3-(1-adamantyl)-5-methyl-1H-pyrazole | 1149054-11-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 3-(1-adamantyl)-5-methyl-1H-pyrazole
• 英文别名: 5-methyl-3-(adamant-1-yl)-1H-pyrazole；3-adamantyl-5-methyl-1H-pyrazol；3-adamantyl-5-methylpyrazole
• CAS: 1149054-11-4
• 化学式: C₁₄H₂₀N₂
• 分子量: 216.326
• InChiKey: AREKAJBIACJDHC-UHFFFAOYSA-N

物化性质

• 熔点：
  193-195.5 °C(Solvent: Ethanol)
• 沸点：
  372.5±11.0 °C(predicted)
• 密度：
  1.161±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  28.7
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-(1-adamantyl)-5-methyl-1H-pyrazole 、 水杨醛 在 sodium hydride 、 氯化亚砜 、 cobalt(II) chloride hexahydrate 作用下， 以 四氢呋喃 为溶剂， 反应 22.83h， 以36%的产率得到2-hydroxyphenyl-bis(3-adamantyl-5-methylpyrazolyl)methane
  参考文献：
  名称：

  Metalation of Aryl‐bis(3‐alkyl‐5‐methylpyrazol‐1‐yl)‐ methane (Alkyl=Me, Ad; Aryl=Ph, C ₆ H ₄ ‐2−OH) with NaN(SiMe ₃ ) ₂ , KN(SiMe ₃ ) ₂ , and Ca{N(SiMe ₃ ) ₂ } ₂

  摘要：

  AbstractDeprotonation of phenyl‐bis(3,5‐dimethylpyrazolyl)methane (HC(Ph)(PzMe2)2, 1 a) with [(thf)2Ca{N(SiMe3)2}2] in THF at −40 °C yields heteroleptic [(thf)2Ca{N(SiMe3)2}{C(Ph)(PzMe2)2}] (2 a) and finally homoleptic [(thf)Ca{C(Ph)(PzMe2)2}2] (2 b). However, these complexes degrade at room temperature to calcium bis(pyrazolate) and 2‐phenyl‐4,6‐dimethylpyrimidine (3 a). This degradation is accelerated when bulky phenyl‐bis(3‐adamantyl‐5‐methylpyrazolyl)methane (HC(Ph)(PzAd,Me)2, 1 b) is treated similarly and 2‐phenyl‐4‐adamantyl‐6‐methylpyrimidine (3 b) forms quickly. Sodiation of 1 a and 1 b with NaN(SiMe3)2 yields [{HC(Ph)(PzMe2)2}Na{C(Ph)(PzMe2)2}] (4 a) and [{HC(Ph)(PzAd,Me)2}Na{C(Ph)(PzAd,Me)2}] (4 b). The stronger metalation reagent benzylpotassium is able to quantitatively deprotonate 1 b leading to dinuclear [K{C(Ph)(PzAd,Me)2}]2 (4 c). The metathetical approach and the reaction of 4 c with metal(II) halides of Mg, Ca and Zn again leads to degradation and formation of pyrimidine 3 b. This decomposition of the ligand can be circumvented when the sidearm contains the anionic charge. Thus, 2‐hydroxyphenyl‐bis(3‐adamantyl‐5‐methylpyrazol‐1‐yl)methane (1 c) reacts with [(thf)2Ca{N(SiMe3)2}2] in THF to the homoleptic complex [(thf)4Ca{O−C6H4−CH(PzAd,Me)2}] (2 c). In this complex, THF and pyrazolyl bases compete in the coordination sphere and preparation of a heteroleptic complex fails. To avoid the binding competition between THF and pyrazolyl bases and to stabilize heteroleptic calcium complexes, the reaction has been repeated in toluene yielding [Ca{N(SiMe3)2}{O−C6H4−CH(PzAd,Me)2}]2 (2 d).

