A. Loupy, B.Tchoubar. Salt Effects in Organic and Organometallic Chemistry
|
|
- Elaine Blankenship
- 5 years ago
- Views:
Transcription
1 A. Loupy, B.Tchoubar Salt Effects in Organic and Organometallic Chemistry
2
3 1 Introduction - Classification of Specific Salt Effects Specific Salt Effects Involving the Salt's Lewis Acid or Base Character Salt Effects Arising from Exchange Reactions between Two Ion Pairs Salt Effects Connected with the Position of Ionic Dissociation Equilibria Specific Salt Effects Affecting the Structure of the Activated Complex i n the Transition State: Effect on the Stereo- and Regioselectivities Salt Effects Arising from Specific Associations with Protic Solvent s (Drying Effect) 6 References 8 2 Effects of Salts on the Rates of Single Bond Cleavage Reactions Specific Salt Effects Concerning the Heterolytic Cleavage of C-X Bonds Ionization of C-X Bonds Electrophilic assistance Nucleophilic assistance by salts - effects of anions Unimolcular Solvolysis Reactions (S N 1, E 1) Common ion mass effect "Normal" and "special" salt effects Retardation by the drying salt effect : S N1 reactions in mixed solvents Specific Salt Effects in Bimolecular Nucleophilic Reactions SN2 Reactions Brought About by Anionic Nucleophiles [Scheme (2-23)] Effect of the cation accompanying the anionic nucleophile ; ionic association or complexation of the electrophile Salt effects in SN2 reactions involving hard anionic reactants Salt effects in SN2 reactions involving soft anionic reactants SN2 Reactions Involving Electrically Neutral Nucleophiles Effect according to the nature of the salt anion The case of alkali metal fluorides Use of tetraalkylammonium fluorides Use of fluorides on solid mineral supports Other Cases of Heterolytic C-X Bond Cleavage Aromatic nucleophilic substitutions (SN Ar) Elimination reactions Nucleophilic Reactions with a Hydrogen Atom Reactive Site Cation Effects on C-H Bond Ionization caused by a Base Be C-H Bond Ionization Caused by Alkali Metal Fluorides 4 6 References 47
4 3 Effects of Salts on Rates of Addition Reactions to Multiple Bonds Anionic Nucleophilic Addition (AdN) to )C=O and Similar Bonds Effect of the Cation Introduced with the Anionic Reagent: Carbonyl Complexation or Ionic Association Carbonyl complexation : )C=O. M Ionic association Nu M Cation effects in AN. C=O reactions Types of Salt Effects in AN C=0 Reactions Effects due to added salt cations : carbonyl complexation or associatio n with the reactant Drying effects in protic media Salt Effects in Alkaline Ester Hydrolysis Aliphatic esters Aromatic esters The case of phenyl acetate Explanation in terms of frontier orbitals Examples of Salt Effects in AN C=0 Reactions Positive salt effects,..., Negative salt effects......_. _ Catalysis by trityl perchlorate AN C=0 Reactions Caused by Electrically Neutral Reagents Case of Other Unsaturated Compounds Having Electrophilic Character : Nucleophilic Addition to Nitriles Double Activation : Bifunctional Catalysis The Salt Taking Part as one of the Components in Double Activation As an electrophilic catalyst by means of M As nucleophilic catalyst by means of X _ The Salt Taking Part as a Bifunctional Catalyst Addition Reactions to C=C Double Bonds General Points : Substituent Effects and Types of Addition Donor substituent effects Withdrawing substituent effects Particular case of C=C double bond a to C= Electrophilic Addition (AdE) Acceleration resulting from the cation effect Acceleration brought about by the anion Acceleration of olefin oxidation by thallic salts in aqueous media throug h salt drying effects Aromatic Electrophilic Substitution Anisole acylation - : : ~,_ Mercuration of benzene ; salt drying effects Nucleophilic Addition to Double Bonds a to C= Accelerating effects due to the cation Inhibiting effects due tothe cation Salt effects 94
