1-benzyl-4,5-dihydro-1H-pyrazole

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-benzyl-4,5-dihydro-1H-pyrazole
• 英文别名: 1-Phenylmethyl-4,5-di-hydropyrazole；2-benzyl-3,4-dihydropyrazole
• 化学式: C₁₀H₁₂N₂
• mdl: MFCD09032134
• 分子量: 160.219
• InChiKey: OOIUEWOQTBCYIR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  15.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-benzyl-4,5-dihydro-1H-pyrazole 在 N-氯代丁二酰亚胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 12.0h， 以85%的产率得到1-benzyl-3-chloro-4,5-dihydro-1H-pyrazole
  参考文献：
  名称：

  Fe(III)-Catalyzed Aerobic Intramolecular N–N Coupling of Aliphatic Azides with Amines

  摘要：

  An Fe(III)-catalyzed intramolecular N-N coupling of aliphatic azidoamines that forms diverse five-and six-membered semisaturated diazoheterocycles using air as an oxidant is reported, providing an alternative to hydrazine-based methods. Mechanistic studies suggest that a N-radical induced intramolecular homolytic substitution (S(H)2) is involved in ring closure. The power of this N-N bond-forming method is also demonstrated by using it as the final step in a total synthesis of (-)-newbouldine.

  DOI：

  10.1021/acs.orglett.9b01396
• 作为产物：
  描述：

  6-phenyl-1,5-diazabicyclo[3.1.0]hexane 在 zinc trifluoromethanesulfonate 作用下， 以 甲苯 为溶剂， 以87 %的产率得到1-benzyl-4,5-dihydro-1H-pyrazole
  参考文献：
  名称：

  氧化还原中性锌催化级联 [1,4]-H 移位/二氮丙啶与供体-受体氮丙啶环化

  摘要：

  使用锌催化实现二氮丙啶与供体-受体氮丙啶 (DAA) 的偶联，通过[1,4]-氢化物转移提供咪唑并吡唑-4,4-二羧酸酯。锌催化、[1,4]-氢化物变换、天然产物修饰和后期分子对接研究的使用是重要的实用特征。

  DOI：

  10.1039/d4cc00226a

文献信息

• Microwave-assisted cyclocondensation of hydrazine derivatives with alkyl dihalides or ditosylates in aqueous media: syntheses of pyrazole, pyrazolidine and phthalazine derivatives
  作者：Yuhong Ju、Rajender S. Varma

  DOI：10.1016/j.tetlet.2005.07.018

  日期：2005.9

  Direct syntheses of 4,5-dihydro-pyrazole, pyrazolidine, and 1,2-dihydro-phthalazine derivatives via double-alkylation of hydrazines by alkyl dihalides or ditosylates were accomplished in aqueous media under microwave irradiation conditions; the environmentally friendlier chemical transformation occurred in a single step and eliminated the use of expensive metal catalysts in building two C–N bonds.

  在微波辐射条件下，在含水介质中，通过烷基二卤化物或二甲苯磺酸盐对肼的双烷基化反应，直接合成4，5-二氢吡唑，吡唑烷和1，2-二氢邻苯二甲酰肼衍生物。有利于环境的化学转化过程一步完成，消除了使用昂贵的金属催化剂来构建两个C–N键的过程。
• Generation and metathesis of azomethine imines in reaction of 6-aryl-1,5-diazabicyclo[3.1.0]hexanes with het(aryl)methylidenemalononitriles
  作者：M. I. Pleshchev、V. Yu. Petukhova、V. V. Kuznetsov、D. V. Khakimov、T. S. Pivina、Yu. V. Nelyubina、N. N. Makhova

  DOI：10.1007/s11172-013-0143-9

  日期：2013.4

  give in situ new azomethine imines inaccessible by common synthetic methods. New azomethine imines are detected as pyrazolines formed via a 1,4-H shift and trapped by the [3+2] cycloaddition with various dipolarophiles to yield 1,5-diazabicyclo[3.3.0]octane derivatives bearing pharmacophoric heterocycles, e.g. furan, nitrofuran, thiophene, and indole. The best results are achieved in the Et2O·BF3-catalyzed

