Advanced Organic Chemistry

Size: px
Start display at page:

Download "Advanced Organic Chemistry"

Transcription

1 >... / ' :. <.. Advanced Organic Chemistry FOURTH EDITION Part A: Structure and Mechanisms FRANCIS A. CAREY and RICHARD J. SUNDBERG University of Virginia Charlottesville, Virginia Kluwer Academic /Plenum Publishers New York, Boston, Dordrecht, London, Moscow

2 Contents of Part A Chapter 1. Chemical Bonding and Structure Valence Bond Description of Chemical Bonding Orbital Hybridization Resonance Bond Energy, Polarity, and Polarizability \ Bond Energies Electronegativity and Polarity Polarizability Hardness and Softness Molecular Orbital Theory and Methods Hiickel Molecular Orbital Theory Qualitative Application of Molecular Orbital Theory Application of Molecular Orbital Theory to Reactivity Interactions between a and n Systems Hyperconjugation Other Quantitative Descriptions of Molecular Structure Atoms in Molecules Electron Density Functionals Modern Valence Bond Approaches 64 General References 65 Problems 65 Chapter 2. Principles of Stereochemistry Enantiomeric Relationships Diastereomeric Relationships Stereochemistry of Reactions Prochiral Relationships 105 vii

3 viii General References 114 Problems 114 CONTENTS OF PART A Chapter 3. Conformational, Steric, and Stereoelectronic Effects Strain and Molecular Mechanics Conformations of Acyclic Molecules Conformations of Cyclohexane Derivatives Carbocyclic Rings Other Than Six-Membered The Effect of Heteroatoms on Conformational Equilibria The Anomeric Effect Conformational Effects on Reactivity Angle Strain and Its Effect on Reactivity Relationships between Ring Size and Rate of Cyclization Torsional and Stereoelectronic Effects on Reactivity 171 General References 177 Problems 177 Chapter 4. Study and Description of Organic Reaction Mechanismns Thermodynamic Data Kinetic Data Substituent Effects and Linear Free-Energy Relationships Basic Mechanistic Concepts: Kinetic versus Thermodynamic Control, Hammond's Postulate, the Curtin-Hammett Principle Kinetic versus Thermodynamic Control Hammond's Postulate The Curtin-Hammett Principle Isotope Effects Isotopes in Labeling Experiments Characterization of Reaction Intermediates Catalysis by Bransted Acids'and Bases Lewis Acid Catalysis Solvent Effects Substituent Effects in the Gas Phase Stereochemistry Conclusion 248 General References 248 Problems 250 Chapter 5. Nucleophilic Substitution The Limiting Cases Substitution by the Ionization (S^l) Mechanism The Limiting Cases Substitution by the Direct Displacement (S N 2) Mechanism Detailed Mechanistic Description and Borderline Mechanisms 269

4 5.4. Carbocations Nucleophilicity and Solvent Effects Leaving-Group Effects Steric and Strain Effects on Substitution and Ionization Rates : Effects of Conjugation on Reactivity Stereochemistry of Nucleophilic Substitution Neighboring-Group Participation Mechanism of Rearrangements of Carbocations The Norbornyl Cation and Other Nonclassical Carbocations 327 General References 334 Problems 335 IX CONTENTS OF PART A Chapter 6. Polar Addition and Elimination Reactions Addition of Hydrogen Halides to Alkenes Acid-Catalyzed Hydration and Related Addition Reactions Addition of Halogens Electrophilic Additions Involving Metal Ions Additions to Alkynes and Allenes The E2, El, and Elcb Mechanisms Regiochemistry of Elimination Reactions Stereochemistry of E2 Elimination Reactions Dehydration of Alcohols Eliminations Not Involving C-H Bonds 393 General References 398 Problems 398 Chapter 7. Carbanions and Other Nucleophilic Carbon Species Acidity of Hydrocarbons Carbanions Stabilized by Functional Groups Enols and Enamines Carbanions as Nucleophiles in S N 2 Reactions ' 432 General References 439 Problems 440 Chapter 8. Reactions of Carbonyl Compounds Hydration and Addition of Alcohols to Aldehydes and Ketones Addition-Elimination Reactions of Ketones and Aldehydes Addition of Carbon Nucleophiles to Carbonyl Groups Reactivity of Carbonyl Compounds toward Addition Ester Hydrolysis Aminolysis of Esters Amide Hydrolysis Acylation of Nucleophilic Oxygen and Nitrogen Groups 484

5 X 8.9. Intramolecular Catalysis 488 General References 495 CONTENTS OF PART A,,.-, Problems 496 Chapter 9. Aromaticity The Concept of Aromaticity The Annulenes Aromaticity in Charged Rings Homoaromaticity Fused-Ring Systems Heterocyclic Rings 540 General References 543 Problems 543 Chapter 10. Aromatic Substitution Electrophilic Aromatic Substitution Reactions Structure-Reactivity Relationships Reactivity of Polycyclic and Heteroaromatic Compounds Specific Substitution Mechanisms Nitration Halogenation Protonation and Hydrogen Exchange Friedel-Crafts Alkylation and Related Reactions Friedel-Crafts Acylation and Related Reactions Coupling with Diazonium Compounds Substitution of Groups Other Than Hydrogen Nucleophilic Aromatic Substitution by the Addition-Elimination Mechanism Nucleophilic Aromatic Substitution by the Elimination-Addition Mechanism 593 General References 597 Problems 597 Chapter 11. Concerted Pericyclic Reactions Electrocyclic Reactions Sigmatropic Rearrangements Cycloaddition Reactions 636 General References 651 Problems 651 Chapter 12. Free-Radical Reactions Generation and Characterization of Free Radicals 663

