(1S)-3endo-deuterio-norbornan-2-one | 18139-04-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S)-3endo-deuterio-norbornan-2-one
• 英文别名: (1S)-3exo-deuterio-norbornan-2-one；2-norbornanone-3-exo-d；3-exo-deuterionorcamphor；exo-<3-D>Bicyclo<2.2.1>heptan-2-one；exo-3-deuterionorcamphor；exo-3-deuteriobicyclo<2.2.1>heptan-2-one；exo-3-D-norbanan-2-one
• CAS: 18139-04-3；18139-05-4；103773-30-4；103773-33-7；120442-25-3；120442-26-4
• 化学式: C₇H₁₀O
• 分子量: 111.148
• InChiKey: KPMKEVXVVHNIEY-NNHTVELRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.38
• 重原子数：
  8.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (1S)-3endo-deuterio-norbornan-2-one 在 2,6-二甲基吡啶 、 sodium acetate 、 溶剂黄146 作用下， 以 乙醚 为溶剂， 反应 6.58h， 生成 N,N-dimethylbicyclo[2.2.1]hept-2-ene-2-carbothioamide
  参考文献：
  名称：

  Solvolytic elimination reactions of tertiary .alpha.-CSNMe2-substituted systems

  摘要：

  The tertiary benzylic alpha-CSNMe2-substituted p-nitrobenzoates and trifluoroacetates of general structure Ar(CH3)C(CSNMe2)(OCOR), 7 and 8, solvolyze to give exclusively elimination products H2C = C(CSNMe2)Ar. A Hammett study gave a nonlinear correlation. Variation in rate with solvent ionizing power was small for the unsubstituted trifluoroacetate derivative of 8, and the beta-CD3 isotope effect on rate was negligible. There is, however, a large isotope effect (2.5-2.8) in formation of the elimination product when Ph(CH2D)C(CSNMe2)(OCOCF3) solvolyzes. It is concluded that an intermediate must be involved since the product-determining step and the rate-determining step have differing isotope effects. The likely intermediate is an alpha-CSNMe2-substituted cation (as an ion pair), despite the fact that the reaction has few characteristics of a typical E1 reaction. Tertiary norbornyl, cyclohexyl, and 2-propyl alpha-CSNMe2-substituted systems also react to give exclusively elimination products at rates far in excess of alpha-CONMe2 analogues. It is suggested that alpha-CSNMe2 cations are also intermediates and that these cations undergo proton loss at an early ion pair stage. These cations are proposed to derive substantial stabilization by charge delocalization onto sulfur of the thiocarbonyl group. By way of contrast, the secondary system CH3CH(CSNMe2)(OCOCF3), 25, solvolyzes to give mainly a rearranged product CH3CH(CONMe2)(SCOCH3) via a k(DELTA) mechanism involving neighboring thiocarbonyl participation leading to a cyclized ion.

  DOI：

  10.1021/jo00032a051
• 作为产物：
  描述：

  3-二环[2.2.1]庚-2-烯氧基(三甲基)硅烷 在 氘代甲醇-d 、 三氟乙酸 作用下， 反应 3.5h， 以81%的产率得到(1S)-3endo-deuterio-norbornan-2-one
  参考文献：
  名称：

