1-(2-chloroethyl)-3-methyl-3-carbethoxytriazene | 113274-29-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机碳酸及其衍生物
• 英文名称: 1-(2-chloroethyl)-3-methyl-3-carbethoxytriazene
• 英文别名: 1-(2-Chloroethyl)-3-methyl-3-carbetoxytriazene；1-(2-chloroethyl)-3-methyl-3-carbethoytriazene
• CAS: 113274-29-6
• 化学式: C₆H₁₂ClN₃O₂
• 分子量: 193.633
• InChiKey: USWACFKAYKLOCN-CMDGGOBGSA-N

物化性质

• 沸点：
  60-62 °C(Press: 0.003 Torr)
• 密度：
  1.20±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.68
• 重原子数：
  12.0
• 可旋转键数：
  4.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  54.26
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  1-(2-chloroethyl)-3-methyl-3-carbethoxytriazene 在 异丙胺 作用下， 反应 12.0h， 生成 1-Vinyl-3-methyltriazene 、 1-Vinyl-3-methyl-3-carbethoxytriazene
  参考文献：
  名称：

  The Base-Promoted Dehydrohalogenation of 1-(2-Chloroethyl)-3-alkyl-3-acyltriazenes

  摘要：

  DOI：

  10.1021/jo00119a049
• 作为产物：
  描述：

  3-carbethoxy--2-(hydroxyethyl)-3-methyltriazene 、 四氯化碳 以58%的产率得到
  参考文献：
  名称：

  SMITH, RICHARD H. , JR.;MEHL, ANDREW F.;SHANTZ, DONALD L. , JR.;CHMURNY, +, J. ORG. CHEM., 53,(1988) N 7, 1467-1471

  摘要：

  DOI：

文献信息

• Specificity of DNA Alkylation by 1-(2-Chloroethyl)-3-alkyl-3-acyltriazenes Depends on the Structure of the Acyl Group:  Kinetic and Product Studies
  作者：Marilyn B. Kroeger Smith、Brigitte F. Schmidt、Grzegorz Czerwinski、Lisa A. Taneyhill、Emily J. Snyder、Adam M. Kline、Christopher J. Michejda、Richard H. Smith

  DOI：10.1021/tx950155y

  日期：1996.1.1

  principal reaction product. In the absence of esterase, the order of DNA alkylation for all of the acyltriazenes did not correlate with their respective rates of decomposition, leading to the conclusion that the triazenes did not decompose by the expected mode of uncatalyzed N(2)-N(3) heterolyic cleavage. The major DNA alkylation product from the N(3)-methyltriazenes was 7-methylguanine, instead of the expected

  单独研究了小牛胸腺DNA与十个具有不同酰基侧链结构的1-（2-氯乙基）-3-烷基-3-酰基苯甲酰氮的反应，或在pH 7.0磷酸盐缓冲液中在猪肝酯酶存在下的反应。在几种关键的三氮烯中，酰基取代基包含一个游离的羧酸基团。在反应混合物中存在酯酶的情况下，所得的DNA烷基化水平可能与三氮烯分解的动力学速率相关。在这些条件下，主要的分解途径涉及母体三氮烯的脱酰作用并最终产生链烷重氮离子。该中间体随后将DNA-鸟嘌呤烷基化，得到7-烷基鸟嘌呤作为主要反应产物。在没有酯酶的情况下，DNA烷基化的顺序对所有的acyltriazenes都不与它们各自的分解速率相关，从而得出结论，三氮烯不会被未催化的N（2）-N（3）杂多裂解的预期模式分解。N（3）-甲基三氮烯的主要DNA烷基化产物是7-甲基鸟嘌呤，而不是预期的7-（氯乙基）-和7-（羟乙基）鸟嘌呤，这表明酰基正在被水解。但是，与预测相反，在该位置具有N（3
• Base Sequence Selectivity in the Alkylation of DNA by 1,3-Dialkyl-3-acyltriazenes
  作者：Marilyn B. Kroeger Smith、Lisa A. Taneyhill、Christopher J. Michejda、Richard H. Smith

