41500-48-5

Upstream product

• 116-15-4 perfluoropropylene 
• 591-50-4 iodobenzene 
• 113612-36-5 Z-pentafluoropropenylzinc iodide 
• 113612-36-5 E-pentafluoropropenylzinc iodide 
• 131510-37-7 1,2,2,3,3,3-hexafluoro-1-phenyl-propane 
• 677-56-5 1,1,1,2,2,3-hexafluoropropane 
• 345-40-4 2,2,3,3,3-Pentafluoro-1-phenyl-propan-1-ol 
• 394-52-5 pentafluoroethyl phenyl ketone 
• 5123-13-7 5,5-dimethyl-2-phenyl-1,3,2-dioxaborinane 
• 100-58-3 phenylmagnesium bromide 
• 100-52-7 benzaldehyde 

Downstream Products

• 1493-86-3 (perfluoroprop-1-ene-1,1-diyl)dibenzene 
• 93119-76-7 Z-1-fluoro-2-(trifluoromethyl)-stilbene 
• 36029-59-1 3,3,3-Trifluoro-1,1,2-triphenylpropene 
• 41424-71-9 E-1-fluoro-2-(trifluoromethyl)-stilbene 
• 2074-70-6 Pentafluor-1-(4-nitro-phenyl)-propen-⁽¹⁾ 
• 68424-01-1 erythro-1,2-Dibromo-1,2,3,3,3-pentafluoro-1-phenylpropane 
• 68424-02-2 threo-1,2-Dibromo-1,2,3,3,3-pentafluoro-1-phenylpropane 
• 36029-62-6 1-(Trifluormethyl)-2-(p-fluorphenyl)-1,2-diphenylethylen 
• 34288-92-1 (Z)-1-(4-methoxyphenyl)-1,2-diphenyl-3,3,3-trifluoropropene 
• 36750-88-6 1-phenyl-3,3,3-trifluoro-1,2-propanedione 
• 41424-70-8 (Z)-1-phenyl-1,2,3,3,3-pentafluoro-1-propene 
• 13798-95-3 4.4'-Bis-pentafluorpropenyl-azobenzol 
• 13651-00-8 α,β,β,β-Tetrafluor-4-amino-propiophenon 
• 14685-23-5 α,β-Difluor-4-nitro-zimtsaeure 

Relevant academic research and scientific papers

PREPARATION METHOD FOR FLUORINE-CONTAINING OLEFINS HAVING ORGANIC-GROUP SUBSTITUENTS

An object of the present invention is to provide a method that enables the easy and efficient (high yield, high selectivity, low cost) preparation of a fluorine-containing olefin substituted with an organic group or groups from a fluorine-containing olefin. [Solution] The method for preparing a fluorine-containing olefin substituted with an organic group or groups, the method comprising a step of reacting a fluorine-containing olefin with an organic boron compound in the presence of an organic transition metal catalyst containing at least one transition metal selected from the group consisting of nickel, palladium, platinum, rhodium, ruthenium, and cobalt.

METHOD FOR PRODUCING SUBSTITUTED FLUORINE-CONTAINING OLEFIN

This invention relates to a method of reacting fluoroolefin with an organic magnesium compound in the presence of a catalyst comprising nickel or palladium so as to efficiently produce fluoroolefin, such as TFE, in which a fluorine (F) atom or atoms bonded to the sp2 hybridized carbon atom are substituted with an organic group.

An efficient stereoselective preparation of cis-perfluoroalkenylzinc reagents [(E)-RFCF{double bond, long}CFZnCl] by the metallation of 1H,1H-perfluoroalkanes and their derivatization to cis-1-arylperfluoroalkenes [(Z)-RFCF{double bond, long}CFAr]

Various 1H,1H-perfluoroalkanes (RFCF2CH2F, RF = CF3, C2F5, C4F9, C5F11, C6F13, C10F21) were metallated using LDA in a THF solution of ZnCl2 at RT or -78 °C to produce the corresponding perfluoroalkenylzinc reagents (RFCF{double bond, long}CFZnCl) in a cis-selective fashion. An increased yield (75-83%) and cis-selectivity (>89%) of the perfluoroalkenylzinc reagents were observed for metallation reactions performed at -78 °C. The cis selectivity was excellent for 1H,1H-perfluoroalkanes with larger RF groups (C4F9, C5F11, C6F13, >96%). The cis-perfluoroalkenylzinc [(E)-RFCF{double bond, long}CFZnCl] reagents were coupled with aryl iodides to obtain cis-1-arylperfluoroalkenes [(Z)-RFCF{double bond, long}CFAr] in 71-95% isolated yields. The cis-perfluoroalkenylzinc reagents upon iodinolysis produced cis-1-iodoperfluoroalkenes [(E)-RFCF{double bond, long}CFI] in 68-70% isolated yield.

