ORGANOPHOSPHORUS CHEMISTRY

Author: LLAMAS LORENTE PILAR.
Year: 2005.
University: MURCIA.
Place of defense: FACULTAD DE QUÍMICAS.
Place of preparation: FACULTAD DE QUÍMICAS DE LA UNIVERSIDAD DE MURCIA.

Summary: The work contained in this report consists of three parts: the first part describes the synthesis and structural elucidation of certain derivatives of methane bis (difenilfosfino): N-aril-P, P-difenil-P-difenilfosfinoilmetil iminofosforanos, starting from a (difenilfosfino) methane. These processes are also isolated salts N-arilamino-P, P-difenil-P-difenilfosfinoilmetil fosfonio, undescribed species so far, and performed an analysis multinuclear NMR and a structural study by X-ray diffraction some of . The iminofosforanos experienced a reaction of fragmentation that occurred in the breakdown of a link carbono-fósforo, leading to the formation of oxide difenilmetilfosfina and anilida acid difenilfosfínico. The overall process involves the addition of a water molecule and also required the presence of catalytic amounts of acid. It has been proposed that a mechanism consists of a catalytic cycle in which several species including salts N-arilamino-P, P-difenil-P-difenilfosfinoilmetil fosfonio. The second section describes a simple method of preparing ligands N, P, N, N and N, S-bidentados and N, N, N-tridentados, which have in its structure a group iminofosforano, conjugate additions of P , N or S-nucleófilos to P-vinil iminofosforanos. It also studied the diastereoselectividad of reaction with P-vinil iminofosforanos proquirales (substituents on the double bond) although the results showed high levels of asymmetric induction low. Reactions conjugate addition to P-vinil iminofosforanos were also applicable to systems differ and trivinílicos and on the other hand, also found success in the addition of amines and tiofenoles to P-alquinil iminofosforanos. It was prepared and characterized a series of complexes of palladium (II) with ligands iminofosforano obtained according to the above methodology. The analysis by X-ray diffraction of some of the complex led to the identification of their molecular structures in the solid state. A third describes a series of reactions P-alquilación of aminofosfinas N, P, P-trisustituidas as a new method of synthesis of iminofosforanos. Reactions aminofosfinas with halides of rent activated led to the formation of salts aminofosfosfonio, which desprotonaron easily forming iminofosforanos. Transforming aminofosfinas in iminofosforanos also occurred by adding pH of aminofosfinas to olefins and alquinos conjugated groups electroaceptores. On the one hand, it used the character electroaceptor of groups iminofosforanilo, fosfinoilo and tiofosfinoilo in the reactions of aminofosfinas with P-vinil and P-alquinil iminofosforanos and oxide and sulphide difenilvinilfosfina. On the other hand, there were also reactions aminofosfinas with ketones, aldehydes, esters and nitrilos to, b-insaturados. In these processes, the aminofosfinas act as synthetic equivalents group iminofosforanilo. In the reactions of aminofosfinas with ketones and aldehydes, a b-insaturados was observed that after the addition Michael was a reaction aza-Wittig intramolecular. Reactions aminofosfinas with difenilciclopropenona evolved towards the formation of 3-difenilfosfinoil-2 ,3-difenil propionamidas, processes that are consumed an amount of water. These amides were obtained as a mixture of two diastereomers separable by crystallization and analysis by X-ray diffraction an example of each of the isomers allowed assign estereoquímica of them and found that these molecules are associated with using hydrogen bridges intermoleculares formed dimers of symmetry Ci.