  DOI：10.1021/tx9500742

  日期：1996.1.1

  The base sequence selectivity of DNA alkylation for a series of structurally related 1,3-dialkyl-3-acyltriazenes was examined with calf thymus DNA or polymers containing the sequences GGG, CGC, TGT, and AGA. The reaction products at the N7 and the O-6 positions of guanine were identified, quantitated, and then correlated with the decomposition rates of the triazenes, 1-(2-chloroethyl)-3-methyl-3-carbethoxy-(CMC), 1-(2-chloroethyl)-3-methyl-3-acetyl-(CMA), 1-(2-hydroxyethyl)-3-methyl-3-carbethoxy-(HMC), 1-(2-hydroxyethyl)-3-methyl-3-acetyl-(HMA), and 1,3-dimethyl-3-acetyl- (DMA). The results of these studies revealed that DNA sequences with runs of purines were more reactive toward alkylation by all of the triazenes tested, irrespective of whether the alkylation was measured by N7, O-6, or total guanine adducts. Within this generalization, the (hydroxyethyl)triazenes showed a preference for the AGA sequence, while the (chloroethyl)triazenes favored the GGG sequence. The structure of the 3-acyl group of the triazene also played a role in the extent of alkylation of a particular sequence of DNA. Both the (chloroethyl)- and the (hydroxyethyl)triazenes produced higher alkylation product yields for the 3-carbethoxytriazenes as compared with the 3-acetyl derivatives for most of the sequences examined. These overall patterns correlated well with the order of decomposition of the triazenes at 37 degrees C: HMC > DMA > HMA > CMC > CMA. This study has demonstrated how varying the structure of 1,3-dialkyl-3-acyltriazenes can modulate DNA alkylation, a finding which may be important in the design of new triazene antitumor agents.
• Novel triazenes and triazolines from the base-catalyzed hydrolysis of 1,3-dialkyl-3-acyltriazenes
  作者：Richard H. Smith、Brian D. Wladkowski、Julie A. Herling、Timothy D. Pfaltzgraff、Jesse E. Taylor、Erin J. Thompson、Brunon Pruski、John R. Klose、Christopher J. Michejda

  DOI：10.1021/jo00050a016

  日期：1992.11

  The products and mechanism of hydrolytic decomposition of a series of 1,3-dialkyl-3-acyltriazenes were studied in alkaline buffers. In general the mechanism of decomposition involves deacylation leading to the formation of the parent 1,3-dialkyltriazene. The solvent deuterium isotope effect (k(H2O)/k(D2O)) is less than 1.0, indicating specific base catalysis. A plausible mechanistic explanation is rapid reversible attack by hydroxide ion, followed by rate-limiting heterolysis of the N(l)-acyl bond. The resultant, 1,3-dialkyltriazene is somewhat unstable under the reaction conditions and undergoes subsequent hydrolysis, a reaction previously shown to be specific acid-catalyzed. When the N(l) alkyl group is 2-chloroethyl, unusual products are obtained. For the 3-acetyl and 3-carbethoxy derivatives, the initial deacylation product, 1-(2-chloroethyl)-3-methyltriazene, efficiently cyclizes to form 1-methyltriazoline. The 3-(methylcarbamoyl) derivative does not deacylate, but instead undergoes dehydrohalogenation to 1-vinyl-3-methyl-3-(methylcarbamoyl)triazene.
• MICHEJDA, CHRISTOPHER J.;SMITH, RICHARD H. (JR)
  作者：MICHEJDA, CHRISTOPHER J.、SMITH, RICHARD H. (JR)

  DOI：——

  日期：——
• US4923970A
  申请人：——

  公开号：US4923970A

  公开（公告）日：1990-05-08