6 Background 663 x Stable and Persistent Free Radicals 664,,- _. _... r-r. J- i T ^ J- x sr*, CONTENTS OF PART t Direct Detection or Radical Intermediates Sources of Free Radicals Structural and Stereochemical Properties of Radical Intermediates Charged Radical Species Characteristics of Reaction Mechanisms Involving Radical Intermediates Kinetic Characteristics of Chain Reactions Structure-Reactivity Relationships Free-Radical Substitution Reactions Halogenation Oxidation Free-Radical Addition Reactions Addition of Hydrogen Halides Addition of Halomethanes Addition of Other Carbon Radicals Addition of Thiols and Thiocarboxylic Acids Halogen, Sulfur, and Selenium Group Transfer Reactions Intramolecular Free-Radical Reactions Rearrangement and Fragmentation Reactions of Free Radicals Rearrangement Reactions Fragmentation Electron-Transfer Reactions Involving Transition-Metal Ions SRNI Substitution Processes 727 General References 733 Problems 734 Chapter 13. Photochemistry General Principles Orbital Symmetry Considerations Related to Photochemical Reactions Photochemistry of Carbonyl Compounds, Photochemistry of Alkenes and Dienes Photochemistry of Aromatic Compounds 779 General References 781 Problems 781 References to Problems 791 Index 807

Benzene Benzene is best represented as a resonance hybrid:

Benzene Benzene is best represented as a resonance hybrid: Electrophilic Aromatic Substitution (EAS) is a substitution reaction usually involving the benzene ring; more specifically it is a reaction in which the hydrogen atom of an aromatic ring is replaced as

More information

Boston University Dresden Science Program ORGANIC CHEMISTRY CAS CH 203 Lecture

Boston University Dresden Science Program ORGANIC CHEMISTRY CAS CH 203 Lecture Boston University Dresden Science Program ORGANIC CHEMISTRY CAS CH 203 Lecture Instructor: Professor Wolf D. Habicher, Professor Claus Rüger Meeting Times Lectures: twice a week at 90 minutes each Discussions:

More information

1 Lecture 5 Resonance 1. Lone pair next to empty 2p orbital

1 Lecture 5 Resonance 1. Lone pair next to empty 2p orbital 1 Lecture 5 esonance 1. Lone pair next to empty 2p orbital sp 2 + is more common sp + is less common + needs electrons, has to overlap with a. an adjacent 2p lone pair with electrons b. an adjacent pi

More information

Chapter 10. Conjugation in Alkadienes and Allylic Systems. Class Notes. B. The allyl group is both a common name and an accepted IUPAC name

Chapter 10. Conjugation in Alkadienes and Allylic Systems. Class Notes. B. The allyl group is both a common name and an accepted IUPAC name Chapter 10 Conjugation in Alkadienes and Allylic Systems Chapter 10 suggested problems: I. The allyl group Class Notes A. B. The allyl group is both a common name and an accepted IUPAC name 1. Allyl alcohol

More information

Benzene benzene aromatic hydrocarbons aromatic not not

Benzene benzene aromatic hydrocarbons aromatic not not Benzene 1 NT 87 90 ompound 87 has the formula 6 6, is known as benzene, and it is a hydrocarbon derived from petroleum distillates. Benzene is the parent compound for a class of compounds known as aromatic

More information

4/18/2011. 9.8 Substituent Effects in Electrophilic Substitutions. Substituent Effects in Electrophilic Substitutions

4/18/2011. 9.8 Substituent Effects in Electrophilic Substitutions. Substituent Effects in Electrophilic Substitutions 9.8 Substituent effects in the electrophilic substitution of an aromatic ring Substituents affect the reactivity of the aromatic ring Some substituents activate the ring, making it more reactive than benzene

More information

An alkyne is a hydrocarbon that contain a Carbon carbon triple bond. Acetylene, the simplest alkyne, widely used in industry for the synthesis of

An alkyne is a hydrocarbon that contain a Carbon carbon triple bond. Acetylene, the simplest alkyne, widely used in industry for the synthesis of Alkynes An alkyne is a hydrocarbon that contain a Carbon carbon triple bond. Acetylene, the simplest alkyne, widely used in industry for the synthesis of acetaldehyde, acetic acid, vinyl chloride O O H

More information

Carboxylic Acids When a carbonyl carbon also bears a hydroxyl group, then these compounds are appreciably acidic, and are called carboxylic acids.

Carboxylic Acids When a carbonyl carbon also bears a hydroxyl group, then these compounds are appreciably acidic, and are called carboxylic acids. Carboxylic Acids When a carbonyl carbon also bears a hydroxyl group, then these compounds are appreciably acidic, and are called carboxylic acids. R Carboxylic acids are classified according to the substituent

More information

Chapter 25 The Chemistry of Life: Organic Chemistry. 25.1 Some General Characteristics of Organic Molecules

Chapter 25 The Chemistry of Life: Organic Chemistry. 25.1 Some General Characteristics of Organic Molecules Chapter 25 The Chemistry of Life: Organic Chemistry general characteristics of organic molecules introduction to hydrocarbons alkanes unsaturated hydrocarbons functional groups: alcohols and ethers compounds

More information

Organic Chemistry II / CHEM 252 Chapter 16 Aldehydes and Ketones I. Nucleophilic Addition to the Carbonyl Group

Organic Chemistry II / CHEM 252 Chapter 16 Aldehydes and Ketones I. Nucleophilic Addition to the Carbonyl Group Organic Chemistry II / CHEM 252 Chapter 16 Aldehydes and Ketones I. Nucleophilic Addition to the Carbonyl Group Bela Torok Department of Chemistry University of Massachusetts Boston Boston, MA 1 Nomenclature

More information

Note: See beginning of Section F for abbreviations, course numbers and coding.

