三甲基-[2-(5-硝基吡啶-2-基)乙炔基]硅烷 | 201026-82-6

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 中文名称: 三甲基-[2-(5-硝基吡啶-2-基)乙炔基]硅烷
• 英文名称: 2-(2-(trimethylsilyl)ethynyl)-5-nitropyridine
• 英文别名: 5-nitro-2-(2-trimethylsilylethynyl)pyridine；5-nitro-2-trimethylsilanylethynylpyridine；5-Nitro-2-((trimethylsilyl)ethynyl)pyridine；trimethyl-[2-(5-nitropyridin-2-yl)ethynyl]silane
• CAS: 201026-82-6
• 化学式: C₁₀H₁₂N₂O₂Si
• 分子量: 220.303
• InChiKey: KIXKSCTUWUKANO-UHFFFAOYSA-N

物化性质

• 熔点：
  110-111 °C(Solv: ethanol (64-17-5))
• 沸点：
  287.3±40.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.22
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  58.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  三甲基-[2-(5-硝基吡啶-2-基)乙炔基]硅烷 在 potassium fluoride 作用下， 以 乙醇 为溶剂， 反应 0.5h， 以90%的产率得到2-乙炔基-5-硝基吡啶
  参考文献：
  名称：

  Nitropyridines: X. Palladium-catalyzed cross-coupling of 2-bromo-5-nitropyridine with terminal acetylenes

  摘要：

  Substituted 5-nitro-2-ethynylpyridines were synthesized by the Sonogashira reaction of 2-bromo-5-5-nitropyridine with terminal acetylenes. Desilylation, oxidative decarbonylation, and the retro-Favorskii reaction of the cross-coupling products of 2-bromo-5-nitropyridine with trimethylsilylacetylene, prop-2-ynyl alcohol, and 2-methylbut-3-yn-2-ol, respectively, gave 2-ethynyl-5-nitropyridine. The hydration of 2-ethynyl-5-nitropyridine and 5-nitro-2-(phenylethynyl)pyridine according to Kucherov afforded 2-acetyl-5-nitropyridine and 5-nitro-2-phenacylpyridine, respectively.

  DOI：

  10.1134/s1070428010120109
• 作为产物：
  描述：

  2-溴-5-硝基吡啶 在 dichlorobis(triphenylphosphine)palladium[II] CuI 、 三乙胺 作用下， 生成 三甲基-[2-(5-硝基吡啶-2-基)乙炔基]硅烷
  参考文献：
  名称：

  Modulators of LXR

  摘要：

  本发明的化合物，例如式（I）的化合物：其中n，m，A，B，R1，R2，R3，R4和R5如本文所定义，可用作肝X受体活性的调节剂。还公开了含有这些化合物的药物组合物和使用这些化合物的方法。

  公开号：

  US20050080111A1

文献信息

• Syntheses and quadratic hyperpolarizabilities of some (pyridylalkynyl)metal complexes: crystal structures of [Ni{2-(CC)C5H3NNO2-5}(PPh3)(η-C5H5)], [Au{2-(CC)C5H3NNO2-5}(PPh3)] and [Au{2-(CC)C5H4N}(PPh3)] ‡
  作者：Raina H. Naulty、Marie P. Cifuentes、Mark G. Humphrey、Stephan Houbrechts、Carlo Boutton、André Persoons、Graham A. Heath、David C. R. Hockless、Barry Luther-Davies、Marek Samoc

