1-butyryl-3,5-dimethyl-1H-pyrazole | 37612-62-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 1-butyryl-3,5-dimethyl-1H-pyrazole
• 英文别名: 1-Butyryl-3,5-dimethyl-1H-pyrazol；1-(3,5-Dimethylpyrazol-1-yl)butan-1-one
• CAS: 37612-62-7
• 化学式: C₉H₁₄N₂O
• 分子量: 166.223
• InChiKey: AKVFZTYXZPLIOU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 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-butyryl-3,5-dimethyl-1H-pyrazole 在 N,N-二异丙基乙胺 、 magnesium bromide 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以56%的产率得到1-(2-ethyl-3-oxo)hexanoyl-3,5-dimethylpyrazole
  参考文献：
  名称：

  Kashima, Choji; Takahashi, Katsumi; Fukusaka, Kiyoshi, Journal of Heterocyclic Chemistry, 1995, vol. 32, # 6, p. 1775 - 1778

  摘要：

  DOI：
• 作为产物：
  描述：

  3,5-二甲基吡唑 在 乙醚 、 ethyl magnesium halide 作用下， 生成 1-butyryl-3,5-dimethyl-1H-pyrazole
  参考文献：
  名称：

  Mingoia; Ingraffia, Gazzetta Chimica Italiana, 1934, vol. 64, p. 279,282

  摘要：

  DOI：

文献信息

• The Preparation of<i>N</i>-Acylpyrazoles and Their Behavior Toward Alcohols
  作者：Choji Kashima、Hajime Harada、Isanobu Kita、Iwao Fukuchi、Akira Hosomi

  DOI：10.1055/s-1994-25406

  日期：——

  According to four different methods, various types of N-acylpyrazoles were prepared from the corresponding pyrazoles and carboxylic acids or their acid chlorides. Although N-acylpyrazoles were inert to alcohols under neutral or weakly basic conditions, the alcoholysis was dramatically accelerated by the action of strong acid or base. On the basis of these chemical properties, the regioselective synthesis of methyl benzyl 2,2-dimethylglutarate was achieved by selective protection and functionalization of a carboxylic acid derivative using N-acylpyrazoles.

  根据四种不同的方法，从相应的吡唑和羧酸或其酰氯制备了多种类型的N-酰基吡唑。尽管在中性或弱碱性条件下，N-酰基吡唑对醇呈惰性，但强酸或碱的作用下，醇解反应显著加速。基于这些化学性质，通过选择性保护和功能化羧酸衍生物，成功实现了甲基苄基2,2-二甲基戊二酸酯的区域选择性合成。
• Visible‐Light‐Induced Synthesis of 1,2,3,4‐Tetrahydroquinolines through Formal [4+2] Cycloaddition of Acyclic α,β‐Unsaturated Amides and Imides with <i>N</i> , <i>N</i> ‐Dialkylanilines
  作者：Kennosuke Itoh、Shun‐ichi Nagao、Ken Tokunaga、Shigeto Hirayama、Fumika Karaki、Takaaki Mizuguchi、Kenichiro Nagai、Noriko Sato、Mitsuaki Suzuki、Masashi Hashimoto、Hideaki Fujii

  DOI：10.1002/chem.202004186

  日期：2021.3.17

  facile synthesis of 1,2,3,4‐tetrahydroquinolines that is achieved by a photoinduced formal [4+2] cycloaddition reaction of acyclic α,β‐unsaturated amides and imides with N,N‐dialkylanilines under visible‐light irradiation, in which a new IrIII complex photosensitizer, a thiourea, and an oxidant act cooperatively in promoting the reaction, is reported. The photoreaction enables the synthesis of a wide