Note: See beginning of Section F for abbreviations, course numbers and coding. CHEM CHEMISTRY Note: See beginning of Section F for abbreviations, course numbers and coding. CHEM 1041 General Chemistry I 3 ch (3C 1T) Introductory course designed primarily for B.Sc. students. Topics

More information

Chapter 18. Reactions of Aldehydes and Ketones

Chapter 18. Reactions of Aldehydes and Ketones hapter 18. Reactions of 1 Aldehydes and Ketones Reaction of a nucleophile with an aldehyde or ketone gives an alkoxide, and subsequent hydrolysis leads to an alcohol. This chapter will define differences

More information

CH101 Course Outline with Learning Outcomes

CH101 Course Outline with Learning Outcomes CH101 Course Outline with Learning Outcomes Staff: Dr. Fawaz Aldabbagh, Dr. David Cheung, Dr. Paul Kavanagh, Dr. Luca Ronconi (Coordinator) Module overview and general aims This Module lays a broad foundation

More information

Mass Spec - Fragmentation

Mass Spec - Fragmentation Mass Spec - Fragmentation An extremely useful result of EI ionization in particular is a phenomenon known as fragmentation. The radical cation that is produced when an electron is knocked out of a neutral

More information

methyl RX example primary RX example secondary RX example secondary RX example tertiary RX example

methyl RX example primary RX example secondary RX example secondary RX example tertiary RX example ucleophilic Substitution & Elimination hemistry 1 eginning patterns to knowfor S and E eactions - horizontal and vertical templates for practice Example 1 - two possible perspectives (deuterium and tritium

More information

Electrophilic Aromatic Substitution Reactions

Electrophilic Aromatic Substitution Reactions Electrophilic Aromatic Substitution Reactions, Course Notes Archive, 1 Electrophilic Aromatic Substitution Reactions An organic reaction in which an electrophile substitutes a hydrogen atom in an aromatic

More information

Q.1 Draw out some suitable structures which fit the molecular formula C 6 H 6

Q.1 Draw out some suitable structures which fit the molecular formula C 6 H 6 Aromatic compounds GE 1 BENZENE Structure Primary analysis revealed benzene had an... empirical formula of and a molecular formula of 6 6 Q.1 Draw out some suitable structures which fit the molecular formula

More information

CHEM 208(Organic Chemistry I) Instructor: Dr. Niranjan Goswami. Tel: (618)545-3361. Email: Ngoswami@kaskaskia.edu. Web: www.kc.cc.il.

CHEM 208(Organic Chemistry I) Instructor: Dr. Niranjan Goswami. Tel: (618)545-3361. Email: Ngoswami@kaskaskia.edu. Web: www.kc.cc.il. CHEM 208(Organic Chemistry I) Instructor: Dr. Niranjan Goswami Tel: (618)545-3361 Email: Ngoswami@kaskaskia.edu Web: www.kc.cc.il.us/ngoswami CHEM 208 COURSE SYLLABUS KASKASKIA COLLEGE NAME TERM YEAR TEXT:

More information

Aromaticity and Reactions of Benzene

Aromaticity and Reactions of Benzene Aromaticity and eactions of Benzene ark College Benzene is a unique molecule it is highly unsaturated with 6 carbons and 6 hydrogens, it is planar, and has a high degree of symmetry. These features explain

More information

Alkynes and Their Reactions

Alkynes and Their Reactions Alkynes and Their Reactions Naming Alkynes Alkynes are named in the same general way that alkenes are named. In the IUPAC system, change the ane ending of the parent alkane name to the suffix yne. Choose

More information

But in organic terms: Oxidation: loss of H 2 ; addition of O or O 2 ; addition of X 2 (halogens).

But in organic terms: Oxidation: loss of H 2 ; addition of O or O 2 ; addition of X 2 (halogens). Reactions of Alcohols Alcohols are versatile organic compounds since they undergo a wide variety of transformations the majority of which are either oxidation or reduction type reactions. Normally: Oxidation

More information

It does not react N.R.

It does not react N.R. Benzene versus yclohexene versus yclohexadiene 1 l l cyclohexene l l cyclohexadiene l Expect this to react similarly "cyclohexatriene" It does not react l N.R. benzene Benzene is resonance stabilized,

More information

Protonation. favored H 3 O + R O O H

Protonation. favored H 3 O + R O O H arboxylic Acids arboxylic acids have one property that distinguishes them from most other organic compounds they re acidic. Now not as acidic as fuming sulfuric acid, but still pretty darned acidic. The

More information

KJM 3200 Required Reading (Pensum), Spring 2016

KJM 3200 Required Reading (Pensum), Spring 2016 KJM 3200 Required Reading (Pensum), Spring 2016 Paula Y. Bruice, Organic Chemistry 7 nd ed. as specified below, or John McMurry: Organic Chemistry 8 nd ed. as specified below. Lise-Lotte Gundersen KJM

More information

CHEM 322 Organic Chemistry II - Professor Kathleen V. Kilway. CHAPTER 14 Substitution Reactions of Aromatic Compounds

CHEM 322 Organic Chemistry II - Professor Kathleen V. Kilway. CHAPTER 14 Substitution Reactions of Aromatic Compounds CHEM 322 Organic Chemistry II - Professor Kathleen V. Kilway "Organic Chemistry" by Maitland Jones, 4 th edition Chapter 14 Homework: 1, 2, 5, 7, 13, 19, 20, 23, 26, 27, 28, 30, 31, 34, 35, 36, 41, 46,

