1-(Hydroxymethyl)-1,2-dihydro-1,4-naphthalenedicarbonitrile | 154463-61-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 1-(Hydroxymethyl)-1,2-dihydro-1,4-naphthalenedicarbonitrile
• 英文别名: 1-(hydroxymethyl)-dihydronaphthalenedicarbonitrile；1-(hydroxymethyl)-2H-naphthalene-1,4-dicarbonitrile
• CAS: 154463-61-3
• 化学式: C₁₃H₁₀N₂O
• 分子量: 210.235
• InChiKey: YIWLEMZHZBZIMF-UHFFFAOYSA-N

物化性质

• 沸点：
  439.5±45.0 °C(Predicted)
• 密度：
  1.27±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  67.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-(Hydroxymethyl)-1,2-dihydro-1,4-naphthalenedicarbonitrile 在 氢氧化钾 作用下， 以 乙醇 为溶剂， 反应 3.0h， 以58%的产率得到4-(羟基甲基)萘-1-甲腈
  参考文献：
  名称：

  SET Photochemical Reactions between 1,4-Naphthalenedicarbonitrile and Benzylic Donors. Medium Effects

  摘要：

  The electron transfer induced photochemical reactions of 1,4-naphthalenedicarbonitrile (NDN) with toluene (1a), diphenylmethane (1b), p-methoxytoluene (1c), and benzyltrimethylsilane (1d) in MeOH-MeCN and 0.1 M KOH-MeOH-MeCN were examined. The results were compared with those of reactions occurring in neat MeCN. Under the former conditions, the cation radical derived from 1a undergoes deprotonation after diffusion from (rather than within) the geminate ion pair (as in MeCN). The formed benzyl radical abstracts a hydrogen from MeOH leading to hydroxymethylation of NDN competitively with its benzylation. Under basic conditions MeO(-) adds to 1a(+.) yielding 1c. The reaction of 1b in MeOH-MeCN and 0.1 M KOH-MeOH-MeCN is similar to that of 1a. However, in the reaction of 1c under these conditions, the arene cation radical undergoes deprotonation out of cage. Finally, desilylation of the cation radical from 1d is a fast process occurring from the geminate pair in all the media explored.

  DOI：

  10.1021/jo00083a025
• 作为产物：
  描述：

  甲醇 、 萘-1,4-二腈 、 甲苯 以 乙腈 为溶剂， 反应 3.0h， 以30%的产率得到1-(Hydroxymethyl)-1,2-dihydro-1,4-naphthalenedicarbonitrile
  参考文献：
  名称：

  用萘-1,4-二腈光敏化从甲苯中得到苄基自由基——不饱和化合物的苄基化和羟甲基化

  摘要：

  在非质子介质中，光诱导电子从甲苯转移到 1,4-萘二甲腈 (DCN) 之后是笼内质子转移和自由基偶联。然而，在质子共溶剂的存在下，自由基离子扩散出笼子，并且甲苯自由基阳离子从游离溶剂化物质中发生去质子化。使用 tBuOH，这会通过苄基自由基与 DCN-· 的偶联导致 DCN 的还原性苄基化。使用 MeOH，PhCH2· 二次夺氢产生羟甲基自由基，其与 DCN-· 偶联。苄基和羟甲基自由基都被亲电烯烃有效捕获。因此，在马来酸二甲酯存在下，底物的 DCN 光敏化苄基化（或羟甲基化）是通过直接激活 C-H 键而发生的。

  DOI：

  10.1002/(sici)1099-0690(199909)1999:9<2137::aid-ejoc2137>3.0.co;2-r

文献信息

• SET Photochemical Reactions between 1,4-Naphthalenedicarbonitrile and Benzylic Donors. Medium Effects
  作者：E. Fasani、N. d'Alessandro、A. Albini、P. S. Mariano

  DOI：10.1021/jo00083a025

  日期：1994.2

  The electron transfer induced photochemical reactions of 1,4-naphthalenedicarbonitrile (NDN) with toluene (1a), diphenylmethane (1b), p-methoxytoluene (1c), and benzyltrimethylsilane (1d) in MeOH-MeCN and 0.1 M KOH-MeOH-MeCN were examined. The results were compared with those of reactions occurring in neat MeCN. Under the former conditions, the cation radical derived from 1a undergoes deprotonation after diffusion from (rather than within) the geminate ion pair (as in MeCN). The formed benzyl radical abstracts a hydrogen from MeOH leading to hydroxymethylation of NDN competitively with its benzylation. Under basic conditions MeO(-) adds to 1a(+.) yielding 1c. The reaction of 1b in MeOH-MeCN and 0.1 M KOH-MeOH-MeCN is similar to that of 1a. However, in the reaction of 1c under these conditions, the arene cation radical undergoes deprotonation out of cage. Finally, desilylation of the cation radical from 1d is a fast process occurring from the geminate pair in all the media explored.
• Benzyl Radicals from Toluene by Photosensitization with Naphthalene-1,4-dicarbonitrile – Benzylation and Hydroxymethylation of Unsaturated Compounds
  作者：Mariella Mella、Maurizio Fagnoni、Angelo Albini

  DOI：10.1002/(sici)1099-0690(199909)1999:9<2137::aid-ejoc2137>3.0.co;2-r

  日期：1999.9

  transfer from toluene to 1,4-naphthalenedicarbonitrile (DCN) is followed by in-cage proton transfer and radical coupling. However, in the presence of a protic co-solvent, the radical ions diffuse out of the cage and deprotonation of the toluene radical cation takes place from the free solvated species. With tBuOH, this results in reductive benzylation of DCN through coupling of benzyl radicals with DCN–·

  在非质子介质中，光诱导电子从甲苯转移到 1,4-萘二甲腈 (DCN) 之后是笼内质子转移和自由基偶联。然而，在质子共溶剂的存在下，自由基离子扩散出笼子，并且甲苯自由基阳离子从游离溶剂化物质中发生去质子化。使用 tBuOH，这会通过苄基自由基与 DCN-· 的偶联导致 DCN 的还原性苄基化。使用 MeOH，PhCH2· 二次夺氢产生羟甲基自由基，其与 DCN-· 偶联。苄基和羟甲基自由基都被亲电烯烃有效捕获。因此，在马来酸二甲酯存在下，底物的 DCN 光敏化苄基化（或羟甲基化）是通过直接激活 C-H 键而发生的。