2-(N-phenylhydroxyamino)cyclohexanone | 38382-25-1

• 分子结构分类: 有机化合物 - 苯类化合物 - N-苯基羟胺
• 英文名称: 2-(N-phenylhydroxyamino)cyclohexanone
• 英文别名: 2-N-Phenylhydroxyaminocyclohexanon；Cyclohexanone, 2-(hydroxyphenylamino)-；2-(N-hydroxyanilino)cyclohexan-1-one
• CAS: 38382-25-1
• 化学式: C₁₂H₁₅NO₂
• 分子量: 205.257
• InChiKey: FBWKRUDONJSQPI-UHFFFAOYSA-N

物化性质

• 沸点：
  360.0±42.0 °C(Predicted)
• 密度：
  1.225±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  40.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  环己酮 、 亚硝基苯 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以47%的产率得到2-(N-phenylhydroxyamino)cyclohexanone
  参考文献：
  名称：

  α-羟氨基羰基化合物的简单合成：亚硝基羟醛反应的新范围。

  摘要：

  [反应：见正文]亚硝基化合物与烯醇化物的反应，即“亚硝基羟醛反应”，以高收率发生，生成α-羟氨基羰基化合物。从市售的芳族或脂族亚硝基化合物和各种碱金属或烯醇锡的收率范围为42％至98％，N选择性> 99：1。

  DOI：

  10.1021/ol026443k

文献信息

• Enantioselective <i>O</i>- and <i>N</i>-Nitroso Aldol Synthesis of Tin Enolates. Isolation of Three BINAP−Silver Complexes and Their Role in Regio- and Enantioselectivity
  作者：Norie Momiyama、Hisashi Yamamoto

  DOI：10.1021/ja039103i

  日期：2004.5.1

  ratio and/or choice of silver salt. Indeed, the X-ray crystallographic study has been used to gain insight into the structure of the catalyst. After the evaluation of each species, 1:1 (AgX.(R)-BINAP) complex was found to be the real active species in the O-selective nitroso aldol reaction. On the other hand, a systematic survey of solvent has shown that the optimal 2:1 (AgX.(R)-BINAP) complex is the effective

  通过金属/配体比例的适当组合和/或银盐的选择，实现了三种不同银-BINAP 催化剂的选择性生成。事实上，X 射线晶体学研究已被用于深入了解催化剂的结构。在对每种物质进行评估后，发现 1:1 (AgX.(R)-BINAP) 复合物是 O-选择性亚硝基醛醇反应中真正的活性物质。另一方面，对溶剂的系统调查表明，最佳的 2:1 (AgX.(R)-BINAP) 配合物是 N-选择性途径中的有效催化剂。因此，银-BINAP 催化剂的新生成方法和合成转化不仅为催化对映选择性亚硝基羟醛合成的发展领域提供了新的见解，而且为有效催化剂的设计提供了明确的指导。
• Enantioselective Nitroso Aldol Reaction Catalyzed by QuinoxP*·Silver(I) Complex and Tin Methoxide
  作者：Akira Yanagisawa、Satoshi Takeshita、Youhei Izumi、Kazuhiro Yoshida

  DOI：10.1021/ja910588w

  日期：2010.4.21

  A catalytic enantioselective O-nitroso aldol reaction of alkenyl trichloroacetates with nitrosoarenes was achieved using the (R,R)-t-Bu-QuinoxP*.AgOAc complex as the chiral catalyst and Bu(2)Sn(OMe)(2) as the achiral cocatalyst in the presence of methanol. Optically active alpha-aminooxy ketones with up to 99% ee were regioselectively obtained in high yields from various alkenyl trichloroacetates of

  使用 (R,R)-t-Bu-QuinoxP*.AgOAc 配合物作为手性催化剂和 Bu(2)Sn(OMe)(2) 作为手性催化剂，实现了烯基三氯乙酸酯与亚硝基芳烃的催化对映选择性 O-亚硝基羟醛反应在甲醇存在下的非手性助催化剂。具有高达 99% ee 的光学活性 α-氨基氧基酮以高产率从环酮的各种烯基三氯乙酸酯中获得。
• Thieme Chemistry Journal Awardees - Where are They Now? Dibutyltin Dimethoxide Catalyzed <i>N</i>-Nitrosoaldol Reaction of Alkenyl Trichloroacetate
  作者：Akira Yanagisawa、Youhei Izumi、Satoshi Takeshita

  DOI：10.1055/s-0028-1087815

  日期：——

  Nitrosoaldol reaction between alkenyl trichloroacetates and nitrosobenzene has been achieved using dibutyltin dimethoxide as a catalyst, which is regenerated in the presence of methanol. The corresponding α-hydroxyamino ketones (N-adducts) have exclusively formed not only from cyclic alkenyl trichloroacetates but also from acyclic ones.

