1,1-二氟-2-辛酮 | 89264-22-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 1,1-二氟-2-辛酮
• 中文别名: 2-辛酮,1,1-二氟-
• 英文名称: 1,1-difluoro-2-octanone
• 英文别名: 1,1-difluorooctan-2-one
• CAS: 89264-22-2
• 化学式: C₈H₁₄F₂O
• 分子量: 164.195
• InChiKey: PFOYLZWXMOUFRP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  11
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1,1-二氟-2-辛酮 在 sodium tetrahydroborate 作用下， 以 乙醇 为溶剂， 反应 5.0h， 以91%的产率得到1,1-Difluorooctan-2-ol
  参考文献：
  名称：

  A microbially-based approach for the synthesis of chiral secondary alcohols bearing the difluoromethyl or chlorodifluoromethyl group

  摘要：

  A synthetic approach to both enantiomers of the secondary alcohols [Ph(CH2)n CH(OH)CXF2 (n = 0-2) C6H13(CH2)n CH(OH)CFX2 (n = 0 or 2) and CXF2CH(OH)CH2CO2Et [X = H or Cl], involving the stereoselective hydrolysis of ester derivatives, is described. The absolute configurations of these difluoromethylated or chlorodifluoromethylated molecules were determined.

  DOI：

  10.1016/s0022-1139(00)81174-4
• 作为产物：
  描述：

  1-chloro-1,1-difluoro-2-octanone 在 四(三苯基膦)钯 、 碘 、 锌 作用下， 以 乙腈 为溶剂， 反应 20.5h， 生成 1,1-二氟-2-辛酮
  参考文献：
  名称：

  Synthesis of .alpha.,.alpha.-Difluoro-Functionalized Ketones

  摘要：

  In the presence of a catalytic amount of tetrakis(triphenylphosphine) palladium [Pd(PPh(3))(4)], iododifluoromethyl alkyl and phenyl ketones 1 react with alkenes to give the corresponding alpha,alpha-difluoro-gamma-iodo ketones in high yields at room temperature either neat or in hexane at 60 degrees C. A variety of functional groups, such as alkyl, trimethylsilyl, hydroxy, epoxy, ketone, and ester, are tolerated under the reaction conditions. The reaction can be completely suppressed by a radical inhibitor, di-tert-butyl nitroxide or hydroquinone. A ring closure reaction occurs when 1 reacts with diethyl diallylmalonate in the presence of a catalytic amount of Pd(PPh(3))(4). Under UV irradiation, the reaction of 1 with diallyl ether gives a tetrahydrofuran derivative. All these results are consistent with a radical chain mechanism initiated by single electron transfer from Pd(PPh(3))(4) to 1. In the presence of a catalytic amount of nickel dichloride hexahydrate, the iodine in the 1:1 addition adducts is readily reduced by zinc in moist THF under mild conditions to give the corresponding alpha,alpha-difluoro ketones in high yields. A one-pot addition-reduction reaction has been developed for the synthesis of alpha,alpha-difluoro ketones without the isolation of the 1:1 addition adducts, which provides a new, efficient, and practical method for the preparation of a variety of alpha,alpha-difluoro-functionalized ketones.

  DOI：

  10.1021/jo00122a044

文献信息

• Conversion of methyl ketones and methyl sulfones into α-deutero-α,α-difluoromethyl ketones and α-deutero-α,α-difluoromethyl sulfones in three synthetic steps
  作者：Munia F. Sowaileh、Changho Han、Robert A. Hazlitt、Eun Hoo Kim、Jinu P. John、David A. Colby

  DOI：10.1016/j.tetlet.2016.12.018

  日期：2017.2

  Deuterodifluoromethyl ketones and sulfones were assembled in three synthetic steps from methyl ketones and sulfones, respectively. The key synthetic transformation is the deuteration of the difluorocarbanion generated by the release of trifluoroacetate from highly α-fluorinated gem-diols. High levels of deuterium on the "CF2D" group were routinely observed. This strategy is mild and versatile and it

  在三个合成步骤中，分别从甲基酮和砜中组装了氘代二氟甲基酮和砜。关键的合成转化是由高度α-氟化的宝石二醇释放出三氟乙酸盐而产生的二氟乙二酮的氘代。常规观察到“ CF2D”组的氘水平很高。该策略温和且用途广泛，可用于酮和砜，而无需担心过度氟化或氟化不足。另外的例子解决了当具有其他酸性质子的化合物经受反应条件时的氘化过度的问题。该过程不仅证明了安装“ CF2D”基团的新方法，而且将三氟乙酸盐释放的范围扩展到了砜。
• Organocuprate-induced substitution of the enol oxygen moiety in 2,2-difluoro enol phosphates with allyl halides: a novel route to -diffluoroolefins from chlorodifluoromethyl ketones
  作者：Takashi Ishihara、Masayuki Yamana、Teiichi Ando

  DOI：10.1016/s0040-4039(00)94166-2

  日期：1983.1

  2,2-Difluoro-1-arylethenyl diphenyl phosphates, prepared from chloro-difluoromethyl ketones and diphenyl phosphite, reacted with dibutylcopperlithium and successively with various allyl halides to give allylated gem-difluoroolefins in moderate to excellent yields.

