1-(3,5-二甲基吡唑-1-基)-2-甲基丙-2-烯-1-酮 | 25832-38-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 中文名称: 1-(3,5-二甲基吡唑-1-基)-2-甲基丙-2-烯-1-酮
• 英文名称: 1-(2-methylpropenoyl)-3,5-dimethylpyrazole
• 英文别名: 1-(3,5-Dimethyl-1H-pyrazol-1-yl)-2-methylprop-2-en-1-one；1-(3,5-dimethylpyrazol-1-yl)-2-methylprop-2-en-1-one
• CAS: 25832-38-6
• 化学式: C₉H₁₂N₂O
• 分子量: 164.207
• InChiKey: JSNSHSLFWDABHK-UHFFFAOYSA-N

物化性质

• 沸点：
  64-65 °C(Press: 2 Torr)
• 密度：
  1.5011 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  34.9
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-(3,5-二甲基吡唑-1-基)-2-甲基丙-2-烯-1-酮 在 4DPAIPN 、 草酸 、 四甲基胍 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 1,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)-2,5-dimethylhexane-1,6-dione
  参考文献：
  名称：

  以草酸为无痕关键分子的缺电子烯烃光催化偶联

  摘要：

  还原性烯烃交叉偶联代表了从现成的烯烃原料构建 C-C 键的直接策略。已经开发出一种利用草酸作为无痕关键的一锅法来实现缺电子烯烃的直接交叉偶联。整个过程是一个两步转化，涉及加氢羧化，然后是脱羧交叉偶联。双光催化剂系统对于成功至关重要，并协同促进两个反应步骤。该反应支持生物活性分子的有效合成。光氧化还原催化为 CO 2的生成提供了一种简单而温和的途径从草酸中分离出自由基阴离子，这为这种活性中间体在精细化学品合成中的广泛应用铺平了道路。

  DOI：

  10.1016/j.chempr.2022.12.013
• 作为产物：
  描述：

  3,5-二甲基吡唑 、 甲基丙烯酰氯 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 1-(3,5-二甲基吡唑-1-基)-2-甲基丙-2-烯-1-酮
  参考文献：
  名称：

  溴自由基介导的光氧化还原醛脱羰对丙烯酰胺在室温下的无过渡金属加氢烷基化

  摘要：

  在这里，我们报告了一种可见光介导的烯烃加氢烷基化反应，使用容易获得的醛作为烷基源，通过溴自由基促进的光氧化还原脱羰。该协议为 C( sp 3 )-C( sp 3 ) 键的形成提供了一种替代方法，具有相当大的优势，包括温和和清洁的反应条件、无需过渡金属催化剂和良好的官能团相容性。

  DOI：

  10.1002/adsc.202101188

文献信息

• Enantioselective 1,3-Dipolar Cycloaddition of Nitrile Imines to α-Substituted and α,β-Disubstituted α,β-Unsaturated Carbonyl Substrates: A Method for Synthesizing Dihydropyrazoles Bearing a Chiral Quaternary Center
  作者：Mukund P. Sibi、Levi M. Stanley、Takahiro Soeta

  DOI：10.1002/adsc.200600307

  日期：2006.11

  Dihydropyrazoles bearing a chiral quaternary center at the 5-position have been prepared by enantioselective 1,3-dipolar cycloaddition of nitrile imines to α-substituted- and α,β-disubstituted-α,β-unsaturated carbonyl substrates. Use of α,β-unsaturated carbonyl substrates with a 1-benzyl-5,5-dimethylpyrazolidin-3-one auxiliary in conjunction with MgI2 and a bisoxazoline ligand derived from (1R,2S)-(+

  通过将腈亚胺对映选择性地1，3-偶极环加成到α-取代的和α，β-二取代的α，β-不饱和羰基底物上，制备了在5-位具有手性季中心的二氢吡唑。α，β-不饱和羰基底物与1-苄基5,5-二甲基吡唑烷丁-3-酮助剂与MgI 2和衍生自（1 R，2 S）-（+）-顺式-的双恶唑啉配体一起使用事实证明，1-氨基-2-茚满醇6是获得高对映体选择性（至多99％ee）的手性二氢吡唑的最佳选择。
• Formation of Functionalized Cyclopentenes via Catalytic Asymmetric [3+2] Cycloaddition of Acrylamides with an Allenoate Promoted by Dipeptide-Derived Phosphines
  作者：Yixin Lu、Xiaoyu Han、Su-Xi Wang、Fangrui Zhong

  DOI：10.1055/s-0030-1260460

  日期：2011.6

  Acrylamides derived from 3,5-dimethyl-1H-pyrazole are employed in the asymmetric [3+2] cycloaddition with the allenoate, tert-butyl buta-2,3-dienoate, for the first time. d-Threonine-l-tert-leucine-based bifucntional phosphines are effective catalysts for the above reactions, affording regiospecific [3+2]-annulation products in excellent yields and with moderate enantioselectivities.

