1-<<3-(o-Nitrophenyl)propyl>oxy>-2-methyl-9,10-anthraquinone | 114446-46-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: 1-<<3-(o-Nitrophenyl)propyl>oxy>-2-methyl-9,10-anthraquinone
• 英文别名: 1-<3-(o-nitrophenyl)propyl>-2-methyl-9,10-anthraquinone；2-Methyl-1-[3-(2-nitrophenyl)propoxy]anthracene-9,10-dione
• CAS: 114446-46-7
• 化学式: C₂₄H₁₉NO₅
• 分子量: 401.419
• InChiKey: YCAQVEJRLCRZEZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  30
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  89.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1-<<3-(o-Nitrophenyl)propyl>oxy>-2-methyl-9,10-anthraquinone 在 air 、 potassium carbonate 作用下， 以 四氢呋喃 、 丁酮 为溶剂， 反应 66.0h， 生成 1-(甲氧基(苯基)甲氧基)-2-甲基蒽-9,10-二醇
  参考文献：
  名称：

  Photochemistry of 1-alkoxy- and 1-(benzyloxy)-9,10-anthraquinones in methanol: A facile process for the preparation of aldehydes and ketones

  摘要：

  The facile production of acid sensitive aldehydes and ketones via photochemical intramolecular delta-hydrogen atom transfer in 1-alkoxy- and 1-(benzyloxy)-9,10-anthraquinones (1) was investigated. Irradiation of 1 in argon purged methanol generates the primary photoproducts, 1-(RCH(OMe)O)-and 1-(ArCH(OMe)O)-9,10-antharahydroquinones (2), respectively. Upon exposure to air, the intermediate anthrahydroquinone is rapidly converted to the corresponding aldehyde and 1-hydroxy-9,10-anthraquinone (3), which can be recycled. Aldehydes containing an acetal or ketal were prepared in high yields using this photoprocess. Apparent rate constants for the photodemethylation of 1-methoxy-2-X-9,10-anthraquinones (X = H, Me, Et, Pr, Bu, i-Bu, and benzyl) were measured and found to vary by a factor of 10 separating the slowest anthraquinone (X = H) and the fastest (X = benzyl), indicating a strong dependency upon the size of the substituent at the a-position. These rate constants are ascribed to equilibrium populations of confonmers in the geometry required for reaction in the n,pi* triplet state.

  DOI：

  10.1021/jo00126a040
• 作为产物：
  描述：

  1-(Cyclopropylmethoxy)-2-methylanthracene-9,10-dione 在 air 、 potassium carbonate 作用下， 以 丁酮 为溶剂， 反应 17.0h， 生成 1-<<3-(o-Nitrophenyl)propyl>oxy>-2-methyl-9,10-anthraquinone
  参考文献：
  名称：

  Photochemistry of 1-alkoxy- and 1-(benzyloxy)-9,10-anthraquinones in methanol: A facile process for the preparation of aldehydes and ketones

  摘要：

  The facile production of acid sensitive aldehydes and ketones via photochemical intramolecular delta-hydrogen atom transfer in 1-alkoxy- and 1-(benzyloxy)-9,10-anthraquinones (1) was investigated. Irradiation of 1 in argon purged methanol generates the primary photoproducts, 1-(RCH(OMe)O)-and 1-(ArCH(OMe)O)-9,10-antharahydroquinones (2), respectively. Upon exposure to air, the intermediate anthrahydroquinone is rapidly converted to the corresponding aldehyde and 1-hydroxy-9,10-anthraquinone (3), which can be recycled. Aldehydes containing an acetal or ketal were prepared in high yields using this photoprocess. Apparent rate constants for the photodemethylation of 1-methoxy-2-X-9,10-anthraquinones (X = H, Me, Et, Pr, Bu, i-Bu, and benzyl) were measured and found to vary by a factor of 10 separating the slowest anthraquinone (X = H) and the fastest (X = benzyl), indicating a strong dependency upon the size of the substituent at the a-position. These rate constants are ascribed to equilibrium populations of confonmers in the geometry required for reaction in the n,pi* triplet state.