An efficient dehyrohalogenation method for the synthesis of α,β,β-trifluorostyrenes, α-chloro-β,β- difluorostyrenes and E-1-arylperfluoroalkenes

Dehydrofluorination of 1-aryl-1,2,2,2-tetrafluoroethanes (ArCHFCF 3) and 1-aryl-1-chloro-2,2,2-trifluoroethane (ArCHClCF3) using lithiumhexamethyldisilazide (LHMDS) in tetrahydrofuran (THF) at room temperature produced 1,2,2-trifluorostyrene and 1-chloro-2,2-difluorostyrene, respectively, in very good isolated yields. Dehydrofluorination of 1,2,2,3,3,3-hexafluoro-1-phenyl-propane (PhCHFCF2CF3) and 1,2,2,3,3,4,4,4-octafluoro-1-phenyl-butane (PhCHFCF2CF 2CF3) using LHMDS produced the corresponding substituted olefins (1-phenyl-1,2,3,3,3-pentafluoroprop-1-ene and 1-phenyl-1,2,3,3,4,4,4- pentafluorobut-1-ene) in good yield and high E-selectivity. Dehydrofluorination of 1-chloro-1-phenyl-2,2,3,3,3-pentafluoropropane (PhCHClCF2CF 3) and 1-chloro-1-phenyl-2,2,3,3,4,4,4-heptafluorobutane (PhCHClCF2CF2CF3) produced a mixture of the corresponding E and Z olefins (PhCClCFCF3 and PhCClCFCF 2CF3) in good yield.

A Facile Stereoselcetive Synthesis of (E)-1-Aryl-1,2,3,3,3-pentafluoropropenes and (E)-1-Aryl-2-chloro-1,3,3,3-tetrafluoropropenes

Arenecarbaldehydes ArCHO were allowed to react with a carbenoid reagent CF3CX2Mtl (X=Cl, Mtl=ZnCl, X=F, Mtl=LI) to give the adducts ArCH(OH)CX2CF3 whose hydroxyl group was substituted by fluorine.Dehydrohalogenating of the resultant ArCHFCX2CF3 (X=Cl or F

Palladium - Catalyzed Cross - Coupling of Perfluoroalkenylzinc Reagents with Aryl Iodides. A New, Simple Synthesis of α,β,β-Trifluorostyrenes and the Stereoselective Preparation of 1-Arylperfluoroprepanes

Perfluoroalkenylzinc reagents coupled with aryl iodides in the presence of Pd(PPh3)4 (1-3 molpercent) to give the corresponding arylalkenes.A series of substituted α,β,β-trifluorostyrenes were prepared in good yields.This method provides ready availability of these fluorinated styrenes, which were previously obtained with difficulty.For the first time, 1-arylperfluoropropenes were prepared stereoselectively.Palladium-catalyzed reactions of 2 with aryl iodides gave stereospecific (E)-1-arylperfluoropropenes, and the same procedure with 3 gave stereoselective Z/E ratios ranging from 98/2 to 92/8.

PALLADIUM CATALYZED COUPLING OF F-VINYL ZINC REAGENTS WITH ARYL IODIDES. AN IMPROVED SYNTHESIS OF α,β,β-TRIFLUOROSTYRENES AND THE STEREOSPECIFIC PREPARATION OF 1-PHENYL-F-PROPENES

Palladium catalyzed coupling of trifluorovinyl zinc reagents with substituted aryl iodides provides a practical high yield route to α,β,β-trifluororstyrenes.Ortho, meta, and para substituted aryl iodides all work equally well.Similar coupling with E- and Z-1-iodo-F-propenes outlines the first stereospecific preparative route to 1-aryl-F-olefins.This approach provides a rapid, easily scaled-up synthesis via a one pot procedure to these valuable styrenes from commercially available precursors without recourse to low temperature processes or the use of unstable reaction intermediates.

An Improved Synthesis of 1-Phenylpentafluoropropenes

1-Phenylpentafluoropropene and a number of its para- and ortho-substituted derivatives were prepared in high yields by reaction of hexafluoropropene with etheral solutions of corresponding phenylmagnesium bromides in sealed glass tubes under autogenous pressure.The products were obtained as mixtures of the Z and E isomers, which ratios varied from 1/2 to 1/6 in favour of the E forms. 19F n.m.r. and i.r. spectra and b.p. of the 1-phenylpentafluoropropenes are reported.