Organic Chemistry 213

Lecture Schedule:

 

I. Introduction

                A. Origins of Organic Chemistry

                                1. Wohler - (1828) urea from ammonium cyanate, death of vitalism

                                2. Kolbe - (1845) acetic acid from its elements C,H,O

                                3. Kekule - (1865) structure of benzene

                                4. van’t Hoff - (1874) structural theory, tetrahedral carbon

                B. Organic Chemistry today

                                1. Structure - Spectroscopy (IR,NMR,MassSpec)

                                2. Polymers - innovative materials, consumer products

                                3. Medicine - isolation and synthesis

                                4. Petroleum - fuels, solvents, raw materials

 

II. Review of fundamentals - Chemical Bonding

                A. Bonding - attraction between (+) nucleus and neighbor’s (-) electrons

                                1. H2 model -PE vs. inter-nuclear distance, PE well,  Bond length

                                2. Ionic and covalent bonding

                                                a. Metal + non-metal, non-metal + non-metal

                                                b. EN, DEN, pure covalent, polar covalent, ionic

                                                c. Bond polarity  d+, d-

                B. Lewis Dot - Valence electrons, Group #, valences - mono,di,tri,tetra

                                1. Octet rule (& some non-octets)

                                                a. Single,double,triple bonds,molecular ions

                                                b. examples of non-octets - boron,radicals

                                2. Formal charge, stability

                                3. Resonance, stability

                C. Orbital overlap - s/s, s/p, p/p

                                1. s, p bonding

                                2. Single,double,triple bonding

                D. Molecular Geometry - VSEPR theory

                                1. AX2/linear/180o;   AX3/trigonal planar/120o,   AX2E/bent/<120o;

                                    AX4/tetrahedral/109.5o,   AX3E/trigonal pyramid/<109.5o,   AX2E2/bent/<<109.5o

                E. Molecular Polarity

                                1. Molecule - induced (van der Waals), dipole/dipole, Hydrogen bonding

                                2. Effects on MP, BP, & solubility

                F. Hybridization

                                1.  Models - sp3 (methane, ammonia, water), sp2 (boron, ethene), sp (acetylene)

                                2. Bond lengths - single,double,triple, % s & % p character

                                3. Bond strengths  and reactivity

 

III. Structures of Carbon compounds

                                1. Structural theory - mono,di,tri,tetra valences

                A. Representation of structural formulas

                                1. Dash/Lewis structures

                                2. Condensed

                                3. Bond-line

                B. Recognition of Functional groups

                                1. Hydrocarbons - saturated,unsaturated                       6. Ketones

                                    Alkanes, Alkenes, Alkynes, Aromatic                       7. Carboxylic Acids

                                2. Haloalkanes                                                                     8. Esters               

                                3. Alcohols                                                                            9. Amines                             

                                4. Ethers                                                                              10. Amides             

                                5. Aldehydes                                                        

                C. Constitutional Isomers

                                1. Empirical and Molecular Formulas

                                2. Connectivity

                                3. Functional groups

                                4. IHD - multiple bonds and rings, determination of structure

                D. Stereoisomerism - chirality

                                1. Enantiomers - R & S

                                2. Diastereomers - cis & trans

 

IV. Alkanes and Alkylhalides

                A. Basic Nomenclature - IUPAC, radicofunctional (Alkanes, Cycloalkanes, Alkylhalides)

                B. Basic Physical Properties

                                1. MP,BP - Odd/even chains, Branching

                                2. Solubility

                C. Conformational Analysis

                                1. Ethane - Newman projection, PE vs. rotation (anti & eclipse)

                                2. Butane - Newman projection, PE vs. rotation (major and minor eclipses, anti, gauche)

                                3. Cycloalkanes - Angle strain, Torsional strain

                                4. Cyclohexane - Boat & Chair, Axial & Equatorial, Stability, Cis vs. trans

                D. Synthesis of Alkanes

                                1. Hydrogenation

                                2. Reduction of alkyhalide (include 1,3 dihalides)

                                3. Corey - House

                E. Reactions of Alkanes

                                1. Free radical halogenation (mechanism)

 

V. Reaction Fundamentals

                A. Acid/Base concept - Arrhenius theory, Bronsted-Lowry theory (Conjugate acid/base pairs), Lewis theory

                     [nucleophiles (oxygen,nitrogen,halogens) and electrophiles (boron,carbocation,alkene)]

