4,4,4-trichloro-2-methyl-1-phenylbutane-1,3-dione | 470467-32-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4,4,4-trichloro-2-methyl-1-phenylbutane-1,3-dione
• 英文别名: 1,1,1-trichloro-3-methyl-4-phenylbutan-2,4-dione
• CAS: 470467-32-4
• 化学式: C₁₁H₉Cl₃O₂
• 分子量: 279.55
• InChiKey: VZJXBKGGUMDNBK-UHFFFAOYSA-N

物化性质

• 熔点：
  65-68 °C(Solv: hexane (110-54-3))
• 沸点：
  326.0±37.0 °C(Predicted)
• 密度：
  1.382±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4,4,4-trichloro-2-methyl-1-phenylbutane-1,3-dione 在 盐酸羟胺 作用下， 以 甲醇 为溶剂， 反应 10.0h， 生成 3-phenyl-4-methyl-5-hydroxy-5-trichloromethyl-4,5-dihydroisoxazole
  参考文献：
  名称：

  Synthesis and structure of new trichloromethyl-β-diketones — 5-Trichloromethylisoxazole and 5-isoxazolecarboxylic acid derivatives

  摘要：

  一种改进的方法用于合成一系列新的三氯甲基-β-二酮，包括1,1,1-三氯戊二酮（2a）、1,1,1-三氯-3-甲基己二酮（2b）、4,4,4-三氯-1-苯基丁二酮（2c）、4,4,4-三氯-2-甲基-1-苯基丁二酮（2d）、2-三氯乙酰环己酮（2e）、4-叔丁基环己酮（2f）、4-叔丁基环庚酮（2g）和4-叔丁基环辛酮（2h）。多核NMR研究表明，β-二羰基化合物2b和2d至2h主要以酮形式存在，而2a和2c以烯醇形式存在。三氯甲基-β-二酮与盐酸羟胺反应，生成三组异噁唑衍生物。关键词：缩醛，酰化，三氯甲基-1,3-二酮，2-三氯乙酰环烷酮，异噁唑，环缩合。

  DOI：

  10.1139/v05-130
• 作为产物：
  描述：

  C₁₂H₁₁Cl₃O₂ 在 硫酸 、 水 作用下， 以 氯仿 为溶剂， 反应 2.0h， 生成 4,4,4-trichloro-2-methyl-1-phenylbutane-1,3-dione
  参考文献：
  名称：

  Synthesis and Structure of Novel 1-Aryl-4,4,4-trichloro-1,3-butanediones

  摘要：

  Novel 1-aryl-4,4,4-trichloro-1,3-butanediones in good yields (80-97%) were synthesized in one pot through acetal acylation with trichloroacetyl chloride followed by acid hydrolysis. Structures of all compounds were elucidated by elemental analysis, mass spectrometry, and H-1/C-13 nuclear magnetic resonance (NMR) measurements. The H-1/C-13 NMR data showed that trichloromethyl-beta-diketones 2a-k in solution are predominantly ketoenol. However, the spectroscopic data from 4,4,4-trichloro-2-methyl-1-phenyl-1,3-butabedione (2l) with methyl substituent between carbonyls showed a bias toward the diketo form in solution. X-ray diffraction of monocrystals from 2g and 2i showed that these compounds are cis-ketoenol tautomers.Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communcations (R) to view the free supplemental file.

  DOI：

  10.1080/00397911.2010.530376

文献信息

• Synthesis of hydroxypyrazoles and 1-methyl-3-isoxazolones via haloform reactions
  作者：Alex F.C. Flores、Nilo Zanatta、Adriano Rosa、Sergio Brondani、Marcos A.P. Martins

  DOI：10.1016/s0040-4039(02)00874-2

  日期：2002.7

  hydroxypyrazoles (2a–f) and 2-methyl-3-isoxazolones (3a–d) from the cyclocondensation reaction of trichloromethyl-substituted 1,3-dielectrophiles (1a–f) with dry hydrazine and N-methylhydroxylamine is reported. The regiospecific cyclocondensation took place with the elimination of the trichloromethyl group in a haloform type reaction when acetonitrile under basic medium was used. The structure of compounds 2

  的一个新系列hydroxypyrazoles（合成2A - ˚F（和2-甲基-3- isoxazolones）3A - d从三氯甲基取代的1,3- dielectrophiles的环化缩合反应）（1A - ˚F）与干燥的肼和ñ -报道了甲基羟胺。当在碱性介质下使用乙腈时，区域特异性的环缩合反应在卤仿型反应中消除了三氯甲基。化合物2和3的结构主要由1 H和13 C NMR光谱确定。
• HALOACETYLATED ENOL ETHERS: 16[5] REGIOSPECIFIC SYNTHESIS OF 5-TRICHLOROMETHYL-PYRAZOLES
  作者：Alex F. C. Flores、Marcos A. P. Martins、Adriano Rosa、Darlene Correia Flores、Nilo Zanatta、Helio G. Bonacorsso