  DOI：10.1039/a702249b

  日期：——

  The complexes [Ru2-(CC)C5H3NR-5}(PPh3)2(η-C5H5)] (R = NO2 1 or H 2), [Ni2-(CC)C5H3NR-5}(PPh3)(η-C5H5)] (R = NO2 3 or H 4) and [Au2-(CC)C5H3NR-5}L] (L = PPh3, R = NO2 5 or H 6; L = PMe3, R = NO2 7) have been synthesized and 3, 5 and 6 structurally characterized; no significant increase in quinoidal vinylidene contribution to the acetylide ground-state structure is apparent on progression from structurally characterized phenylacetylide complexes to the new pyridylacetylide complexes, or upon replacement of 5-H by 5-NO2 in progressing from 6 to 5. The molecular quadratic optical non-linearities of 1–7 have been determined by hyper-Rayleigh scattering (HRS). The HRS measurements at 1064 nm are consistent with an increase in β upon replacement of phenyl by an N-heterocyclic ring (replacing a nitrophenylacetylide by a nitropyridylacetylide ligand) for the ruthenium and gold systems, but with no change for the nickel complexes, and with an increase in non-linearity upon replacement of PMe3 by PPh3 in progressing from 7 to 5. The bulk second-order susceptibilities of the series have been determined by Kurtz powder measurements at 1064 nm, with the only significant response (about eight times that of urea) being that of 3; this complex was the only one of the three structurally characterized to pack non-centrosymmetrically in the crystal lattice. Electrochemical data for 1–4 have been obtained; comparison to analogous nitrophenylacetlylide complexes reveals that replacing nitrophenylacetylide by nitropyridylacetylide leads to a significant increase in MII/III oxidation potential for the ruthenium complexes, but to no change for the nickel examples. The parameter E°MII/III – E°NO2/NO2– was evaluated for 1–4, results for M = Ru vs. Ni being consistent with experimentally determined non-linearities, i.e. smaller ΔE° and larger non-linearities for ruthenium vs. nickel.

  复合物 [Ru2-(CC)C5H3NR-5}(PPh3)2(η-C5H5)] (R = NO2 1 或 H 2)、[Ni2-(CC)C5H3NR-5}(PPh3)(η-C5H5)] (R = NO2 3 或 H 4) 和 [Au2-(CC)C5H3NR-5}L] (L = PPh3, R = NO2 5 或 H 6; L = PMe3, R = NO2 7) 已被合成并结构表征 3、5 和 6；从结构表征的苯乙炔基复合物到新的吡啶乙炔基复合物，或从 6 到 5 替换 5-H 为 5-NO2 的过程中，乙炔基的醌式乙烯基贡献对乙炔基基态结构的显著增加并不明显。分子二阶非线性光学性质已通过超雷利散射(HRS)测定。HRS 测量在 1064 nm 处与通过用 N-杂环替代苯基 (用硝基吡啶乙炔基取代硝基苯乙炔基配体) 在钌和金系统中增加 β 一致，但对镍复合物没有变化，并且在从 7 到 5 的过程中用 PPh3 替代 PMe3 时非线性增加。通过 Kurtz 粉末测量在 1064 nm 处确定了系列的有效二阶极化率，唯一显著的响应 (约为尿素的八倍) 来自 3；这种复合物是三个结构表征中唯一一个在晶格中非中心对称排列的。获得了 1-4 的电化学数据; 与类似的硝基苯乙炔基复合物比较，用硝基吡啶乙炔基替代硝基苯乙炔基会导致钌复合物的 MII/III 氧化电位显著增加，但对镍复合物没有变化。对 1-4 评估了参数 E°MII/III - E°NO2/NO2，结果 M = Ru 和 Ni 与实验确定的非线性一致，即较小的 ΔE° 和较大的非线性对于钌比镍。
• Metal-free Synthesis of 2-Alkenyl/Alkynyl-5-nitropyridines Using a Three-component Ring Transformation
  作者：Song Thi Le、Haruyasu Asahara、Nagatoshi Nishiwaki

  DOI：10.1246/cl.150045

  日期：2015.6.5

  A metal-free, facile, and efficient protoco lf or synthesizing a series of 2-alkenyl/alkynyl-5-nitropyridines was developed by using a three-component ring transformation of 1-methyl-3,5-dinitro-2-pyridone with α,β-unsaturated ketones and ammonium acetate. As 2-alkenyl/alkynyl-5-nitropyridines are not easily prepared by Heck or Sonogashira reactions, this method will be a supplementary to these reactions

  通过使用 1-甲基-3,5-二硝基-2-吡啶酮的三组分环转化，开发了一种不含金属、简便且高效的方案或合成一系列 2-烯基/炔基-5-硝基吡啶。 α,β-不饱和酮和醋酸铵。由于 Heck 或 Sonogashira 反应不容易制备 2-烯基/炔基-5-硝基吡啶，因此该方法将是这些反应的补充。
• Modulators Of Nuclear Receptors
  申请人：Bayne Christopher D.