  DOI：

  10.1021/jo00126a040

文献信息

• Photochemistry of 1-alkoxy- and 1-(benzyloxy)-9,10-anthraquinones in methanol: a .delta.-hydrogen atom abstraction process that exhibits a captodative effect
  作者：Ronald L. Blankespoor、Randall L. De Jong、Robert Dykstra、Daniel A. Hamstra、David B. Rozema、Derek P. VanMeurs、Paul Vink

  DOI：10.1021/ja00009a042

  日期：1991.4

  support a mechanism in which a biradical intermediate is formed by an intramolecular δ-hydrogen atom transfer that occurs in one step but not a reaction pathway in which the hydrogen atom transfer is accomplished in two discrete steps via separate electron and proton transfers. Apparent rate constants for the disappearance of 1-(p-XPhCH 2 O)-2-methyl-9,10-anthraquinone (X=H, Cl, CH 3 , NO 2 , OCH 3 , CF

  各种 1-烷氧基-和 1-（苄氧基）-9,10-蒽醌在甲醇中的光化学已被检查。在没有氧气的情况下，这些反应的主要光产物是 9,10-蒽氢醌，分别在 1 位具有 MeOCH 2 O 和 ArCH(OMe)O 基团。淬火研究人员将激发态的多重性确定为三重态。氘同位素效应、取代基效应和溶剂极性研究支持了一种机制，其中双自由基中间体是通过分子内 δ-氢原子转移形成的，该转移发生在一个步骤中，而不是氢原子转移在两个离散的反应路径中完成的反应途径。通过单独的电子和质子转移步骤。1-(p-XPhCH 2 O)-2-methyl-9,10-anthraquinone (X=H, Cl, CH 3 , NO 2 , OCH 3 , CF 3 , 和CN)被测量并且发现从最大(X=NO 2 )到最小(X=OCH 3 )以3.4的因子变化。Captodative 相互作用解释了这些速率常数的微小差异
• Photodemethylation of methoxy-substituted 9,10-anthraquinones in methanol
  作者：Ronald L. Blankespoor、Richard Hsung、David L. Schutt

  DOI：10.1021/jo00247a052

  日期：1988.6
• BLANKESPOOR, R. L.;HSUNG, R.;SCHUTT, D. L., J. ORG. CHEM., 53,(1988) N 12, 2877-2878
  作者：BLANKESPOOR, R. L.、HSUNG, R.、SCHUTT, D. L.

  DOI：——

  日期：——
• Photochemistry of 1-alkoxy- and 1-(benzyloxy)-9,10-anthraquinones in methanol: A facile process for the preparation of aldehydes and ketones
  作者：Ronald L. Blankespoor、Robert P. Smart、Eric D. Batts、Alan A. Kiste、Rebecca E. Lew、Marc E. Van der Vliet

  DOI：10.1021/jo00126a040

  日期：1995.10

  The facile production of acid sensitive aldehydes and ketones via photochemical intramolecular delta-hydrogen atom transfer in 1-alkoxy- and 1-(benzyloxy)-9,10-anthraquinones (1) was investigated. Irradiation of 1 in argon purged methanol generates the primary photoproducts, 1-(RCH(OMe)O)-and 1-(ArCH(OMe)O)-9,10-antharahydroquinones (2), respectively. Upon exposure to air, the intermediate anthrahydroquinone is rapidly converted to the corresponding aldehyde and 1-hydroxy-9,10-anthraquinone (3), which can be recycled. Aldehydes containing an acetal or ketal were prepared in high yields using this photoprocess. Apparent rate constants for the photodemethylation of 1-methoxy-2-X-9,10-anthraquinones (X = H, Me, Et, Pr, Bu, i-Bu, and benzyl) were measured and found to vary by a factor of 10 separating the slowest anthraquinone (X = H) and the fastest (X = benzyl), indicating a strong dependency upon the size of the substituent at the a-position. These rate constants are ascribed to equilibrium populations of confonmers in the geometry required for reaction in the n,pi* triplet state.