5-氯-2,4-双三甲基甲硅烷氧基-嘧啶 | 58990-53-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 中文名称: 5-氯-2,4-双三甲基甲硅烷氧基-嘧啶
• 英文名称: 5-chloro-2,4-bis-O-trimethylsilyluracil
• 英文别名: 5-Chloro-2,4-bis[(trimethylsilyl)oxy]pyrimidine；(5-chloro-2-trimethylsilyloxypyrimidin-4-yl)oxy-trimethylsilane
• CAS: 58990-53-7
• 化学式: C₁₀H₁₉ClN₂O₂Si₂
• 分子量: 290.897
• InChiKey: LSPJTQNKLHFVOX-UHFFFAOYSA-N

物化性质

• 保留指数：
  1459;1461

计算性质

• 辛醇/水分配系数(LogP)：
  3.56
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  44.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5-氯-2,4-双三甲基甲硅烷氧基-嘧啶 在 2,4,6-三甲基苯磺酰羟胺 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 生成 1-氨基-5-氯嘧啶-2,4-二酮
  参考文献：
  名称：

  新型尿嘧啶衍生物：新合成的中枢作用剂。

  摘要：

  合成了一系列的1-氨基-5-取代的尿嘧啶及其4-硫或2,4-二硫取代的类似物，并测定了其在大鼠中的抗冲突活性和在小鼠中的麻醉活性。1-氨基-5-卤代尿嘧啶3b-e，1-氨基-4-硫代尿嘧啶（9a）和1-氨基-5-卤代-4-硫尿嘧啶9c，d显示出抗冲突和麻醉作用。活性最高的化合物是1-氨基-5-氯-4-硫尿嘧啶（9d），在改良的Geller-Seifter冲突时间表上，口服2 mg / kg（po）表现出抗焦虑活性。它的最小有效剂量（MED）低于地西epa。化合物（9d）对小鼠的麻醉活性的50％有效剂量（ED50）为32.9 mg / kg，口服

  DOI：

  10.1248/cpb.40.1808
• 作为产物：
  描述：

  5-氯尿嘧啶 、 N,O-双三甲硅基乙酰胺 以 乙腈 为溶剂， 生成 5-氯-2,4-双三甲基甲硅烷氧基-嘧啶
  参考文献：
  名称：

  使用叠氮甲基酯与三氟甲磺酸硅酯对核碱基和相关 N-杂环、苯并唑和双（芳烃）磺酰亚胺进行叠氮甲基化

  摘要：

  描述了一种使用叠氮甲基酯与三氟甲磺酸硅酯对胺进行叠氮甲基化的有效方法。该方案能够实现各种胺的叠氮甲基化，这些胺可以用甲硅烷基（包括核碱基）激活。

  DOI：

  10.1021/acs.orglett.4c00938

文献信息

• A Surprising Ring Opening Mechanism in the Formation of α-D-Arabinofuranosyl Nucleosides from 5-Substituted Uracils
  作者：Per Trolle Jørgensen、Erik B. Pedersen、Claus Nielsen

  DOI：10.1055/s-1992-26363

  日期：——

  Reaction of silylated 5-substituted uracil derivatives 6 with methyl 2,3,5-tri-O-benzoyl-α-D-arabinofuranoside (3) in the presence of trimethylsilyl trifluoromethanesulfonate afforded a mixture of the corresponding 5-substituted 1-(2,3,5-tri-O-benzoyl-α-D-arabinofuranosyl)uracils 7 and the acyclo 2,3,5-tri-O-benzoyl-1-O-methyl-1-(uracil-1-yl)-D-arabinitols 9 with the methoxy group intact at C-1. Compound 7 was deprotected with methanolic ammonia to give 8. Compound 7 was also reacted with Lawesson's Reagent to generate the corresponding 4-thio-α-D-arabinofuranoside nucleoside 14 which was deprotected by treatment with methanolic ammonia to give the nucleosides 15. Deprotected acyclo nucleosides 10 were likewise obtained from compounds 9. The mechanism for formation of the nucleosides 7 is discussed and the acyclo nucleosides 9 are believed to be intermediates.