  DOI：

  10.1002/ejic.202101051
• 作为产物：
  描述：

  1-金刚烷甲酮 以 乙醇 为溶剂， 反应 10.0h， 生成 3-(1-adamantyl)-5-methyl-1H-pyrazole
  参考文献：
  名称：

  Synthesis of difluoroboron adamantyl-containing complexes and pyrazoles based thereon

  摘要：

  One-stage synthesis has been developed for the preparation of adamantyl-containing difluoroboron complexes of 1,3-dicarbonyl compounds from 1-(1-adamantyl)ethanone, boron trifluoride etherate, and carboxylic acids anhydrides. The reaction of the complexes with hydrazine hydrate and its derivatives afforded the corresponding adamantyl-containing pyrazoles.

  DOI：

  10.1134/s1070428014110165

文献信息

• An Extremely Bulky Tris(pyrazolyl)methanide: A Tridentate Ligand for the Synthesis of Heteroleptic Magnesium(II) and Ytterbium(II) Alkyl, Hydride, and Iodide Complexes
  作者：Ralte Lalrempuia、Andreas Stasch、Cameron Jones

  DOI：10.1002/asia.201403089

  日期：2015.2

  The tris(pyrazolyl)methane compound HC(3‐Ad‐5‐Mepz)3 [1, 3‐Ad‐5‐Mepz=3‐(1‐adamantyl)‐5‐methylpyrazolyl] and its regioisomer, HC(3‐Ad‐5‐Mepz)2(3‐Me‐5‐Adpz), were synthesized and crystallographically characterized. Deprotonation of 1 with MeLi afforded the lithium complex [κ3‐N‐C(3‐Ad‐5‐Mepz)3}Li(thf)], which incorporates a tris(pyrazolyl)methanide ligand of unprecedented bulk. Reaction of 1 with MeMgI

  三（吡唑基）甲烷化合物HC（3-AD-5-Mepz）3 [ 1，3-AD-5-Mepz = 3-（1-金刚烷基）-5- methylpyrazolyl]及其区域异构体，HC（3-广告‐5‐Mepz）2（3‐Me‐5‐Adpz）已合成并进行了晶体学表征。去质子化1与将MeLi，得到锂复合[κ 3 -N-C（3-AD-5-Mepz）3 }的Li（THF）]，它结合了前所未有的散装三（吡唑基）甲烷化配体。的反应1与MeMgI，得到离子性配位络合物[κ 3 -N-HC（3-AD-5-Mepz）3 } MgMe] I，将其容易地去质子化以得到中性化合物[κ 3 -N-C （3-AD-5-Mepz）3} MgMe]。相关的镁化合物丁酯[κ 3 -N-C（3-AD-5-Mepz）3 } MgBu]从反应制备1和MgBu 2。用的LiAlH处理该4或LiAlD 4导致氢化终端镁/氘化复合物，的罕见例子[κ
• Synthesis and Structure of a New Bulky Hybrid Scorpionate/Cyclopentadienyl Ligand and its Lithium Complex
  作者：Miles J. Mandel、Helmar Görls、Matthias Westerhausen

  DOI：10.1002/zaac.202100385

  日期：2022.10.14

  ((H2C(PzAd,Me)(PzMe,Ad), 2 b) and bis(3-methyl-5-adamantylpyrazolyl)methane (H2C(PzMe,Ad)2, 2 c). Lithiation of sterically congested H2C(PzAd,Me)2 (2 a) and subsequent addition of diphenylfulvene yields lithium 1,1-bis(3-adamantyl-5-methylpyrazolyl)-2,2-diphenyl-2-ethyl-cyclopentadienide, [(thf)LiCp−CPh2−CHPzAd,Me}] (3) which is unable to form a thf adduct but can be hydrolyzed to H5C5−CPh2−CHPzAd,Me (4)