  1,2,3,4-四氢喹啉应适用于新药物的开发。在可见光下，通过无环α，β-不饱和酰胺和酰亚胺与N，N-二烷基苯胺的光诱导形式[4 + 2]形式加成[4 + 2]环加成反应，可轻松合成1,2,3,4-四氢喹啉。报道了一种新的Ir III复合光敏剂，硫脲和氧化剂在促进反应中的协同作用。通过光反应，可以合成多种1,2,3,4-四氢喹啉，同时控制反式/顺式非对映选择性（> 99：1）和构建连续的立体生成中心。证明了无环酰亚胺助剂的化学选择性裂解。
• Enantiomerically enriched preparation of enolizable β-keto amides. Diastereoselective α-acylation and subsequent aminolysis of 2-acyl-3-phenyl-l-menthopyrazoles
  作者：Choji Kashima、Iwao Fukuchi、Katsumi Takahashi、Akira Hosomi

  DOI：10.1016/0040-4020(96)00550-9

  日期：1996.7

  After deprotonation with LDA, 2-acyl-3-phenyl-l-menthopyrazoles (13) were diastereomerically α-acylated to give N-(3-phenyl-l-menthopyrazolyl) β-keto amides (14–19). The subsequent amides were converted into the corresponding N-alkyl amides (21–24) retaining their enantiomeric enrichment on the α-position. These are the first examples of enolizable β-keto acid derivatives having only one chiral center

  用LDA去质子化后，2-酰基-3-苯基-升-menthopyrazoles（13）的非对映体α -酰化，得到N-（3-苯基升-menthopyrazolyl）β酮酰胺（14-19）。随后的酰胺被转化为相应的N-烷基酰胺（21-24），使它们的对映体富集在α位。这些是在α位仅具有一个手性中心的可烯醇化的β-酮酸衍生物的第一个实例。这些手性β-酮酰胺在干燥的苯中出奇地稳定，并且它们的光学不对称性在室温下几乎保留了两周而没有任何差向异构化。
• Synthesis of optically active β-lactams by the reaction of 2-acyl-3-phenyl-<i>l</i>-menthopyrazoles with CN compounds
  作者：Choji Kashima、Kiyoshi Fukusaka、Katsumi Takahashi

  DOI：10.1002/jhet.5570340529

  日期：1997.9

  The reaction of 1-acyl-3,5-dimethylpyrazoles 1 with CN compounds was kinetically controlled with syn stereoselectivity through a lithium enolate intermediate using lithium diisopropylamide. In contrast, the anti stereoselective reaction of 1 was caused by the action of diisopropylethylamine in the presence of magnesium bromide under the thermodynamic control. Reaction of 2-acyl-3-phenyl-l-menthopyrazoles

  1-酰基-3，5-二甲基吡唑1与C N化合物的反应是通过使用二异丙基氨基化锂的烯醇锂中间体以顺式立体选择性动力学控制的。相反，在热力学控制下，在溴化镁存在下，二异丙基乙胺的作用引起1的抗立体选择性反应。观察到2-酰基-3-苯基-1-薄荷脑吡唑12与C N化合物以主要的2'S构型以较高的化学和光学产率反应。在2-丙酰基-3-苯基-1-薄荷脑吡唑（12a）与N-亚苄基-4-甲苯磺酰胺（2）。将N-酰基-吡唑和C N化合物的产物直接或以短转化步骤进一步环化成β-内酰胺。
• Diastereoselective .alpha.-Alkylation of 2-Acyl-3-phenyl-l-menthopyrazoles
  作者：Choji Kashima、Iwao Fukuchi、Akira Hosomi

  DOI：10.1021/jo00104a045

  日期：1994.12

  N-Acylpyrazoles were alpha-alkylated in good yields by the treatment with alkyl halides after metalation with LDA or LiHMDS, In the case of chiral N-acylpyrazoles, e.g., 2-acyl-3-phenyl-l-menthopyrazoles (4), the alpha-alkylation was highly diastereoselective. The subsequent alpha-alkylation products could be converted into esters in good yield in the presence of BF3.OEt(2) without the loss of the optical purity.