4-(mesyloxymethyl)-6-methyl-5-tosyl-1,2,3,4-tetrahydropyrimidin-2-one | 1143491-02-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-(mesyloxymethyl)-6-methyl-5-tosyl-1,2,3,4-tetrahydropyrimidin-2-one
• 英文别名: 4-mesyloxymethyl-6-methyl-5-tosyl-1,2,3,4-tetrahydropyrimidin-2-one；[6-methyl-5-(4-methylphenyl)sulfonyl-2-oxo-3,4-dihydro-1H-pyrimidin-4-yl]methyl methanesulfonate
• CAS: 1143491-02-4
• 化学式: C₁₄H₁₈N₂O₆S₂
• 分子量: 374.439
• InChiKey: ACTGORXVXDGOAU-UHFFFAOYSA-N

物化性质

• 熔点：
  148.5 °C (decomp)(Solvent: Acetonitrile)
• 沸点：
  604.1±55.0 °C(predicted)
• 密度：
  1.372±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  135
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4-(mesyloxymethyl)-6-methyl-5-tosyl-1,2,3,4-tetrahydropyrimidin-2-one 在 sodium hydride 作用下， 以 乙腈 为溶剂， 反应 3.25h， 以91.9%的产率得到9-methyl-5-methylene-6,8-ditosyl-1,2,4,5,6,6a,7,10-octahydro-1,6-methano[1,3]diazepino[1,7-e][1,3,5]triazocine-3,11-dione
  参考文献：
  名称：

  通过亲核试剂介导的四氢嘧啶扩环制备6-甲苯磺酰基-2,3,4,5-四氢-1 H -1,3-二氮杂-2-酮的一般方法

  摘要：

  已经开发了一种通常的六步法制备6-甲苯磺酰基-2,3,4,5-四氢-1 H -1,3-二氮杂-2--2-酮。关键步骤涉及由亲核试剂介导的4-甲磺酰氧基甲基-或4-甲磺酰氧基甲基-5-甲磺酰基-1,2,3,4-四氢嘧啶-2-酮的扩环反应。

  DOI：

  10.1016/j.tet.2009.01.015
• 作为产物：
  描述：

  4-(hydroxymethyl)-6-methyl-5-tosyl-1,2,3,4-tetrahydropyrimidin-2-one 、 甲基磺酰氯 在 4-二甲氨基吡啶 作用下， 以 氯仿 为溶剂， 反应 1.02h， 以95.6%的产率得到4-(mesyloxymethyl)-6-methyl-5-tosyl-1,2,3,4-tetrahydropyrimidin-2-one
  参考文献：
  名称：

  通过亲核试剂介导的四氢嘧啶扩环制备6-甲苯磺酰基-2,3,4,5-四氢-1 H -1,3-二氮杂-2-酮的一般方法

  摘要：

  已经开发了一种通常的六步法制备6-甲苯磺酰基-2,3,4,5-四氢-1 H -1,3-二氮杂-2--2-酮。关键步骤涉及由亲核试剂介导的4-甲磺酰氧基甲基-或4-甲磺酰氧基甲基-5-甲磺酰基-1,2,3,4-四氢嘧啶-2-酮的扩环反应。

  DOI：

  10.1016/j.tet.2009.01.015

文献信息

• The dramatic effect of thiophenol on the reaction pathway of ethyl 4-chloromethyl-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate with thiophenolates: ring expansion versus nucleophilic substitution
  作者：Anastasia A. Fesenko、Ludmila A. Trafimova、Dmitry A. Cheshkov、Anatoly D. Shutalev

  DOI：10.1016/j.tetlet.2010.07.098

  日期：2010.9

  result of ring expansion and/or nucleophilic substitution. The reaction pathway was affected strongly by the basicity–nucleophilicity of the reaction media. The results obtained were confirmed by reactions of 4-mesyloxymethyl-6-methyl-5-tosyltetrahydropyrimidin-2-one with PhSNa/PhSH and ethyl 4-chloromethyl-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate with NaCN/HCN or NaCH(COOEt)2/CH2(COOEt)2

  4-甲基-2-氧代-7-苯硫基-2,3,6,7-四氢-1 H -1,3-二氮杂-5-羧酸酯和/或6-甲基-2-氧代-4-（在4-氯甲基-6-甲基-2-氧-2-，1,2,3,4-四氢嘧啶-5-羧酸乙酯与PhSNa的反应中获得苯硫基甲基）-1,1,2,3,4-四氢嘧啶-5-羧酸酯环的扩展和/或亲核取代的结果，取决于试剂比率，反应时间或温度，有无PhSH的PhSK或PhSK。反应途径受到反应介质的碱性-亲核性的强烈影响。通过4-甲氧基氧甲基-6-甲基-5-甲苯磺酰基四氢嘧啶-2-酮与PhSNa / PhSH和乙基4-氯甲基-6-甲基-2-氧代-1,2,3,4-四氢嘧啶的反应证实了所获得的结果用NaCN / HCN或NaCH（COOEt）2 -5-羧酸盐/ CH 2（COOEt）2。
• Nucleophile-mediated ring expansion of 4-chloromethyl- and 4-mesyloxymethyl-5-tosyl-1,2,3,4-tetrahydropyrimidin-2-ones to 6-tosyl-2,3,4,5-tetrahydro-1H-1,3-diazepin-2-ones: effect of the leaving group and the substituent at C6
  作者：Anastasia A. Fesenko、Anatoly D. Shutalev

  DOI：10.1016/j.tet.2011.06.089

  日期：2011.9

  A five-step synthesis of 4-chloromethyl- and 4-mesyloxymethyl-5-tosyl-1,2,3,4-tetrahydropyrimidin-2-ones has been developed. The reaction of N-[(2-benzoyloxy-1-tosyl)ethyl]urea with sodium enolates of alpha-tosylketones followed by cyclization-dehydration, and debenzoylation gave 4-hydroxymethyl-5-tosyl-1,2,3,4-tetrahydropyrimidin-2-ones, which were transformed into the 4-chloromethyl- or 4-mesyloxymethyl-derivatives. Treatment of the latter with nucleophilic reagents, such as sodium cyanide, sodium diethyl malonate, sodium thiophenolate, or potassium phthalimide, afforded the corresponding 4,7-disubstituted 6-tosyl-2,3,4,5-tetrahydro-1H-1,3-diazepin-2-ones as a result of ring expansion. The effect of the leaving group and the substitution at the position C6 on the reactivity of the pyrimidines is discussed. (C) 2011 Elsevier Ltd. All rights reserved.
• General approach to 6-tosyl-2,3,4,5-tetrahydro-1H-1,3-diazepin-2-ones via nucleophile-mediated ring expansion of tetrahydropyrimidines
  作者：Anastasia A. Fesenko、Marcus L. Tullberg、Anatoly D. Shutalev

  DOI：10.1016/j.tet.2009.01.015

  日期：2009.3

  A general six-step approach to 6-tosyl-2,3,4,5-tetrahydro-1H-1,3-diazepin-2-ones has been developed. The key step involves a ring expansion reaction of 4-mesyloxymethyl- or 4-tosyloxymethyl-5-tosyl-1,2,3,4-tetrahydropyrimidin-2-one mediated by nucleophilic reagents.

  已经开发了一种通常的六步法制备6-甲苯磺酰基-2,3,4,5-四氢-1 H -1,3-二氮杂-2--2-酮。关键步骤涉及由亲核试剂介导的4-甲磺酰氧基甲基-或4-甲磺酰氧基甲基-5-甲磺酰基-1,2,3,4-四氢嘧啶-2-酮的扩环反应。