16005-58-6

Upstream product

• 17412-11-2 dimethyl pyridazine-4,5-dicarboxylate 
• 103-72-0 phenyl isothiocyanate 
• 103-71-9 phenyl isocyanate 
• 102-08-9 N,N-diphenylthiourea 

Relevant academic research and scientific papers

Computational tools for mechanistic discrimination in the reductive and metathesis coupling reactions mediated by titanium(IV) isopropoxide

A theoretical study has been carried out at the B3LYP/LANL2DZ level to compare the reactivity of phenyl isocyanate and phenyl isothiocyanate towards titanium(IV) alkoxides. Isocyanates are shown to favour both mono insertion and double insertion reactions. Double insertion in a head-to-tail fashion is shown to be more exothermic than double insertion in a head-to-head fashion. The head-to-head double insertion leads to the metathesis product, a carbodiimide, after the extrusion of carbon dioxide. In the case of phenyl isothiocyanate, calculations favour the formation of only mono insertion products. Formation of a double insertion product is highly unfavourable. Further, these studies indicate that the reverse reaction involving the metathesis of N,N ′-diphenyl carbodiimide with carbon dioxide is likely to proceed more efficiently than the metathesis reaction with carbon disulphide. This is in excellent agreement with experimental results as metathesis with carbon disulphide fails to occur. In a second study, multilayer MM/QM calculations are carried out on intermediates generated from reduction of titanium(IV) alkoxides to investigate the effect of alkoxy bridging on the reactivity of multinuclear Ti species. Bimolecular coupling of imines initiated by Ti(III) species leads to a mixture of diastereomers and not diastereoselective coupling of the imine. However if the reaction is carried out by a trimeric biradical species, diastereoselective coupling of the imine is predicted. The presence of alkoxy bridges greatly favours the formation of the d,l (±) isomer, whereas the intermediate without alkoxy bridges favours the more stable meso isomer. As a bridged trimeric species, stabilized by bridging alkoxy groups, correctly explains the diastereoselective reaction, it is the most likely intermediate in the reaction.

Pyridazine-4,5-dicarboxylic Anhydride: Versatile Synthon for the Preparation of 1,3,7,8-Tetra-azaspirodecane Derivatives with Nitrogen 1,3-Binucleophiles

The title compound (1) reacted smoothly with 1,2,3-triphenyl- and 1,3-diphenyl-guanidine, with N,N'-diphenyl- and N-phenyl-thiourea, and with benzamidine to give in very good yields the 1,3,7,8-tetra-azaspirodecane derivatives (2), (4), (6), (9), and (11), respectively, through a Smiles-type rearrangement.The reaction of compound (1) with 1,3-diphenylguanidine showed a different regiospecificity from that observed for the spiro-cyclization of dimethyl pyridazine-4,5-dicarboxylate (15) into methyl 4-oxo-1-phenyl-2-phenylimino-1,3,7,8-tetra-azaspirodeca-6,9-diene- 10-carboxylate (19), carried out with the same reagent in the presence of sodium hydride.The structures of the new heterospiro compounds were determined on the basis of chemical and specteroscopic evidence.