were utilized in the structural assignment of the epimers. The data clearly indicate that steric considerations play an important role in determining the face of the ring which O-1(2) approaches. Isopropylidenecyclobutenes 6 and 7 reacted with singlet oxygen more slowly than their monoolefinic analogs, yielding upon reduction allylic alcohols 21b and 22, respectively. Benzo analog 7 also generated a small and solvent-dependent amount of isomeric aldehydes 23 and 24, presumably via a free-radical mechanism. n-Butyl diene 8 underwent rapid photosensitized oxygenation producing allylic alcohol 35 (as the O-1(2) ene product) and dione 37 (the Hock-cleavage product of allylic hydroperoxide 39, formed in turn via a free-radical route) in a 1:9 ratio. Ah initio (STO-3G) calculations confirm that, in their lowest energy conformations, compounds 2-8 are planar with the methylene ring hydrogens displaced ca. 36 degrees from the perpendicular. As a result, only exocyclic ene product is formed, since O-1(2) strongly prefers axial or pseudoaxial allylic hydrogens. These calculations combined with the relative rate data suggest that the initial interaction between the electrophilic O-1(2) and alkylidenecyclobutenes involves both ends of the singlet dioxygen molecule, in which the ''front'' end attacks the reactive exocyclic double bond while the ''back'' end obtains stabilization by interacting with the more electron rich but unreactive endocyclic olefin linkage. Because of this added, and presumably substantial, stabilization, the relative rates within this system are determined in part by the orbital coefficients at the latter olefinic center.

  DOI：

  10.1021/jo00083a019
• 作为产物：
  描述：

  1-Isopropylbenzocyclobuten-1-ol 在 碘 作用下， 95.0 ℃ 、3.33 kPa 条件下， 以36%的产率得到Isopropylidenebenzocyclobutene
  参考文献：
  名称：

  Preparation and Photosensitized Oxidation of Isopropylidenecyclobutanes and -cyclobutenes

  摘要：

  Isopropylidenecyclobutanes 2-5 underwent facile ene reaction with singlet dioxygen, yielding (upon Ph(3)P reduction) the corresponding pairs of epimeric allylic alcohols 9 and 10, 11 and 12, 13 and 14, and 15 and 16, respectively. A combination of spectral evidence and molecular modeling studies were utilized in the structural assignment of the epimers. The data clearly indicate that steric considerations play an important role in determining the face of the ring which O-1(2) approaches. Isopropylidenecyclobutenes 6 and 7 reacted with singlet oxygen more slowly than their monoolefinic analogs, yielding upon reduction allylic alcohols 21b and 22, respectively. Benzo analog 7 also generated a small and solvent-dependent amount of isomeric aldehydes 23 and 24, presumably via a free-radical mechanism. n-Butyl diene 8 underwent rapid photosensitized oxygenation producing allylic alcohol 35 (as the O-1(2) ene product) and dione 37 (the Hock-cleavage product of allylic hydroperoxide 39, formed in turn via a free-radical route) in a 1:9 ratio. Ah initio (STO-3G) calculations confirm that, in their lowest energy conformations, compounds 2-8 are planar with the methylene ring hydrogens displaced ca. 36 degrees from the perpendicular. As a result, only exocyclic ene product is formed, since O-1(2) strongly prefers axial or pseudoaxial allylic hydrogens. These calculations combined with the relative rate data suggest that the initial interaction between the electrophilic O-1(2) and alkylidenecyclobutenes involves both ends of the singlet dioxygen molecule, in which the ''front'' end attacks the reactive exocyclic double bond while the ''back'' end obtains stabilization by interacting with the more electron rich but unreactive endocyclic olefin linkage. Because of this added, and presumably substantial, stabilization, the relative rates within this system are determined in part by the orbital coefficients at the latter olefinic center.