  在三甲基硅基三氟甲磺酸酯的存在下，硅烷化的5-取代尿嘧啶衍生物6与甲基2,3,5-三-O-苯甲酰基-α-D-阿拉伯呋喃糖苷（3）反应，生成相应的5-取代1-(2,3,5-三-O-苯甲酰基-α-D-阿拉伯呋喃糖基)尿嘧啶7和非环状的2,3,5-三-O-苯甲酰基-1-O-甲基-1-(尿嘧啶-1-基)-D-阿拉伯醇9的混合物，其中C-1位的甲氧基保持完整。化合物7通过与甲醇氨反应去保护，得到8。化合物7还与Lawesson试剂反应，生成相应的4-硫-α-D-阿拉伯呋喃糖核苷14，后者通过甲醇氨处理去保护，得到核苷15。从化合物9也得到了去保护的非环状核苷10。讨论了核苷7的形成机理，并且认为非环状核苷9是中间体。
• Nucleic acid related compounds. 37. Convenient and high-yield syntheses of <i>N</i>-[(2-hydroxyethoxy)methyl] heterocycles as "acyclic nucleoside" analogues
  作者：Morris J. Robins、Peter W. Hatfield

  DOI：10.1139/v82-081

  日期：1982.3.1

  Treatment of 1,3-dioxolane with acetyl bromide gave (2-acetoxyethoxy)methyl bromide (2a) in 88% yield. A number of pyrimidines and three chloropurines were trimethylsilylated and coupled with 2a. The respective N-1 and N-9 alkylated products (obtained in 79–89% yields) were deacetylated to give N-[(2-hydroxyethoxy)methyl] heterocycles. The 6-amino or 6-chloro substituent of the 2-amino-6-substituted-purine derivatives was hydrolyzed smoothly with adenosine deaminase to give 9-[(2-hydroxyethoxy)methyl]guanine (acycloguanosine), the potent antiviral agent.

  1,3-二氧杂环戊烷与乙酰溴反应，得到（2-乙酰氧乙氧基）溴甲烷（2a），收率为88%。多种嘧啶和三种氯代嘌呤经过三甲基硅基化处理后与2a偶联。相应的N-1和N-9烷基化产物（收率为79-89%）经去乙酰化处理后得到N-[(2-羟基乙氧基)甲基]杂环化合物。2-氨基-6-取代嘌呤衍生物的6-氨基或6-氯取代基经过腺苷脱氨酶顺利水解，得到9-[(2-羟基乙氧基)甲基]鸟苷（无环鸟苷），这是一种有效的抗病毒药物。
• HMDS/KI a simple, a cheap and efficient catalyst for the one-pot synthesis of <i>N</i>-functionalized pyrimidines
  作者：Az-Eddine El Mansouri、Mohamed Zahouily、Hassan B. Lazrek

  DOI：10.1080/00397911.2019.1602655

  日期：2019.7.18

  Abstract The syntheses of N-Alkylpyrimidine derivatives by reacting pyrimidin-2,4-diones with appropriate alkyl halide under microwave irradiation at 400 W were compared to the conventional synthesis route. These methodologies are regioselective and compatible with numerous substrates and furnish the corresponding N-alkylpyrimidines in good yields using a cheap catalyst HMDS/KI in MeCN. A comparison

  摘要 将嘧啶-2,4-二酮与适当的卤代烷在400 W微波辐射下反应合成N-烷基嘧啶衍生物与常规合成路线进行了比较。这些方法具有区域选择性并与许多底物相容，并使用 MeCN 中的廉价催化剂 HMDS/KI 以良好的产率提供相应的 N-烷基嘧啶。研究了这两种不同加热模式之间的比较研究。图形概要
• Synthesis and Structural Elucidation of 2′-Deoxy-4′-thio-L-threo-pentofuranosylpyrimidine and -purine Nucleosides
  作者：Jörn Wirsching、Jürgen Voss、Gunadi Adiwidjaja、Anja Giesler、Jürgen Kopf