5 3.3.5 Particular Case of Halogen Addition to C=C-C=0 Conjugated Systems 9 5 References Effects of Salts on Reaction Orientation (Regioselectivity) Reactant Organization in the Vicinity of the Cation Macrocycle Synthesis : the "Template Effect" Synthesis of macrocycles in basic media Acid catalyzed macrocycle synthesis Effects of Salts on Intramolecular Cyclizations "Intramolecular self-solvation" effect Synthesis of benzo-18-crown Effect of Salts on Metallation Regioselectivity Effects of Salts on Regioselectivity of Anionic Reactions Effects involving Electrophilic Reactants Epoxide ring opening I3-Elimination reactions Reactions involving carbonyl compounds Effects Arising from the Nucleophilic Reagen t (Case of Mesomeric Anions) Effect of salts on the O/C ratio in an aprotic solvent Effect of salts on the O/C ratio in protic solvents Effect of salts on the O/C ratio in the case of aryloxy anions Effects of salts on the regioselectivity of alkylation of oximate s ()C=N-O Mm) Effects of salts on the ambident reactivity of aminoacid s (0/N alkylation ratio) The case of allylic carbanions a to SPh Effects of Salts on the Nature and Distribution of AdE2 Reactio n Products References Effects of Salts on Reaction Stereochemistry Effects Concerning the Electrophilic Reactant Bimolecular Nucleophilic Substitutions Effects at carbon Effects at silicon Effects at germanium Effects at phosphorus Ring-opening of Epoxides I3-Elimination (Syn vs. Anti Elimination) Reactions of Addition to Carbonyl Compounds Stereochemistry of additions to cyclic ketones Stereochemistry of aldol condensations Stereochemistry of the Wittig-reaction 159
6 Salt effects in asymmetric synthesis Nucleophilic Addition to Double Binds Conjugated with Electron With - drawing Groups Stereochemistry of Michael-type reactions Michael-type asymmetric synthesis Salt effects in asymmetric Michael reactions Salt Effects on the Steric Course of Nucleophilic Addition of Halogens Effects on the Anionic Nucleophilic Reactant C-Alkylation of Carbanionic Species Influence of association between the carbanion and its Mu counterion Role of the cation in the alkylation of carbanionic species a to a sulfoxid e group; salt effects Role of the cation in asymmetric alkylations a-alkylation of ketones Alkylation of Enolates of ß-Dicarbonyl Compounds Electrophilic Additions : Effects of Salts on Stereochemistry Salt Effects on the Steric Course of the Favorskii Rearrangement Case of a-haloketones Without a Mobile a' Hydrogen Case of a-haloketones with a Mobile a' Hydrogen Medium Effects on the Stereochemistry of Enolate Ketonizatio n (Protonation) Dissociating Protic Medium ; Effect of ph Cation Effects on Ketonization Stereochemistry in Inert Solvents 202 References Specific Effects of Salts on Equilibria Concepts of Activity and Activity Coefficients. Their Significance in Equilibria Specific Effects of Salts on Equilibria Preceding the Slow Step of Various Reactions Some Examples Illustrating the Effects of Salts on Uncatalyzed Pre - Equilibrated Reactions Salt Effects resulting from Equilibria between Ion Pairs Reactions between Neutral Molecules to Give two Oppositely Charged Ions Acid-Base equilibria between neutral species Equilibria for the acylation of neutral molecules Effects of Salts on Product Distribution for Reactions Taking Plac e Within Ion Pairs Reactions of "activated sulfoxides", S m -O-CO-R, X Epoxide ring opening in acid media Electrophilic additions to alkenes 229
7 Aromatic electrophilic substitutions Reductions by silanes in acid media Carbon-Carbon bond formation in oxidizing media Reactions Involving Radical Ions Photoisomerizations Photochemical organic reactions Reactivity of aromatic radical cations 23 7 References Salt Effects in Organometallic Chemistry Main Group Metals : Li, Mg Salt Effects in Organolithium Chemistry Salt effects involving the organolithium reagent Salt effects onvolving the substrate Stabilization of a-halo organolithium reagents by lithium salts : )C(X)Li (carbenoids) Case of organolithium reagents of the type R(Li)C=O Structure and reactivity of lithium amides Salt Effects in Grignard Reagent Chemistry Structure of Grignard reagents Salt effects Salt Effects in Transition Metal Chemistry Anion Effects Anion effects on the structure of complexes Effect of Xe anions on nucleophilicity of complexes Enhancement by anions of the reducing power of zerovalen t metal complexes Anion effects on the stereo- and regioselectivity of reactions catalyzed by palladium complexes Cation Effects Cation participation in migratory insertions Cation effects on the structure of anionic complexes Cation effects on the reactivity of anionic complexes Reactions Taking Place Within a Contact Ion Pair 27 9 References Appendix Revision of Some General Concepts Ionic Strength of a Solution Acidity Functions Solvent Classification Protic and Aprotic Solvents Donor and Acceptor Solvents 291
