methyl 4,6-O-benzylidene-2-chloro-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside | 131474-39-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: methyl 4,6-O-benzylidene-2-chloro-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside
• 英文别名: (4aR,6S,8aS)-7-chloro-6-methoxy-2-phenyl-4,4a,6,8a-tetrahydropyrano[3,2-d][1,3]dioxine
• CAS: 131474-39-0
• 化学式: C₁₄H₁₅ClO₄
• 分子量: 282.724
• InChiKey: NUBBKBLYMMTTBP-PIGZVRMJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl 4,6-O-benzylidene-2-chloro-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside 在 吡啶 、 盐酸 作用下， 以 甲醇 为溶剂， 反应 5.0h， 生成 methyl 4,6-di-O-acetyl-2-chloro-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside
  参考文献：
  名称：

  Halogenation reactions of derivatives ofd-glucose and sucrose

  摘要：

  Treatment of methyl 4,6-O-benzylidene-alpha-D-glucopyranoside (1) with triphenylphophine-carbon tetrachloride-pyridine (reagent A) gave methyl 4,6-O-benzylidene-2-chloro-2-deoxy-alpha-D-mannopyranoside (2). When reagent A was used in excess, a further elimination reaction occurred to give methyl 4,6-O-benzylidene-2-chloro- (6, 60%) and -3-chloro-2,3-dideoxy-alpha-D-erythro-hex-2-enopyranoside (7, 16%). Treatment of 1 with triphenylphosphine-carbon tetrabromide-pyridine (reagent B) caused little or no elimination, and 47% of methyl 4,6-O-benzylidene-2-bromo-2-deoxy-alpha-D-mannopyranoside (14) was obtained. On treatment with reagent A, methyl alpha-D-glucopyranoside (16) gave exclusively methyl 2,4,6-trichloro- 2,3,4,6-tetradeoxy-alpha-D-erythro-hex-2-enopyranoside (17), and methyl 4,6-O-benzylidene-beta-D-glucopyranoside (19) gave methyl 4,6-O-benzylidene-3-chloro-3-deoxy-beta-D-allopyranoside (20, 70%). However, with reagent B, 19 gave methyl 4,6-O-benzylidene-3-bromo-3-deoxy-beta-D-glucopyranoside (23, 66%), probably by way of double inversion of configuration at C-3. Likewise, with reagent A, methyl beta-D-glucopyranoside (25) gave methyl 2,4,6-trichloro- (26) and3,4,6-trichloro-2,3,4,-6-tetradeoxy- beta-D-threo-hex-2-enopyranoside (27), and 4,6-O-isopropylidenesucrose (28) gave mainly 3-chloro-3-deoxy-4,6-O-isopropylidene-alpha-D-allopyranosyl 1,4,6-trichloro-1,4,6-trideoxy-beta-D-lyxo-hexulofuranoside (29) together with 3-chloro-3-deoxy-4,6-O-isopropylidene-alpha-D-allopyranosyl 1,4,6-trichloro-1,4,6-trideoxy-beta-D-fructofuranoside (30). The assignment of structure to 29 is tentative.

  DOI：

  10.1016/0008-6215(90)80141-o
• 作为产物：
  描述：

  甲基-4,6-O-亚苄基-Α-D-吡喃葡糖苷 在 吡啶 、 四氯化碳 、 三苯基膦 作用下， 以16%的产率得到methyl 4,6-O-benzylidene-3-chloro-2,3-dideoxy-α-D-erythro-hex-2-enopyranoside
  参考文献：
  名称：

  Halogenation reactions of derivatives ofd-glucose and sucrose

  摘要：

  Treatment of methyl 4,6-O-benzylidene-alpha-D-glucopyranoside (1) with triphenylphophine-carbon tetrachloride-pyridine (reagent A) gave methyl 4,6-O-benzylidene-2-chloro-2-deoxy-alpha-D-mannopyranoside (2). When reagent A was used in excess, a further elimination reaction occurred to give methyl 4,6-O-benzylidene-2-chloro- (6, 60%) and -3-chloro-2,3-dideoxy-alpha-D-erythro-hex-2-enopyranoside (7, 16%). Treatment of 1 with triphenylphosphine-carbon tetrabromide-pyridine (reagent B) caused little or no elimination, and 47% of methyl 4,6-O-benzylidene-2-bromo-2-deoxy-alpha-D-mannopyranoside (14) was obtained. On treatment with reagent A, methyl alpha-D-glucopyranoside (16) gave exclusively methyl 2,4,6-trichloro- 2,3,4,6-tetradeoxy-alpha-D-erythro-hex-2-enopyranoside (17), and methyl 4,6-O-benzylidene-beta-D-glucopyranoside (19) gave methyl 4,6-O-benzylidene-3-chloro-3-deoxy-beta-D-allopyranoside (20, 70%). However, with reagent B, 19 gave methyl 4,6-O-benzylidene-3-bromo-3-deoxy-beta-D-glucopyranoside (23, 66%), probably by way of double inversion of configuration at C-3. Likewise, with reagent A, methyl beta-D-glucopyranoside (25) gave methyl 2,4,6-trichloro- (26) and3,4,6-trichloro-2,3,4,-6-tetradeoxy- beta-D-threo-hex-2-enopyranoside (27), and 4,6-O-isopropylidenesucrose (28) gave mainly 3-chloro-3-deoxy-4,6-O-isopropylidene-alpha-D-allopyranosyl 1,4,6-trichloro-1,4,6-trideoxy-beta-D-lyxo-hexulofuranoside (29) together with 3-chloro-3-deoxy-4,6-O-isopropylidene-alpha-D-allopyranosyl 1,4,6-trichloro-1,4,6-trideoxy-beta-D-fructofuranoside (30). The assignment of structure to 29 is tentative.

  DOI：

  10.1016/0008-6215(90)80141-o

文献信息

• KHAN, RIAZ;PATEL, GITA, CARBOHYDR. RES., 205,(1990) C. 211-223
  作者：KHAN, RIAZ、PATEL, GITA

  DOI：——

  日期：——