More information

2.7 Acids and Bases: The Brønsted-Lowry Definition. Acids and Bases: The Brønsted-Lowry Definition. Acids and Bases: The Brønsted-Lowry Definition

2.7 Acids and Bases: The Brønsted-Lowry Definition. Acids and Bases: The Brønsted-Lowry Definition. Acids and Bases: The Brønsted-Lowry Definition 2.7 Acids and Bases: The Brønsted-Lowry Definition Two frequently used definitions of acidity The Brønsted-Lowry definition Lewis definition Brønsted-Lowry acid A substance that donates a hydrogen ion

More information

Chapter 8: Chemistry of Alkynes (C n H 2n-2 )

Chapter 8: Chemistry of Alkynes (C n H 2n-2 ) hapter 8: hemistry of Alkynes ( n 2n-2 ) Bonding & hybridization Both are sp-hybridized Bond angles = 180 o 1 σ + 2 π bonds Linear around lassification R R R' σ bond energy: 88 kcal/mol π bond energy:

More information

Benzene and aromatic compounds (McMurry Ch. 15 & 16) The resonance hybrid model explains these properties of benzene:

Benzene and aromatic compounds (McMurry Ch. 15 & 16) The resonance hybrid model explains these properties of benzene: Benzene and aromatic compounds (McMurry Ch. 15 & 16) C 6 H 6 is an unusually stable molecule that does NOT react like alkenes do A model was proposed by Kekule in 1865: The resonance hybrid model explains

More information

Electrophilic Aromatic Substitution

Electrophilic Aromatic Substitution Electrophilic Aromatic Substitution Electrophilic Aromatic Substitution: a reaction in which the hydrogen atom of an aromatic ring is replaced as a result of an electrophilic attack on the aromatic ring

More information

Reaction 2. Radical addition of hydrogen bromide (HBr) to alkenes. (NOT COVERED THIS TIME)

Reaction 2. Radical addition of hydrogen bromide (HBr) to alkenes. (NOT COVERED THIS TIME) http://courses.chem.psu.edu/chem38/reactions/reactions.html Reaction 1. Electrophilic addition of hydrogen halides (HX) to alkenes. HCl, HBr in ether KI + H 3 PO 4 room temperature electrophilic addition

More information

Ozonolysis of Alkenes

Ozonolysis of Alkenes zonolysis of Alkenes 1 When 2-methyl-2-pentene reacts with ozone, the initial 1,2,3-trioxolane product is 144, but this rearranges to ozonide 145. If 145 is treated with hydrogen peroxide as above, one

More information

Chemistry 121 General Chemistry I. Course Competencies. 1. Gain a fundamental understanding of the nature of atoms, ions, and molecules.

Chemistry 121 General Chemistry I. Course Competencies. 1. Gain a fundamental understanding of the nature of atoms, ions, and molecules. Chemistry 121 General Chemistry I 1. Gain a fundamental understanding of the nature of atoms, ions, and molecules. 2. Gain a detailed understanding of the quantitative relationships governing chemical

More information

Chapter 22 Carbonyl Alpha-Substitution Reactions

Chapter 22 Carbonyl Alpha-Substitution Reactions John E. McMurry www.cengage.com/chemistry/mcmurry Chapter 22 Carbonyl Alpha-Substitution Reactions The α Position The carbon next to the carbonyl group is designated as being in the α position Electrophilic

More information

Organometallics Study Seminar Chapter 13: Metal-Ligand Multiple Bonds

Organometallics Study Seminar Chapter 13: Metal-Ligand Multiple Bonds Organometallics Study Seminar Chapter 13: Metal-Ligand Multiple Bonds Contents 1. Carbene Complexes 2. Silylene Complexes 3. Metal-Heteroatom Multiple Bonds 1. Carbene Complexes 1.1 Classes of Carbene

More information

Syllabus for General Organic Chemistry M07A- Fall 2013 Prof. Robert Keil

Syllabus for General Organic Chemistry M07A- Fall 2013 Prof. Robert Keil Syllabus for General Organic Chemistry M07A- Fall 2013 Prof. Robert Keil Textbook and Materials What you must buy: Organic Chemistry 4 th Ed. Janice G. Smith, McGraw Hill. (Older edition is fine) Chem

More information

Electrophilic Aromatic Substitution

Electrophilic Aromatic Substitution Electrophilic Aromatic Substitution Electrophilic substitution is the typical reaction type for aromatic rings. Generalized electrophilic aromatic substitution: E E Electrophile Lewis acid: may be or neutral.

More information

Chapter 6 An Overview of Organic Reactions

Chapter 6 An Overview of Organic Reactions John E. McMurry www.cengage.com/chemistry/mcmurry Chapter 6 An Overview of Organic Reactions Why this chapter? To understand organic and/or biochemistry, it is necessary to know: -What occurs -Why and

More information

Alkynes: An Introduction to Organic Synthesis. Based on McMurry s Organic Chemistry, 6 th edition, Chapter 8

Alkynes: An Introduction to Organic Synthesis. Based on McMurry s Organic Chemistry, 6 th edition, Chapter 8 Alkynes: An Introduction to Organic Synthesis Based on McMurry s Organic Chemistry, 6 th edition, Chapter 8 Alkynes! Hydrocarbons that contain carbon-carbon triple bonds! Acetylene, the simplest alkyne

More information

13.1 Alcohols and Phenols. Nomenclature. Nomenclature. Nomenclature. Alcohols possess a hydroxyl group ( OH). Hydroxyl groups in natural compounds.

