Fluorinated polymerizable phosphonium salts from PH3: Surface properties of photopolymerized films

An array of highly fluorinated polymerizable phosphonium salts (HFPPS) were synthesized from PH₃ and utilized in UV‐curable formulations. Inclusion of these salts at very low loading (0.1–1 wt %) into hexanediol diacrylate (HDDA) resulted in hydrophobic surfaces. The water repellency was achieved with short C₄F₉ fluorocarbon appendages in the monomer as opposed to the bioaccumulative C₈F₁₇ appended polymers. The physical properties of these new monomers were also characterized. The molecular architecture of the monomers had a pronounced effect on both their physical properties along with the degree of hydrophobicity imparted in the polymer. Salts utilizing the bis(trifluoromethylsulfonyl)imide anion displayed excellent compatibility with HDDA, while the chloride salts were insoluble. Time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS) confirmed the presence of the HFPPS at the surface of the polymer coating. For the first time this demonstrates how these salts may be used to functionalize the surface of a UV‐cured film with ionic species. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2782–2792     

Triphenyl Phosphonium Perchlorate–Catalyzed Imino Diels–Alder Synthesis of Azabicyclo[2.2.2]octan‐5‐ones

Abstract

A facile synthesis of azabicyclo[2.2.2]octan‐5‐ones by triphenyl phosphonium perchlorate–catalyzed imino Diels–Alder reaction of Schiff bases with cyclohex‐2‐enone.     

New phosphonium salts based on 3-(diphenylphosphino)propanoic and ω-haloalkanoic acids

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Reactions of alkyl diazoacetates with pyridinium ylides

Pyridinium (methoxycarbonyl)methylide generated from (methoxycarbonyl)methyl-pyridinium halides under the action of K₂CO₃ reacts with alkyl diazoacetates in CH₂Cl₂ at 20 °C, resulting in the successive addition of three CHCOOMe fragments from the ylide to form 3,6-bis(alkoxycarbonyl)-4,5-diazaoctadienoic acid diesters. Heating of the latter in the presence of pyridine leads to their isomerization to give tetraalkyl tetrahydropyridazine-tetracarboxylates in high yields. Under more drastic conditions (refluxing xylene in the presence of pyridine), the acyclic tetraesters undergo another transformation to form pyrrole-tetracarboxylic acid esters in yields of up to 60%. Dedicated to Corresponding Member of the Russian Academy of Sciences E. P. Serebryakov on the occasion of his 70th birthday. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 984–988, April, 2005.     

A facile synthesis of novel endo-selective polycyclic spiropyrrolidine oxindoles via 1,3-dipolar cycloaddition of α,γ-dialkylallenoate esters

Novel polycyclic spiropyrrolidine oxindoles that bear two vicinal quaternary centers and an exocyclic CC double bond have been synthesized by a three-component reaction involving α,γ-dialkylallenoate esters, isatin derivatives and amino acids, by way of an endo-selective 1,3-dipolar cycloaddition. These reactions proceed in high yields and diastereoselectivities. The structures and relative stereochemistry of products were confirmed by NMR, HRMS and X-ray crystallography.