亚硝基叔丁烷 | 917-95-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 中文名称: 亚硝基叔丁烷
• 中文别名: 2-甲基-2-亚硝基丙烷
• 英文名称: t-butylnitrite
• 英文别名: 2-methyl-2-nitrosopropane
• CAS: 917-95-3
• 化学式: C₄H₉NO
• mdl: MFCD00044598
• 分子量: 87.1216
• InChiKey: LUQZKEZPFQRRRK-UHFFFAOYSA-N

物化性质

• 熔点：
  29 °C
• 沸点：
  50 °C
• 密度：
  0.86±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  6
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  29.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  亚硝基叔丁烷 在 meso-tetraphenylporphyrin iron(III) chloride 亚碘酰苯 作用下， 以 二氯甲烷 为溶剂， 以75%的产率得到2-甲基-2-硝基丙烷
  参考文献：
  名称：

  过渡金属卟啉作为亚硝基化合物氧化的催化剂

  摘要：

  铁（III）和锰（III）卟啉被发现是非常有效的催化剂，即使在–78°C下也能将亚硝基氧化为硝基化合物。

  DOI：

  10.1039/c39870001405
• 作为产物：
  描述：

  2-methyl-2-nitrosopropane dimer 以 重水 为溶剂， 反应 24.0h， 生成 亚硝基叔丁烷
  参考文献：
  名称：

  脉冲辐射分解法测定羟基自由基与自旋阱2-甲基-2-亚硝基丙烷的二聚体和单体之间的反应和速率常数

  摘要：

  Reaction rate constants between OH radicals and the dimer and monomer of the spin trap 2-methyl-2-nitrosopropane (MNP) were determined by the pulse radiolysis method. Before pulse radiolysis experiments, the molar absorbance coefficients of the dimer and monomer were determined by a method combining NMR and optical absorbance spectrometries. First, NMR signal intensities of the dimer and monomer were related to their molar concentrations using deuterated tert-butyl alcohol, (CH3)(3)C-OD, as a standard. Since the monomer was eliminated by bubbling the solution with Ar gas and the remaining dimer was found to gradually decompose to the monomer, the changes of molar concentrations against time starting from the dimer alone until reaching dimer-monomer equilibrium were next measured by monitoring both NMR and optical absorbance spectra (at delta = 1.59 and lambda = 320 nm for the dimer and at delta = 1.28 and lambda = 662 nm for the monomer). The molar absorbance coefficients were finally determined to be epsilon(320) (nm) = 410 +/- 40 M(-1) cm(-1) for the dimer and epsilon(662) (nm) = 10 +/- 5 M(-1) Cm-1 for the monomer by comparing the curves measured by NMR with those measured by optical absorbance spectrometry. Pulse radiolysis experiments on the reaction rate constant between OH radicals and the dimer were carried out in aqueous solutions containing different amounts of the MNP dimer alone, and it was determined to be (3.0 +/- 0.3) x 10(9) M(-1) s(-1). Experiments on the reaction rate constant between OH radicals and the monomer were carried out in solutions containing both the dimer and monomer, and it was determined to be (1.3 +/- 0.9) x 10(10) M(-1) s(-1).

  DOI：

  10.1021/j100038a045
• 作为试剂：
  描述：

  甲基苯甲醇-D1 、 苯甲酰肼 在 亚硝基叔丁烷 、 (1,4-dimethyl-5,7-diphenyl-1,2,3,4-tetrahydro-6H-cyclopenta[b]pyrazin-6-one)ruthenium tricarbonyl complex 、 sodium t-butanolate 作用下， 以 叔丁醇 为溶剂， 反应 24.0h， 以68%的产率得到N'-(1-phenylethyl)benzohydrazide-d₁
  参考文献：
  名称：

  无磷钌络合物催化借位氢策略催化单或二烷基化酰肼的合成

  摘要：

  在本文中，我们报道了在各种取代的伯醇和仲醇作为烷基化试剂的情况下，使用借用氢策略，用二氨基环戊二烯酮钌三羰基络合物催化的单或二烷基化酰肼化合物的合成。氘标记实验证实，醇是该级联过程中的氢化物来源。密度泛函理论（DFT）计算揭示了单烷基化和二烷基化之间的起源和阈值。

  DOI：

  10.1021/acs.joc.1c00654

文献信息

• Free-Radical Bromotrifluoromethylation of Olefin via Single-Electron Oxidation of NaSO₂CF₃ by NaBrO₃
  作者：Zhong-Quan Liu、Dong Liu

  DOI：10.1021/acs.joc.6b02812

  日期：2017.2.3

  A free-radical bromotrifluoromethylation of olefin by using NaSO2CF3 and NaBrO3 has been achieved. Sodium bromate acts not only as a single-electron oxidant but also as a bromine source. A radical-clock experiment and electron-spin-resonance detection support a radical process.