  来源于3,5-二甲基-1H-吡唑的丙烯酰胺首次用于与全烯酸酯（即叔丁基丁烯-2,3-二酸酯）进行不对称[3+2]环加成反应。基于d-脯氨酸-1-叔亮氨酸的双功能膦催化剂对上述反应有效，能够生成具有区域选择性的[3+2]环化产物，收率优异且具有适度的对映选择性。
• Enantioselective Radical Hydroacylation of α,β-Unsaturated Carbonyl Compounds with Aldehydes by Triplet Excited Anthraquinone
  作者：Yao Luo、Qi Wei、Liangkun Yang、Yuqiao Zhou、Weidi Cao、Zhishan Su、Xiaohua Liu、Xiaoming Feng

  DOI：10.1021/acscatal.2c04047

  日期：2022.10.21

  hydroacylation of α-substituted α,β-unsaturated carbonyl compounds through direct hydrogen atom transfer in the presence of the photocatalyst anthraquinone and chiral N,N′-dioxide/metal complexes. This mild, robust method provided a facile access to a wide array of chiral ketones with α-tertiary stereocenters by using the readily available aldehyde as a hydroacylation reagent. Based on the spectroscopy experiments

  手性酮的合成一直是化学研究的长期焦点。对映选择性自由基加氢酰化作为获得各种手性酮的有用策略，仅限于与 β-取代烯烃的反应，其中通过立体控制的自由基加成到前手性烯烃产生 β-立体中心。在此，我们通过在光催化剂蒽醌和手性N ,'-二氧化物/金属配合物。这种温和、稳健的方法通过使用容易获得的醛作为氢化酰化试剂，提供了一种容易获得具有 α-叔立体中心的手性酮的方法。基于光谱实验和控制实验以及DFT计算，提出了氢原子转移/自由基加成/对映选择性反向氢原子转移序列。
• The Role of the Achiral Template in Enantioselective Transformations. Radical Conjugate Additions to α-Methacrylates Followed by Hydrogen Atom Transfer
  作者：Mukund P. Sibi、Justin B. Sausker

  DOI：10.1021/ja016839b

  日期：2002.2.1

  We have evaluated various achiral templates (1a-g, 10, and 16) in conjunction with chiral Lewis acids in the conjugate addition of nucleophilic radicals to alpha-methacrylates followed by enantioselective H-atom transfer, Of these, a novel naphthosultam template (10) gave high enantioselectivity in the H-atom-transfer reactions with ee's up to 90%. A chiral Lewis acid derived from MgBr2 and bisoxazoline (2) gave the highest selectivity in the enantioselective hydrogen-atom-transfer reactions. Non-C-2 symmetric oxazolines (20-25) have also been examined as ligands, and of these, compound 25 gave optimal results (87% yield and 80% ee). Insights into rotamer control in alpha-substituted acrylates and the critical role of the tetrahedral sulfone moiety in realizing high selectivity are discussed.
• NEAR-INFRARED-ABSORBING COMPOSITION, NEAR-INFRARED CUT FILTER OBTAINED USING SAME, PROCESS FOR PRODUCING SAID CUT FILTER, CAMERA MODULE AND PROCESS FOR PRODUCING SAME, AND SOLID PHOTOGRAPHING ELEMENT
  申请人：FUJIFILM Corporation

  公开号：US20160178816A1

  公开（公告）日：2016-06-23

  Provided are a near-infrared-absorbing composition capable of forming a cured film having excellent heat resistance while maintaining high near-infrared-shielding properties, a near-infrared cut filter obtained using the same, a process for producing said cut filter, a camera module and a process for producing the same, and a solid photographing element. The near-infrared-absorbing composition includes a near-infrared-absorbing compound (A1) obtained from a reaction between a low-molecular-weight compound which has two or more coordination sites to a metal component or a coordination site to a metal component and a cross-linking group and has a molecular weight of 1800 or lower or a salt thereof and the metal component and a near-infrared-absorbing compound (B) obtained from a reaction between a high-molecular-weight compound having a repeating unit represented by Formula (II) below or a salt thereof and a metal component. In Formula (II), R 2 represents an organic group, Y 1 represents a single bond or a divalent linking group, and X 2 represents the coordination site to the metal component.