(+/-)-10-methyl-5-oxo-5,10-dihydro-5λ⁴-phenothiazine-3-carbaldehyde | 459454-35-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并噻嗪类
• 英文名称: (+/-)-10-methyl-5-oxo-5,10-dihydro-5λ⁴-phenothiazine-3-carbaldehyde
• 英文别名: 3-formyl-10-methyl-10H-phenothiazine-5-oxide；10-Methyl-5-oxophenothiazine-3-carbaldehyde；10-methyl-5-oxophenothiazine-3-carbaldehyde
• CAS: 459454-35-4；459454-55-8
• 化学式: C₁₄H₁₁NO₂S
• 分子量: 257.313
• InChiKey: JQAZMCLRZOMLMY-UHFFFAOYSA-N

物化性质

• 熔点：
  205-207 °C(Solv: ethanol (64-17-5))
• 沸点：
  502.9±49.0 °C(Predicted)
• 密度：
  1.45±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  67.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+/-)-10-methyl-5-oxo-5,10-dihydro-5λ⁴-phenothiazine-3-carbaldehyde 在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 反应 1.0h， 以85%的产率得到(+/-)-(10-methyl-5-oxo-5,10-dihydro-5λ⁴-phenothiazin-3-yl)methanol
  参考文献：
  名称：

  Synthesis of optically active 3-substituted-10-alkyl-10H-phenothiazine-5-oxides by enantioselective biotransformations

  摘要：

  A series of racemic 10-alkyl-3-formyl-10H-phenothiazine-5-oxides (+/-)-2a-h were subjected to biotransformation with baker's yeast resulting in optically active aldehydes (+)-2a-h and alcohols (-)-3a-h in moderate enantiomeric excess. The racemic 10-alkyl-3-hydroxymethyl-10H-phenothiazine-5-oxides (+/-)-3a-h and 3-acetoxymethyl-10-alkyl-10H-phenothiazine-5-oxides (+/-)-4a-h obtained from the racemic aldehydes ()-2a-h were also tested in enantioselective lipase-catalyzed acetylations and alcoholysis reactions. The highest enantiomeric purities were achieved by a Novozyme 435-catalyzed acetylation-ethanolysis sequence, leading to optically active alcohols (-)-3a h in 83-92% e.e. A novel NMR method using enantiopure dibenzoyl tartaric acid as chiral additive was developed for determination of the enantiomeric composition of the optically active products. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00077-0
• 作为产物：
  描述：

  10-甲基-10H-吩噻嗪-3-甲醛 在 copper(II) nitrate 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以90%的产率得到(+/-)-10-methyl-5-oxo-5,10-dihydro-5λ⁴-phenothiazine-3-carbaldehyde
  参考文献：
  名称：

  （E）-3-（2-烷基-10H-吩噻嗪-3-基）-1-芳基丙-2-烯-1-酮：肼解和超声处理中取代基依赖性反应的制备，IR，NMR和DFT研究硝酸铜辅助氧化。

  摘要：

  通过相应的（E）-3-（2-烷基-10H-吩噻嗪-3-基）的取代基依赖性区域选择性缩合，获得了一系列新颖的3（5）-芳基/二茂铁基-5（3）-吩噻嗪并吡唑啉和吡唑啉。 ）-1-芳基/二茂铁基丙-2-烯-1-酮与肼或甲基肼的乙酸溶液。用溶剂模型通过DFT计算的互变异构平衡常数解释了初次形成的β-肼基加合物发生竞争性逆曼尼希反应的不同倾向。还通过对简化模型分子进行的比较DFT计算，使与甲基肼的环化反应的区域选择性以及吡唑啉的取代基依赖性氧化还原特性也得到了合理化。关于超声促进含硝酸吩噻嗪铜的吡唑啉的氧化促进作用，烯酮和含氧化合物被选择性地转化为亚砜。仅一种亚砜烯酮部分转化为环氧乙烷衍生物。通过IR和NMR光谱法（包括COSY，HSQC，HMBC和DNOE测量）确定新产物的结构。

  DOI：

  10.1039/b608455a

文献信息

• (E)-3-(2-Alkyl-10H-phenothiazin-3-yl)-1-arylprop-2-en-1-ones: preparative, IR, NMR and DFT study on their substituent-dependent reactivity in hydrazinolysis and sonication-assisted oxidation with copper(<scp>ii</scp>)nitrate
  作者：Luiza Găină、Antal Csámpai、György Túrós、Tamás Lovász、Virág Zsoldos-Mády、Ioan A. Silberg、Pál Sohár

  DOI：10.1039/b608455a

  日期：——

  beta-hydrazino adducts to undergo competitive retro-Mannich reaction was interpreted in terms of tautomerisation equilibrium constants calculated by DFT using a solvent model. The regioselectivity of the cyclisation reactions with methylhydrazine and the substituent-dependent redox properties of pyrazolines were also rationalized by comparative DFT calculations performed for simplified model molecules. On the

  通过相应的（E）-3-（2-烷基-10H-吩噻嗪-3-基）的取代基依赖性区域选择性缩合，获得了一系列新颖的3（5）-芳基/二茂铁基-5（3）-吩噻嗪并吡唑啉和吡唑啉。 ）-1-芳基/二茂铁基丙-2-烯-1-酮与肼或甲基肼的乙酸溶液。用溶剂模型通过DFT计算的互变异构平衡常数解释了初次形成的β-肼基加合物发生竞争性逆曼尼希反应的不同倾向。还通过对简化模型分子进行的比较DFT计算，使与甲基肼的环化反应的区域选择性以及吡唑啉的取代基依赖性氧化还原特性也得到了合理化。关于超声促进含硝酸吩噻嗪铜的吡唑啉的氧化促进作用，烯酮和含氧化合物被选择性地转化为亚砜。仅一种亚砜烯酮部分转化为环氧乙烷衍生物。通过IR和NMR光谱法（包括COSY，HSQC，HMBC和DNOE测量）确定新产物的结构。
• Synthesis of optically active 3-substituted-10-alkyl-10H-phenothiazine-5-oxides by enantioselective biotransformations
  作者：Monica Toşa、Csaba Paizs、Cornelia Majdik、Lajos Novák、Pál Kolonits、Florin-Dan Irimie、László Poppe

  DOI：10.1016/s0957-4166(02)00077-0

  日期：2002.2

  A series of racemic 10-alkyl-3-formyl-10H-phenothiazine-5-oxides (+/-)-2a-h were subjected to biotransformation with baker's yeast resulting in optically active aldehydes (+)-2a-h and alcohols (-)-3a-h in moderate enantiomeric excess. The racemic 10-alkyl-3-hydroxymethyl-10H-phenothiazine-5-oxides (+/-)-3a-h and 3-acetoxymethyl-10-alkyl-10H-phenothiazine-5-oxides (+/-)-4a-h obtained from the racemic aldehydes ()-2a-h were also tested in enantioselective lipase-catalyzed acetylations and alcoholysis reactions. The highest enantiomeric purities were achieved by a Novozyme 435-catalyzed acetylation-ethanolysis sequence, leading to optically active alcohols (-)-3a h in 83-92% e.e. A novel NMR method using enantiopure dibenzoyl tartaric acid as chiral additive was developed for determination of the enantiomeric composition of the optically active products. (C) 2002 Elsevier Science Ltd. All rights reserved.