  公开号：US20080119488A1

  公开（公告）日：2008-05-22

  Compounds of the invention, such as compounds of formula (I), where n, m, A, R1, R2, R3, R4 and R5 are defined herein, are useful as modulators of the activity of liver X receptors. Pharmaceutical compositions containing the compounds and methods of using the compounds are also disclosed.

  本发明的化合物，例如式（I）中的化合物，其中n，m，A，R1，R2，R3，R4和R5在此定义，可用作肝X受体活性调节剂。还公开了含有该化合物的制药组合物和使用该化合物的方法。
• Organometallic complexes for nonlinear optics. 15. Molecular quadratic hyperpolarizabilities of trans-bis{bis(diphenylphosphino)methane}ruthenium σ-aryl- and σ-pyridyl-acetylides: X-ray crystal structure of trans-[Ru(2-CCC5H3N-5-NO2)Cl(dppm)2]
  作者：Raina H Naulty、Andrew M McDonagh、Ian R Whittall、Marie P Cifuentes、Mark G Humphrey、Stephan Houbrechts、Joachim Maes、André Persoons、Graham A Heath、David C.R Hockless

  DOI：10.1016/s0022-328x(98)00573-7

  日期：1998.7

  The complexes trans-[Ru(2-C=CC5H3N-5-R)Cl(dppm)(2)] [R = H (6), NO2 (7)] have been prepared and 7 has been structurally characterized; comparison with the structural study of trans-[Ru(4-C=CC6H4NO2)Cl(dppm)(2)] (3) reveals a decrease in Ru-C(I) distance and increase in Ru-Cl(1) distance, consistent with stronger sigma-bonding by the nitropyridylalkynyl ligand in 7 compared to the nitrophenylalkynyl ligand in 3. Electrochemical data for 3, 6, 7, precursor dichloro complexes [RuCl2(dppm)(2)] [cis (1a), trans (1b)], and related alkynyl complexes trans-[Ru(4-C=CC6H4R)Cl(dppm)(2)] [R=H (2), 4-C6H4NO2 (4), (E)-4CH=CHC6H4NO2 (5)] have been determined by cyclic voltammetry. Introduction of nitro substituent in progressing from 2 to 3 or 6 to 7 leads to a substantial increase in E degrees(Ru)(II/III), most of which is lost on chain-lengthening the alkynyl ligand in progressing from 3 to 4 or 5. Replacement of phenyl by pyridyl in progressing from 2 to 6 or 3 to 7 results in a 0.1 V increase in E degrees(Ru)(II/III) The optical spectra of representative complexes have been examined. Introduction of a nitro substituent onto the phenylalkynyl ligand, in progressing from 2 to 3, results in a substantial (ca. 11 000 cm(-1)) red-shift in the intense MLCT band of the Ru-II-C=C-Ar-NO2 moiety. Complexes 3, 4 and 5 exhibit sizable solvatochromic shifts, suggestive of significant optical nonlinearities. Quadratic hyperpolarizabilities for 2-7 were determined by hyper-Rayleigh scattering (HRS) at 1064 nm; measurements are consistent with an increase in beta(HRS) upon incorporation of nitro substituent (progressing from 2 to 3 or 6 to 7), chain-lengthening the alkynyl ligand (progressing from 3 to 4 and then to 5) and replacing phenyl by pyridyl in progressing from 2 to 6, general trends that are maintained with the two-level-corrected data, and which parallel shifts in lambda(max) to low energy. The observed and two-level-corrected beta(HRS) values for 7 are lower than expected; it is perhaps significant that lambda(max) for 7 is close to the second-harmonic. (C) 1998 Elsevier Science S.A. All rights reserved.
• Modulators of LXR
  申请人：Bayne D. Christopher

  公开号：US20050080111A1

  公开（公告）日：2005-04-14

  Compounds of the invention, such as compounds of formula (I): where n, m, A, B, R 1 , R 2 , R 3 , R 4 and R 5 are defined herein, are useful as modulators of the activity of liver X receptors. Pharmaceutical compositions containing the compounds and methods of using the compounds are also disclosed.

  本发明的化合物，例如式（I）的化合物：其中n，m，A，B，R1，R2，R3，R4和R5如本文所定义，可用作肝X受体活性的调节剂。还公开了含有这些化合物的药物组合物和使用这些化合物的方法。