9-bromo-3,4-dihydro-1-methoxy-7-methyl-1H-pyrimido<6,1-c><1,4>oxazine-6,8(7H)-dione | 146723-51-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: 9-bromo-3,4-dihydro-1-methoxy-7-methyl-1H-pyrimido<6,1-c><1,4>oxazine-6,8(7H)-dione
• 英文别名: 9-bromo-1-methoxy-7-methyl-3,4-dihydro-1H-pyrimido[6,1-c][1,4]oxazine-6,8-dione
• CAS: 146723-51-5
• 化学式: C₉H₁₁BrN₂O₄
• 分子量: 291.101
• InChiKey: BSKYFUIIDDFKEX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  59.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  9-bromo-3,4-dihydro-1-methoxy-7-methyl-1H-pyrimido<6,1-c><1,4>oxazine-6,8(7H)-dione 在 氢溴酸 作用下， 反应 2.0h， 以82%的产率得到9-bromo-3,4-dihydro-1-hydroxy-7-methyl-1H-pyrimido-<6,1-c><1,4>oxazine-6,8(7H)-dione
  参考文献：
  名称：

  Pyrimidine Derivatives. VIII. One-Step Synthesis of 3,4-Dihydro-pyrimido(6,1-c)(1,4)oxazine Derivatives by Reactions of 5-Bromo-1-(2-bromoethyl)-6-bromomethyl-2,4(1H,3H)-pyrimidinedione with Sodium Alkoxides and 2-Nitropropane.

  摘要：

  5-溴-1-(2-溴乙基)-6-溴甲基-3-甲基-2,4(1H,3H)-嘧啶二酮(1)与醇钠/2-硝基丙烷体系以及5-溴-1-(2-羟乙基)-6-羟甲基-3-甲基-2,4(1H,3H)-嘧啶二酮二硝酸盐(2)与醇钠的反应为一系列3,4-二氢-嘧啶并[6,1-c][1,4]恶嗪衍生物(3)提供了简便的合成途径，且收率极高。

  DOI：

  10.1248/cpb.40.2668
• 作为产物：
  描述：

  2-(5-bromo-6-formyl-3-methyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-1-yl)ethyl nitrate 生成 9-bromo-3,4-dihydro-1-methoxy-7-methyl-1H-pyrimido<6,1-c><1,4>oxazine-6,8(7H)-dione
  参考文献：
  名称：

  Kinoshiia Toshio, Ohishi Hiroshi, Tanimoto Youko, Chem. and Pharm. Bull, 41 (1993) N 12, S 2073- 2076

  摘要：

  DOI：

文献信息

• Pyrimidine Derivatives. XI. Facile Carbon-Carbon Bond-Cleavage Reaction of 6-Bromomethylpyrimidinediones and (2,4-Dioxo-1,2,3,4-tetrahydropyrimidin-6-yl)methyl Nitrate via 6-Formyl Derivatives.
  作者：Toshio KINOSHITA、Hiroshi OHISHI、Youko TANIMOTO

  DOI：10.1248/cpb.41.2073

  日期：——

  The reaction of 5-bromo-6-bromomethyl-1, 3-dimethyl- (1a) and 5-bromo-6-bromomethyl-1-(3-bromopropyl)-3-methyl-2, 4(1H, 3H)-pyrimidinedione (4a) with 1.0 and 2.0 eq of the sodium salt of 2-nitropropane yielded a mixture of 6-formyl (2 and 5a) and carbon-carbon bond-cleavage products (3 and 6a). When a large excess of the sodium salt of 2-nitropropane was used, 3 and 6a were obtained as sole products, respectively. The nitrates [(5-bromo-1, 3-dimethyl-2, 4-dioxo-1, 2, 3, 4-tetrahydropyrimidin-6-yl)methyl nitrate (1b) and the dinitrate of 5-bromo-6-hydroxymethyl-1-(3-hydroxypropyl)-3-methyl-2, 4(1H, 3H)-pyrimidinedione (4b)] were exclusively converted to 6-formylpyrimidines (2 and 5b) or 6-unsubstituted pyrimidinediones (3 and 6b) by reaction with 1.0 or 2.0 eq of sodium methoxide, respectively. The dinitrate of 5-bromo-1-(2-hydroxyethyl)-6-hydroxymethyl-3-methyl-2, 4(1H, 3H)-pyrimidinediones (7) was treated with sodium methoxide to yield 2-(5-bromo-6-formyl-3-methyl-2, 4-dioxo-1, 2, 3, 4-tetrahydropyrimidin-1-yl)ethyl nitrate (8), a 3, 4-dihydropyrimido[6, 1-c][1, 4]oxazine derivative (9) and 2-(5-bromo-3-methyl-2, 4-dioxo-1, 2, 3, 4-tetrahydropyrimidin-1-yl)ethyl nitrate (10). A plausible reaction mechanism is presented.

