(E)-(N-Nitrosoisopropylamino)methyl acetate | 70715-91-2

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (E)-(N-Nitrosoisopropylamino)methyl acetate
• 英文别名: Acetic acid, (isopropylnitrosoamino)methyl ester；[nitroso(propan-2-yl)amino]methyl acetate
• CAS: 70715-91-2
• 化学式: C₆H₁₂N₂O₃
• 分子量: 160.173
• InChiKey: AYYKWRQRJMXEHP-UHFFFAOYSA-N

物化性质

• 沸点：
  286.06°C (rough estimate)
• 密度：
  1.2751 (rough estimate)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  59
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  1,3,5-三异丙基六氢-1,3,5-三嗪 、 溶剂黄146 在 nitrosonium tetrafluoroborate 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成 (E)-(N-Nitrosoisopropylamino)methyl acetate 、 (E)-(N-Nitrosoisopropylamino)methyl acetate
  参考文献：
  名称：

  Reexamination of the Mechanisms of Decomposition of Simple .alpha.-Acetoxynitrosamines in the Physiological pH Range

  摘要：

  Rate constants, k(0), for the buffer independent decay of eight alpha-(acyloxy)nitrosamines were determined in aqueous media, 25 degrees C, ionic strength 1 M (NaClO4), 1% (v/v) in acetonitrile in the pH range 2-13. The pH-rate profile of log k(0) against pH, from pH 2 to 13, indicates a rate law that includes two terms: k(1), a pH independent term, and k(OH), a hydroxide ion dependent term. Values of the entropy of activation for the pH independent reactions of 1-(N-nitrosoethylamino)ethyl acetate (3), (N-nitrosomethylamino)methyl acetate (1), and (N-nitrosobutylamino)methyl acetate (9) are determined to be Delta S-double dagger = 0.7 (+/-1.5), 3 (+/-3), and -5 (+/-3) cal deg(-1) mol(-1), respectively. (N-Nitrosobutylamino)methyl benzoate (11) and (N-nitrosobutylamino)methyl pivaloate (12) decompose with pH independent rate constants that are larger than that of the corresponding acetate 9 by factors of 2.3 and 3.4, respectively. The value of rho(*) for allkyl substituents attached to nitrogen; not containing the acetoxy group, is rho(*) = -5.99 for four methyl acetates. It is concluded that the pH independent decomposition involves the formation of N-nitrosiminium ion intermediates. The greater reactivity of the benzoate and pivaloate, compared to the acetate, in the case of (N-nitrosobutylamino)methyl esters, combined with the product analysis previously reported for the reaction of the ethyl acetates indicates no measurable anchimeric assistance in the decay of the Z forms of the alpha-(acyloxy)nitrosamines studied in the present report. The value of rho(*) for the pH independent decay of the ethyl acetates is rho(*) = -1.50. The smaller value, in comparison to that for the methyl acetates, is ascribed either to a change in transition structure or to a difference, between methyl and ethyl acetates, in the nature of the rate-limiting step of the reactions. The rate constants, k(OH), for the hydroxide ion-catalyzed decay of (N-nitrosobutylamino)methyl benzoate (11) and (N-nitrosobutylamino)methyl pivaloate (12) are smaller than that for the corresponding acetate 9 by factors of 7 and 16, respectively. This observation is consistent with the deduction of others that the mechanism of this reaction involves a rate-limiting reaction at the carbonyl group.

  DOI：

  10.1021/jo00129a011

文献信息

• MUELLER, E.;KETTLER, R.;WIESSLER, M., LIEBIGS ANN. CHEM., 1984, N 8, 1468-1493
  作者：MUELLER, E.、KETTLER, R.、WIESSLER, M.

  DOI：——

  日期：——
• MOCHIZUKI MASATAKA; ANJO TAKAKO; OKADA MASASHI, CHEM. AND PHARM. BULL., 1978, 26, NO 12, 3905-3908
  作者：MOCHIZUKI MASATAKA、 ANJO TAKAKO、 OKADA MASASHI

  DOI：——

  日期：——
• Reexamination of the Mechanisms of Decomposition of Simple .alpha.-Acetoxynitrosamines in the Physiological pH Range
  作者：Cynthia Revis、Markku Rajamaki、James C. Fishbein

  DOI：10.1021/jo00129a011

  日期：1995.12

  Rate constants, k(0), for the buffer independent decay of eight alpha-(acyloxy)nitrosamines were determined in aqueous media, 25 degrees C, ionic strength 1 M (NaClO4), 1% (v/v) in acetonitrile in the pH range 2-13. The pH-rate profile of log k(0) against pH, from pH 2 to 13, indicates a rate law that includes two terms: k(1), a pH independent term, and k(OH), a hydroxide ion dependent term. Values of the entropy of activation for the pH independent reactions of 1-(N-nitrosoethylamino)ethyl acetate (3), (N-nitrosomethylamino)methyl acetate (1), and (N-nitrosobutylamino)methyl acetate (9) are determined to be Delta S-double dagger = 0.7 (+/-1.5), 3 (+/-3), and -5 (+/-3) cal deg(-1) mol(-1), respectively. (N-Nitrosobutylamino)methyl benzoate (11) and (N-nitrosobutylamino)methyl pivaloate (12) decompose with pH independent rate constants that are larger than that of the corresponding acetate 9 by factors of 2.3 and 3.4, respectively. The value of rho(*) for allkyl substituents attached to nitrogen; not containing the acetoxy group, is rho(*) = -5.99 for four methyl acetates. It is concluded that the pH independent decomposition involves the formation of N-nitrosiminium ion intermediates. The greater reactivity of the benzoate and pivaloate, compared to the acetate, in the case of (N-nitrosobutylamino)methyl esters, combined with the product analysis previously reported for the reaction of the ethyl acetates indicates no measurable anchimeric assistance in the decay of the Z forms of the alpha-(acyloxy)nitrosamines studied in the present report. The value of rho(*) for the pH independent decay of the ethyl acetates is rho(*) = -1.50. The smaller value, in comparison to that for the methyl acetates, is ascribed either to a change in transition structure or to a difference, between methyl and ethyl acetates, in the nature of the rate-limiting step of the reactions. The rate constants, k(OH), for the hydroxide ion-catalyzed decay of (N-nitrosobutylamino)methyl benzoate (11) and (N-nitrosobutylamino)methyl pivaloate (12) are smaller than that for the corresponding acetate 9 by factors of 7 and 16, respectively. This observation is consistent with the deduction of others that the mechanism of this reaction involves a rate-limiting reaction at the carbonyl group.