- 3-(PERFLUOROALKYL)PROPANAL PRODUCTION METHOD
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PROBLEM TO BE SOLVED: To provide a method of producing 3-(perfluoroalkyl)propanal with high selectivity, which is an important compound as a fluorine-containing building block for drug and functional material synthesis. SOLUTION: (Perfluoroalkyl)ethylene represented by the general formula (2) is reacted with carbon monoxide and hydrogen in the presence of a rhodium compound and diphosphine to produce 3-(perfluoroalkyl)propanal represented by the general formula (3). (In the formulas, Rf represents the same C1-16 perfluoroalkyl group.) COPYRIGHT: (C)2015,JPOandINPIT
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Paragraph 0033-0036; 0038-0061; 0063-0075; 0077-0079
(2018/10/31)
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- Highly selective hydroformylation of 3,3,3-trifluoropropene to 4,4,4-trifluorobutanal using Rh/Xantphos catalyst
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Synthesis of 4,4,4-trifluorobutanal by Rh-catalyzed hydroformylation of 3,3,3-trifluoropropene with bis(4,5-diphenylphosphino)xanthene as a ligand was investigated. The uses of [Rh(OH)(cod)]2 (cod = 1,5-cyclooctadinene) and dimethylformamide in CO/H2 = 75/25 mixed gas under atmospheric pressure at 80 C for 15 h provided the highest aldehyde yield 90%. The molar ratio of linear aldehyde (4,4,4-trifluorobutanal) to branched aldehyde (3,3,3-trifluoro-2-methylpropanal) was 99/1. The successive addition of dimethylformamide solution of 3,3,3-trifluoropropene under atmospheric pressure revealed that 4,4,4-trifluorobutanal formation increased linearly with the reaction time and the total turnover number reached 500 after 10 h retaining 99% selectivity of 4,4,4-trifluorobutanal at 80 C.
- Ohtsuka, Yuhki,Kobayashi, Osamu,Yamakawa, Tetsu
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- Studies on the preparation of 2-(trifluoromethyl)acrylic acid and its esters from 3,3,3-trifluoropropene via hydrocarbonylation reactions
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The synthesis of methyl α-(trifluoromethyl)acrylate (MTFMA) has been carried out in three steps starting from commercially available 3,3,3,-trifluoropropene; this route involving the cobalt-catalyzed carbonylation of 2-bromo-3,3,3-trifluoropropene (2-Br-TFP) under very mild reaction conditions, gave only about 30% yield of the desired methyl ester. 2-(Trifluoromethyl)propanal, available in 90% yield by rhodium catalyzed hydroformylation of 3,3,3-trifluoropropene, proved to be an interesting starting product for the preparation of MTFMA: while the synthetic route involving the α-halogenation of 2-(trifluoromethyl)propanoic acid (TFMPA) failed to give any results, the reaction scheme based on the α-selenenylation of the above aldehyde followed by H2O2-oxidation afforded 68% yield of 2-(trifluoromethyl)acrylic acid (TFMAA).
- Botteghi, Carlo,Lando, Claudia,Matteoli, Ugo,Paganelli, Stefano,Menchi, Gloria
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- Hydroformylation of Fluoro Olefins, RfCH=CH2, Catalyzed by Group VIII Transition-Metal Catalysts. Crucial Factors for Extremely High Regioselectivity
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Hydroformylations of fluoro olefins, trifluoroprop-1-ene (TFP), pentafluorobut-1-ene (PFB), heptafluoropent-1-ene (HPFP), heptadecafluorodec-1-ene (HPDFD), vinyl fluoride (VF), pentafluorostyrene (PFS), and allylpentafluorobenzene (4a), promoted by transition-metal catalysts were studied.Remarkable dependency of the regioselectivity of the reaction on the catalyst metal species (Co, Pt, Ru, and Rh) was found in the reactions of TFP and PFS; e.g., n-aldehyde was obtained with >93percent selectivity by a cobalt catalyst whereas iso-aldehyde was obtained with >96percent selectivity by a rhodium catalyst for the reaction of TFP.On the contrary, the reaction of VF gave 2-fluoropropanal (2-FPA) exclusively, regardless of the metal catalyst species.The effects of temperature and carbon monoxide pressure on the regioselectivity were investigated.Possible mechanisms for the uniquely regioselective hydroformylations are discussed on the basis of the results obtained, and a mechanism that involves an initial formation of isoalkyl-metal species followed by isomerization to n-alkyl-metal species and/or followed by carbon monoxide insertion to form isoacyl-metal intermediate was proposed to be the one operating in these reactions.
- Ojima, Iwao,Kato, Koji,Okabe, Masami,Fuchikami, Takamasa
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p. 7714 - 7720
(2007/10/02)
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