methyl 3-O-acetyl-4,6-O-benzylidene-2-chloro-2-deoxy-α-D-mannopyranoside | 73159-22-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: methyl 3-O-acetyl-4,6-O-benzylidene-2-chloro-2-deoxy-α-D-mannopyranoside
• 英文别名: [(4aR,6S,7S,8S,8aR)-7-chloro-6-methoxy-2-phenyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-8-yl] acetate
• CAS: 73159-22-5
• 化学式: C₁₆H₁₉ClO₆
• 分子量: 342.776
• InChiKey: URNPXRSEKIJYDT-YLUFJFMLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 3-O-acetyl-4,6-O-benzylidene-2-chloro-2-deoxy-α-D-mannopyranoside 在 sodium methylate 作用下， 以 吡啶 、 甲醇 、 水 、 溶剂黄146 为溶剂， 反应 52.0h， 生成 methyl 2-chloro-2-deoxy-α-D-mannopyranoside
  参考文献：
  名称：

  甲基α-D-吡喃葡萄糖苷和蔗糖衍生物中的C-2处的氯首次取代氯磺酰氧基

  摘要：

  摘要3-甲基-O-乙酰基-4,6-O-亚苄基-α-D-吡喃葡萄糖苷2-氯代硫酸盐（2），3,4,6,3'，4'，6'-六-O-乙酰基蔗糖的处理2,1'-双（氯代硫酸盐），3,4,6,3'，4'，6'-六-O-乙酰基-1'-O-苯甲酰蔗糖2-氯代硫酸盐和3,4,3'，4六甲基磷酸三酰胺中的'-四-O-乙酰基-6,6'-二氯-6,6'-二脱氧蔗糖2,1'-双（氯硫酸盐）与氯化锂得到相应的氯代脱氧-甘露糖衍生物。用亲核试剂如溴化锂，叠氮化钠，氯化钠和苯甲酸钠在六甲基磷酸三酰胺中处理2-氯硫酸盐2，得到2-羟基化合物，为主要产物。当在吡啶和氯仿的混合物中用硫酰氯处理3,4,6,3'，4'，6'-六-O-乙酰基蔗糖时，在C-1'处实现了选择性氯化。

  DOI：

  10.1016/s0008-6215(00)83670-8
• 作为产物：
  描述：

  甲基3-O-苯甲酰基-4,6-O-亚苄基-alpha-D-吡喃葡萄糖苷 在 吡啶 、 四氯化碳 、 sodium methylate 、 三苯基膦 作用下， 反应 3.0h， 生成 methyl 3-O-acetyl-4,6-O-benzylidene-2-chloro-2-deoxy-α-D-mannopyranoside
  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：——
• A method for the preparation of 2-chloro-2-deoxy saccharides and some 2-chloro-2-deoxy saccharides
  申请人：TATE & LYLE PATENT HOLDINGS LIMITED

  公开号：EP0010410B1

  公开（公告）日：1982-03-03
• US4262115A
  申请人：——

  公开号：US4262115A

  公开（公告）日：1981-04-14
• The first replacement of a chlorosulphonyloxy group by chlorine at C-2 in methyl α-D-glucopyranoside and sucrose derivatives
  作者：Riaz Khan、Michael R. Jenner、Harald Lindseth

  DOI：10.1016/s0008-6215(00)83670-8

  日期：1980.1

  corresponding chlorodeoxy- manno derivatives. Treatment of the 2-chlorosulphate 2 with such nucleophilic reagents as lithium bromide, sodium azide, sodium chloride, and sodium benzoate in hexamethylphosphoric triamide gave the 2-hydroxy compound as a major product. Selective chlorination at C-1′ was achieved when 3,4,6,3′,4′,6′-hexa- O -acetylsucrose was treated with sulphuryl chloride in a mixture of

  摘要3-甲基-O-乙酰基-4,6-O-亚苄基-α-D-吡喃葡萄糖苷2-氯代硫酸盐（2），3,4,6,3'，4'，6'-六-O-乙酰基蔗糖的处理2,1'-双（氯代硫酸盐），3,4,6,3'，4'，6'-六-O-乙酰基-1'-O-苯甲酰蔗糖2-氯代硫酸盐和3,4,3'，4六甲基磷酸三酰胺中的'-四-O-乙酰基-6,6'-二氯-6,6'-二脱氧蔗糖2,1'-双（氯硫酸盐）与氯化锂得到相应的氯代脱氧-甘露糖衍生物。用亲核试剂如溴化锂，叠氮化钠，氯化钠和苯甲酸钠在六甲基磷酸三酰胺中处理2-氯硫酸盐2，得到2-羟基化合物，为主要产物。当在吡啶和氯仿的混合物中用硫酰氯处理3,4,6,3'，4'，6'-六-O-乙酰基蔗糖时，在C-1'处实现了选择性氯化。
• Halogenation reactions of derivatives ofd-glucose and sucrose
  作者：Riaz Khan、Gita Patel

  DOI：10.1016/0008-6215(90)80141-o

  日期：1990.9

  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.