- Insertion of CO2 and related heteroallenes into the Si–N-bond of methyl(N-morpholino)silanes
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Trimethyl(N-morpholino)silane (Me3SiMorph) and dimethyl-di(N-morpholino)silane (Me2SiMorph2) were synthesised. The insertion reactions of both silanes with CO2, n-butylisocyanate (nBuNCO), phenylisocyanate (PhNCO), methylisothiocyanate (MeNCS), n-butylisothiocyanate (nBuNCS) and phenylisothiocyanate (PhNCS) into the Si–N-bond were investigated. One CO2 molecule inserts into each Si–N-bond forming carbamoylic moieties. The insertion reaction of isocyanates depends on the organic substituents bound to the heteroallene unit. PhNCO inserts twofold forming a biuret moiety, while nBuNCO yields urea units by insertion of just one molecule per Si–N-bond. The isothiocyanates are less reactive forming thiourea moieties. Aliphatic isothiocyanates furnish equilibria between the reactants and the insertion product at room temperature. All products have been characterized by spectroscopic methods. Single crystal X-ray diffraction analyses of five insertion products have been performed. The observed reactivity is discussed on the basis of NBO charges and calculated Gibbs free energies of the insertion reactions.
- Herbig, Marcus,B?hme, Uwe,Kroke, Edwin
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- Low cost apparatus for rapid boiling point determination of small air sensitive samples under inert atmosphere
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The boiling point is a characteristic property of substances and mixtures. We have developed a new low cost apparatus which uses standard Schlenk technique for measuring the boiling point of small samples (0.2?ml) under inert atmosphere.
- Herbig, Marcus,Kroke, Edwin
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- Preparation, Characterization, and Reactivity of Aliphatic Amino Iodane(III) Reagents
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The preparation of a new class of aliphatic amino iodane(III) reagents has been realized with the N-TMS?amine and acetoxybenziodazole participated in the formation of N?I bond. The amino-containing iodane(III) reagent 2 d was characterized by single-crystal X-ray diffraction, which revealed the expected hypervalent iodane distorted T-shaped geometry. A practical copper-catalyzed, directed electrophilic amination of aryl amines employing amino-iodane(III) as amination agents was disclosed that proceeded smoothly without external additives.
- Zhang, Yue,Lu, Jing,Lan, Tianlei,Cheng, Shaoling,Liu, Wei,Chen, Chao
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supporting information
p. 436 - 442
(2020/12/21)
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- An Alumino-Mannich Reaction of Organoaluminum Reagents, Silylated Amines, and Aldehydes
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A multi-component coupling using organoaluminum reagents, silylated amines, and aldehydes results in the formation of tertiary amines. Both alkenyl- and alkylaluminum reagents undergo reaction with iminium ion substrates for which the corresponding Petasis borono-Mannich reactions are unsuccessful.
- Tarasewicz, Anika,Ensan, Deeba,Batey, Robert A.
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supporting information
p. 6071 - 6074
(2018/04/27)
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- Nucleophilic bromodifluoromethylation of iminium ions
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A method for bromodifluoromethylation of iminium ions using Me3SiCF2Br is described. The reaction involves room temperature activation of the silicon reagent by HMPA to generate difluorocarbene, which upon interacting with excess of bromide ion provides bromodifluoromethyl carbanionic species. The iminium electrophiles are generated in situ from aldehydes, secondary amines, proton sponge, and silyl triflate. The reaction can be extended for introduction of chlorodifluoromethyl and iododifluoromethyl groups.
- Tsymbal, Artem V.,Kosobokov, Mikhail D.,Levin, Vitalij V.,Struchkova, Marina I.,Dilman, Alexander D.
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p. 7831 - 7835
(2015/03/18)
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- A NEW SYNTHESIS OF AMIDES FROM ACYL FLUORIDES AND N-SILYLAMINES
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Amide bonds are formed readily under mild conditions by the reaction of N-silylamines with the hydrolytically stable acyl fluorides.
- Rajeswari, Sundaramoorthi,Jones, Robert J.,Cava, Michael P.
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p. 5099 - 5102
(2007/10/02)
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- SYNTHESIS AND PROPERTIES OF SOME β-TRIORGANOSILYLENAMINES
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Ten β-triorganosilyl-substituted enamines were synthesized by the silylation of β-lithioenamines.They are thermally stable oils but are easily desilylated with protic compounds to give the parent enamines.
- Kuno, Suzumitsu,Sato, Yoshiro
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p. 309 - 314
(2007/10/02)
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