8 Donor solvents; donor number scale Acceptor solvents ; acceptor number scale Ionic Associations Coulombic Interactions "Hard" and "Soft" Ions (HSAB Classification : Hard and Soft Acids and Bases) Preferential Ionic Associations : "Symbiotic Effect" The Various Types of Ion Pair Concept of Aggregates Perturbation Theory Applied to Chemical Reactivity Klopman Equation : Charge and Orbital Control Applications to Reactivity Reaction kinetics Reaction regioselectivity Application to the HSAB Principle : Interactions Between Soft Ion s (Symbiotic Effect) Concerning Transition Metal Chemistry Degree of Coordination Unsaturation of a Transition Metal in a Complex Formal Oxidation State of a Transition Metal in a Complex Oxidative Addition and Reductive Elimination Intramolecular Insertions Hydrophobic and Hydrophilic Effects ; Salting-In and Salting-Out Effects 30 1 References Supplement - Recent Publications 30 5 Index 311
Additions to the Carbonyl Groups
Chapter 18 Additions to the Carbonyl Groups Nucleophilic substitution (S N 2andS N 1) reaction occurs at sp3 hybridized carbons with electronegative leaving groups Why? The carbon is electrophilic! Addition
More informationp Bonds as Electrophiles
Chapter 7 p Bonds as Electrophiles REACTIONS OF CARBONYLS AND RELATED FUNCTIONAL GROUPS Copyright 2018 by Nelson Education Limited 1 7.2.1 Orbital structure of the carbonyl group Because oxygen is more
More informationCHEMISTRY 263 HOME WORK
Lecture Topics: CHEMISTRY 263 HOME WORK Module7: Hydrogenation of Alkenes Hydrogenation - syn and anti- addition - hydrogenation of alkynes - synthesis of cis-alkenes -synthesis of trans-alkenes Text sections:
More informationModule9. Nuclear Magnetic Resonance Spectroscopy Nuclear Magnetic Resonance (NMR) spectroscopy - Chemical shift - Integration of signal area
1 CHEMISTRY 263 HOME WORK Lecture Topics: Module7. Hydrogenation of Alkenes The Function of the Catalyst - Syn and anti- addition Hydrogenation of Alkynes - Syn- addition of hydrogen: Synthesis of cis-alkenes
More informationCHEM 251 (4 credits): Description
CHEM 251 (4 credits): Intermediate Reactions of Nucleophiles and Electrophiles (Reactivity 2) Description: An understanding of chemical reactivity, initiated in Reactivity 1, is further developed based
More informationKOT 222 Organic Chemistry II
KOT 222 Organic Chemistry II Course Objectives: 1) To introduce the chemistry of alcohols and ethers. 2) To study the chemistry of functional groups. 3) To learn the chemistry of aromatic compounds and
More informationELECTRON FLOW IN ORGANIC CHEMISTR Y. Paul H. Scudder
ELECTRON FLOW IN ORGANIC CHEMISTR Y Paul H. Scudder 1 BONDING AND ELECTRON DISTRIBUTION 1 2 THE PROCESS OF BOND FORMATION 3 4 3 STABILITY AND REACTIVITY OF INTERMEDIATES 5 6 4 CLASSIFICATION OF ELECTRON
More informationCHAPTER 19: CARBONYL COMPOUNDS III
CHAPTER 19: CARBONYL COMPOUNDS III A hydrogen bonded to a carbon adjacent to a carbonyl carbon is sufficiently acidic to be removed by a strong base. The carbon adjacent to a carbonyl carbon is called
More informationAldehydes and Ketones : Aldol Reactions
Aldehydes and Ketones : Aldol Reactions The Acidity of the a Hydrogens of Carbonyl Compounds: Enolate Anions Hydrogens on carbons a to carbonyls are unusually acidic The resulting anion is stabilized by
More informationKeynotes in Organic Chemistry
Keynotes in Organic Chemistry Second Edition ANDREW F. PARSONS Department of Chemistry, University of York, UK Wiley Contents Preface xi 1 Structure and bonding 1 1.1 Ionic versus covalent bonds 1 1.2
More informationChapter 16. Aldehydes and Ketones I. Nucleophilic Addition to the Carbonyl Group. Physical Properties of Aldehydes and Ketones. Synthesis of Aldehydes