  5-(1-金刚烷基)-3-甲基-1 H-吡唑与二溴甲烷反应产生双(3-金刚烷基-5-甲基吡唑基)甲烷(H 2 C(Pz Ad,Me ) 2 , 2的产物混合物a )、(3-金刚烷基-5-甲基吡唑基)-(3-甲基-5-金刚烷基吡唑基)甲烷((H 2 C(Pz Ad,Me )(Pz Me,Ad ), 2 b ) 和双(3-甲基-5-金刚烷基吡唑基)甲烷 (H 2 C(Pz Me,Ad ) 2 , 2 c ). 空间拥挤 H 2 C(Pz Ad,Me ) 2 ( 2 a 的锂化) 并随后添加二苯基富烯，得到 1,1-双(3-金刚烷基-5-甲基吡唑基)-2,2-二苯基-2-乙基-环戊二烯锂，[(thf)LiCP-CPh 2 -CHPz Ad, Me }] ( 3 ) 不能形成 thf 加合物但可以水解为 H 5 C 5 -CPh 2 -CHPz Ad,Me ( 4 )。双（吡唑基）甲烷的 5 位上的金刚烷基，即。e
• A Terminal N₂ Complex of High-Spin Iron(I) in a Weak, Trigonal Ligand Field
  作者：Alex McSkimming、W. Hill Harman

  DOI：10.1021/jacs.5b06337

  日期：2015.7.22

  potential relevance to these processes. Although a number of low-coordinate Fe-(N2) featuring varying degrees of fidelity to the nitrogenase active site are now known, these complexes frequently feature strongly donating ligands that either enforce low- or intermediate-spin states or result in linear Fe-(N2)-Fe bridging motifs. Given that the nitrogenase active site uses weak-field sulfide ligands to

  Fe 在生物和工业 N2 固定中的作用激发了对与这些过程潜在相关的 Fe-(NxHy) 中间体的小分子类似物的深入研究。尽管现在已知许多对固氮酶活性位点具有不同程度保真度的低配位 Fe-(N2)，但这些复合物通常具有强供体配体，这些配体要么强制执行低自旋状态或中度自旋状态，要么导致线性 Fe-( N2)-Fe 桥接图案。鉴于固氮酶活性位点使用弱场硫化物配体来稳定其反应性 Fe 中心，N2 与高自旋 Fe 的结合非常有趣。在此，我们报告了高自旋 (S = 3/2) Fe(I) 以及桥接 Fe-(N2)-Fe 类似物的第一个末端 N2 复合物的合成和表征。电子顺磁共振和溶液磁矩测定证实了高自旋状态，振动实验表明这些复合物中 N≡N 键的激活程度很高。密度泛函理论计算揭示了末端加合物的电子结构，其特征是未配对自旋在 N2 配体上的大量离域。
• Catalyst for addition polymerization and process for producing an addition polymer
  申请人：——

  公开号：US20030032743A1

  公开（公告）日：2003-02-13

  A catalyst obtained by contacting a specific transition metal compound (A) of Group 7 of the Periodic Table of the Elements, having a pyrazolyl group with an aluminum compound selected from organoaluminums and aluminoxanes and/or a specific boron compound, and a process for producing an addition polymer which comprises polymerizing an addition polymerizable monomer with the catalyst.

  一种催化剂，通过将元素周期表第7族的特定过渡金属化合物(A)中的吡唑基与有机铝化合物和/或特定硼化合物中的铝化合物接触而获得，以及生产加成聚合物的方法，该方法包括使用该催化剂聚合加成聚合可聚合单体。
• Synthesis of pyrazoles and pyrazolones from 1,3- and 1,4-diketones of the adamantane series
  作者：S. A. Kon’kov、I. K. Moiseev

  DOI：10.1134/s1070428009120124

  日期：2009.12

  Various pyrazole and dihydropyrazolones containing an adamantane fragment were synthesized from adamantyl-substituted 1,3- and 1,4-diketones, ethyl 4-(1-adamantyl)-2-R-4-oxobutanoates (R = CN, Ac), and ethyl 2-(1-adamantylcarbonyl)-4-oxo-4-phenylbutanoate.