A STUDY ON THE CATALYTIC ACTIVITY OF THE ZEOLITE ZSM-5 IN HETEROGENEOUS PHASE

Mr. Balin Kumar Bhuyan Department of Chemistry, Gauhati University, Guwahati-781014, Assam

The thesis entitled A STUDY ON THE CATALYTIC ACTIVITY OF THE ZEOLITE ZSM-5 IN HETEROGENEOUS PHASE includes six chapters as follows. 1. Introduction 2. Synthesis and characterisation of Ti-ZSM-5 3. Ti-exchanged ZSM-5 as heterogeneous catalyst for

allylation of aldehydes with allyltributylstannane 4. Acetylation of various alcohols using Ti-ZSM-5 as catalyst 5. Oxidation of alcohols and carbonyl compounds using Ti-ZSM-5 as catalyst . 6. Mukaiyama aldol reaction of ketene silyl acetals with aldehyde catalyzed by Ti-ZSM-5

CHAPTER I
INTRODUCTION
Chapter I gives a general introduction about the zeolite emphasizing its wide scientific interest as a solid acid catalyst. This chapter describes briefly the definition, structure, nomenclature, classification and properties of the
1

zeolites. The applications of zeolites in various fields are highlighted with a special reference to ZSM-5. Some shape selective reactions and a few ZSM-5 catalysed reactions studied so far have been incorporated in this chapter with references.

CHAPTER II
SYNTHESIS AND CHARACTERISATION OF Ti-ZSM-5
Chapter II gives a brief description of chronological development in the history of zeolite synthesis science so far. Parameters influencing zeolite synthesis and modification of zeolites by metal substitution are also discussed. An efficient method of incorporation of Titanium in ZSM-5 by ion-exchange is included in this chapter. Characterisations of the various samples of synthesized Ti-ZSM-5 by different analytical techniques such as X-ray Powder diffraction, FTIR spectroscopy. SEM, EDX analysis and UV-VIS spectroscopy are described and analyses are given.

CHAPTER III
Ti-exchanged ZSM-5 as heterogeneous catalyst for allylation of aldehydes with allyltributylstannane The addition of allyl metal reagents to aldehydes is an important method for formation of carbon-carbon bond. Allyltributylstannane is one of the most common reagents used for the synthesis of homoallylic alcohols. A method

has been described in this chapter, for the synthesis of homoallylic alcohols using Ti-exchanged ZSM-5 as heterogeneous catalyst (Scheme 1).
O OH Ti-ZSM -5 Toluene, r.t. R

+
R H

SnBu3

Scheme 1

CHAPTER IV
ACETYLATION OF VARIOUS ALCOHOLS USING Ti-ZSM-5 AS CATALYST
The acetylation of alcohols occupies an important role in organic synthesis and biochemistry. Conventional acetylations have been carried out by using homogeneous acid or base catalysts. In order to overcome the difficulties associated with homogeneous catalysts the development and utilization of solid catalysts are important. This chapter deals with the catalytic evaluation of Ti-ZSM-5 as heterogeneous catalyst for the acetylation of alcohols (Scheme 2).

OH

Ac2O Ti-ZSM-5, room temp

OAc

Scheme 2

CHAPTER V
OXIDATION OF ALCOHOLS WITH AQUEOUS PRESENCE OF Ti-ZSM-5 AS CATALYST. TBHP IN

Since the first synthesis of TS-1 by Tarramasso et al. in 1983, TS-1 has attracted much attention for its unique catalytic oxidation properties, especially in selective oxidation reactions under mild conditions. In this chapter, oxidation reactions have been investigated for certain secondary alcohols and benzyl alcohols with aqueous tert-butyl hydroperoxide as oxidant in presence of TiZSM-5 as catalyst. (scheme 3).
OH Ti-ZSM 5 TBHP,MeOH O

scheme 3

CHAPTER VI

MUKAIYAMA ALDOL REACTION OF KETEN SILYL ACETALS WITH ALDEHYDE CATALYZED BY Ti-ZSM-5

Mukaiyama aldol reaction is an efficient methodology of carbon-carbon bond formation reaction. Both Lewis acids and bases are known to catalyze this reaction. Various metal compounds have been developed to catalyse Mukaiyama aldol reaction.

This chapter presents an investigation on the catalytic activity of TiZSM-5 for Mukaiyama aldol reaction of silyl keten acetal with various aldehydes. (Scheme 4).

R-CHO

OTMS OMe

Ti-ZSM-5 , DMF

OH O OMe

Scheme 4