  通过使用NaSO 2 CF 3和NaBrO 3已经实现了烯烃的自由基溴三氟甲基化。溴酸钠不仅充当单电子氧化剂，而且还充当溴源。自由基钟实验和电子自旋共振检测支持自由基过程。
• Electron spin resonance of spin trapped radicals in γ-irradiated polycrystalline dipeptides. Chromatographic separation of radicals
  作者：Keisuke Makino、Peter Riesz

  DOI：10.1139/v82-214

  日期：1982.6.15

  Polycrystalline dipeptides (glycyl-glycine, glycyl-L-valine, glycyl-L-leucine, L-alanyl-glycine, and L-prolyl-L-alanine) were γ-irradiated at room temperature in the absence of air. Subsequently they were dissolved in aqueous solutions containing 2-methyl-2-nitrosopropane as the spin trap. From the esr spectra of the nitroxide radicals separated by high-performance liquid chromatography, structural assignments of the radicals were made. For glycyl peptides, H-abstraction from the α-carbon atoms of the carboxyl terminal residues and from the side-chains were observed. For L-alanyl-glycine, H-abstraction from the glycyl residue and the formation of the deamination radical could be shown to occur. For L-prolyl-L-alanine, the ring opening (deamination) reaction, decarboxylation and H-abstraction from the C-terminal a-carbon were seen.

  多晶二肽（甘氨酸-甘氨酸，甘氨酸-L-缬氨酸，甘氨酸-L-亮氨酸，L-丙氨酰-甘氨酸和L-脯氨酰-L-丙氨酸）在室温下在无空气的情况下进行γ辐照。随后，它们被溶解在含2-甲基-2-亚硝基丙烷作为自旋陷阱的水溶液中。通过高效液相色谱分离的亚硝基自由基的esr光谱，对自由基的结构进行了确定。对于甘氨酸肽，观察到了从羧基末端残基的α-碳原子和侧链中的氢抽取。对于L-丙氨酰-甘氨酸，可以显示从甘氨酸残基中抽取氢和形成去氨基自由基的反应发生。对于L-脯氨酰-L-丙氨酸，观察到了环开启（去氨基）反应，脱羧和从C-末端α-碳中的氢抽取。
• Field-Induced Ferrimagnetic State in a Molecule-Based Magnet Consisting of a Co^II Ion and a Chiral Triplet Bis(nitroxide) Radical
  作者：Youhei Numata、Katsuya Inoue、Nikolai Baranov、Mohamedally Kurmoo、Koichi Kikuchi

  DOI：10.1021/ja064828i

  日期：2007.8.1

  one-dimensional chains that are packed parallel to each other in the noncentrosymmetric P1 space group. 1 exhibits four magnetic ground states: paramagnetic; antiferromagnetic; forced ferrimagnetic; field-induced metastable ferrimagnetic. In the paramagnetic state (T > 20 K), it presents short-range antiferromagnetic interaction between Co ion and nitroxide radical and has a minimum of chimT value at 220 K. The

  我们介绍了一种新的基于分子的磁体 [Co(hfac)2].BNO* (1)，其中 hfac = 1,1,1,5，的磁特性的合成、晶体结构以及温度和场依赖性， 5,5-六氟乙酰丙酮和 BNO* 是手性三联体双（硝基氧化物），1,3-双（N-叔丁基-N-氧基氨基）-5-1'-甲基-1'-[2''- (S)-甲基丁氧基]乙基}苯。对映异构体纯 BNO 的存在诱导手性一维链的形成，这些链在非中心对称 P1 空间群中相互平行排列。1 表现出四种磁性基态：顺磁性；反铁磁性；强制亚铁磁性；场致亚稳态亚铁磁体。在顺磁性状态下（T > 20 K），它呈现出 Co 离子和氮氧自由基之间的短程反铁磁相互作用，并且在 220 K 时具有最小的 chimT 值。发现在 220-300 K 温度范围内估计的 Weiss 温度为 -89.9 K。在 20 K (TN) 处，建立了反铁磁长程排序。在 4 K < T <
• Iron-Catalyzed Highly para-Selective Difluoromethylation of Arenes
  作者：Wei-Tai Fan、Yuting Li、Dongjie Wang、Shun-Jun Ji、Yingsheng Zhao

  DOI：10.1021/jacs.0c09545

  日期：2020.12.9

  bond at either the meta or para position by only changing the catalyst system poses a significant challenge. We herein report the [Fe(TPP)Cl]-enabled, selective, C-H difluoromethylation of arenes using BrCF2CO2Et as the difluoromethylation source, which successfully altered the selectivity from the meta to the para position. A preliminary mechanistic study revealed the iron porphyrin complex not only

  仅通过改变催化剂体系在间位或对位直接官能化 CH 键是一项重大挑战。我们在此报告了使用 BrCF2CO2Et 作为二氟甲基化源的 [Fe(TPP)Cl] 启用的、选择性的、CH 二氟甲基化芳烃，这成功地改变了从间位到对位的选择性。初步的机理研究表明，铁卟啉配合物不仅激活了芳环，而且由于配体空间的影响，还诱导了对位选择性。
• Mild and selective catalytic oxidation of organic substrates by a carbon nanotube-rhodium nanohybrid
  作者：Simon Donck、Edmond Gravel、Alex Li、Praveen Prakash、Nimesh Shah、Jocelyne Leroy、Haiyan Li、Irishi N. N. Namboothiri、Eric Doris

  DOI：10.1039/c5cy00985e

  日期：——

  A heterogeneous catalyst was assembled by stabilization of rhodium nanoparticles on carbon nanotubes. The nanohybrid was used for the catalytic aerobic oxidation of diverse substrates such as hydroquinones, hydroxylamines, silanes, hydrazines and thiols, at room temperature. The system proved very efficient on the investigated substrates and demonstrated high selectivity.

  通过将铑纳米颗粒稳定在碳纳米管上来组装非均相催化剂。在室温下，将纳米杂化物用于各种底物（如氢醌，羟胺，硅烷，肼和硫醇）的催化好氧氧化。该系统在所研究的底物上证明是非常有效的，并显示出高选择性。