Fluorinated biphenyl derivatives

Keywords Aryl bromides, fluorinated phenylboronic acids, ds-Pd(Ph2PCH2COO)2, K3PO4, THF-H2O, room temperature, Suzuki coupling, fluorinated biphenyl derivatives... 

Guo, M., Jian, F., and He, R. (2006). Efficient synthesis of fluorinated biphenyl derivatives via Pd-catalyzed Suzuki coupling reactions in aqueous solvents at room temperature. 7. Fluorine Chem., 127, 177 181. 

Cesium fluonde in dimethylformamide catalyzes the isomerization offluori-nated cyclobutenes, perfluorobipyntmdines, and their oligomers to products with expanded rings [30, 31, 32] The product distribution in cobalt tnfluonde fluorina-tion depends strongly on the temperature of the reaction [33] Fluorinated 1-dimethylamino-5,6,7,8-tetrafluoro-l,4-dihydro-l,4-ethenonaphthalene rearranges in protic media to a biphenyl derivative [34] (equation 8)... 

The benzene derivatives containing the fluorinated sulfone have been prepared either by nucleophilic substitution of the 4-fluorophenyl derivative (e.g. 1) or by starting with the appropriately substituted sodium thiophenoxide and reacting with perfluoroalkyl iodide follow by oxidation with either MCPBA or chromium oxide (12. li.) The biphenyl derivatives have been prepared by palladium catalyzed cross coupling chemistry of the 4-bromophenyl derivative (e.g. 2) with substituted phenyl boronic acid (yields 37-84%) (JLH, .). Compound 16 has been prepared by palladium catalyzed cross coupling of (4-bromophenyl)perfluorohexyl sulfone with vinyl anisole in 37 % yield (JJL). The vinyl sulfones, 7 and 9, have been prepared by condensation of CH3S02Rf (JJL) with the appropriate aldehyde (yields 70,and 73%) following a literature procedure (1 ). Yields were not optimized. 

It has been concluded from pKa measurements and fluorine NMR data on pentafluoro-biphenyl derivatives, for example C6F5C6H4CO2H, C6F5C6H4F etc., that the penta-fluorophenyl group inductively withdraws electrons more strongly than phenyl but much less strongly than trifluoromethyl, whilst pentafluorophenyl and pentachlorophenyl have a similar capacity for electron withdrawal [40],... 

The above groups contain plasticizers which have several representatives of similar chemical structure. There still are plasticizers in common use or that were invented for specific purposes. These can be grouped as follows biphenyl derivatives,calcium stearate,carbon dioxide, difurans, " fluorine-containing plasticizers, " hydroxyben-zoic acid esters, " isocyanate adducts, " " malonates, " multi-ring aromatic... 

S.H. Hsiao, C.P. Yang, C.Y. Tsai, G.S. Lion, A novel class of organosoluble and light-colored fluorinated polyamides derived from 2,2 -bis(4-amino-2-trifluoromethylphenoxy)biphenyl or 2,2 -i> s(4-amino-2-trifluoromethylphenoxy)-1,1 -binaphthyl, Eur. Polym. J. 40 (6) (2004) 1081-1094. 

The fluorene (FL) based D-A copolymers may be the first and most classical D-A copolymers based on bridged biphenyl derivatives (see Scheme 2.10). In 2003, Andersson et al reported the photovoltaic properties of a D-A copolymer containing a fluorine (FL) donor unit and BT with a thiophene n-bridge (DTBT) the PCE of the PSC based on PFDTBTrPCBM reached 2.2%. ... 

Glatt H, Anklam E, Robertson LW. 1992. Biphenyl and fluorinated derivatives liver enzyme-mediated mutagenicity deteced in Salmonella typhimurium and Chinese hamster V79 cells. Mutat Res 281(3) 151-156. 

Simultaneous use of the Fricdcl-Craft catalytic properties of anhydrous hydrogen fluoride and its fluorinating activity in Cl-F replacement reactions has been utilized in the synthesis of numerous trifluoromethyl aromatics (phenyl, biphenyl, and naphthyl derivatives).246 247 The process is based on the action of carbon tetrachloride/hydrogen fluoride (excess) on aromatics, for example, formation of 16,246 17,246 18 and 19.246... 

We have found that use of fluorinated sulfone and SSI acceptors leads to materials with better nonlinearity for their transparency compared with materials containing the conventional acceptors. Figure 3 summarizes our findings, and is a plot of jlp vs Xmax for donor-acceptor CT molecules of benzene, styrene, biphenyl, fluorene, and stil-bene derivatives with fluorinted sulfone, SSI, and other common acceptors (SC>2Me, CN, COH, COMe, and NO2) groups. 

It has been demonstrated that the presence of chlorine or bromine in the nucleus facilitates replacement of the diazo group by hydrogen little or no ether formation occurs.26 Apparently iodine also favors the redudng action of alcohols, but this point has not been investigated carefully.26 27 No attempts to deaminate fluorinated amines are recorded. Representative of the effitiency with which ethanol reduces diazonium salts derived from halogenated amines are the deaminations of m-chloroaniline 26 (87% yield), of 2-bromo-4-methylaniline 28 (67% yield), of 2,4,6-tribfomoaniline 29 (ca. 80% yield), and of 2-carboxy-4-iodoaniline30 (ca. 45% yield) in the biphenyl series the deamination of VIII in 53% yield 31 may be dted. 

The UV-visible absorption maxima and edges of the various PPV derivatives are summarized in Table 1. PFPV [7] with electron-withdrawing substituent shows a blue-shifted absorption at 410 nm and perfluorinated biphenyl substituted PPFPV [20] shows more blue-shifted absorption at 400 nm. Benjamin et al. [21] have reported that a copolymer composed of the PPV part and the 2,3,5,6-tetrafluoro-PPV part showed a blue-shifted absorption compared with that of unsubstituted PPV. These shifts are explained as being a result of the inductive electron withdrawing properties of the fluorine substitution leading to reduced electron density in the conjugated polymers and leading to an increase in the HOMO-LUMO band gap. 

S. Banerjee, M.K. Madhra, A.K. Salunke, D.K. Jaiswal, Synthesis and properties of fluorinated polyimides. 3. Derived from novel l,3- w[3 -trifluoromethyl-4 (4"-amino benzoxy) benzyl] benzene and 4,4-fc 5 [3 -trifluoromethyl-4 (4-amino benzoxy) benzyl] biphenyl, Polymer 44 (3)(2003) 613-622. 

IMDA reactions of a-fluorinated dienyl acrylates was also a difficult reaction owing to the low reactivity of a-fluoroacrylate parts and the formation of defluorinated byproducts from the initially formed IMDA adducts under Lewis acid-catalyzed conditions. For these reactions, the authors found an effective bidentate Lewis acid (133) derived from 3,3, 5,5 -tetrabromo-l,l -biphenyl-2,2 -diol (Br4BIPOL) and... 

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