100-74-3Relevant articles and documents
Novel Synthesis of Carbamic Ester from Carbon Dioxide, Amine, and Ortho Ester
Ishii, Shideru,Nakayama, Hidenobu,Yoshida, Yasuhiko,Yamashita, Tadataka
, p. 455 - 458 (1989)
Carbon dioxide reacted with aliphatic amines and ortho esters to form carbamic esters in good yields.The influence of different ortho esters on the carbamate synthetic reaction is described.In the case of orthocarbonates, carbamic esters were obtained in high yields.The reaction of carbon dioxide, amines, and ortho esters may involve a competitive reaction between the esterification of carbamic acid produced by a reaction of carbon dioxide with amine, and the alkylation of amine.
The Me3Si Substituent Effect on the Reactivity of Silanes. Structural Correlations between Silyl Radicals and Their Parent Silanes
Chatgilialoglu, C.,Guerrini, A.,Lucarini, M.
, p. 3405 - 3409 (1992)
Good linear correlations exist both between the bond dissociation energy of an Si-H bond and the corresponding SiH stretching frequency and between the (29)Si hyperfine splitting of a silicon-centered radical and J((29)Si-H) for the corresponding silane, when the successive substitution at the Si-H function takes place inside a family, i.e., (Me3Si)3-nSi(H)Men, n = 0-3.Explanations for these phenomena are advanced.Such structural correlations allow the characterization of (Me3Si)2Si(H)Me as a radical-based reducing agent with low hydrogen-donating abilities.Rate constants for the reaction of primary alkyl radicals with (Me3Si)2Si(H)Me have been measured over a range of temperatures by using competing unimolecular radical reactions as timing devices.The radical trapping abilities of this silane and other common radical-based reducing agents are compared.
Selective Synthesis of Secondary and Tertiary Amines by Reductive N-Alkylation of Nitriles and N-Alkylation of Amines and Ammonium Formate Catalyzed by Ruthenium Complex
Alshakova, Iryna D.,Nikonov, Georgii I.
, p. 5370 - 5378 (2019)
A new ruthenium catalytic system for the syntheses of secondary and tertiary amines via reductive N-alkylation of nitriles and N-alkylation of primary amines is proposed. Isomeric complexes 8 catalyze transfer hydrogenation and N-alkylation of nitriles in ethanol to give secondary amines. Unsymmetrical secondary amines can be produced by N-alkylation of primary amines with alcohols via the borrowing hydrogen methodology. Aliphatic amines were obtained with excellent yields, while only moderate conversions were observed for anilines. Based on kinetic and mechanistic studies, it is suggested that the rate determining step is the hydrogenation of intermediate imine to amine. Finally, ammonium formate was applied as the amination reagent for alcohols in the presence of ruthenium catalyst 8. Secondary amines were obtained from primary alcohols within 24 hours at 100 °C, and tertiary amines can be produced after prolonged heating. Secondary alcohols can only be converted to secondary amines with moderate yield. Based on mechanistic studies, the process is suggested to proceed through an ammonium alkoxy carbonate intermediate, where carbonate acts as an efficient leaving group.
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Coulson
, p. 429,430 (1971)
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Mild N-Alkylation of Amines with Alcohols Catalyzed by the Acetate Ru(OAc)2(CO)(DiPPF) Complex
Figliolia, Rosario,Baldino, Salvatore,Nedden, Hans G.,Zanotti-Gerosa, Antonio,Baratta, Walter
, p. 14416 - 14419 (2017)
The acetate complex Ru(OAc)2(DiPPF) (2) obtained from Ru(OAc)2(PPh3)2 (1) and 1,1′-bis(diisopropylphosphino)ferrocene (DiPPF) reacts cleanly with formaldehyde affording Ru(OAc)2(CO)(DiPPF) (3) in high yield. The monocarbonyl complex 3 (0.4-2 mol %) efficiently catalyzes the N-alkylation of primary and secondary alkyl and aromatic amines using primary alcohols ROH (R=Et, nPr, nBu, PhCH2) under mild reaction conditions (30–100 °C) with an alcohol/amine molar ratio of 10-100. Formation of the monohydride RuH(OAc)(CO)(DiPPF) (4) has been observed by reaction of 3 with iPrOH in the presence of NEt3 at RT through an equilibrium reaction.
Ionic liquid/H2O-mediated synthesis of mesoporous organic polymers and their application in methylation of amines
Yu, Xiaoxiao,Yang, Zhenzhen,Zhang, Hongye,Yu, Bo,Zhao, Yanfei,Liiu, Zhenghui,Ji, Guipeng,Liu, Zhimin
, p. 5962 - 5965 (2017)
Mesoporous Tr?ger's base-functionalized polymers (Meso-TBPs) were prepared using a sulfonic acid group functionalized ionic liquid/H2O system, with surface areas up to 431 m2 g-1 and pore sizes of 3-15 nm. Ir(ii) coordinated Meso-TBPs exhibited extraordinary catalytic performance in the N-methylation of amines using methanol.
Transition-metal complex-catalyzed reduction of amides with hydrosilanes: A facile transformation of amides to amines
Igarashi, Mamoru,Fuchikami, Takamasa
, p. 1945 - 1947 (2001)
The reaction of amides with hydrosilanes is catalyzed by a variety of transition-metal complexes in the presence or absence of halides and amines as co-catalysts to afford the corresponding amines in good yields.
Electroactivated alkylation of amines with alcohols: Via both direct and indirect borrowing hydrogen mechanisms
Appiagyei, Benjamin,Bhatia, Souful,Keeney, Gabriela L.,Dolmetsch, Troy,Jackson, James E.
supporting information, p. 860 - 869 (2020/02/21)
A green, efficient N-alkylation of amines with simple alcohols has been achieved in aqueous solution via an electrochemical version of the so-called "borrowing hydrogen methodology". Catalyzed by Ru on activated carbon cloth (Ru/ACC), the reaction works well with methanol, and with primary and secondary alcohols. Alkylation can be accomplished by either of two different electrocatalytic processes: (1) in an undivided cell, alcohol (present in excess) is oxidized at the Ru/ACC anode; the aldehyde or ketone product condenses with the amine; and the resulting imine is reduced at an ACC cathode, combining with protons released by the oxidation. This process consumes stoichiometric quantities of current. (2) In a membrane-divided cell, the current-activated Ru/ACC cathode effects direct C-H activation of the alcohol; the resulting carbonyl species, either free or still surface-adsorbed, condenses with amine to form imine and is reduced as in (1). These alcohol activation processes can alkylate primary and secondary aliphatic amines, as well as ammonia itself at 25-70 °C and ambient pressure.
