1-(2-chloroethyl)-3-methyl-3-acetyltriazene | 113274-30-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 1-(2-chloroethyl)-3-methyl-3-acetyltriazene
• 英文别名: 3-acetyl-1-(2-chloroethyl)-3-methyltriazene；3-Acetyl-1-(2-chlorethyl)-3-methyltriazene
• CAS: 113274-30-9
• 化学式: C₅H₁₀ClN₃O
• 分子量: 163.607
• InChiKey: QEIMBUYAZCMEGX-BQYQJAHWSA-N

物化性质

• 沸点：
  195.7±42.0 °C(Predicted)
• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.07
• 重原子数：
  10.0
• 可旋转键数：
  3.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  45.03
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  1-(2-chloroethyl)-3-methyl-3-acetyltriazene 在 lysine buffer 作用下， 反应 0.58h， 以68.9%的产率得到1-methyltriazoline
  参考文献：
  名称：

  Novel triazenes and triazolines from the base-catalyzed hydrolysis of 1,3-dialkyl-3-acyltriazenes

  摘要：

  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.

  DOI：

  10.1021/jo00050a016
• 作为产物：
  描述：

  3-carboethoxy-1-(2-hydroxyethyl)-3-methyltriazene 、 白炭黑 在 三苯基膦 作用下， 以 四氯化碳 、 正戊烷 为溶剂， 生成 1-(2-chloroethyl)-3-methyl-3-acetyltriazene
  参考文献：
  名称：

  Substituted 1-(2-chloroethyl)-3-acyl-3-alkyltriazenes

  摘要：

  公式为：##STR1##，其中R.sub.1是1-氧代烷基，含有2至8个碳原子，含有最多三个氟原子的氟代1-氧代烷基，苯甲酰基，苯乙酰基，含有2至8个碳原子的羧基烷基，含有2至8个碳原子和最多三个氟原子的氟代羧基烷基，羰基苯氧基，N-苯基氨基甲酰基，含有2至8个碳原子的N-烷基氨基甲酰基，硫代氨基甲酰基，含有2至8个碳原子的N-烷基硫代氨基甲酰基，N-苯基硫代氨基甲酰基，二烷基磷酸酯，其中烷基基团可以相同也可以不同，每个含有1至7个碳原子，苯磺酰基，以及间位或对位取代的苯磺酰基，其中间位或对位取代基是甲基，乙基，甲氧基，乙氧基，氟和氯；R.sub.2是独立的烷基，含有1至7个碳原子，含有2至7个碳原子和1至3个氟原子的氟代烷基，其中氟代烷基群的α碳未被氟取代，苄基，间位或对位取代的苄基，其中间位或对位取代基是氯，氟和含有1至3个碳原子的烷氧基，含有2至7个碳原子的烯基，以及含有2至7个碳原子的炔基，作为抗肿瘤剂。

  公开号：

  US04923970A1

文献信息

• 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.
• The Base-Promoted Dehydrohalogenation of 1-(2-Chloroethyl)-3-alkyl-3-acyltriazenes
  作者：David W. Farnsworth、Brunon Pruski、Richard H. Smith

  DOI：10.1021/jo00119a049

  日期：1995.7
• SMITH, RICHARD H. , JR.;MEHL, ANDREW F.;SHANTZ, DONALD L. , JR.;CHMURNY, +, J. ORG. CHEM., 53,(1988) N 7, 1467-1471
  作者：SMITH, RICHARD H. , JR.、MEHL, ANDREW F.、SHANTZ, DONALD L. , JR.、CHMURNY, +

  DOI：——

  日期：——
• US4923970A
  申请人：——

  公开号：US4923970A

  公开（公告）日：1990-05-08
• [EN] 1-(2-CHLOROETHYL)-3-ACYL-3-ALKYLTRIAZENES
  申请人：BIONETICS RESEARCH, INC.

  公开号：WO1989009207A1

  公开（公告）日：1989-10-05

  (EN) A substituted 1-(2-chlorethyl)-3-acyl-3-alkyltriazene of formula (I), in which R1 is 1-oxoalkyl containing from two to eight carbon atoms, fluorinated 1-oxoalkyls containing from two to eight carbon atoms and substituted with up to three fluorine atoms, benzoyl, phenylacetyl, carboalkoxy containing from two to eight carbon atoms, fluorinated carboalkoxy containing from two to eight carbon atoms and up to three fluorine atoms, carbophenoxy, N-phenyl aminocarbonyl, N-alkyl aminocarbonyl containing from two to eight carbon atoms, thiocarbamoyl, N-alkylthiocarbamoyls, with from two to eight carbon atoms, N-phenylthiocarbamoyl, dialkylphosphonates in which the alkyl groups can be the same or different and each contains from one to seven carbon atoms, phenylsulfonyl, and meta or para-substituted phenylsulfonyl in which the meta or para substituent is methyl, ethyl, methoxy, ethoxy, fluoro and chloro; and R2 is independently alkyl containing from one to seven carbon atoms, fluoroalkyl containing from two to seven carbon atoms and from one to three fluorine atoms in which the $g(a) carbon of the fluoroalkyl group is not substituted with fluorine, benzyl, meta or para-substituted benzyl in which the meta or para substituent is chloro, fluoro and alkoxy with from one to three carbon atoms, alkenyl containing from two to seven carbon atoms, and alkynyl containing from two to seven carbon atoms.(FR) 1-(2-chloroéthyl)-3-acyl-3-alkyltriazene substitué est représenté par la formule (I) où R1 représente un 1-oxoalkyle contenant deux à huit atomes de carbone, des 1-oxoalkyles fluorés contenant deux à huit atomes de carbone et substitués par au maximum trois atomes de fluor, un benzoyle, un phénylacétyle, un carboalkoxy contenant deux à huit atomes de carbone, un carboalkoxy fluoré contenant deux à huit atomes de carbone et au maximum trois atomes de fluor, un carbophénoxy, un aminocarbonyle N-phényle, un aminocarbonyle N-alkyle contenant deux à huit atomes de carbone, thiocarbamoyle, des N-alkylthiocarbamoyle contenant deux à huit atomes de carbone, un N-phénylthiocarbamoyle, des dialkylphosphonates dans lesquels les groupes alkyle peuvent être identiques ou différents et qui contiennent chacun un à sept atomes de carbone, un phénylsulfonyle et un phénylsulfonyle à substitution méta ou para dans lequel le substituant méta ou para est représenté par un méthyle, un éthyle, un méthoxy, un éthoxy, un fluoro et un chloro; et R2 représente séparément un alkyle contenant un à sept atomes de carbone, un fluoroalkyle contenant deux à sept atomes de carbone et un à trois atomes de fluor où le carbone $g(a) du groupe fluoroalkyle n'est pas substitué par un fluor, un benzyle, un benzyle à substitution méta ou para dans lequel le substituant méta ou para est représenté par un chloro, un fluoro, ainsi qu'un alkoxy contenant un à trois atomes de carbone, un alkényl contenant deux à sept atomes de carbone et un alkynyle contenant sept à deux atomes de carbone.