2,4-双(乙酰氨基)-6-氯嘧啶 | 7148-63-2

• 分子结构分类: 有机化合物 - 有机氮化合物
• 中文名称: 2,4-双(乙酰氨基)-6-氯嘧啶
• 英文名称: 2,4-Bis(acetylamino)-6-chloropyrimidine
• 英文别名: 2,6-Diacetamido-4-chloropyrimidine；2,4-diacetylamino-6-chloropyrimidine；N-[2-(acetylamino)-6-chloropyrimidin-4-yl]acetamide；N-(2-acetamido-6-chloropyrimidin-4-yl)acetamide
• CAS: 7148-63-2
• 化学式: C₈H₉ClN₄O₂
• 分子量: 228.638
• InChiKey: CWYKGJYYAJPKKJ-UHFFFAOYSA-N

物化性质

• 密度：
  1.484±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  84
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  乙基5-氧代-2,5-二氢-1,2-恶唑-4-羧酸酯 、 2,4-双(乙酰氨基)-6-氯嘧啶 以 硝基苯 为溶剂， 反应 10.0h， 以87%的产率得到ethyl 2-(4,6-diaminopyrimidin-4-yl)-5-oxo-2,5-dihydroisoxazole-4-carboxylate
  参考文献：
  名称：

  Prager, Rolf H.; Rosenzweig, Teresa K.; Singh, Yogendra, Australian Journal of Chemistry, 1992, vol. 45, # 11, p. 1825 - 1832

  摘要：

  DOI：
• 作为产物：
  描述：

  2,4-二氨基-6-氯嘧啶 、 乙酸酐 反应 0.5h， 以99%的产率得到2,4-双(乙酰氨基)-6-氯嘧啶
  参考文献：
  名称：

  Relative Reactivity in Piperidino-Dechlorination of 2,4-Diamino-6-chloropyrimidine and 2,4-Diamino-6-chloropyrimidine N(3)-Oxide and Their Acetylamino Analogs

  摘要：

  The second-order rate constants k(A) for the piperidino-dechlorination of 2,4-diamino-6-chloropyrimidine (1a), 2,4-bis(acetylamino)-6-chloropyrimidine (1b), 2,4-diamino-6-chloropyrimidine N(3)-oxide (2a), and 2,4-bis(acetylamino)-6-chloropyrimidine N(3)-oxide (2b) have been determined from the corresponding pseudo-first-order rate constants, k psi, measured in DMSO at 21.0 degrees C by the UV spectrophotometric procedure. The second-order rate coefficients of the less reactive substrates 1a and 2a at 21 degrees C have been obtained as extrapolated values from Arrhenius plots of k(A) values, calculated through the pseudo-first-order-type relationship, k psi = k(A)[P] (where [P] is the amine concentration), from the k psi measured at higher temperatures (k(A)(1a) = 1.36 x 10(-5) and k(A)(2a) = 3.44 x 10(-5) L mol(-1) min(-1)). The reactivities of the acetyl derivatives 1b and 2b are remarkably higher than that of the parent compounds 1a and 2a. The pseudo-first-order rate constants of the more reactive substrates Ib and 2b, measured as a function of piperidine concentration, increase linearly for 1b, with a decreasing curvilinear slope only in the higher concentration region of base; in contrast, the reactivity of 2b remains almost constant and lower than that of ib for most of the employed base concentrations. This behavior is due to the acidic character of compound 2b, which is almost totally transformed by excess piperidine into an anionic form, much less reactive than the protonated one toward the nucleophilic attack, even at relatively low base concentrations. Compound Ib is much less acidic than 2b and shows deviations from the second-order-type linear behavior only for the higher base concentrations. The equilibrium constant for the acid-base reaction of 2b with piperidine has been obtained spectrophotometrically (K = 0.007 +/- 0.001), and the second-order rate coefficient k(A) has been calculated from the constant apparent reactivity h psi by means of the formula k(A) = k psi[PH+]/K (where [PH+] is the piperidinium ion concentration) (k(A)(2b) = 2.7 L mol(-1) min(-1)). That of 1b is given by the slope of the experimental curve k psi vs [P] in the proximity of the origin (k(A)(lb) = 0.15 L mol(-1) min(-1)). The results indicate that both the acetylation of the exocyclic -NH2 groups and the oxidation of the cyclic N(3)-atom increase the reactivity of the parent compounds toward piperidinolysis, but that the first modification is much more effective than the second one: The dependence of k psi of 1b and 2b on the amine concentration does not give any evidence for base catalysis, as expected in the model of the intermediate complex mechanism when the leaving group is fast to separate (as the -Cl group is) and/or the complex formation is rate-limiting.