  发现了偶氮甲碱亚胺的新复分解反应。6-芳基-1,5-二氮杂双环[3.1.0]己烷的催化或热二氮丙啶开环导致偶氮甲亚胺与杂（芳基）亚甲基丙二腈进一步反应，原位生成新的偶氮甲亚胺，这是普通合成方法无法获得的。新的偶氮甲碱亚胺被检测为通过 1,4-H 位移形成的吡唑啉，并通过 [3+2] 环加成与各种偶极试剂捕获，产生带有药效杂环的 1,5-二氮杂双环 [3.3.0] 辛烷衍生物，例如呋喃，硝基呋喃、噻吩和吲哚。在 Et2O·BF3 催化的离子液体反应中取得了最好的结果。
• Thermally Induced Tandem Cycloaddition of 2-Alkyl-3-phenylcyclopropenones to 6-Aryl-1,5-diazabicyclo[3.1.0]hexanes
  作者：A. P. Molchanov、D. I. Sipkin、Yu. B. Koptelov、R. R. Kostikov

  DOI：10.1007/s11178-005-0205-z

  日期：2005.4

  Thermolysis of 6-aryl-1,5-diazabicyclo[3.1.0]hexanes in the presence of 2-alkyl-3-phenylcyclopropenones gives fused polycyclic systems of the 4a,7b-diazacyclopenta[cd]inden-7-one series as a result of addition of two cyclopropenone molecules and extrusion of CO molecule. The first step of the process is characterized by 100% regioselectivity, leading to the adduct with vicinal arrangement of the aryl groups, while the regioselectivity of the second step is likely to be determined by spatial interactions between substituents in the cyclopropenone molecule and trimethylene bridge of the diazabicyclohexane. Steric hindrances in the second step could eliminate formation of stable products.

  6- 芳基-1,5-二氮杂双环[3.1.0]己烷在 2-烷基-3-苯基环丙烯酮存在下发生热解，产生 4a,7b-二氮杂环戊并[cd]茚-7-酮系列的融合多环体系，这是两个环丙烯酮分子相加和 CO 分子挤出的结果。该过程第一步的特点是具有 100% 的区域选择性，可产生芳基邻接排列的加合物，而第二步的区域选择性可能取决于环丙烯酮分子中的取代基和二氮杂双环己烷的三亚甲基桥之间的空间相互作用。第二步中的立体阻碍可能会导致无法形成稳定的产物。
• Selective and reversible 1,3-dipolar cycloaddition of 6-aryl-1,5-diazabicyclo[3.1.0]hexanes with 1,3-diphenylprop-2-en-1-ones under microwave irradiation
  作者：Alexander P Molchanov、Mariia M Efremova、Mariya A Kryukova、Mikhail A Kuznetsov

  DOI：10.3762/bjoc.16.218

  日期：——

  cycloaddition of in situ-generated azomethine imine under microwave conditions is described. The reaction of 6-aryl-1,5-diazabicyclo[3.1.0]hexanes with 1,3-diphenylprop-2-en-1-ones proceeds regio- and stereoselectively giving mostly good yields of the corresponding perhydropyrazolopyrazoles. The products of the reaction undergo cycloreversion under the reaction conditions.

  描述了在微波条件下原位生成的甲亚胺亚胺环加成的第一个例子。6-芳基-1,5-二氮杂双环[3.1.0]己烷与1,3-二苯基丙-2-烯-1-酮的反应在区域和立体选择性上进行，从而大部分相应的全氢吡唑并吡唑具有良好的收率。反应产物在反应条件下进行环还原。
• Comparative characterization of thermal isomerization rates of 6-phenyl-1,5-diazabicyclo[3.1.0]hexane at convection and microwave heating
  作者：Tatiana A. Kornilova、Rafael R. Kostikov、Alexander F. Khlebnikov、Igor G. Zenkevich

  DOI：10.1002/poc.3843

  日期：2018.7

  Rate constants of thermal isomerization of 6‐phenyl‐1,5‐diazabicyclo[3.1.0]hexane into 1‐(benzyl)‐4,5‐dihydro‐1H‐pyrazole at convection and microwave heating in toluene and chlorobenzene (solvents) were determined within the temperature range 90°C to 120°С. These data were used for the calculation of activation parameters of isomerization. It is shown that microwave heating increases the rate constants

  在甲苯和氯苯中的对流和微波加热下，将6-苯基-1,5-二氮杂双环[3.1.0]己烷热异构化为1-（苄基）-4,5-二氢-1 H-吡唑的速率常数在90°C至120°С的温度范围内测定。这些数据用于计算异构化的活化参数。结果表明，与使用对流加热相比，微波加热在相同温度下的速率常数增加2到2.5倍。原因是在甲苯中，微波加热的有效温度比对流加热的温度高6°C至9°С，在氯苯中的有效温度超过对流加热12°C至20°С。