Nomenclature of Aldehydes and Ketones Chapter 16 Aldehydes and Ketones I. Aldehydes replace the -e of the parent alkane with -al The functional group needs no number Nucleophilic Addition to the Carbonyl
More informationChapter 8. Substitution reactions of Alkyl Halides
Chapter 8. Substitution reactions of Alkyl Halides There are two types of possible reaction in organic compounds in which sp 3 carbon is bonded to an electronegative atom or group (ex, halides) 1. Substitution
More informationOrganic Reactions and Mechanisms
Organic Reactions and Mechanisms Organic reactions are chemical reactions involving organic compounds. The basic organic chemistry reaction types are addition reactions, elimination reactions, substitution
More informationChap 11. Carbonyl Alpha-Substitution Reactions and Condensation Reactions
Chap 11. Carbonyl Alpha-Substitution eactions and Condensation eactions Four fundamental reactions of carbonyl compounds 1) Nucleophilic addition (aldehydes and ketones) ) Nucleophilic acyl substitution
More informationPAPER No. 5: REACTION MECHANISM MODULE No. 2: Types of Organic Reaction Mechanisms
Subject Chemistry Paper No and Title Module No and Title Module Tag Paper No. 5:Organic Chemistry-II Module No. 2: Overview of different types of Organic Reaction Mechanisms CHE_P5_M2 TABLE OF CONTENTS
More informationOrganic Reactions Susbstitution S N. Dr. Sapna Gupta
Organic Reactions Susbstitution S N 2 Dr. Sapna Gupta Kinetics of Nucleophilic Reaction Rate law is order of reaction 0 order is when rate of reaction is unaffected by change in concentration of the reactants
More informationS N 1 Displacement Reactions
S N 1 Displacement Reactions Tertiary alkyl halides cannot undergo S N 2 reactions because of the severe steric hindrance blocking a backside approach of the nucleophile. They can, however, react via an
More informationExam 1 (Monday, July 6, 2015)
Chem 231 Summer 2015 Assigned Homework Problems Last updated: Friday, July 24, 2015 Problems Assigned from Essential Organic Chemistry, 2 nd Edition, Paula Yurkanis Bruice, Prentice Hall, New York, NY,
More informationJEFFERSON COLLEGE COURSE SYLLABUS CHM201 ORGANIC CHEMISTRY II. 5 Credit Hours. Prepared by: Richard A. Pierce
JEFFERSON COLLEGE COURSE SYLLABUS CHM201 ORGANIC CHEMISTRY II 5 Credit Hours Prepared by: Richard A. Pierce Revised Date: January 2008 by Ryan H. Groeneman Arts & Science Education Dr. Mindy Selsor, Dean
More informationTips for taking exams in 852
Comprehensive Tactical Methods in rganic Synthesis W. D. Wulff 1) Know the relative reactivity of carbonyl compounds Tips for taking exams in 852 Cl > > ' > > ' N2 eg: 'Mg Et ' 1equiv. 1equiv. ' ' Et 50%
More informationCh 20 Carboxylic Acids and Nitriles
Ch 20 Carboxylic Acids and Nitriles Carboxylic Acids (RCO 2 H) are compounds with an OH attached to a carbonyl. Nitriles (RC N) are compounds a carbon-nitrogen triple bond. Naming Carboxylic Acids 1. Replace
More informationWhen we deprotonate we generate enolates or enols. Mechanism for deprotonation: Resonance form of the anion:
Lecture 5 Carbonyl Chemistry III September 26, 2013 Ketone substrates form tertiary alcohol products, and aldehyde substrates form secondary alcohol products. The second step (treatment with aqueous acid)
More informationChapter 16 Aldehydes and Ketones I. Nucleophilic Addition to the Carbonyl Group
Chapter 16 Aldehydes and Ketones I. Nucleophilic Addition to the Carbonyl Group Nomenclature of Aldehydes and Ketones Aldehydes are named by replacing the -e of the corresponding parent alkane with -al
More informationCarboxylic Acids and Nitriles
Carboxylic Acids and Nitriles Why this Chapter? Carboxylic acids present in many industrial processes and most biological processes They are the starting materials from which other acyl derivatives are
More informationChapter 9. Nucleophilic Substitution and ß-Elimination
Chapter 9 Nucleophilic Substitution and ß-Elimination Nucleophilic Substitution Nucleophile: From the Greek meaning nucleus loving. A molecule or ion that donates a pair of electrons to another atom or
More informationChapter 19. Synthesis and Reactions of b-dicarbonyl Compounds: More Chemistry of Enolate Anions. ß-dicarbonyl compounds. Why are ß-dicarbonyls useful?