  DOI：

  10.1021/jo00113a025

文献信息

• Liu, Quanying; Marchington, Allan P.; Boden, Neville, Journal of the Chemical Society. Perkin transactions I, 1997, # 4, p. 511 - 525
  作者：Liu, Quanying、Marchington, Allan P.、Boden, Neville、Rayner, Christopher M.

  DOI：——

  日期：——
• Prager, Rolf H.; Rosenzweig, Teresa K.; Singh, Yogendra, Australian Journal of Chemistry, 1992, vol. 45, # 11, p. 1825 - 1832
  作者：Prager, Rolf H.、Rosenzweig, Teresa K.、Singh, Yogendra

  DOI：——

  日期：——
• Relative Reactivity in Piperidino-Dechlorination of 2,4-Diamino-6-chloropyrimidine and 2,4-Diamino-6-chloropyrimidine N(3)-Oxide and Their Acetylamino Analogs
  作者：M. Maltese

  DOI：10.1021/jo00113a025

  日期：1995.4

  The second-order rate constants k(A) for the piperidino-dechlorination of 2,4-diamino-6-chloropyrimidine (1a), 2,4-bis(acetylamino)-6-chloropyrimidine (1b), 2,4-diamino-6-chloropyrimidine N(3)-oxide (2a), and 2,4-bis(acetylamino)-6-chloropyrimidine N(3)-oxide (2b) have been determined from the corresponding pseudo-first-order rate constants, k psi, measured in DMSO at 21.0 degrees C by the UV spectrophotometric procedure. The second-order rate coefficients of the less reactive substrates 1a and 2a at 21 degrees C have been obtained as extrapolated values from Arrhenius plots of k(A) values, calculated through the pseudo-first-order-type relationship, k psi = k(A)[P] (where [P] is the amine concentration), from the k psi measured at higher temperatures (k(A)(1a) = 1.36 x 10(-5) and k(A)(2a) = 3.44 x 10(-5) L mol(-1) min(-1)). The reactivities of the acetyl derivatives 1b and 2b are remarkably higher than that of the parent compounds 1a and 2a. The pseudo-first-order rate constants of the more reactive substrates Ib and 2b, measured as a function of piperidine concentration, increase linearly for 1b, with a decreasing curvilinear slope only in the higher concentration region of base; in contrast, the reactivity of 2b remains almost constant and lower than that of ib for most of the employed base concentrations. This behavior is due to the acidic character of compound 2b, which is almost totally transformed by excess piperidine into an anionic form, much less reactive than the protonated one toward the nucleophilic attack, even at relatively low base concentrations. Compound Ib is much less acidic than 2b and shows deviations from the second-order-type linear behavior only for the higher base concentrations. The equilibrium constant for the acid-base reaction of 2b with piperidine has been obtained spectrophotometrically (K = 0.007 +/- 0.001), and the second-order rate coefficient k(A) has been calculated from the constant apparent reactivity h psi by means of the formula k(A) = k psi[PH+]/K (where [PH+] is the piperidinium ion concentration) (k(A)(2b) = 2.7 L mol(-1) min(-1)). That of 1b is given by the slope of the experimental curve k psi vs [P] in the proximity of the origin (k(A)(lb) = 0.15 L mol(-1) min(-1)). The results indicate that both the acetylation of the exocyclic -NH2 groups and the oxidation of the cyclic N(3)-atom increase the reactivity of the parent compounds toward piperidinolysis, but that the first modification is much more effective than the second one: The dependence of k psi of 1b and 2b on the amine concentration does not give any evidence for base catalysis, as expected in the model of the intermediate complex mechanism when the leaving group is fast to separate (as the -Cl group is) and/or the complex formation is rate-limiting.