  DOI：10.1081/scc-120004150

  日期：2002.1

  ABSTRACT The regiospecific synthesis and isolation of three series of 5-trichloromethyl-pyrazoles 2f–j, 3a–j and 4a–j from the cyclocondensation of 1,1,1-trichloro-4-alkoxy-3-alken-2-ones (1a–f) or trichloroacetyl containing β-diketones (1g–j) with dry hydrazine and phenyl-hydrazine is reported. It was established by 1H- and 13C-NMR spectroscopy that the 5-hydroxy-5-trichloromethyl-4,5-dihydro-1H-pyrazole

  摘要 从 1,1,1-trichloro-4-alkoxy-3-alken-2-ones 的环缩合反应中区域特异性合成和分离了三个系列的 5-三氯甲基-吡唑 2f-j、3a-j 和 4a-j（ 1a-f) 或含三氯乙酰的 β-二酮 (1g-j) 与干燥的肼和苯肼被报道。通过 1H- 和 13C-NMR 光谱确定 5-羟基-5-三氯甲基-4,5-二氢-1H-吡唑中间体 2a-j 是定量形成的。
• Synthesis and structure of new trichloromethyl-β-diketones — 5-Trichloromethylisoxazole and 5-isoxazolecarboxylic acid derivatives
  作者：Marcos A.P Martins、Sergio Brondani、Victor L Leidens、Darlene C Flores、Sidnei Moura、Nilo Zanatta、Manfredo Hörner、Alex FC Flores

  DOI：10.1139/v05-130

  日期：2005.8.1

  An improved method for the synthesis of a new series of trichloromethyl-β-diketones including 1,1,1-trichloropentan-2,4-dione (2a), 1,1,1-trichloro-3-methylhexan-2,4-dione (2b), 4,4,4-trichloro-1-phenylbutan-1,3-dione (2c), 4,4,4-trichloro-2-methyl-1-phenylbutan-1,3-dione (2d), 2-trichloroacetylcyclohexanone (2e), 4-tert-butylcyclohexanone (2f), 4-tert-butylcycloheptanone (2g), and 4-tert-butylcyclooctanone (2h) is reported. A multinuclear NMR study showed that β-dicarbonyl compounds 2b and 2d–2h are predominantly in the keto form and 2a and 2c are in the enol form. The trichloromethyl-β-diketones react with hydroxylamine hydrochloride leading to three sets of isoxazole derivatives.Key words: acetals, acylation, trichloromethyl-1,3-diketones, 2-trichloroacetylcycloalkanones, isoxazoles, cyclocondensation.

  一种改进的方法用于合成一系列新的三氯甲基-β-二酮，包括1,1,1-三氯戊二酮（2a）、1,1,1-三氯-3-甲基己二酮（2b）、4,4,4-三氯-1-苯基丁二酮（2c）、4,4,4-三氯-2-甲基-1-苯基丁二酮（2d）、2-三氯乙酰环己酮（2e）、4-叔丁基环己酮（2f）、4-叔丁基环庚酮（2g）和4-叔丁基环辛酮（2h）。多核NMR研究表明，β-二羰基化合物2b和2d至2h主要以酮形式存在，而2a和2c以烯醇形式存在。三氯甲基-β-二酮与盐酸羟胺反应，生成三组异噁唑衍生物。关键词：缩醛，酰化，三氯甲基-1,3-二酮，2-三氯乙酰环烷酮，异噁唑，环缩合。
• Synthesis and Structure of Novel 1-Aryl-4,4,4-trichloro-1,3-butanediones
  作者：Alex F. C. Flores、Mauro J. Martins、Leandro M. Frigo、Pablo Machado、Patrick T. Campos、Juliana L. Malavolta

  DOI：10.1080/00397911.2010.530376

  日期：2012.3.1

  Novel 1-aryl-4,4,4-trichloro-1,3-butanediones in good yields (80-97%) were synthesized in one pot through acetal acylation with trichloroacetyl chloride followed by acid hydrolysis. Structures of all compounds were elucidated by elemental analysis, mass spectrometry, and H-1/C-13 nuclear magnetic resonance (NMR) measurements. The H-1/C-13 NMR data showed that trichloromethyl-beta-diketones 2a-k in solution are predominantly ketoenol. However, the spectroscopic data from 4,4,4-trichloro-2-methyl-1-phenyl-1,3-butabedione (2l) with methyl substituent between carbonyls showed a bias toward the diketo form in solution. X-ray diffraction of monocrystals from 2g and 2i showed that these compounds are cis-ketoenol tautomers.Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communcations (R) to view the free supplemental file.