  DOI：

  10.1021/jo00083a019

文献信息

• Carboxylic acid ester and an insecticidal and/or acaricidal composition
  申请人：Sumitomo Chemical Company, Limited

  公开号：US04480118A1

  公开（公告）日：1984-10-30

  This invention relates to a novel carboxylic acid ester represented by the following general formula (I) and an insecticidal and/or acaricidal composition containing the same as an active ingredient: ##STR1## wherein X is represented by the formula, ##STR2## and further also relates to a carboxylic acid or a reactive derivative thereof represented by the general formula, ##STR3## wherein R.sub.16 is hydroxy group, chlorine or bromine atom, or a C.sub.1-2 alkoxy group, W is oxygen atom or --CH.sub.2 -- group, k is an integer of 0 or 1, E is hydrogen, chlorine, fluorine or bromine atom, and n is an integer of 1 to 4.

  本发明涉及一种由以下通式（I）表示的新型羧酸酯，以及含有该羧酸酯作为活性成分的杀虫剂和/或杀螨剂组合物：##STR1## 其中X由以下式表示，##STR2## 进一步还涉及由通式表示的羧酸或其活性衍生物，##STR3## 其中R.sub.16是羟基、氯或溴原子，或C.sub.1-2烷氧基，W是氧原子或--CH.sub.2--基团，k是0或1的整数，E是氢、氯、氟或溴原子，n是1到4的整数。
• Preparation of Isopropylidenebenzocyclobutenes <i>via</i> the Photochemical Cyclization of 1-(<i>o</i>-Alkylaryl)-3-hydroxy-2,2-dimethyl- alkan-1-ones
  作者：Michikazu Yoshioka、Katsumi Iida、Etsuya Kawata、Kazutaka Maeda、Shigekazu Kumakura、Tadashi Hasegawa

  DOI：10.1021/jo962167+

  日期：1997.4.1
• Preparation and Photosensitized Oxidation of Isopropylidenecyclobutanes and -cyclobutenes
  作者：Aryeh A. Frimer、Joseph Weiss、Hugo E. Gottlieb、Joel L. Wolk

  DOI：10.1021/jo00083a019

  日期：1994.2

  Isopropylidenecyclobutanes 2-5 underwent facile ene reaction with singlet dioxygen, yielding (upon Ph(3)P reduction) the corresponding pairs of epimeric allylic alcohols 9 and 10, 11 and 12, 13 and 14, and 15 and 16, respectively. A combination of spectral evidence and molecular modeling studies were utilized in the structural assignment of the epimers. The data clearly indicate that steric considerations play an important role in determining the face of the ring which O-1(2) approaches. Isopropylidenecyclobutenes 6 and 7 reacted with singlet oxygen more slowly than their monoolefinic analogs, yielding upon reduction allylic alcohols 21b and 22, respectively. Benzo analog 7 also generated a small and solvent-dependent amount of isomeric aldehydes 23 and 24, presumably via a free-radical mechanism. n-Butyl diene 8 underwent rapid photosensitized oxygenation producing allylic alcohol 35 (as the O-1(2) ene product) and dione 37 (the Hock-cleavage product of allylic hydroperoxide 39, formed in turn via a free-radical route) in a 1:9 ratio. Ah initio (STO-3G) calculations confirm that, in their lowest energy conformations, compounds 2-8 are planar with the methylene ring hydrogens displaced ca. 36 degrees from the perpendicular. As a result, only exocyclic ene product is formed, since O-1(2) strongly prefers axial or pseudoaxial allylic hydrogens. These calculations combined with the relative rate data suggest that the initial interaction between the electrophilic O-1(2) and alkylidenecyclobutenes involves both ends of the singlet dioxygen molecule, in which the ''front'' end attacks the reactive exocyclic double bond while the ''back'' end obtains stabilization by interacting with the more electron rich but unreactive endocyclic olefin linkage. Because of this added, and presumably substantial, stabilization, the relative rates within this system are determined in part by the orbital coefficients at the latter olefinic center.

表征谱图