1943-08-4Relevant articles and documents
High Purity Limonene Dicarbonate as Versatile Building Block for Sustainable Non-Isocyanate Polyhydroxyurethane Thermosets and Thermoplastics
Schimpf, Vitalij,Ritter, Benjamin S.,Weis, Philippe,Parison, Karsten,Mülhaupt, Rolf
, p. 944 - 955 (2017)
Oxidation and subsequent catalytic carbonation of limonene, gained from orange peels, afford high purity limonene dicarbonate (LC) as a versatile building block for tailoring linear and cross-linked non-isocyanate polyurethanes (NIPU) from renewable resources. Spectroscopic investigations reveal so far unknown highly colored carbonation byproducts which are successfully removed to yield crystalline LC. Melt-phase polyaddition of a dimer fatty acid based diamine and its diamine-terminated LC-prepolymers with carbonated 1,4-butanediol diglycidyl ether (BDGC) produces 100% bio-based linear NIPU thermoplastics. Side-reactions occurring during polymerization account for decreasing molar mass with increasing LC content. Curing carbonated pentaerythritol glycidyl ether (PGC)/LC blends with 1,5-diaminopentane, gained from lysine, enables tailoring of 100% bio-based NIPU thermosets exhibiting unconventional property profiles. The incorporation of small amounts high purity LC substantially improves NIPU glass temperature, stiffness, and strength without sacrificing elongation at break. High purity LC prevents color formation of LC-based NIPU coatings.
Switchable palladium-catalyst reaction of bromomethyl sulfoxides, CO, and N-nucleophiles: Aminocarbonylation at Csp3 versus oxidative carbonylation of amines
Mollar, Cristian,Ramirez De Arellano, Carmen,Medio-Simón, Mercedes,Asensio, Gregorio
, p. 9693 - 9701 (2013/01/15)
The palladium-catalyzed reaction of α-bromomethyl sulfoxides, carbon monoxide, and N-nucleophiles follows different reaction pathways according to the catalytic system and the reaction conditions. The Pd-xantphos catalyst affords high yields of α-sulfinyl amides by an aminocarbonylation process and is the first example of this type of transformation for a nonbenzylic sp3-hybridized carbon. On the other hand, the oxidative carbonylation of amines occurs with α-bromomethyl sulfoxides, carbon monoxide, and catalytic Pd(PPh3)4 under aerobic conditions, yielding ureas and oxalamides from either primary or secondary amines. The reaction with ambident nucleophiles such as amino alcohols was highly selective and took place exclusively at the amino group despite the presence of the alcohol functionality. In parallel to the reaction paths for simple amines, amino alcohols were converted into hydroxy sulfinyl amides when the reaction was catalyzed by Pd-xantphos, while Pd(PPh3)4 catalyst afforded cyclic carbamates. The alkoxycarbonylation reaction of bromomethyl sulfoxides with simple alcohols and CO leading to the corresponding sulfinyl esters is also described.
Synthesis Utilizing Reducing Ability of Carbon Monoxide. New Methods for Synthesis of N-Substituted Selenoamides
Ogawa, Akiya,Miyake, Jun-ichi,Kambe, Nobuaki,Murai, Shinji,Sonoda, Noboru
, p. 1448 - 1451 (2007/10/02)
Convenient, one-pot syntheses of N-substituted selenoamides (2) from nitriles,metallic selenium, carbon monoxide, water, and amines have been developed on the basis of an amino-group-exchange reaction of in situ formed N-unsubstituted selenoamides (1) with primary or secondary amines.The reactions consist of two processes, i.e., the formation of selenoamides 1 by the reaction of nitriles and H2Se formed from selenium, carbon monoxide and water, and the subsequent amino-group-exchange reaction of 1 with aliphatic amines.The obtained 2 are generally stable enough to bekept for several weeks under the atmosphere of nitrogen at 0 deg C without any appreciable degradation.In the cases of primary amines, the corresponding selenoamides were also obtained from nitriles, selenium, carbon monoxide, and primary amines by a single-step mixing at the beginning of the reaction.
