DEVELOPMENT OF ORGANIC SYNTHETIC METHODOLOGIES USING NON-METALLIC CATALYST

ABSTRACT SUBMITTED TO GAUHATI UNIVERSITY

FOR THE AWARD OF THE DEGREE OF DOCTOR OF PHILOSOPHY IN THE FACULTY OF SCIENCE

By

RAJ SEKHAR LODH

May, 2011

DEVELOPMENT OF ORGANIC SYNTHETIC METHODOLOGIES USING NON-METALLIC CATALYST

The

Thesis

entitled

DEVELOPMENT

OF

ORGANIC

SYNTHIC

METHODOLOGIES USING NON-METALLIC CATALYST is divided into seven Chapters as follows.

1. Introduction 2. Synthesis of homoallylic alcohols using tetrabutyl ammonium bi-benzoate as catalyst. 3. Synthesis of imines in presence of tetrabutyl ammonium bi-benzoate as catalyst. 4. Comparative study of catalytic property of few pyridines for acetylation reaction under solvent free condition 5. Nitroaldol reaction in presence of phase transfer catalyst 6. Knoevenagel condensation reaction in presence of phase transfer catalyst 7. Synthesis of bromohydrins using NBS in presence of Iodine catalyst

CHAPTER-I
Introduction
In this Chapter, a brief introduction of the subject is given highlighting the importance of use of non-metallic catalysts. The use of different non metallic catalysts such as organo-catalyst, iodine, PTC etc. for Organic transformations has been discussed with references.

CHAPTER-II
Synthesis of homoallylic alcohols using Tetrabutyl ammonium bi-benzoate as catalyst
This chapter deals with the preparation of homoallylic alcohols from various aldehydes and allyl-tri-butyltin in presence of tetrabutylammonium bi-benzoate (TBABB) as catalyst. The reaction was carried out by reacting 1 mmol of aldehyde with allyl-tributyltin in presence of catalytic amount of TBABB in THF to produce corresponding homoallyl alcohols in good yield ( Scheme 1).
O OH

SnBu3

TBABB THF

Scheme 1

CHAPTER-III
Synthesis of imines in presence of Tetrabutyl ammonium bi-benzoate as catalyst
This chapter deals with synthesis of imines from aldehyde and benzyl amine. Different imines are synthesized by reacting an aromatic aldehyde (1 equiv.) with benzyl amine (1.05 equiv) in presence of catalytic amount of tetrabutylammonium bi-benzoate (TBABB) in THF at room temperature ( Scheme 2).
CHO

NH2

TBABB THF, rt

Scheme 2

CHAPTER-IV
Comparative study of catalytic property of few pyridines for acetylation reaction under solvent free condition
This chapter deals with a study on the catalytic efficiency of pyridine, DMAP and 44-di-tert-butyl-22-dipyridyl (DTBDP) for acetylation of alcohols with Ac2O. The catalytic efficiency was evaluated in presence of an equimolar amount of acetic anhydride in presence of catalytic amount of the pyridine derivative at room temperature under solvent free condition ( Scheme 3).
R-OH Ac2O Cat. R-OAc

Catalyst= pyridine, DMAP, DTBDP Scheme 3

CHAPTER-V
Nitroaldol Reaction in presence of phase transfer catalyst
In this chapter we are discussing about the catalytic efficiency of three different phase transfer catalyst such as, tetrabutyl ammonium bibanzoate, tetrabutyl ammonium hydroxide and Ambersap 900 OH for nitroaldol reaction. This reaction was carried out between aldehyde (1equiv) and nitromethane (1.1equiv) in THF at room temperature in presence of the catalyst (Scheme 4).
O OH H CH3NO2 NO2

Catalyst (10mol%) THF, rt

Catalyst : (a) TBABB and (b) tetrabutyl ammonium hydroxide (c) Ambersep 900 OH Scheme 4

CHAPTER-VI
Knoevenagel condensation reaction in presence of phase transfer catalyst
This chapter deals with synthesis of ,-unsaturated cyanoesters from aldehydes and ethyl cyano acetate in presence of three different phase transfer catalyst such as tetrabutyl ammonium bibenzoate,tetrabutyl ammonium hydroxide and Ambersep 900 OH. This reaction was carried out between aldehyde (1 equiv.) and ethyl cyanoacetate(1 equiv.) in ethanol at room temperature in presence of the catalyst (Scheme 5).

O H

NC O

OC2H5

cat(15mol%) EtOH,r.t. OC2H5 CN

Catalyst: a) Tetrabutyl ammonium bibenzoate (b) Tetrabutyl ammonium hydroxide (c) Ambersep 900 OH Scheme 5

CHAPTER-VII
Synthesis of bromohydrins using NBS in presence of Iodine Catalyst
This chapter deals with the synthesis of bromohydrins using NBS in presence of iodine as catalyst. Different olefins such as ,-unsaturated carbonyl compounds, styrene etc. (1equiv.) when treated with NBS (1.2 equiv.) in acetonitrile water mixture (4:1) in presence of iodine (0.1 equiv.) corresponding bromohydrins are formed in high yield (Scheme 6).
O OH O

OEt

NBS(1.2eq)
Br

OEt

I2 10mol% CH3CN :H2O(4:1)

Scheme 6