  以二甲醇二丁基锡为催化剂，在甲醇存在下再生，实现了烯基三氯乙酸酯与亚硝基苯之间的亚硝基醛醇反应。相应的α-羟基氨基酮（N-加合物）不仅由环状三氯乙酸烯基酯形成，而且还由非环状链烯基形成。
• Processes for production of alpha-aminooxyketones and alpha-hydroxyketones
  申请人：Saito Susumu

  公开号：US20070055081A1

  公开（公告）日：2007-03-08

  The present invention provides a method for easily obtaining α-aminooxyketone compound which is a synthetic equivalent for monosaccharide and pentoses, and a equivalent of α-hydroxyketone compound that can be synthetic intermediates of various physiologically active materials, in high yield; to pave the way for the synthesis of monosaccharide and furthermore of oligosaccharide from the resulting α-hydroxyketone compound induced from α-aminooxyketone compound; and to open new possibilities for the synthesis of various sugar medicines such as anticancer agents, antithrombogenic agents, anti-viral agents, anti-HIV agents, inhibitors of cholesterol synthesis, verotoxin neutralizing agents. According to the invention, a carbonyl compound is allowed to react with a nitroso compound to produce an α-aminooxyketone compound using a catalyst containing a heterocyclic compound shown in the general formula (I) (wherein X1, X2 and X3 independently represent nitrogen, carbon, oxygen or sulfur; and Z represents a substituted or unsubstituted 5- to 10-membered ring).

  本发明提供了一种方法，以高产率轻松获得α-氨氧酮化合物，该化合物是单糖和戊糖的合成等效物，以及α-羟基酮化合物的等效物，可用作各种生理活性物质的合成中间体，为从α-氨氧酮化合物诱导的α-羟基酮化合物合成单糖并进一步合成寡糖铺平道路，并为合成各种糖类药物如抗癌剂、抗凝血剂、抗病毒剂、抗HIV剂、胆固醇合成抑制剂、痢疾毒素中和剂开辟新的可能性。根据本发明，允许羰基化合物与亚硝基化合物反应，使用包含在一般式（I）中的杂环化合物的催化剂（其中X1、X2和X3独立地表示氮、碳、氧或硫；Z表示取代或未取代的5至10元环）。
• Process of making alpha-aminooxyketone/alpha-aminooxyaldehyde and alpha-hydroxyketone/alpha-hydroxyaldehyde compounds and a process making reaction products from cyclic alpha,beta-unsaturated ketone substrates and nitroso substrates
  申请人：Momiyama Norie

  公开号：US20070037973A1

  公开（公告）日：2007-02-15

  The present invention is directed to a process of making α-aminooxyketone and α-hydroxyketone compounds. The synthetic pathway generally involves reacting an aldehyde or ketone substrate and a nitroso substrate in the presence of a catalyst of the formula (IV): wherein X a —X c represent independently nitrogen, carbon, oxygen or sulfur and Z represents a 4 to 10-membered ring with or without a substituent and optionally a further step to convert the α-aminooxyketone compound formed to the α-hydroxyketone compound. The present invention results in α-aminooxyketone and α-hydroxyketone compounds with high enantioselectivity and high purity. The present invention is also directed to a catalytic asymmetric O-nitroso Aldol/Michael reaction. The substrates of this reaction are generally cyclic α,β-unsaturated ketone substrate and a nitroso substrate. This methodology generally involves reacting the cyclic α,β-unsaturated ketone substrate and the nitroso substrate in the presence of a proline-based catalyst, to provide a heterocyclic product.

  本发明涉及一种制备α-氨氧基酮和α-羟基酮化合物的方法。合成途径通常涉及在催化剂存在下反应醛或酮底物和亚硝基底物，所述催化剂的公式为（IV）：其中Xa-Xc分别独立表示氮、碳、氧或硫，Z表示具有或不具有取代基的4到10个成员环，并可选择进一步步骤将形成的α-氨氧基酮化合物转化为α-羟基酮化合物。本发明的结果是具有高对映选择性和高纯度的α-氨氧基酮和α-羟基酮化合物。本发明还涉及一种催化不对称O-亚硝基Aldol/Michael反应。该反应的底物通常为环状α,β-不饱和酮底物和亚硝基底物。该方法通常涉及在脯氨酸基催化剂存在下反应环状α,β-不饱和酮底物和亚硝基底物，以提供杂环产物。