  5-bromo-6-bromomethyl-1, 3-dimethyl- (1a)和 5-bromo-6-bromomethyl-1-(3-bromopropyl)-3-methyl-2, 4(1H, 3H)-primidinedione(4a)与 1.0 和 2.0 eq 的 2-硝基丙烷钠盐反应，生成 6-甲酰基（2 和 5a）和碳碳键裂解产物（3 和 6a）的混合物。当使用大量过量的 2-硝基丙烷钠盐时，3 和 6a 分别成为唯一的产物。硝酸盐[（5-溴-1，3-二甲基-2，4-二氧代-1，2，3，4-四氢嘧啶-6-基）硝酸甲酯（1b）和 5-溴-6-羟甲基-1-（3-羟基丙基）-3-甲基-2、4(1H，3H)-嘧啶二酮 (4b)]通过与 1.0 或 2.0 eq 的甲醇钠反应，分别转化为 6-甲酰基嘧啶（2 和 5b）或 6-未取代的嘧啶二酮（3 和 6b）。将 5-溴-1-(2-羟乙基)-6-羟甲基-3-甲基-2，4(1H，3H)-嘧啶二酮（7）的二硝酸盐用甲醇钠处理，得到 2-(5-溴-6-甲酰基-3-甲基-2，4-二氧代-1，2，3，4-四氢嘧啶)、4-四氢嘧啶-1-基）硝酸乙酯（8）、3，4-二氢嘧啶并[6，1-c][1，4]恶嗪衍生物（9）和 2-（5-溴-3-甲基-2，4-二氧代-1，2，3，4-四氢嘧啶-1-基）硝酸乙酯（10）。本文介绍了一种合理的反应机理。
• Kinoshiia Toshio, Ohishi Hiroshi, Tanimoto Youko, Chem. and Pharm. Bull, 41 (1993) N 12, S 2073- 2076
  作者：Kinoshiia Toshio, Ohishi Hiroshi, Tanimoto Youko

  DOI：——

  日期：——
• Pyrimidine Derivatives. VIII. One-Step Synthesis of 3,4-Dihydro-pyrimido(6,1-c)(1,4)oxazine Derivatives by Reactions of 5-Bromo-1-(2-bromoethyl)-6-bromomethyl-2,4(1H,3H)-pyrimidinedione with Sodium Alkoxides and 2-Nitropropane.
  作者：Toshio KINOSHITA、Miho UGA、Youko TANIMOTO、Kiyomi OHISHI、Sunao FURUKAWA

  DOI：10.1248/cpb.40.2668

  日期：——

  The reaction of 5-bromo-1-(2-bromoethyl)-6-bromomethyl-3-methyl-2, 4(1H, 3H)-pyrimidinedione (1) with the sodium alkoxide/2-nitropropane system and that of the dinitrate (2) of 5-bromo-1-(2-hydroxyethyl)-6-hydroxymethyl-3-methyl-2, 4(1H, 3H)-pyrimidinedione with sodium alkoxide provide convenient routes to a wide range of 3, 4-dihydro-pyrimido[6, 1-c][1, 4]oxazine derivatives (3) in excellent yields.

  5-溴-1-(2-溴乙基)-6-溴甲基-3-甲基-2,4(1H,3H)-嘧啶二酮(1)与醇钠/2-硝基丙烷体系以及5-溴-1-(2-羟乙基)-6-羟甲基-3-甲基-2,4(1H,3H)-嘧啶二酮二硝酸盐(2)与醇钠的反应为一系列3,4-二氢-嘧啶并[6,1-c][1,4]恶嗪衍生物(3)提供了简便的合成途径，且收率极高。