            B. Prediction of Strengths

                                1. Structure - Period,Family,Induction

                                2. Table of pKb’s

                C. Prediction of outcome

                D. Reaction transformations - substitution reactions

                                1. Fundamentals - Nucleophile, substrate, leaving group

                                2. SN2 - Kinetics, Mechanism

                                3. SN1 - Kinetics, Mechanism, carbocations

                                4. SN1 vs. SN2 - Substrate, Nucleophilicity, Leaving group, Solvent effects

 

VI. Alkenes, Dienes, Alkynes

                A. Basic Nomenclature

                B. Basic Physical Properties

                C. Synthesis of Alkenes

                                1. E2 - Mechanism

                                2. E1 - Mechanism

                                3. Substitution vs. Elimination - Nucleophilicity, Solvolysis, Substrate, Temperature

                                4. Dehydrohalogenation (Elimination)

                                                a. Stability - unsubstit,mono,cis,trans,iso,tri,tetra

                                                b. Zaitsev/anti-Zaitsev (mechanism)

                                5. Dehydration of Alcohol (mechanism)

                                6. Cis/trans alkene

                D. Reactions of Alkenes

                                1. Hydrogenation

                                2. Direct addition of HX (mechanism, Markovnikov)

                                3. HX and peroxides (anti-Markovnikov)

                                4. Conversion to Alcohol

                                                a. Hydration (mechanism, Markovnikov, skeletal rearrangement)

                                                b. Hydroboration

                                5. Syn hydroxylation (Baeyer test) - KMnO4, cold, dilute (mechanism)

                                6. Oxidative cleavage -  hot conc. KMnO4­

                                7. Addition of Br2­ and debromination (NaI/acetone)

                E. Synthesis of Alkynes

                                1. Double dehydrohalogenation

                                2. Terminal ® Internal

                F. Reactions of Alkynes

                                1. Hydrogenation (alkane,cis-alkene,trans-alkene)

                                2. Addition of HX

                                3. Hydration (HgSO4, H2SO4)

 

VII. Aromatics - Benzene and its derivatives

                A. Basic Nomenclature - IUPAC, common

                B. Basic Physical Properties

                C. Reactions to study

                                1. Friedal-Crafts - alkylation, acylation

                                2. Nitration and Diazotization

                                3. Ortho, meta, para directors

 

VIII. Alcohols & Ethers

                A. Basic Nomenclature - IUPAC, common

                B. Basic Physical Properties

                C. Synthesis of Alcohols

                                1. Hydration of Alkene

                                2. Hydroboration

                D. Synthesis of Diols

                                1. Synhydroxylation - KMnO4

                E. Reactions of Alcohol

                                1. Substitution

                                2. Conversion to Alkyl halide (SOCl2, PBr3)

                                3. Dehydration

                                4. Oxidation - conversion to aldehydes, ketones and carboxylic acids

                F. Synthesis of Ethers

                                1. Williamson ether synthesis

 

IX. Spectroscopy

                A. General concepts

                B. Types - UV,Visible,IR,NMR

                C. IR - molecular vibrations

                                1. stretching,bending,scissoring,twisting

                                2. instrumentation

                                3. spectra format

                                4. fundamental wave numbers (1/l,cm-1) for functional groups

                D. NMR - nuclear spin

                                1. instrumentation

                                2. splitting pattern

                                3. chemical shifts, ppm

 

X. Aldehydes and Ketones

                A. Basic nomenclature - IUPAC, radicofunctional, common

                B. Basic Physical Properties

                C. Synthesis of

                                1. Oxidation of Alcohols

                                2. Oxidative Cleavage of Alkenes w/ hot, conc. KmnO4

                                3. Hydration of Alkynes

                D. Reactions of Aldehydes and Ketones

                                1. Reduction

                                2. Grignard

 

XI. Carboxylic acids and their derivatives

                A. Basic nomenclature - IUPAC, common

                B. Basic physical properties

                C. Synthesis of

                D. Reactions to study

                                1. Fischer Esterification

 

XII. Amines and Amides

                A. Basic nomenclature - IUPAC, common

                B. Basic physical properties

                C. Reactions to study

                                1. Reduction of amides, nitro, and nitrile

                                2. Hoffman rearrangement