13.1 Alcohols and Phenols. Nomenclature. Nomenclature. Nomenclature. Alcohols possess a hydroxyl group ( OH). Hydroxyl groups in natural compounds. 13.1 Alcohols and Phenols Alcohols possess a hydroxyl group ( OH). 13.1 Alcohols and Phenols Hydroxyl groups in natural compounds. Hydroxyl groups are extremely common in natural compounds. 13-1 13-2 13.1

More information

Survival Organic Chemistry Part I: Molecular Models

Survival Organic Chemistry Part I: Molecular Models Survival Organic Chemistry Part I: Molecular Models The goal in this laboratory experience is to get you so you can easily and quickly move between empirical formulas, molecular formulas, condensed formulas,

More information

Alkynes contain a C C triple bond

Alkynes contain a C C triple bond Chapter 8: Alkynes: an introduction to organic synthesis Alkynes contain a C C triple bond Acetylene: H-C C-H is the common name for ethyne, used as a torch fuel Alkyne nomenclature follows normal hydrocarbon

More information

2. Organic Compounds: Alkanes and Cycloalkanes. Based on McMurry s Organic Chemistry, 6 th edition, Chapter 3

2. Organic Compounds: Alkanes and Cycloalkanes. Based on McMurry s Organic Chemistry, 6 th edition, Chapter 3 2. Organic Compounds: Alkanes and Cycloalkanes Based on McMurry s Organic Chemistry, 6 th edition, Chapter 3 Families of Organic Compounds Organic compounds can be grouped into families by their common

More information

REACTIONS OF AROMATIC COMPOUNDS

REACTIONS OF AROMATIC COMPOUNDS A STUDENT SHOULD BE ABLE TO: REACTIONS OF AROMATIC COMPOUNDS 1. Predict the product(s) of Electrophilic Aromatic Substitution (EAS), Nucleophilic Aromatic Substitution (S N Ar) and Elimination-Addition

More information

MOLECULAR REPRESENTATIONS AND INFRARED SPECTROSCOPY

MOLECULAR REPRESENTATIONS AND INFRARED SPECTROSCOPY MLEULAR REPRESENTATINS AND INFRARED SPETRSPY A STUDENT SULD BE ABLE T: 1. Given a Lewis (dash or dot), condensed, bond-line, or wedge formula of a compound draw the other representations. 2. Give examples

More information

Chapter 10 Introduction to Organic Chemistry: Alkanes. Organic Chemistry. 10.1 Organic Compounds. Organic vs. Inorganic.

Chapter 10 Introduction to Organic Chemistry: Alkanes. Organic Chemistry. 10.1 Organic Compounds. Organic vs. Inorganic. Chapter 10 Introduction to Organic Chemistry: Alkanes 10.1 Organic Compounds Organic Chemistry An organic compound is a compound made from carbon atoms. has one or more C atoms. has many H atoms. may also

More information

Reaction Coordinate Diagrams for the Two Benzene Reactions

Reaction Coordinate Diagrams for the Two Benzene Reactions Electrophilic Addition vs. Substitution ( LEAVES!) Electrophilic Aromatic Substitution δ δ E E Y Y Reaction Coordinate Diagrams for the Two Benzene Reactions δ δ E E Y Y Electrophilic aromatic substitutions

More information

Table 1: Requirements for Canonical Forms of Molecules with Resonance

Table 1: Requirements for Canonical Forms of Molecules with Resonance rganic Chemistry esonance Lecture eview esonance theory is a simplified alternative to rigorous mathematical descriptions of molecular structure and when used in qualitatively is a convenient method for

More information

Where R = alkyl group, Nu = nucleophile and L = leaving group.

Where R = alkyl group, Nu = nucleophile and L = leaving group. Organic Chemistry (CEM311) Fall 2005 Dr. Robert F. Dias 9. SUBSTITUTIONS: S N 1, S N 2 2 basic kinds of substitution reactions: S N 2 = Substitution Nucleophillic Bimolecular S N 1 = Substitution Nuclophillic

More information

Benzene and Aromatic Compounds

Benzene and Aromatic Compounds Benzene and Aromatic Compounds Benzene (C 6 H 6 ) is the simplest aromatic hydrocarbon (or arene). Benzene has four degrees of unsaturation, making it a highly unsaturated hydrocarbon. Whereas unsaturated

More information

Under acidic conditions, carbonyl compounds are protonated on O first, then weak base deprotonates at the α-c to give enol.

Under acidic conditions, carbonyl compounds are protonated on O first, then weak base deprotonates at the α-c to give enol. Substitution reactions of carbonyl compounds at the α-position Carbonyl compounds are acidic at α-c (e.g. C 2 C ); this is because of the electrophilic nature of carbonyl C= bond. The pka values of simple

More information

Electrophilic Addition Reactions

Electrophilic Addition Reactions Electrophilic Addition Reactions Electrophilic addition reactions are an important class of reactions that allow the interconversion of C=C and C C into a range of important functional groups. Conceptually,

More information

Chapter 7 - Alkenes and Alkynes I

Chapter 7 - Alkenes and Alkynes I Andrew Rosen Chapter 7 - Alkenes and Alkynes I 7.1 - Introduction - The simplest member of the alkenes has the common name of ethylene while the simplest member of the alkyne family has the common name

More information

Chemistry Notes for class 12 Chapter 13 Amines

Chemistry Notes for class 12 Chapter 13 Amines 1 P a g e Chemistry Notes for class 12 Chapter 13 Amines Amines constitute an important class of organic compounds derived by replacing one or more hydrogen atoms ofnh 3 molecule by alkyl/aryl group(s).

