Pentafluorophenyl acrylate

The organosilane reduction of pentafluorophenyl acrylate in the presence of an imine was shown to lead to /1-lactams in good yields (Eq. 295)476 The conversion of an ethyl ynoate into an E-ethyl enoate in high yield is shown in Eq. 296 477... 

Acrylic acid esters can polymerize readily this must be taken into account during their preparation. Thus, attempts to prepare pentafluorophenyl acrylate from acrylo-yl chloride in the presence of pyridine led to extensive polymerization of the product [24], This polymerization can be prevented by using the less nucleophilic 2,6-dimethylpyridine as base and diethyl ether or pentane instead of THF as solvent (Scheme 7.5). Esterifications of acrylic acid under acidic conditions should be conducted in the presence of small amounts of hydroquinone as radical scavenger. Acrylic acid derivatives can also be prepared by acylation with a propionic acid with a leaving group at C-3 followed by/3-elimination. 

RAFT Pentafluorophenyl acrylate Glucose and galactose amines Amidation reaction Con-A None (linear polymer) [101]... 

Scheme 14 RAFT polymerization of pentafluorophenyl acrylate followed by post-functionalization with an aminoglycoside...

In 2009, Theato and Jochum proposed a concept for modifying poly (pentafluorophenyl acrylate) (PPFPA) sequentially in a two-step reaction [11]. As shown in Scheme 5, the activated PFP-ester was treated with two different primary amines to first obtain a statistical copolymer. Using 4-(aminomethyl) aniline in this step enabled formation of an imide by adding 2-hydroxybenzaldehyde in a subsequent step. This approach facilitated the synthesis of doubly functionalized polymers from simple starting materials. Furthermore, the assignment of different amine ratios appeared to be an easy tool for adjusting the lower critical solution temperature (LCST) properties of the resulting polymers. 

Fig. 9 (a-c) Optical micrographs of a bundle of crosslinked poly(pentafluorophenyl acrylate) (PPFPA) nanorods after conversion into poly(A-isopropyl acrylamide) (PNIPAM) nanorods, showing reversible response to temperature, (d) Plot of the length variation (along the axis of the nanorods) of PNIPAM nanorods dispersed in water versus temperature (heating rate 10°C min ). (e) Temperature-dependent turbidity measiuement curve of an aqueous dispersion of PNIPAM nanorods. Reproduced with permission from Haberkom et al. [172]. Copyright 2011 Royal Society of Chemistry... 

Arnold RM, McMtt CD, Popik W, Locklin J (2014) Direct grafting of poly (pentafluorophenyl acrylate) onto oxides versatile substrates for reactive microcapillary printing and self-sorting modification. Chem Commun 50 5307-5309... 

Kircher L, Theato P, Cameron NR (2013) Reactive thiol-ene emulsion-templated porous polymers incorporating pentafluorophenyl acrylate. Polymer 54 1755-1761... 

Irradiation of 2-[N-(pentafluorophenyI)amino]-3-phenylcyclopropenone promotes decarbonylation to give N-(pentafluorophenyl)phenylethynamine and 2-phenyl-3-[N-(pentafluorophenyl)amino]acrylic acid by a process for which there is no known precedent,and the photoextrusion of carbon monoxide from l,3-bis(ethylenedioxy)indan-2-one has been used as the first step in a new synthesis of 1,2-dioxobenzocyclobutene. This represents an unusual example of the decarbonylation of a five-membered cyclic ketone in the preparation of a highly strained and functionalised cyclobutane derivative. The photolysis of a-naphthaleneacetic acid in aqueous solution proceeds by decarboxylation and oxidation of the aromatic ring, and has been carried out at a variety of different wavelengths. The primary step occurs by pseudo-first order kinetics and the optimum photolysis rate has been observed using Ti02 as photocatalyst. Within the cavity of P-cyclodextrin, naproxene (129) has been photodecarboxylated to... 

Similar cyclization product was also observed in the reaction of N-pentafluorophenyl benzamide with ethyl acrylate on activation with ruthe-nium(II) catalyst by Ackermann (Eq. (7.47)) [57]. 

Several polyfluorinated aryl azides (CeFs-Nj, /J-Ns CeFi Ns, p-Cl CsFi Nj, and i CFJ C F4-Ns) have been synthesized by treatment of the corresponding fluorides with sodium azide in dirnethylformamide. Catalytic hydrogeno-lysis of the azide C,FB-CHg CH(N3) COjH, prepared by Meerwein arylation of acrylic acid with pentafluorobenzenediazonium bromide-cuprous bromide and treatment of the product, a-bromo-/3-pentafluorophenyIpropionic acid (45), with sodium azide, has been used to obtain ( >pentafluorophenyl-alanine this a-amino-acid has also been prepared by the aziactone route shown in Scheme 22 and by the acetamidomalonate procedure depicted in Scheme 23 (the preferred method). Application of the last method to p-MeO-CjFB-CHjBr has been used to obtain the fluoro-tyrosine ( )-p-... 

Eberhardt M, Mruk R, Zentel R, Theato P (2005) Synthesis of pentafluorophenyl(meth) acrylate polymers new precursor polymers for the synthesis of multifunctional materials. Eur Polym J 41 1569-1575... 

The regioselectivity and reactivity of the 1,3-dipolar cycloaddition reactions of nitril-imines with acrylonitrile and methyl acrylate have been investigated. The 1,3-dipolar cycloaddition reactions of nitrilimines with isatin imines yielded spiro[indolin-3,3 -1,2,4-triazol] derivatives under classical and microwave conditions/ An extensive study of the 1,3-dipolar cycloaddition reactions of nitrilimines with a,/ -unsaturated lactones, thiolactones, and lactams has been presented. In all cases, regioisomeric mixtures were obtained with the 5-substituted pyrazole as the major cycloadduct. me5 o-Tetrakis(pentafluorophenyl)porphyrin (51) reacts with iminonitriles (52) yielding pyrazolin-fused chlorines (53) via a 1,3-dipolar cycloaddition reaction (Scheme 17). ... 

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