E. Rouvier

Methodes simples de cis-hydroxylation des F-alkyl ethylenes

Abstract Synthesis of 2-F-alkyl ethane-1,2 diols from F-alkyl ethylenes and permanganates is reported. Among the three methods tested and described, one, carried out in a homogeneous non aqueous phase (CH 2 Cl 2 ) and with a stoechiometric amount of Phase Transfer Catalysis Agent (PCTA) gave the best yields (⋍80%).

Reactivite des (F-alkyl-2 ethylthio)methanols : synthese de nouveaux agents tensio-actifs cationiques

Abstract Reaction of (2-F-alkyl ethylthio) methanols with phosphorus tribomide or trichloride leads to α-halogenated sulfides. These compounds, frequently described in hydrocarbon chemistry, are unknown when substituted by a F-alkyl group. New cationic surfactants are obtained by reaction of these halides with tertiary amines and phosphines. They are characterised by the presence of only one methylene group between the sulfur and the nitrogen or phosphorus atoms. Some special structures and the properties which might be expected are discussed.

Reaction du carboéthoxyméthylènetriphénylphosphorane sur les F-nitriles : une nouvelle voie d'accès aux β-cétoesters perfluoroalkyles

Abstract We report a new method for the preparation of F-alkyl β-ketoesters from F-nitriles. This method has several advantages over the usual approach, namely quantitative yields, intermediate formation of F-alkyl iminophosphoranes which are useful in other syntheses and convenient preparation of a range of new carbonyl compounds.

Synthése et réactivité de di(2-F-alkyléthylthio)méthanes et de leurs produits d'oxydation. I. Alkylation

Abstract The synthesis of new perfluoroalkylated dithioacetals (R F C 2 H 4 S) 2 CH 2 and their oxidation products (R F C 2 H 4 SO n ) 2 CH 2 has been achieved from 2- F -alkyl ethane thiols. Their reactivity towards alkylation reagents has been investigated.

Réactivité des iminophosphoranes F-alkylés : Synthèse de F-alkyl β-dicétones

Abstract In contrast to aliphatic hydrocarbon-type nitriles, F-nitriles react with activated phosphorus ylides, to give the corresponding iminophosphoranes. When the F-alkyl group is a long chain (other than CF3) they are easily hydrolysed in acidic media, and lead to the corresponding β-diketones in quantitative yields. More, this method shows an advantage in avoiding the intermediate formation of metallic chelates, from which it is necessary to isolate β-diketones obtained by the usual ways.

Synthese de nouvelles sulfones F-alkylées saturees et α,β-insaturees

Abstract Different kinds of F-alkyl sulfones were obtained from zinc or potassium F-alkyl sulfinates as starting material: • Exchange reaction with alkyl halides leads to saturated F-alkyl sulfones (I). • Condensation with homo or heterocyclic aromatic aldehydes in a basic medium gives α,β unsaturated F-alkyl sulfones (II). • Michael addition of (I) to activated alkenes leads to functionalized F-alkyl sulfones (III).

Synthèse d'iminocétènes F-alkylés, voie d'accès aux F-alkyl-β-amido esters substitués en position pseudo-malonique

Abstract New F -alkyl iminoketenes [R F C 2 H 4 NC ; R F C 4 F 9 , C 6 F 13 ; RCH 3 , C 2 H 5 ; R′CH 3 , C 2 H 5 , n−C 3 H 7 ] prepared from 2- F -alkyl ethyl isothiocyanates give, on hydration, F -alkyl-β-amido esters which are potential precursors of F -alkylated heterocycles.

Reactivite des F-alkyl sulfones : Synthese de sulfones cyclopropaniques

Abstract Condensation in an alkaline medium of F-alkyl benzyl sulfones with formaldehyde and F-alkyl methyl sulfones with homo- or heterocyclic aromatic aldehydes leads to cyclopropyl F-alkyl sulfones in excellent yields. A mechanism (addition, then intramolecular nucleophilic substitution) is suggested to explain their synthesis.

Synthèse et structure des sulfites cycliques d'éthylène F-alkylés; précurseurs de nouveaux tensioactifs amphotères fluorés

Abstract New F-alkylated cyclic sulfites (4 F -alkyl-1,2,3-dioxathiolane-2-oxides) were prepared from 1 F -alkyl-ethane-1,2-diols and their structures determined. These intermediates can serve as precursors for a new route to new fluorinated amphoteric surfactants.

Rotation genee dans les ylures de phosphore substitues par un groupement f-alkyl-2 ethyl: Mise en evidence par R.M.N. et cristallographie aux rayons x

Abstract (F-alkyl-2 ethyl) triphenylcarboethoxymethylenephosphorane ylides show two different sets of ethyl protons in their 1 H NMR spectra. We have formulated a hypothesis, and proved it by X ray diffraction, that this phenomena in solution was related to hindered rotation. Two rotational isomers were present in equilibrium at low temperature. Each of them could exist as a mesomeric structure. Further, the complete structure of this type of compound was established and the main results are discussed.