2925-22-6Relevant articles and documents
Craig et al.
, p. 3572 (1971)
Van Eijck
, p. 1,3, 5, 8-10, 12 (1977)
Decarbonylative Fluoroalkylation at Palladium(II): From Fundamental Organometallic Studies to Catalysis
Lalloo, Naish,Malapit, Christian A.,Taimoory, S. Maryamdokht,Brigham, Conor E.,Sanford, Melanie S.
supporting information, p. 18617 - 18625 (2021/11/16)
This Article describes the development of a decarbonylative Pd-catalyzed aryl-fluoroalkyl bond-forming reaction that couples fluoroalkylcarboxylic acid-derived electrophiles [RFC(O)X] with aryl organometallics (Ar-M′). This reaction was optimized by interrogating the individual steps of the catalytic cycle (oxidative addition, carbonyl de-insertion, transmetalation, and reductive elimination) to identify a compatible pair of coupling partners and an appropriate Pd catalyst. These stoichiometric organometallic studies revealed several critical elements for reaction design. First, uncatalyzed background reactions between RFC(O)X and Ar-M′ can be avoided by using M′ = boronate ester. Second, carbonyl de-insertion and Ar-RF reductive elimination are the two slowest steps of the catalytic cycle when RF = CF3. Both steps are dramatically accelerated upon changing to RF = CHF2. Computational studies reveal that a favorable F2C-H - -X interaction contributes to accelerating carbonyl de-insertion in this system. Finally, transmetalation is slow with X = difluoroacetate but fast with X = F. Ultimately, these studies enabled the development of an (SPhos)Pd-catalyzed decarbonylative difluoromethylation of aryl neopentylglycol boronate esters with difluoroacetyl fluoride.
Synthetic method of difluoroacetyl fluoride
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Paragraph 0041; 0045-0046; 0058; 0062-0063; 0066; 0070-0071, (2020/12/10)
The invention relates to a synthesis method of difluoroacetyl fluoride, which comprises the following steps: 1. reacting trichloroethylene with oxygen under the catalytic action of trialkyl boron shown in the formula I to generate dichloroacetyl chloride, and 2. reacting dichloroacetyl chloride with inorganic fluoride shown in the formula II under the action of a catalyst to generate difluoroacetyl fluoride. According to the synthetic method of difluoroacetyl fluoride, the raw materials are simple and easy to obtain, high-temperature reaction is not needed, and the yield is high.
Preparation method of 2,2-difluoroacetyl fluoride and derivative thereof
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Paragraph 0029-0046, (2017/07/21)
The invention belongs to the field of fluorine chemical industry and particularly relates to a preparation method of 2,2-difluoroacetyl fluoride and a derivative thereof. The preparation method takes 1,1,2,2-tetrafluoroethyl ethyl ether as a raw material, and the raw material reacts under the action of a catalyst to prepare the product. The catalyst is prepared by adopting a method comprising the following steps: taking rare-earth metal oxide as a raw material and activating at high temperature; and introducing CHF2Cl and reacting. The preparation method takes the 1,1,2,2-tetrafluoroethyl ethyl ether as the raw material, and the 1,1,2,2-tetrafluoroethyl ethyl ether has oxidization reaction under the action of the catalyst at 140 DEG C to 160 DEG C to generate acyl fluoride; and the preparation method has simple and safe production steps and short reaction time.