More information

Alkynes: An Introduction to Organic Synthesis

Alkynes: An Introduction to Organic Synthesis Alkynes: An Introduction to Organic Synthesis Alkynes Hydrocarbons that contain carbon-carbon triple bonds Acetylene, the simplest alkyne is produced industrially from methane and steam at high temperature

More information

Learning Guide for Chapter 11 - Alkynes

Learning Guide for Chapter 11 - Alkynes Learning Guide for Chapter 11 - Alkynes Introduction to s - p 1 ybridization and geometry, Reactivity, Types of s, Cyclic s, Physical properties, Spectroscopy, Acidity, Natural occurrence and uses Nomenclature

More information

MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question.

MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question. CHM 210 Chemistry Homework #6 Alkanes (Ch. 10) Due: MULTIPLE CHOICE. Choose the one alternative that best completes the statement or answers the question. 1) Compounds that have the same molecular formula

More information

Conjugation is broken completely by the introduction of saturated (sp3) carbon:

Conjugation is broken completely by the introduction of saturated (sp3) carbon: Chapter 16 Conjugation, resonance, and dienes Conjugation relies on the partial overlap of p-orbitals on adjacent double or triple bonds. A common conjugated system involves 1,3-dienes, such as 1,3-butadiene.

More information

Addition Reactions of Carbon-Carbon Pi Bonds - Part 1

Addition Reactions of Carbon-Carbon Pi Bonds - Part 1 Addition eactions of arbon-arbon Pi Bonds - Part 1 3 δ+ 2 δ 3 3 3 + 2 3 2 3 What Is an Addition eaction? Addition reaction: Atoms or groups are added to opposite ends of a pi bond. X Y Why should I study

More information

Everything You Need to Know About Mechanisms. First rule: Arrows are used to indicate movement of electrons

Everything You Need to Know About Mechanisms. First rule: Arrows are used to indicate movement of electrons Everything You eed to Know About Mechanisms A) The orrect Use of Arrows to Indicate Electron Movement The ability to write an organic reaction mechanism properly is key to success in organic chemistry

More information

Substituted Alkanes. Alcohol Amine Ether Thiol

Substituted Alkanes. Alcohol Amine Ether Thiol Substituted Alkanes While alkanes have very few reactions that occur, combustion and some radical reactions, substituted alkanes display a variety of reactions and properties X ften the amount of information

More information

Carbonyl Chemistry (12 Lectures)

Carbonyl Chemistry (12 Lectures) arbonyl hemistry (12 Lectures) Aim of ourse Professor Donna G. Blackmond d.blackmond@imperial.ac.uk tel. 41193 oom 639 1 To build upon elements of Dr E.. Smith s and Dr. D.. Braddocks s course. To introduce

More information

Unit Vocabulary: o Organic Acid o Alcohol. o Ester o Ether. o Amine o Aldehyde

Unit Vocabulary: o Organic Acid o Alcohol. o Ester o Ether. o Amine o Aldehyde Unit Vocabulary: Addition rxn Esterification Polymer Alcohol Ether Polymerization Aldehyde Fermentation Primary Alkane Functional group Saponification Alkene Halide (halocarbon) Saturated hydrocarbon Alkyne

More information

Chapter 2 Polar Covalent Bonds; Acids and Bases

Chapter 2 Polar Covalent Bonds; Acids and Bases John E. McMurry http://www.cengage.com/chemistry/mcmurry Chapter 2 Polar Covalent Bonds; Acids and Bases Javier E. Horta, M.D., Ph.D. University of Massachusetts Lowell Polar Covalent Bonds: Electronegativity

More information

Alkenes: Alkynes: Example: What are all the structural possibilities for C 3 H 4? Unsaturated hydrocarbons: Bonding Patterns of Multiple Bonds

Alkenes: Alkynes: Example: What are all the structural possibilities for C 3 H 4? Unsaturated hydrocarbons: Bonding Patterns of Multiple Bonds Chapter 3 Organic Chem: Alkenes & Alkynes Don t need to know the following reactions found on summary pages 110-112: 1. Hydroboration-Oxidation 2. Cycloaddition to Conjugated Dienes 3. Alkyne reaction

More information

Principles Of Drug Action 1, Spring 2005, Halogenated Hydrocarbons HALOGENATED HYDROCARBON STRUCTURE AND CHEMISTRY.

Principles Of Drug Action 1, Spring 2005, Halogenated Hydrocarbons HALOGENATED HYDROCARBON STRUCTURE AND CHEMISTRY. Principles f Drug Action 1, Spring 2005, alogenated ydrocarbons ALGENATED YDRCARBN STRUCTURE AND CEMISTRY I. Introduction Jack DeRuiter alogenated hydrocarbons are organic compounds consisting of C-C,

More information

Resonance Structures Arrow Pushing Practice

Resonance Structures Arrow Pushing Practice Resonance Structures Arrow Pushing Practice The following is a collection of ions and neutral molecules for which several resonance structures can be drawn. For the ions, the charges can be delocalized

More information

Homework Chapter 21 Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions mandatory problems are highlighted (up to page 16)

Homework Chapter 21 Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions mandatory problems are highlighted (up to page 16) Homework Chapter 21 Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions mandatory problems are highlighted (up to page 16) SHORT ANSWER IUPAC Naming Instructions: Provide proper IUPAC

More information

Chapter 5 Classification of Organic Compounds by Solubility

Chapter 5 Classification of Organic Compounds by Solubility Chapter 5 Classification of Organic Compounds by Solubility Deductions based upon interpretation of simple solubility tests can be extremely useful in organic structure determination. Both solubility and

More information

AROMATIC COMPOUNDS A STUDENT SHOULD BE ABLE TO:

