1-Benzyl-1,2-dihydro-1,4-naphthalenedicarbonitrile | 83242-05-1

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 1-Benzyl-1,2-dihydro-1,4-naphthalenedicarbonitrile
• 英文别名: 1-benzyl-dihydronaphthalenedicarbonitrile；1-benzyl-1,4-dicyano-1,2-dihydronaphthalene；1-benzyl-2H-naphthalene-1,4-dicarbonitrile
• CAS: 83242-05-1
• 化学式: C₁₉H₁₄N₂
• 分子量: 270.334
• InChiKey: WJJDJUCBRGVULF-UHFFFAOYSA-N

物化性质

• 沸点：
  480.0±45.0 °C(Predicted)
• 密度：
  1.19±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.16
• 拓扑面积：
  47.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-Benzyl-1,2-dihydro-1,4-naphthalenedicarbonitrile 在 氢氧化钾 作用下， 以 乙醇 为溶剂， 反应 1.0h， 以67%的产率得到1-benzyl-4-cyanonaphthalene
  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：

  cis-2-(1,1-Diphenylmethyl)-1,2-dihydro-1,4-naphthalenedicarbonitrile 在 氢氧化钾 作用下， 以 甲醇 、 乙醇 、 乙腈 为溶剂， 反应 3.67h， 生成 1-Benzyl-1,2-dihydro-1,4-naphthalenedicarbonitrile
  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

文献信息

• The Photochemical Reaction between 1,4-Dicyanonaphthalene and benzyl ethers
  作者：Nicola d'Alessandro、Mariella Mella、Elisa Fasani、Lucio Toma、Angelo Albini

  DOI：10.1016/s0040-4020(01)80967-4

  日期：1991.1

  benzyl methyl ether gives the two diastereoisomeric 1-substituted 1,2-dihydronaphthalenes. A stereochemical assignment for these products, and related diastereoisomers pairs is proposed. The reaction occurs via the free radical ions and the low quantum efficiency is due to the slow deprotonation of the radical cation, with only moderate salt effect. In accordance with this scheme, the reaction with benzyl

  辐射1，4-二氰基萘（DCN）和苄基甲基醚得到两种非对映异构体1-取代的1，2-二氢萘。提出了这些产品的立体化学分配，以及相关的非对映异构体对。该反应通过自由基离子发生，并且量子效率低是由于自由基阳离子的缓慢去质子化，仅具有适度的盐效应。按照该方案，与苄基1-薄荷基醚的反应产生低对映体的过程。
• Photochemical reaction between 1,4-naphthalenedicarbonitrile and .alpha.-substituted benzylic derivatives
  作者：Ada Sulpizio、Angelo Albini、Nicola D'Alessandro、Elisa Fasani、Silvio Pietra

  DOI：10.1021/ja00197a041

  日期：1989.7

  Obtention de methano-5,11 dibenzo [a,e] cyclooctenes et d'arylmethyl-2 et -1 dihydro-1,2 naphtalenedicarbonitriles et -carbonitriles

  获得 methano-5,11 dibenzo [a,e] cyclooctenes et d'arylmethyl-2 et -1 dihydro-1,2naphtalenedicarbonitriles et -carbonitriles
• Photoarylmethylation of 1,4-Dicyanonaphthalene by Use of Group 14 Organometallic Compounds
  作者：Kazuhiko Mizuno、Kiyotaro Terasaka、Masahiro Yasueda、Yoshio Otsuji

  DOI：10.1246/cl.1988.145

  日期：1988.1.5

  germane, and stannane in polar solvents gave the arylmethylated products of DCN in high yields. The fluorescence of DCN was efficiently quenched both in polar and nonpolar solvents by these group 14 organometallic compounds. In cyclohexane, the emission from the exciplex between DCN and arylmethylsilanes was observed. The mechanistic features of the photoreaction are described.

  1,4-二氰基萘 (DCN) 与芳甲基硅烷、锗烷和锡烷在极性溶剂中的光反应以高产率得到了 DCN 的芳甲基化产物。DCN 的荧光在极性和非极性溶剂中都被这些第 14 族有机金属化合物有效淬灭。在环己烷中，观察到 DCN 和芳甲基硅烷之间的激基复合物的发射。描述了光反应的机械特征。
• Photoinduced Electron-Transfer Reactions of Arylmethyl-Substituted 14 Group Compounds: Photoarylmethylation and Photooxygenation
  作者：Toshiyuki Tamai、Kazuhiko Mizuno、Isao Hashida、Yoshio Otsuji

  DOI：10.1246/bcsj.66.3747

  日期：1993.12

  oxygenation of the arylmethyl organometallic compounds occurred in the photoreaction under oxygen atmosphere. Key intermediates in these reactions in acetonitrile were radical ions which were generated via photoinduced electron transfer from the arylmethyl organometallic compounds to the excited singlet of DCN or DCA. The cleavage of the carbon–metal bond of the radical cations of the arylmethyl compounds

  在各种条件下研究了芳基甲基硅烷、-锗烷和-锡烷与 1,4-二氰基萘 (DCN) 和 9,10-二氰基蒽 (DCA) 的光反应。DCN和DCA的芳甲基化发生在氮气气氛下的光反应中，而芳甲基有机金属化合物的氧化发生在氧气气氛下的光反应中。乙腈中这些反应的关键中间体是自由基离子，它们是通过光诱导电子从芳甲基有机金属化合物转移到 DCN 或 DCA 的激发单线态而产生的。芳甲基化合物自由基阳离子的碳-金属键断裂导致芳甲基自由基的形成。然后自由基与 DCN 和 DCA 的自由基阴离子反应生成芳甲基化化合物或与氧反应生成含氧化合物。光反应的效率受溶剂和添加到反应系统中的材料的影响。在光反应...
• 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。