Organic Chemistry Volume One

Download or read book A Textbook of Organic Chemistry – Volume 1 written by Mandeep Dalal and published by Dalal Institute. This book was released on 2019-01-01 with total page 450 pages. Available in PDF, EPUB and Kindle. Book excerpt: An advanced-level textbook of organic chemistry for the graduate (B.Sc) and postgraduate (M.Sc) students of Indian and foreign universities. This book is a part of the four-volume series, entitled “A Textbook of Organic Chemistry – Volume I, II, III, IV”. CONTENTS: Chapter 1. Nature of Bonding in Organic molecules: Delocalized chemical bonding; Conjugation; Cross conjugation; Resonance; Hyperconjugation; Tautomerism; Aromaticity in benzenoid and nonbenzenoid compounds; Alternant and non-alternant hydrocarbons; Huckel’s rule: Energy level of p-molecular orbitals; Annulenes; Antiaromaticity; Homo-aromaticity; PMO approach; Bonds weaker than covalent; Addition compounds: crown ether complexes and cryptands, inclusion compounds, cyclodextrins; Catenanes and rotaxanes. Chapter 2. Stereochemistry: Chirality; Elements of symmetry; Molecules with more than one chiral centre: diastereomerism; Determination of relative and absolute configuration (octant rule excluded) with special reference to lactic acid, alanine & mandelic acid; Methods of resolution; Optical purity; Prochirality; Enantiotopic and diastereotopic atoms, groups and faces; Asymmetric synthesis: Cram’s Rule and its modifications, Prelog’s rule; Conformational analysis of cycloalkanes (upto six membered rings); Decalins; Conformations of sugars; Optical activity in absence of chiral carbon (biphenyls, allenes and spiranes); Chirality due to helical shape; Geometrical isomerism in alkenes and oximes; Methods of determining the configuration. Chapter 3. Reaction Mechanism: Structure and Reactivity: Types of mechanisms; Types of reactions; Thermodynamic and kinetic requirements; Kinetic and thermodynamic control; Hammond’s postulate; Curtin-Hammett principle; Potential energy diagrams: Transition states and intermediates; Methods of determining mechanisms; Isotope effects; Hard and soft acids and bases; Generation, structure, stability and reactivity of carbocations, carbanions, free radicals, carbenes and nitrenes; Effect of structure on reactivity; The Hammett equation and linear free energy relationship; Substituent and reaction constants; Taft equation. Chapter 4. Carbohydrates: Types of naturally occurring sugars; Deoxy sugars; Amino sugars; Branch chain sugars; General methods of determination of structure and ring size of sugars with particular reference to maltose, lactose, sucrose, starch and cellulose. Chapter 5. Natural and Synthetic Dyes: Various classes of synthetic dyes including heterocyclic dyes; Interaction between dyes and fibers; Structure elucidation of indigo and Alizarin. Chapter 6. Aliphatic Nucleophilic Substitution: The SN2, SN1, mixed SN1 and SN2, SNi , SN1’, SN2’, SNi’ and SET mechanisms; The neighbouring group mechanisms; Neighbouring group participation by p and s bonds; Anchimeric assistance; Classical and nonclassical carbocations; Phenonium ions; Common carbocation rearrangements; Applications of NMR spectroscopy in the detection of carbocations; Reactivity- effects of substrate structure, attacking nucleophile, leaving group and reaction medium; Ambident nucleophiles and regioselectivity; Phase transfer catalysis. Chapter 7. Aliphatic Electrophilic Substitution: Bimolecular mechanisms – SE2 and SEi; The SE1 mechanism; Electrophilic substitution accompained by double bond shifts; Effect of substrates, leaving group and the solvent polarity on the reactivity. Chapter 8. Aromatic Electrophilic Substitution: The arenium ion mechanism; Orientation and reactivity; Energy profile diagrams; The ortho/para ratio; ipso attack; Orientation in other ring systems; Quantitative treatment of reactivity in substrates and electrophiles; Diazonium coupling; Vilsmeir reaction; Gattermann-Koch reaction. Chapter 9. Aromatic Nucleophilic Substitution: The ArSN1, ArSN2, benzyne and SRN1 mechanisms; Reactivity – effect of substrate structure, leaving group and attacking nucleophile; The von Richter, Sommelet-Hauser, and Smiles rearrangements. Chapter 10. Elimination Reactions: The E2, E1 and E1cB mechanisms; Orientation of the double bond; Reactivity – effects of substrate structures, attacking base, the leaving group and the medium; Mechanism and orientation in pyrolytic elimination. Chapter 11. Addition to Carbon-Carbon Multiple Bonds: Mechanistic and stereochemical aspects of addition reactions involving electrophiles, nucleophiles and free radicals; Regio–and chemoselectivity: orientation and reactivity; Addition to cyclopropane ring; Hydrogenation of double and triple bonds; Hydrogenation of aromatic rings; Hydroboration; Michael reaction; Sharpless asymmetric epoxidation. Chapter 12. Addition to Carbon-Hetero Multiple Bonds: Mechanism of metal hydride reduction of saturated and unsaturated carbonyl compounds, acids, esters and nitriles; Addition of Grignard reagents, organozinc and organolithium reagents to carbonyl and unsaturated carbonyl compounds; Wittig reaction; Mechanism of condensation reactions involving enolates – Aldol, Knoevenagel, Claisen, Mannich, Benzoin, Perkin and Stobbe reactions; Hydrolysis of esters and amides; Ammonolysis of esters.