AROMATIC COMPOUNDS A STUDENT SHOULD BE ABLE TO: A STUDENT SHULD BE ABLE T: ARMATIC CMPUNDS 1. Name benzene derivatives given the structures, and draw the structures given the names. This includes: Monosubstituted benzenes named as derivatives of benzene:

More information

Chapter 22 (Enolate Chemistry) Reaction Summary

Chapter 22 (Enolate Chemistry) Reaction Summary Chem 360 Jasperse Ch. 22 Notes Answers. Enolate Chemistry 1 Chem 360-Jasperse Chapter 22 (Enolate Chemistry) eaction Summary PTN as ELECTPILE 1., -Base-catalyzed keto-enol equilibrium -know mech (either

More information

13C NMR Spectroscopy

13C NMR Spectroscopy 13 C NMR Spectroscopy Introduction Nuclear magnetic resonance spectroscopy (NMR) is the most powerful tool available for structural determination. A nucleus with an odd number of protons, an odd number

More information

Chapter 10 Introduction to Organic Chemistry: Alkanes

Chapter 10 Introduction to Organic Chemistry: Alkanes hapter 10 Introduction to Organic hemistry: Alkanes 1 Organic hemistry An organic compound is a compound made from carbon atoms has one or more atoms has many atoms may also contain O, S, N, and halogens

More information

Writing a Correct Mechanism

Writing a Correct Mechanism Chapter 2 1) Balancing Equations Writing a Correct Mechanism 2) Using Arrows to show Electron Movement 3) Mechanisms in Acidic and Basic Media 4) Electron rich Species: Nucleophile or Base? 5) Trimolecular

More information

EXPERIMENT 1: Survival Organic Chemistry: Molecular Models

EXPERIMENT 1: Survival Organic Chemistry: Molecular Models EXPERIMENT 1: Survival Organic Chemistry: Molecular Models Introduction: The goal in this laboratory experience is for you to easily and quickly move between empirical formulas, molecular formulas, condensed

More information

INTERMOLECULAR FORCES

INTERMOLECULAR FORCES INTERMOLECULAR FORCES Intermolecular forces- forces of attraction and repulsion between molecules that hold molecules, ions, and atoms together. Intramolecular - forces of chemical bonds within a molecule

More information

SOLID SUPPORTS AND CATALYSTS IN ORGANIC SYNTHESIS

SOLID SUPPORTS AND CATALYSTS IN ORGANIC SYNTHESIS SOLID SUPPORTS AND CATALYSTS IN ORGANIC SYNTHESIS Editor Professor K. SMITH, M.SC,PhD. Head of Department of Chemistry University College of Swansea Wales ELLIS HORWOOD PTR PRENTICE HALL NEW YORK LONDON

More information

Worksheet Addition reactions

Worksheet Addition reactions Worksheet Addition reactions The presence of electrons in alkenes allows addition reactions to take place. In general: In each case, the bond is broken and the e - are used to form a new bond in the product

More information

How to Quickly Solve Spectrometry Problems

How to Quickly Solve Spectrometry Problems How to Quickly Solve Spectrometry Problems You should be looking for: Mass Spectrometry (MS) Chemical Formula DBE Infrared Spectroscopy (IR) Important Functional Groups o Alcohol O-H o Carboxylic Acid

More information

CHEM 211 CHAPTER 16 - Homework

CHEM 211 CHAPTER 16 - Homework CHEM 211 CHAPTER 16 - Homework SHORT ANSWER Consider the Friedel-Crafts alkylation reaction below to answer the following question(s): 1. Refer to the reaction above. Draw the structure of the electrophilic

More information

ALKENES AND ALKYNES REACTIONS

ALKENES AND ALKYNES REACTIONS A STUDENT SHULD BE ABLE T: ALKENES AND ALKYNES REACTINS 1. Given the starting materials and reaction conditions, predict the products of the following reactions of alkenes and alkynes. Regioselective Markovnikov

More information

Lecture Topics: I. IR spectroscopy

Lecture Topics: I. IR spectroscopy IR and Mass Spectrometry Reading: Wade chapter 12, sections 12-1- 12-15 Study Problems: 12-15, 12-16, 12-23, 12-25 Key Concepts and Skills: Given an IR spectrum, identify the reliable characteristic peaks

More information

Chapter: Introduction to Organic Chemistry: Alkanes

Chapter: Introduction to Organic Chemistry: Alkanes Chapter: Introduction to Organic Chemistry: Alkanes Organic Chemistry An organic compound is a compound made from carbon atoms. has one or more C atoms. has many H atoms. may also contain O, S, N, and

More information

2. Determine the product that would be formed from the S N 2 reaction of a. (R)-2-bromobutane and hydroxide ion (aprotic solvent) (S)-2-butanol

2. Determine the product that would be formed from the S N 2 reaction of a. (R)-2-bromobutane and hydroxide ion (aprotic solvent) (S)-2-butanol 1. Define and understand the following terms. (I will go over these if you have questions, but will expect that you have attempted to understand them on your own.) a. yperconjugation b. Basicity c. Nucleophile

More information

Acids and Bases: Molecular Structure and Acidity

Acids and Bases: Molecular Structure and Acidity Acids and Bases: Molecular Structure and Acidity Review the Acids and Bases Vocabulary List as needed. Tutorial Contents A. Introduction B. Resonance C. Atomic Radius D. Electronegativity E. Inductive

More information

Study Guide Chapters 19-20 Alkanes, Alkenes and Alkynes

Study Guide Chapters 19-20 Alkanes, Alkenes and Alkynes Study Guide Chapters 19-20 Alkanes, Alkenes and Alkynes 1) Carbon-Carbon Bonding in Alkanes (C-C), Alkenes (C=C) and Alkynes (C C). Understand the hybridization of atomic orbitals (ground state promotion

