Stanisław Krompiec

Double bond migration in Sallyl systems catalysed by [RuClH(CO)(PPh3)3]

Abstract Reactions of S ue5f8allyl systems (allyl sulphides of Rue5f8Sue5f8allyl type, where R=Et, allyl, Ph, Me 3 C, Ph 3 C, as well as of allyl phenyl sulphoxide, allyl phenyl sulphone, 2,5-dihydro-1,1-dioxothiophene) with [RuClH(CO)(PPh 3 ) 3 ] and other ruthenium compounds have been investigated. Double-bond migration was observed in the case of allyl trityl sulphide, allyl t -butyl sulphide and both sulphones, that is, where co-ordinating properties of sulphur were not too strong. High-yielded syntheses of ( E )- and ( Z )-Rue5f8Sue5f8CHue605CHCH 3 (R=Me 3 C, Z : E =96:4 and Ph 3 C, Z : E =92:8), ( E )ue5f8Phue5f8S(O 2 )ue5f8CHue605CHCH 3 and 2,3-dihydro-1,1-dioxothiophene from respective allyl systems are described. The binuclear Ru complex, formed in the model reaction of allyl phenyl sulphide with [RuClH(CO)(PPh 3 ) 3 ] has been isolated and its structure has been resolved. The mechanism of the reaction between S ue5f8allyl systems and [RuClH(CO(PPh 3 ) 3 ] is proposed.

Highly selective synthesis of (E)-N-aryl-N-(1-propenyl) ethanamides via isomerization of N-allyl ethanamides catalyzed by ruthenium complexes

Abstract A convenient and highly selective method of synthesis of (E)-N-aryl-N-(1-propenyl)ethanamides via isomerization of respective N-allyl-N-arylethanamides catalyzed by [RuClH(CO)(PPh3)3] has been described. N-Allyl-N-arylethanamides have been obtained by allylation of respective N-arylethanamides under PTC conditions. It is proposed that the observed selectivity of the double bond migration to (E)-enamides is due to the interaction of the arene ring with the Ru atom in the transition state.

Isomerisation of N-allyl-N-arylethanamides catalysed by ruthenium complexes

Abstract The isomerisation of N -allyl- N -arylethanamides having a general formula of AcN(Ar)allyl (Ar=Yue5f8C 6 H 4 ue5f8 where Y=H; o -, m -, p -OMe; o -, p -Br, Cl, Me, O 2 N; Ar=1- and 2-naphthyl) catalysed by ruthenium complexes—mostly by [RuClH(CO)(PPh 3 ) 3 ] has been studied. N -Allyl- N -arylethanamides were obtained by allylation of respective N -arylethanamides in the PTC conditions (excess of allyl chloride, 50% aq. NaOH, NBu 4 + HSO 4 − ). The products of isomerisation (reaction conditions: 0.5% mol [RuClH(CO)(PPh 3 ) 3 ], 120xa0°C, 2–16xa0h) were mostly or practically solely ( E )- N -aryl- N -(1-propenyl)ethanamides. It is proposed that the observed selectivity of the double bond migration to ( E )-enamides is a result of the interaction of the arene ring with the Ru atom in the transition states. Quantum calculations (PM5 method) done for N -allyl- N -arylethanamides and for ( E )- and ( Z )- N -aryl- N -(1-propenyl)ethanamides (aryl=Yue5f8C 6 H 4 ue5f8 where Y=H; o -, m -, p -OMe; o -, p -Br, Cl, Me, O 2 N) as well as results of isomerisation of AcN(R)allyl (R=H or cyclohexyl) amides support this assumption. Moreover, the impact of substituents in Yue5f8C 6 H 4 N(Ac)allyl and solvents on the rate of the double bond migration has been studied. The structure of the complexes forming in the course of the reaction and the reaction mechanism are also discussed.

Synthesis of 1-propenyl ethers and their using as modifiers of UV-cured coatings in radical and cationic polymerization

Abstract The 1-propenyl ethers of diols and polyols have recently attracted increasing attention as monomers and comonomers because these compounds undergo UV - photoinitiated polymerization. The synthesis of 1-propenyl ethers via the isomerization of corresponding, readily available allyl ethers catalysed by homogenized transition metal complexes with recycling of catalyst has been described. The properties of UV-cured coatings have been investigated for various compositions containing: the model ether (i.e. 1,4-di(1-propenyloxy)-butane), the unsaturated polyester resin [Estromal 103] or epoxy resin [Epidian 6] and radical (i.e. Irgacure 184) or cationic (i.e. triarylsulfonium salts with metal halide anions: PF 6 − , SbF 6 − ) initiators. The purified or unrefined (i.e. including 0.05xa0mol% homogenized ruthenium(II) complex [RuClH(CO)(PPh 3 ) 3 ]) 1,4-di(1-propenyloxy)butane were applied as modifiers. The effect of presence of homogenized [RuClH(CO)(PPh 3 ) 3 ] in the composition has been discussed.

Cleavage of different ether bonds in butyl glycidyl ether and allyl glycidyl ether by K−, K+(15-crown-5)2

Abstract The kind of substituent in alkyl glycidyl ethers affects the course of their reaction with K−, K+(15-crown-5)2. The cyclic oxirane ring is exclusively cleaved in the case of butyl glycidyl ether whereas the presence of the unsaturated allyl group in the glycidyl ether molecule unexpectedly prefers the scission of the linear ether bond. In both the systems organometallic intermediates are formed. They react with crown ether causing its ring opening. Allylpotassium formed from allyl glycidyl ether reacts also with another glycidyl ether molecule; the oxirane ring is opened in this case.