2,2'-Ethylendiimido-diethansulfonsaeure | 25127-57-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: 2,2'-Ethylendiimido-diethansulfonsaeure
• 英文别名: Ethylenediiminobis(ethylenesulfonic acid)；2-[2-(2-sulfoethylamino)ethylamino]ethanesulfonic acid
• CAS: 25127-57-5
• 化学式: C₆H₁₆N₂O₆S₂
• 分子量: 276.335
• InChiKey: ZWIRHXSHSZGHND-UHFFFAOYSA-N

物化性质

• 熔点：
  295-300 °C (decomp)
• 密度：
  1.515±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -7.4
• 重原子数：
  16
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  150
• 氢给体数：
  4
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  1,4-哌嗪二乙磺酸 在 (batho)2Cu^II (batho = 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolinedisulfonate) 、 水 作用下， 反应 24.0h， 生成 草酸醛 、 2,2'-Ethylendiimido-diethansulfonsaeure
  参考文献：
  名称：

  Kinetics and mechanism of aliphatic amine oxidation by aqueous (batho)2CuII

  摘要：

  The kinetics of oxidation of a large series of aliphatic amines by the 'high-potential'' oxidant (batho)2Cu(II) (batho = 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolinedisulfonate) was studied under pseudo-first-order conditions (excess amine) in water or in 30% aqueous methanol (v/v) at 25-degrees-C over the pH range 7-11. The oxidations follow bell-shaped pH-rate profiles, with the low-pH leg reflecting the fact that only the free amine base is subject to oxidation and the high-pH leg representing conversion of (batho)2Cu(II) to an ineffective oxidant at high pH. The latter is thought to be (batho)Cu(II)(OH2)OH on the basis of the observed effect of [batho] on rate at high pH, and curve fitting of the rate data yielded estimates of the unitless K(eq) values governing this conversion. The variation in rate with degree of N-substitution and other structure-reactivity trends (such as the effect of ring size and the non-rate-retarding effect of 2,4,6-trimethyl substitution on PhCH2NR2) support a mechanism involving initial outer-sphere one-electron transfer, followed by proton transfer to the solvent, and then a rapid second one-electron oxidation to give imine/iminium product. Inner-sphere coordination of chelating amines shuts down the redox reaction, presumably as a consequence of displacement of the batho ligand(s) needed for high oxidant strength. Deuterium kinetic isotope effect (DKIE) measurements (i) comparing PhCD2N(CD3)2 vs PhCH2N(CH3)2 (intermolecular DKIE) and (ii) determining N-dealkylation preference in the case of PhCH2N(CH3)CD2Ph (intramolecular DKIE) suggest that the initial electron transfer is mainly rate-limiting. A rate comparison between erythro and three diastereomers of 1,2-diphenyl-2-piperidinoethanol indicates a stereoelectronic preference for one-electron oxidation at nitrogen when held antiperiplanar to a beta-hydroxyl. Stoichiometry studies using an excess of the Cu(II) oxidant reveal regioselective and chemoselective factors governing the overall amine-to-iminium oxidations.

  DOI：

  10.1021/ja00027a032