morpholinium | 45422-42-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 恶嗪烷类
• 英文名称: morpholinium
• 英文别名: morpholine；morpholinium cation；morpholin-1-ium
• CAS: 45422-42-2
• 化学式: C₄H₁₀NO
• 分子量: 88.1295
• InChiKey: YNAVUWVOSKDBBP-UHFFFAOYSA-O

计算性质

• 辛醇/水分配系数(LogP)：
  -0.9
• 重原子数：
  6
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  25.8
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  O-ethyl O'-phenyl thiocarbonate 、 morpholinium 在 potassium chloride 作用下， 以 水 为溶剂， 生成
  参考文献：
  名称：

  Kinetics and Mechanism of the Aminolysis of Phenyl and 4-Nitrophenyl Ethyl Thionocarbonates

  摘要：

  The reactions of the title substrates (PTOC and NPTOC, respectively) with secondary alicyclic amines are subjected to a kinetic study in aqueous solution at 25.0 degrees C, ionic strength 0.2 M (KCI). Under amine excess, pseudo-first-order rate coefficients (k(obsd)) are found throughout. The order in amine is one for the reactions of piperidine but is of intermediate order between 1 and 2 for the reactions of the other amines. The kinetic results can be accommodated by a reaction scheme with two hypothetical tetrahedral intermediates: a zwitterionic (T-+/-) and an anionic (T-) one, whereby amine catalysis (deprotonation of T-+/- to give T-) is kinetically important. Both the pK(a) of T-+/- and the rate coefficient for proton transfer (k(3) ca. 10(10) s(-1) M(-1)) are estimated. The values of the other rate microcoefficients of the scheme are found by a nonlinear least-squares fitting, and these values are compared with those exhibited in the aminolysis of phenyl thionoacetate (PTOA), and S-phenyl and S-(4-nitrophenyl) O-ethyl dithiocarbonates (PDTC and NPDTC, respectively). The Bronsted type plots for amine basicity have slopes beta(N) ca, 0.2 for rate-determining amine attack (k(1)) and beta(N) ca. 0.8 for amine expulsion from T-+/- (k(-1)), in accord with the beta(N) values found in similar aminolyses. The general base catalysis by amine found in the aminolysis of NPTOC, in contrast with the lack of such catalysis in the aminolysis of 4-nitrophenyl methyl carbonate, is explained by a smaller rate coefficient for expulsion of 4-nitrophenoxide (k(2)) from T-+/- (which competes with amine deprotonation of T-+/-) relative to the same expulsion from the analogous oxy intermediate.

  DOI：

  10.1021/jo951726u
• 作为产物：
  描述：

  morpholin-4-yl-methanol 在 水 作用下， 生成 甲烷二醇 、 morpholinium
  参考文献：
  名称：

  Casado, Julia; Mosquera, Manuel; Paz, L. Carlos, Journal of the Chemical Society. Perkin transactions II, 1984, p. 1963 - 1966

  摘要：

  DOI：

文献信息

• Highly sterically hindered carbon acids: the intrinsic reactivity of 5,5′,5″-trimethyl- and 3,3′,3″,5,5′,5″-hexamethyl-2,2′,2″,4,4′,4″-hexanitrotriphenylmethanes
  作者：François Terrier、Lan Xiao、Patrick G. Farrell、Danielle Moskowitz

  DOI：10.1039/p29920001259

  日期：——

  important steric effects are operating in the ionization of 2 and 3. These arise from the accumulation of ortho-nitro groups in the triphenylmethane system which makes the approach of the base reagents from the exocyclic carbon of 2 and 3 very difficult. The finding of extremely low intrinsic reactivities for 2 and 3 and the observation of a much greater catalytic efficiency of primary amines than of

  5,5'，5“-三甲基-和3,3'，3”，5,5'，5“-六甲基-2,2'的可逆去质子化的速率常数（k p B，k – p BH）在H 2 O–Me 2 SO（20：80 ）中测定了伯脂肪族胺，哌啶和吗啉以及苯氧根阴离子和氢氧根阴离子产生的2,2''，4,4'，4''-六硝基三苯基甲烷（2和3））在25°C下。将所得结果与2,2'，2''，4,4'，4''-六硝基三苯基甲烷（1a）的结果进行比较，结果表明，在与硝基相邻的位置引入甲基会显着降低环外的热力学酸性CH基团：ΔP ķa1a 2 = 1.68; ΔP ķ A1A 3 = 6.48。提示这些减少很可能是硝基基团从其连接的芳族平面上扭曲出来的反射，因此降低了共轭碳负离子C-2和C-3的共振稳定性。其他重要的空间效应在2和3的电离中起作用。这些来自三苯基甲烷系统中邻硝基的积累，这使得从2和3的环外碳接近碱性试剂非常困难。发现极低的内在反应
• Bernasconi, Claude F.; Panda, Markandeswar; Stronach, Michael W., Journal of the American Chemical Society, 1995, vol. 117, # 36, p. 9206 - 9212
  作者：Bernasconi, Claude F.、Panda, Markandeswar、Stronach, Michael W.

  DOI：——

  日期：——
• Preparation of Osmium Hydrazido Complexes by Interception of an Osmium(IV) Imido Intermediate
  作者：George M. Coia、Peter S. White、Thomas J. Meyer、David A. Wink、Larry K. Keefer、William M. Davis

  DOI：10.1021/ja00087a081

  日期：1994.4
• Bamkole, Titus O.; Hirst, Jack; Onyido, Ikenna, Journal of the Chemical Society. Perkin transactions II, 1982, p. 889 - 894
  作者：Bamkole, Titus O.、Hirst, Jack、Onyido, Ikenna

  DOI：——

  日期：——
• Kinetics and Mechanism of the Aminolysis of Phenyl and 4-Nitrophenyl Ethyl Thionocarbonates
  作者：Enrique A. Castro、María Cubillos、José G. Santos

  DOI：10.1021/jo951726u

  日期：1996.1.1

  The reactions of the title substrates (PTOC and NPTOC, respectively) with secondary alicyclic amines are subjected to a kinetic study in aqueous solution at 25.0 degrees C, ionic strength 0.2 M (KCI). Under amine excess, pseudo-first-order rate coefficients (k(obsd)) are found throughout. The order in amine is one for the reactions of piperidine but is of intermediate order between 1 and 2 for the reactions of the other amines. The kinetic results can be accommodated by a reaction scheme with two hypothetical tetrahedral intermediates: a zwitterionic (T-+/-) and an anionic (T-) one, whereby amine catalysis (deprotonation of T-+/- to give T-) is kinetically important. Both the pK(a) of T-+/- and the rate coefficient for proton transfer (k(3) ca. 10(10) s(-1) M(-1)) are estimated. The values of the other rate microcoefficients of the scheme are found by a nonlinear least-squares fitting, and these values are compared with those exhibited in the aminolysis of phenyl thionoacetate (PTOA), and S-phenyl and S-(4-nitrophenyl) O-ethyl dithiocarbonates (PDTC and NPDTC, respectively). The Bronsted type plots for amine basicity have slopes beta(N) ca, 0.2 for rate-determining amine attack (k(1)) and beta(N) ca. 0.8 for amine expulsion from T-+/- (k(-1)), in accord with the beta(N) values found in similar aminolyses. The general base catalysis by amine found in the aminolysis of NPTOC, in contrast with the lack of such catalysis in the aminolysis of 4-nitrophenyl methyl carbonate, is explained by a smaller rate coefficient for expulsion of 4-nitrophenoxide (k(2)) from T-+/- (which competes with amine deprotonation of T-+/-) relative to the same expulsion from the analogous oxy intermediate.