p-(dimethylamino)pyridineW(CO)5 | 522595-51-3

• 英文名称: p-(dimethylamino)pyridineW(CO)5
• 英文别名: W(CO)₅(4-dimethylaminopyridine)；[W(CO)5(4-(dimethylamino)pyridine)]；[W(CO)5(4-Me2ampy)]
• CAS: 522595-51-3；157699-07-5
• 化学式: C₁₂H₁₀N₂O₅W
• 分子量: 446.072
• InChiKey: NSFRZBBUDMBBOP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  六羰基钨 以 二氯甲烷 为溶剂， 生成 p-(dimethylamino)pyridineW(CO)5
  参考文献：
  名称：

  含乙酰水杨酰胺-3-吡啶的一氧化碳释放分子的合成，细胞毒性和性质

  摘要：

  一系列CO-释放分子[M（CO）的5 L]（M =铬，钨，钼，L =乙酰基水杨酰胺3-吡啶，1 - 3 ;大号= Ñ，ñ -二甲基-4-吡啶，4 - 6；合成了L =烟酰胺，7 – 9；L = 4-CHO-吡啶，10 – 12）。和在本文中，我们已经研究了主要的细胞毒性和含乙酰salicyamide -3-吡啶的CO释放的分子的性能，即复合物1 - 3。配合物1和2是通过UV-Vis光谱和1 H NMR光谱评估的。结果表明，配合物1和2在甲醇和酸性水溶液中稳定，但在碱性介质（pH 10.0）中不稳定并衰减。在所有配合物中，配合物2是最慢的CO释放剂，其半衰期为73.8分钟。含烟酰胺的Complex 9是最快的CO释放剂，半衰期仅为6.5分钟。另外，通过MTT测定了所有复合物对成纤维细胞系增殖的细胞毒性作用。在所有配合物中，配合物1的IC 50为6 µmol / L，表明配合物1具有比对照组

  DOI：

  10.1002/cjoc.201400824

文献信息

• Tipping the energy balance toward exocyclic-amino coordination of W(CO)5 by methylation of the amino group of 2- and 4-aminopyridines, but not with adenosine
  作者：Thomas W Stringfield、Rex E Shepherd

  DOI：10.1016/s0020-1693(02)01189-1

  日期：2003.1

  2-Aminopyridine (2-ampy) substitutes on [W(CO)(5)(acetone)] or [W(CO)(5)(thf)] to produce 100% endocyclic N-1 coordinated [W(CO)(5)(2-ampy)]. Both N-1 coordinated and exocyclic-amine-bound isomers of [W(CO)(5)(4-ampy)] are formed by the substitution of 4-aminopyridine (4-ampy) on [W(CO)(5)(acetone)] in the ratio of 58% exo-amine coordination: 42% endocyclic amine under kinetic control. The distribution adjusts by linkage isomerism over 15 days to >86% exo-amine bound for the thermodynamic distribution. Within limit of H-1 NMR detection >95% exo-amine coordination occurs for 4-(dimethylamino)pyridine (4-Me(2)ampy), in spite of increased steric hindrance. Coordination of 2-(dimethylamino)pyridine to W(CO)(5) occurs only as the exo-amine donor, reversing the observations of the 2-ampy case. Coordination of W(CO)(5) with adenosine takes place with purine ring N donors (45% N-1, 33% N-3, and 22% N-7). The monomethylated N-6-methyladenosine produced only N-1 coordination in low yield. Apparently steric blocking by the N-6-methyl group retards coordination at N-7, and hydrogen bonding of the 5'- alcohol to N-3 of the purine ring in response to enhanced basicity of the N-3 site upon methylation of the exo-amine retards addition at N-3 for [W(CO)(5)(N(methyl adenosine)]. Surprisingly in relation to the effects of amino methylation for the simple aminopyrimidines where W(CO)(5) adopts >91% of 2-ampym and 100% of 4-ampym coordination via the exo-amine, N-1 is the preferred site of coordination for adenosines over the exo-amine position. The known releasing effect of the five-member portion of the adenine ring, enhancing 6 basicity at N-1 is not overcome by N-6-methylation which directs much of its enhancement of ring basicity to N-3. N-6,N-6-Dimethyladenosine produced no coordination with W(CO)(5) under equivalent photosynthetic conditions; the second methyl group only provides additional steric hindrance to coordination at N-1, showing the powerful influence of conjugation of the amino lone pair with the purine ring in preventing a sufficiently basic exo-amine that can coordinate W(CO)(5) in contrast to the outcome with the analogous pyridine (2-Me(2)ampy). Acetylation of 4-ampy (4-acetamidopyridine = 4-Acampy) should favor the pyridyl coordination; however, coordination to the carbonyl group is observed for [W(CO)(5)(4-Acampy)]. (C) 2002 Elsevier Science B.V. All rights reserved.
• Aumann, Rudolf; Jasper, Beate; Goddard, Richard, Chemische Berichte, 1994, vol. 127, # 4, p. 717 - 724
  作者：Aumann, Rudolf、Jasper, Beate、Goddard, Richard、Krueger, Carl

  DOI：——

  日期：——