FLUORINE COMPOUNDS

Author: ILLA SOLER ONA.
Year: 2004.
University: AUTÓNOMA DE BARCELONA.
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: ESCUELA DE POSTGRADO.

Summary: In this thesis has been studied reactions adding fosfonidiazoalcanos and fosfinocarbenos, with the overall objective of exploring its reactivity in front of olefins and aldehydes. The asymmetrical version has been considered, both as regards the use of substrates as chiral reagents. The results of these studies have been used to make points synthetic methods to prepare different types of products. In the first chapter has conducted a comparative study of the reactivity and selectivity with respect diazomethane from cicloadiciones 1,3-dipolares of fosfinodiazoalcanos to olefins chiral electrodeficientes. It has been observed that diazomethane is always more reactive than the fosfinodiazoalcano considered, and has streamlined the origin of the different reactivity and diastereoselctividad *- facial observed in each case by theoretical calculations. The second chapter has been devoted to the study of the addition of [a (diisopropilamino) fosfino] (trimetilsilil) carbeno to carbonyls of aromatic aldehydes, heteroaromáticos and aliphatic. In the case of the reaction with aromatic aldehydes and heteroaromáticos has been nearing the synthesis of highly substituted epoxides, with good yields and stereoselective manner completely. When it has been used aliphatic aldehydes have witnessed the emergence of a competitive reaction, a kind of addendum [2 +2], which after passing through an intermediate oxafosfeténico not isolated, leading to the formation of vinilfosfonamidas. It also has studied the asymmetric version of the reaction, using chiral aliphatic aldehydes. This would have synthesized epoxides and vinilfosfonamidas optically pure and quite diastereoselectiva. The third chapter has conducted a survey and rationalization through theoretical calculations of the reactivity of carbeno studied in the previous chapter opposite venzaldehído and acetaldehyde. In the case of acetaldehyde has been able to explain the experimentally observed behavior, both in the case of the two competitive reactions to the estereoselectividad of reaction. In the fourth chapter has seen the synthesis and study of the reactivity of new aminofosfino (silil) diazo chiral and their carbenos. In some cases it has been possible to synthesize a ciclopropano optically active and quite diastereoslectiva. The fifth chapter discusses the synthesis and reactivity of [bis (dimethylamino) fosfino] (trimetilsilil) diazomethane. The reaction of aldehydes with diazo this leads to the synthesis of derivatives acetilénicos and alfa-hidroxifosfondiamidas through a reaction initiated by an attack nucleófilo phosphorus carbon carbonílico of aldheído. It has studied the mechanism of the reaction and feedback has been made up muestrasn behavior ambifílico of diazocompuesto of departure and its enormous applicability synthetic.

Author: MUÑOZ RUBIO LOURDES.
Year: 2005.
University: BARCELONA.
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA (UB).

Summary: The trifluorometilcetonas (TFMCs) are an important family of compounds that have been shown to be potent inhibitors of a wide variety of esterases and proteases through interaction with a serine residue in the active center of the enzyme. In this regard, it is worth remarking the inhibitory activity of TFMCs on esterases antenales insects, which are enzymes responsible for the degradation dela sensilas pheromone in the antennas. In this thesis has been granted a series of TFMCs as similar to the components feromonales of pests fruit Zeuzera pyrina and corn Sesamia nonagrioides and Ostrinia nubilales. For their synthesis have been implemented different procedures, notably a new methodology to obtain TFMCs from the corresponding sulfones, taking advantage of its easy desprotonación-to the introduction of group trifluorometilcentona, followed by the elimination of sulfone group through amalgamation Al (Hg) or by treatment with Sml2. However, this procedure is not applicable to the preparation of sulfones alílicas or propargílicas. Accordingly, the TFMC alílica similar to the majority component of the sex pheromone to drill the wood Z.pyrina has been prepared by a new procedure that involves the addition of a alqueno Terminal hemiacetal ethyl of trifluoroacetaldehido and subsequent oxidation trifluorocarbinol resulting the reagent Dess-Martin. In order to assess the effect of fluoride on the activity in TFMCs structure similar to that of the components feromonales majority of S.nonagrioides and O.nubilalis have been prepared with good yields the corresponding metilcetonas not fluoride. Similarly to ketones fluoride in field tests, metilcetonas have also shown to have a potent antagonist of the pheromone, which is argued on the basis of a potential competition, as TFMCs, with the very pheromone receptor feromonales given the structural similarity of the two types of compounds. But unlike the fluorinated compounds, metilcetonas are unable to inhibit esterases antenales insect. On the other hand, and based on the bibliographic record that the substitution of one methylene group by a sulfur atom at position 2 and the introduction of a methyl position 1 regard to other TFMCs led carbonyl compounds with more powerful inhibitory , have prepared a series of -tiotrifluorometilcetonas and -metil-beta-tiotrifluorometilcetonas, such as racemic and enantiopura. Importantly, all of these new compounds are in the chemical literature and that the procedures for obtaining the same occur with good yields and excellent excesses enantioméricos (92-94%%) at the stage of methylation. Similarly, there are compounds derived from the replacement of one methylene group by a sulfur atom at position 3 of the group trifluorometilcetona, new compounds that had not so far been considered as potential antagonists. The activity delas TFMCs structure similar to the genetic components of the pheromone majoritarian sexual Z.pyrina, S.nonagrioides and O.nubilalis, has been evaluated in trials of electrophysiology, conduct wind tunnel and field tests. It has been confirmed once again that those compounds which had a structure similar to that of components feromonal majority of each of the insects have proven to be considered the best antagonists. However, sulfur compounds have not proved good antagonists in field tests, probably because of its low volatility, although their activity in the laboratory as esterases inhibitors may not be descatada, given the precedents 8 bibliog 2cb ráficos and results experimental obtained by our research group in similar compounds. Based on the results obtained, the use of TFMCs as a new agent biorracional for pest control has been protected by a patent application, which is under lease.