  Solvolytic elimination reactions of tertiary .alpha.-CSNMe2-substituted systems

  摘要：

  The tertiary benzylic alpha-CSNMe2-substituted p-nitrobenzoates and trifluoroacetates of general structure Ar(CH3)C(CSNMe2)(OCOR), 7 and 8, solvolyze to give exclusively elimination products H2C = C(CSNMe2)Ar. A Hammett study gave a nonlinear correlation. Variation in rate with solvent ionizing power was small for the unsubstituted trifluoroacetate derivative of 8, and the beta-CD3 isotope effect on rate was negligible. There is, however, a large isotope effect (2.5-2.8) in formation of the elimination product when Ph(CH2D)C(CSNMe2)(OCOCF3) solvolyzes. It is concluded that an intermediate must be involved since the product-determining step and the rate-determining step have differing isotope effects. The likely intermediate is an alpha-CSNMe2-substituted cation (as an ion pair), despite the fact that the reaction has few characteristics of a typical E1 reaction. Tertiary norbornyl, cyclohexyl, and 2-propyl alpha-CSNMe2-substituted systems also react to give exclusively elimination products at rates far in excess of alpha-CONMe2 analogues. It is suggested that alpha-CSNMe2 cations are also intermediates and that these cations undergo proton loss at an early ion pair stage. These cations are proposed to derive substantial stabilization by charge delocalization onto sulfur of the thiocarbonyl group. By way of contrast, the secondary system CH3CH(CSNMe2)(OCOCF3), 25, solvolyzes to give mainly a rearranged product CH3CH(CONMe2)(SCOCH3) via a k(DELTA) mechanism involving neighboring thiocarbonyl participation leading to a cyclized ion.

  DOI：

  10.1021/jo00032a051

文献信息

• Deuterium isotope effects on the carbon-13 chemical shifts in 2-substituted 2-norbornyl cations
  作者：Kenneth L. Servis、Robert L. Domenick、David A. Forsyth、Yi Pan

  DOI：10.1021/ja00258a003

  日期：1987.11

  Deuterium isotope effects on /sup 13/C chemical shifts have been examined as a function of location of deuterium in the C/sub 3/-exo or C/sub 3/-endo positions and as a function of increasing electron demand in the series 2-norbornanone, 2-aryl-2-nonbornyl cations, and 2-methyl-2-norbornyl cation. Comparison with isotope shifts in 2-aryl-2-propyl cations demonstrates a change in the type of response

  已检查氘同位素对 /sup 13/C 化学位移的影响，作为氘在 C/sub 3/-exo 或 C/sub 3/-endo 位置的函数以及系列中电子需求增加的函数2-降冰片酮、2-芳基-2-壬基阳离子和2-甲基-2-降冰片基阳离子。与 2-芳基-2-丙基阳离子中同位素位移的比较表明，随着电子需求的增加，对 2-芳基-2-降冰片基阳离子中同位素扰动的响应类型发生了变化。随着电子需求的增加，结果与 sigma 桥接的开始一致。在阳离子中心观察到的同位素位移被认为是由于西格玛框架的扰动（感应型扰动）引起的小高场位移的贡献，由于超共轭的扰动引起的低场位移，以及来自三中心双电子键合扰动的潜在大的高场偏移。由于同位素效应的振动起源，NMR 同位素位移可能是西格玛桥联的特别敏感的探针。
• Sigmatropic Rearrangement-Based Synthesis of 4-Alkenyl-1,3-dithiol-2-ones
  作者：Pavels Ostrovskis、Andrey A. Mikhaylov、Samir Z. Zard

  DOI：10.1021/acs.orglett.9b01157

  日期：2019.5.17

  have been prepared by microwave-assisted rearrangement of S-(4-acyloxy-2-alkynyl)-O-ethyl xanthates in moderate to good yields. The synthetic approach is based on a combination of [3,3] and [1,5] sigmatropic rearrangements as well as the intermediacy of a reactive betaine that induces the ionic elimination of the acyloxy group. The [1,5] sigmatropic rearrangement was confirmed by a deuterium-labeling

  通过以中等至良好的产率通过微波辅助重排S-（4-酰氧基-2-炔基）-O-乙基黄原酸酯，制备了一系列共轭的4-链烯基-1，3-二硫醇-2-酮。合成方法是基于[3,3]和[1,5]σ重排以及反应性甜菜碱的中间性，该反应性甜菜碱可引起离子性酰氧基的消除。[1,5]σ重排是通过氘标记实验确定的。
• Base-promoted 1,2-eliminations from endo-2-bicyclo[2.2.1]heptyl halides and arenesulfonates
  作者：Richard A. Bartsch、Jong Gun Lee

  DOI：10.1021/jo00305a021

  日期：1990.8
• Werstiuk, Nick Henry; Banerjee, Sujit, Canadian Journal of Chemistry, 1985, vol. 63, p. 534 - 541
  作者：Werstiuk, Nick Henry、Banerjee, Sujit

  DOI：——

  日期：——