  DOI：10.1002/1099-0690(200103)2001:6<1077::aid-ejoc1077>3.0.co;2-0

  日期：2001.3

  (13) was used as glycosyl donor for the synthesis of 4′-thio-L-threo-pentofuranosyluracil derivatives 23−29. The corresponding cytidine analogue 33 was prepared from 13 via the triazolo derivative 31. Adenine and hypoxanthine did not react with 13. Therefore, 13 was transformed into the 1-O-acetate 15, which was a sufficiently reactive donor for the purine bases, yielding 4′-thio-L-threo-pentofuranosylpurines

  苄基 3,5-di-O-benzyl-2-deoxy-1,4-dithio-L-threo-pentofuranoside (13) 用作糖基供体，用于合成 4'-thio-L-threo-pentofuranosyluracil 衍生物 23 －29。相应的胞苷类似物 33 由 13 通过三唑基衍生物 31 制备。腺嘌呤和次黄嘌呤不与 13 反应。因此，13 转化为 1-O-乙酸酯 15，它是嘌呤碱基的足够反应性供体，产生4'-硫代-L-苏式-戊呋喃基嘌呤 36 和 37。在大多数情况下，可以获得脱保护的核苷类似物的纯端基异构体，其中三个适用于 X 射线结构分析。
• Efficient and selective catalytic N-Alkylation of pyrimidine by ammonium Sulfate@Hydro-thermal carbone under eco-friendly conditions
  作者：SOUMIA BELKHARCHACH、HANA IGHACHANE、ABDESSADEK LACHGAR、MUSTAPHA AIT ALI、HASSAN B LAZREK

  DOI：10.1007/s12039-020-01776-3

  日期：2020.12

  An efficient and inexpensive method for the N-alkylation of pyrimidines using ammonium sulfate coated Hydro-Thermal-Carbone (HTC) (AS@HTC) as reused heterogeneous catalyst was developed. The catalyst was characterized by several analytical techniques such as SEM, XRD, and FTIR. The effect of various parameters was studied including catalyst loading, mole ratio, to achieve excellent selectivity and yields in 80–90%. Significantly, the present protocol offers the use of an inexpensive and environmentally friendly catalyst and simple workup. The simplicity of the procedure, excellent yield of the products, and the recyclability of the catalyst are the main advantages of this method. Ammonium sulfate coated Hydro-Thermal-Carbone (HTC) (AS@HTC); an efficient and reused heterogeneous catalyst of the N-alkylation of pyrimidines was developed. Excellent selectivity and yields (80–90%) toward N1-alkylpyrimidines were achieved. Significantly, the present protocol offers the use of an inexpensive and environmentally friendly catalyst and simple workup.

  开发了一种利用硫酸铵包覆的水热碳（HTC）（AS@HTC）作为可重复使用的非均相催化剂，进行嘧啶N-烷基化的有效且经济的方法。通过SEM、XRD和FTIR等多种分析技术对催化剂进行了表征。研究了各种参数的影响，包括催化剂负载量、摩尔比，以实现80-90%的优异选择性和产率。值得注意的是，当前协议提供了使用廉价且环境友好的催化剂和简单后处理的优势。该方法的简单性、产品的优异产率以及催化剂的可回收性是其主要优点。硫酸铵包覆的水热碳（HTC）（AS@HTC）；开发了一种高效且可重复使用的非均相催化剂，用于嘧啶的N-烷基化。实现了对N1-烷基嘧啶的优异选择性和产率（80-90%）。值得注意的是，当前协议提供了使用廉价且环境友好的催化剂和简单后处理的优势。

表征谱图