More information

AP Chemistry Chapter 22 - Organic and Biological Molecules

AP Chemistry Chapter 22 - Organic and Biological Molecules AP Chemistry Chapter - Organic and Biological Molecules.1 Alkanes: Saturated Hydrocarbons A. Straight-chain Hydrocarbons 1. Straight-chain alkanes have the formula C n H n+. Carbons are sp hybridized The

More information

ALCOHOLS: Properties & Preparation

ALCOHOLS: Properties & Preparation ALLS: Properties & Preparation General formula: R-, where R is alkyl or substitued alkyl. Ar-: phenol - different properties. Nomenclature 1. ommon names: Name of alkyl group, followed by word alcohol.

More information

Organic Functional Groups Chapter 7. Alcohols, Ethers and More

Organic Functional Groups Chapter 7. Alcohols, Ethers and More Organic Functional Groups Chapter 7 Alcohols, Ethers and More 1 What do you do when you are in Pain? What do you do when you are in a lot of pain? 2 Functional Groups A functional group is an atom, groups

More information

Acid-Base Chemistry of Sugars

Acid-Base Chemistry of Sugars Acid-Base Chemistry of Sugars Lewis acids are electron pair acceptors while Lewis bases are electron pair donors. Last time we saw that sugar molecules have a carbonyl carbon that acts as a Lewis acid

More information

Double Bonds. Hydration Rxns. Hydrogenation Rxns. Halogenation. Formation of epoxides. Syn addition of 2 OH. Ozonolysis

Double Bonds. Hydration Rxns. Hydrogenation Rxns. Halogenation. Formation of epoxides. Syn addition of 2 OH. Ozonolysis Double Bonds What do we do with double bonds? We do addition reactions. In an addition reaction, something is added to both carbons involved in a double bond (or not involved in the double bond, in the

More information

Ch 12. Alkanes Introduction to Organic Chemistry: Simple Hydrocarbons

Ch 12. Alkanes Introduction to Organic Chemistry: Simple Hydrocarbons Ch 12. Alkanes Introduction to Organic Chemistry: Simple Hydrocarbons Diagram of Methane. Member of Alkane family of hydrocarbons. Alkanes have only single bonds. When carbon is bonded to four atoms, the

More information

Ultraviolet Spectroscopy

Ultraviolet Spectroscopy Ultraviolet Spectroscopy The wavelength of UV and visible light are substantially shorter than the wavelength of infrared radiation. The UV spectrum ranges from 100 to 400 nm. A UV-Vis spectrophotometer

More information

The dipolar nature of acids

The dipolar nature of acids I. Introduction arboxylic Acid Structure and hemistry: Part 1 Jack Deuiter arboxylic acids are hydrocarbon derivatives containing a carboxyl () moiety. ecall that carbon has four valence electrons and

More information

Nucleophilic Substitution and Elimination

Nucleophilic Substitution and Elimination Nucleophilic Substitution and Elimination What does the term "nucleophilic substitution" imply? A nucleophile is an the electron rich species that will react with an electron poor species A substitution

More information

C 2 H 5 L L LC 2 H 5 l max = 256 nm (e = 20,000) 283 nm (e = 5,100) CH 3 H 3 C. CH 3 i. B bimesityl l max = 266 nm (e = 700)

C 2 H 5 L L LC 2 H 5 l max = 256 nm (e = 20,000) 283 nm (e = 5,100) CH 3 H 3 C. CH 3 i. B bimesityl l max = 266 nm (e = 700) 750 CAPTER 6 TE CEITRY F BENZENE AND IT DERIVATIVE This hybridization allows one of its electron pairs to occupy a 2p orbital, which has the same size, shape, and orientation as the carbon 2p orbitals

More information

for excitation to occur, there must be an exact match between the frequency of the applied radiation and the frequency of the vibration

for excitation to occur, there must be an exact match between the frequency of the applied radiation and the frequency of the vibration ! = 1 2"c k (m + M) m M wavenumbers! =!/c = 1/" wavelength frequency! units: cm 1 for excitation to occur, there must be an exact match between the frequency of the applied radiation and the frequency

More information

Carboxylic Acid Derivatives and Nitriles

Carboxylic Acid Derivatives and Nitriles Carboxylic Acid Derivatives and itriles Carboxylic Acid Derivatives: There are really only four things to worry about under this heading; acid chlorides, anhydrides, esters and amides. We ll start with

More information

Determining the Structure of an Organic Compound

Determining the Structure of an Organic Compound Determining the Structure of an Organic Compound The analysis of the outcome of a reaction requires that we know the full structure of the products as well as the reactants In the 19 th and early 20 th

More information

Aldehydes can react with alcohols to form hemiacetals. 340 14. Nucleophilic substitution at C=O with loss of carbonyl oxygen

Aldehydes can react with alcohols to form hemiacetals. 340 14. Nucleophilic substitution at C=O with loss of carbonyl oxygen 340 14. Nucleophilic substitution at C= with loss of carbonyl oxygen Ph In Chapter 13 we saw this way of making a reaction go faster by raising the energy of the starting material. We also saw that the

More information

Carboxylic Acid Structure and Chemistry: Part 2

Carboxylic Acid Structure and Chemistry: Part 2 Principles of Drug Action 1, pring 2005, Carboxylic Acids Part 2 Carboxylic Acid tructure and Chemistry: Part 2 Jack Deuiter IV. eactions of the Carboxylic Acid eactions Depending on their overall structure,

More information