  由氯代-二氟甲基酮和亚磷酸二苯酯制备的2，2-二氟-1-芳基乙烯基二苯基磷酸酯与二丁基铜锂以及依次与各种烯丙基卤化物反应，以中等至极好的收率得到烯丙基化的宝石-二氟烯烃。
• Effect of fluorine on palladium-catalyzed cross-coupling reactions of aryl bromides with trifluoromethyl aryl ketones via difluoroenol silyl or monofluoroenol silyl ethers
  作者：Yong Guo、Jean'ne M. Shreeve

  DOI：10.1039/b705137a

  日期：——

  Palladium-catalyzed cross-coupling reactions of alpha-aryl-beta,beta-difluoroenol silyl and alpha-aryl-beta-fluoroenol silyl ethers with aryl bromides proceed smoothly with good functional compatibility.

  α-芳基-β，β-二氟烯醇甲硅烷基和α-芳基-β-氟烯醇甲硅烷基醚与芳基溴化物的钯催化交叉偶联反应可顺利进行且具有良好的功能相容性。
• A convenient preparative method for α-trifluoromethyl amines
  作者：Shoji Watanabe、Tsutomu Fujita、Masami Sakamoto、Hiroyuki Hamano、Tomoya Kitazume、Takashi Yamazaki

  DOI：10.1016/s0022-1139(96)03574-9

  日期：1997.6

  α-Trifluoromethyl amines (IV) were prepared in three steps: preparation of α-trifluoromethyl ketones (I), their conversion tobenzyloximes (II), and reduction of the oximes (II) with lithium aluminium hydride and sodium methoxide. For example, α-trifluoromethyltridecylamine was obtained from the reduction of trifluoromethyl dodecyl ketone benzyl oxime.

  分三步制备α-三氟甲基胺（IV）：制备α-三氟甲基酮（I），将其转化为苄基肟（II），以及用氢化铝锂和甲醇钠还原肟（II）。例如，通过还原三氟甲基十二烷基酮苄基肟获得α-三氟甲基十三烷基胺。
• Selective reductions. 53. Asymmetric reduction of α-fluoromethyl ketones with B-chlorodiisopinocampheylborane and B-isopinocampheyl-9-borabicyclo[3.3.1]nonane. Combined electronic and steric contributions to the enantiocontrol process
  作者：P.Veeraraghavan Ramachandran、Aleksandar V. Teodorovic'、Baoqing Gong、Herbert C. Brown

  DOI：10.1016/0957-4166(94)80057-x

  日期：1994.6

  A systematic study of the asymmetric reduction of aryl and alkyl α-fluoroalkyl ketones with (−)-diisopinocampheylchloroborane ((−)-DIP-Chloride, 1), and (−)-B-isopinocampheyl-9-borabicyclo[3.3.1]nonane (R-Alpine-Borane, 2) has been made. In the case of reagent 1, the direction of asymmetric induction in the chiral reduction of aryl trifluoromethyl ketones differs from that of the corresponding mono-

  （ - ） -芳基的不对称还原，并与烷基α氟烷基酮的系统性研究diisopinocampheylchloroborane（（ - ） - DIP-氯化物，1），和（ - ） -乙-isopinocampheyl-9-硼杂双环[3.3.1]制备了壬烷（R -Alpine-Borane，2）。在试剂1的情况下，在芳基三氟甲基酮的手性还原中的不对称诱导的方向不同于相应的单和二氟甲基酮的方向。例如，在室温下的纯净条件下，在95％ee和85％ee中，2-氟和2,2-二氟苯乙酮分别被1还原为R-醇，而2,2,2-三氟苯乙酮被还原了，到S-酒精含量为90％的ee。尽管DIP-Chloride可以在不良ee中还原未受阻的前手性二烷基酮，但根据酮中存在的α-氟原子的数量，烷基α-氟代烷基酮在改良的ee中会降低。单氟甲基酮在R-异构体中提供中等的ee，而在相反的异构体中，二氟和三氟甲基酮的ee降低到中等。例如