- Dialkylcyanamides are more reactive substrates toward metal-mediated nucleophilic addition than alkylcyanides
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The dialkylcyanamide complexes Q[PtCl3(NCNR2)] (Q = Ph3PCH2Ph, R2 = Me21, Et 22, C5H103, C4H8O 4; Q = NMe4, R2 = Me25; Q = NEt4, R 2 = Me26) were synthesized either by dissolving Q 2[Pt2(μ-Cl)2Cl4] in neat NCNR2 (1-4) or by substitution of a NCNR2 ligand with Cl- in [PtCl2(NCNR2)2] by its treatment with QCl (5, 6). Nucleophilic addition of dibenzylhydroxylamine, HON(CH2Ph)2, to 1-6 results in the formation of the complexes Q[PtCl3{NHC(NR2)ON(CH2Ph) 2}] (Q = Ph3PCH2Ph, R2 = Me 2, 7; Et2, 8; C5H10, 9; C 4H8O, 10; Q = Me4N, R2 = Me 211; Q = Et4N, R2 = Me2, 12) that further convert at room temperature in the solid state (1-24 h) or in a solution (0.5-2 h) to the imine complexes Q[PtCl3{N(CH2Ph)C(H)Ph}] (Q = Ph3PCH2Ph, 13; Me4N, 14; Et4N, 15) and the corresponding dialkylureas H2NC(O)NR2. The competitive reactivity study of the nucleophilic addition of HON(CH 2Ph)2 to (Ph3PCH2Ph)[PtCl 3(NCR′)] (R′ = Ph, NR2, CH2Ph) indicated that the reactivity of the coordinated NCNR2 is comparable to NCPh, while NCCH2Ph appeared to be much less reactive than the former two ligands. Compounds 1-6 and 13 were fully characterized by elemental analyses (C, H, N), high resolution ESI-MS, IR, and 1H and 13C{1H} NMR spectroscopy. The structure of 1 was additionally verified by a single-crystal X-ray diffraction.
- Anisimova, Tatyana B.,Bokach, Nadezhda A.,Dolgushin, Fedor M.,Kukushkin, Vadim Yu.
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p. 12460 - 12467
(2013/09/02)
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- N-methylation of nitrogen-containing heterocycles with dimethyl carbonate
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Reactivity of dimethyl carbonate, the environmentally friendly reagent, as methylating agent for nitrogen-containing heterocyclic compounds has been studied. Reactions of imidazole, pyrazole, pyrrole, morpholine, and piperazine with dimethyl carbonate to afford N-methylated products were reported. The reactions were carried out with neither catalyst nor solvent at a temperature range of 110-170°C under atmospheric pressure. Copyright Taylor & Francis, Inc.
- Ouk, Samedy,Thiebaud, Sophie,Borredon, Elisabeth,Chabaud, Bernard
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p. 3021 - 3026
(2007/10/03)
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- Preparation of tertiary amides from carbamoyl chlorides and organocuprates
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(Chemical Equation Presented) Reaction of carbamoyl chlorides with cyano-Gilman cuprates affords tertiary amides in good to excellent yields. The reaction is general due to the possibility of using reagents made either from organolithium or from Grignard compounds. The characterization of the main side products allowed for the suggestion of a possible mechanism.
- Lemoucheux, Laurent,Seitz, Thomas,Rouden, Jacques,Lasne, Marie-Claire
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p. 3703 - 3706
(2007/10/03)
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