Ethyl Cyanotartronate and Its Reactions With Amines.

Abstract

Precipitated by Mayer's reagent, of which about 16.9 cc. were required, a white fiocculent mercury salt was obtained which yielded 0.2255 gram of alkaloid equivalent to 0.52 per cent.The leaf of D. glaucum when assayed by this method yielded but one crop of ¿-mannitol that weighed 0.18 gram and melted at about 160o. Recrystallization from 95% of alcohol raised the melting point to 165o. The yield is therefore 0.36%. The determination of crude alkaloid in 43 grams of the plant showed that ether extracted o. 1608 gram that required 1.87 cc. 0.1 N sulfuric acid, after which chloroform extracted 0.0388 gram requiring 0.51 cc. o. 1 N sulfuric acid. These were purified in the usual manner and there was obtained 0.1358 gram, equivalent to 0.32%. The resin precipitated weighed 0.9802 gram or 2.28%.An analysis of the ash of the leaves of D. geyeri by Mr. Fred V. Skinner gave the following results: CO,.

Direct coupling of nitriles and aniline to form the triazapentadiene species RhIII{NHC(R)N(Ph)C(R)NH}

“…To our knowledge, the only previous example of direct coupling between two nitriles and a primary amine, reported in 1913, was observed in the metal-free reaction between benzylamine and ethyl cyanotartronate, yielding unstable triazapentadiene. 13 Complexes 4 and 5 were isolated as white solids in excellent yields: 85% (4) and 87% (5). The identity of these complexes is supported by elemental analysis data, and 1 H, 19 F and 13 C{ 1 H} NMR spectroscopy.…”

“…13 Complexes 4 and 5 were isolated as white solids in excellent yields: 85% (4) and 87% (5). The identity of these complexes is supported by elemental analysis data, and 1 H, 19 F and 13 C{ 1 H} NMR spectroscopy. Complex 4 was also structurally characterized by X-ray diffraction analysis.…”

“…) reacts with coordinating solvents such as nitriles to give the corresponding bis(solvento) derivatives [( t bpy) 2 Rh(NCR) 2 ][OTf ] 3 [R = Me (2), Ph (3)] (ESI †). Both 2 and 3 were isolated as white solids in good yields [98% (2) and 79% (3)] and characterized by elemental analysis and 1 H, 19 F, and 13 C{ 1 H} NMR spectroscopy. Complex 2 was structurally characterized by X-ray crystallography.…”

“…10 In agreement with the presence of acetonitrile ligands in 2, its 1 H NMR spectrum in CD 2 Cl 2 shows a singlet at 2.61 ppm. In the 13 C{ 1 H} NMR spectrum the acetonitrile groups resonate at 128.0 ppm (CN) and 5.4 ppm (CH 3 ). The aromatic region of the 1 H NMR spectrum of 3 in CD 2 Cl 2 shows resonances corresponding to the phenyl substituent of the nitrile ligands appearing in the range 7.5-7.8 ppm.…”

“…The aromatic region of the 1 H NMR spectrum of 3 in CD 2 Cl 2 shows resonances corresponding to the phenyl substituent of the nitrile ligands appearing in the range 7.5-7.8 ppm. In the 13 C{ 1 H} NMR spectrum a characteristic signal is the CN of the benzonitrile ligands, which resonates at 107.5 ppm.…”