syn-7-chloro-2-norbornanone

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: syn-7-chloro-2-norbornanone
• 英文别名: anti-7-Chlornorcamphor；syn-7-Chlorbicyclo<2.2.1>heptan-2-on；(+/-)-7syn-chloro-norbornan-2-one；(+/-)-7syn-Chlor-norbornan-2-on；(1R,4S,7R)-7-chlorobicyclo[2.2.1]heptan-2-one
• 化学式: C₇H₉ClO
• 分子量: 144.601
• InChiKey: YLRMBQJKJLCKDO-HBPOCXIASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  syn-7-chloro-2-norbornanone 在 hydroxylamine-O-sulfonic acid 作用下， 以 溶剂黄146 为溶剂， 反应 2.0h， 以49%的产率得到(1S,5S,8R)-8-Chloro-2-aza-bicyclo[3.2.1]octan-3-one
  参考文献：
  名称：

  Regioselective Functionalization. 6.¹ Migratory Preferences in Hydroxylamine-O-sulfonic Acid and Schmidt Rearrangements of 7-Substituted Norcamphors

  摘要：

  Hydroxylamine-O-sulfonic acid reacted with syn-7-X- and anti-7-Y-substituted norcamphor derivatives [X = H, OMe, Cl, Br, OTos; Y = H, COOMe, Cl, Br, Tos, COOMe(5-exo-Br)], to give solely bridgehead migrated 2-azalactams, except for minor amounts of methylene migrated S-azalactams from norcamphor (1) and the syn-7-Br ketone 19. Schmidt reactions of the same ketones provided varying mixtures of methylene and bridgehead migrated lactams, except for norcamphor (1) and anti-7-Br ketone 31, which provided solely 3-azalactams. Significant ratios (> 0.4) of bridgehead migration to cleavage products were observed in the Schmidt reactions only with 7-OTos ketones 22 and 24 with exo-5-bromo-anti-7-methoxycarbonyl ketone 37. The Schmidt rearrangements most likely involve iminodiazonium ion intermediates in light-of the large amounts of cleavage observed relative to lactam formation and the insensitivity of methylene migration to the substituent size in the reactions of syn-7-substituted norcamphors.

  DOI：

  10.1021/jo960604e
• 作为产物：
  描述：

  双环[2.2.1]庚-1-烯 在 水 、 硝酸 、 次氯酸 作用下， 生成 syn-7-chloro-2-norbornanone
  参考文献：
  名称：

  降冰片烷（双环[2.2.1]庚烷）的一些氯衍生物

  摘要：

  内顺式和反式 5,6-二氯降冰片烯是通过将顺式和反式二氯乙烯分别加入环戊二烯来制备的。通过偶极矩研究证实了立体化学分配。顺式二氯化物对水解呈惰性，而反式异构体水解为 3,5-二羟基降三环烯。二氯化物异构体的氢化得到内-顺-和反-2,3-二氯降冰片烷。与基于卤化氢优先反式消除的预期相反，饱和的顺式二氯化物似乎比反式异构体更不容易脱卤化氢，尽管在两种情况下反应都很慢。两种异构体产生相同的脱卤化氢产物，2-氯降冰片烯，其结构通过氧化为顺式-环戊烷-1,3-二羧酸和水解为降樟脑而得到证实。降冰片烯在 - 75o 下氯化得到降三环基氯和 syn-7-exo-2-dichloronorbornane。由于化合物对脱卤化氢试剂的相对惰性，后者的结构被指定（优先于外-顺-2,3-二氯降冰片烷）。内-顺-2,3-二氯降冰片烷不容易水解，但反式-2,3-二氯降冰片烷和syn-7-exo-2-二氯降冰片烷分别水

  DOI：

  10.1021/ja01651a027

文献信息

• Nash, John J.; Carlson, Dean V.; Kasper, Annette M., Journal of the American Chemical Society, 1993, vol. 115, # 20, p. 8969 - 8979
  作者：Nash, John J.、Carlson, Dean V.、Kasper, Annette M.、Love, Dan E.、Jordan, Kenneth D.、Morrison, Harry

  DOI：——

  日期：——
• Notes - Bromination Rate of Some Norcamphor Derivatives
  作者：William Woods、John Roberts

  DOI：10.1021/jo01360a618

  日期：1957.9
• Solvolytic behavior of the four epimeric 7-chloro-2-hydroxybicyclo[2.2.1]heptane p-toluenesulfonates
  作者：Paul G. Gassman、Joseph M. Hornback

  DOI：10.1021/ja00775a024

  日期：1972.10
• Ionic reactions in bicyclic systems. VIII. Acetolysis of syn- and anti-7-chloro-exo-norbornyl p-toluenesulfonates
  作者：Harlan L. Goering、Michael J. Dagani

  DOI：10.1021/ja01044a033

  日期：1969.7
• Regioselective Functionalization. 6.¹ Migratory Preferences in Hydroxylamine-<i>O</i>-sulfonic Acid and Schmidt Rearrangements of 7-Substituted Norcamphors
  作者：Grant R. Krow、Osbert H. Cheung、Zilun Hu、Yoon B. Lee

  DOI：10.1021/jo960604e

  日期：1996.1.1

  Hydroxylamine-O-sulfonic acid reacted with syn-7-X- and anti-7-Y-substituted norcamphor derivatives [X = H, OMe, Cl, Br, OTos; Y = H, COOMe, Cl, Br, Tos, COOMe(5-exo-Br)], to give solely bridgehead migrated 2-azalactams, except for minor amounts of methylene migrated S-azalactams from norcamphor (1) and the syn-7-Br ketone 19. Schmidt reactions of the same ketones provided varying mixtures of methylene and bridgehead migrated lactams, except for norcamphor (1) and anti-7-Br ketone 31, which provided solely 3-azalactams. Significant ratios (> 0.4) of bridgehead migration to cleavage products were observed in the Schmidt reactions only with 7-OTos ketones 22 and 24 with exo-5-bromo-anti-7-methoxycarbonyl ketone 37. The Schmidt rearrangements most likely involve iminodiazonium ion intermediates in light-of the large amounts of cleavage observed relative to lactam formation and the insensitivity of methylene migration to the substituent size in the reactions of syn-7-substituted norcamphors.