Chapter 19 Synthesis and Reactions of b-dicarbonyl Compounds: More Chemistry of Enolate Anions ß-dicarbonyl compounds Two carbonyl groups separated by a carbon Three common types ß-diketone ß-ketoester
More informationNuggets of Knowledge for Chapter 17 Dienes and Aromaticity Chem 2320
Nuggets of Knowledge for Chapter 17 Dienes and Aromaticity Chem 2320 I. Isolated, cumulated, and conjugated dienes A diene is any compound with two or C=C's is a diene. Compounds containing more than two
More informationAldol Reactions pka of a-h ~ 20
Enolate Anions Chapter 17 Hydrogen on a carbons a to a carbonyl is unusually acidic The resulting anion is stabilized by resonance to the carbonyl Aldehydes and Ketones II Aldol Reactions pka of a-h ~
More informationChapter 16 Aldehydes and Ketones I Nucleophilic Addition to the Carbonyl Group
Chapter 16 Aldehydes and Ketones I Nucleophilic Addition to the Carbonyl Group Nomenclature of Aldehydes and Ketones Aldehydes are named by replacing the -e of the corresponding parent alkane with -al
More informationSuggested solutions for Chapter 27
uggested solutions for Chapter 27 27 PRBLEM 1 uggest a mechanism for this reaction, commenting on the selectivity and the stereochemistry. Me 2 1. t-buk 2. Raney Ni Et The opportunity to explore the consequences
More informationORGANIC CHEMISTRY. Fifth Edition. Stanley H. Pine
ORGANIC CHEMISTRY Fifth Edition Stanley H. Pine Professor of Chemistry California State University, Los Angeles McGraw-Hill, Inc. New York St. Louis San Francisco Auckland Bogota Caracas Lisbon London
More informationChapter 5. Nucleophilic aliphatic substitution mechanism. by G.DEEPA
Chapter 5 Nucleophilic aliphatic substitution mechanism by G.DEEPA 1 Introduction The polarity of a carbon halogen bond leads to the carbon having a partial positive charge In alkyl halides this polarity
More informationAldehydes and Ketones: Nucleophilic Addition Reactions
Aldehydes and Ketones: Nucleophilic Addition Reactions Why this Chapter? Much of organic chemistry involves the chemistry of carbonyl compounds Aldehydes/ketones are intermediates in synthesis of pharmaceutical
More information+ + CH 11: Substitution and Elimination Substitution reactions
C 11: Substitution and Elimination Substitution reactions Things to sort out: Nucleophile Electrophile -- > substrate Leaving Group S N 2 S N 1 E 1 E 2 Analysis Scheme Kinetics Reaction profile Substrates
More informationCape Cod Community College
Cape Cod Community College Departmental Syllabus Prepared by the Department of Natural Sciences & Applied Technology Date of Departmental Approval: February 3, 2014 Date Approved by Curriculum and Programs:
More informationSpring Term 2012 Dr. Williams (309 Zurn, ex 2386)
Chemistry 242 Organic Chemistry II Spring Term 2012 Dr. Williams (309 Zurn, ex 2386) Web Page: http://math.mercyhurst.edu/~jwilliams/ jwilliams@mercyhurst.edu (or just visit Department web site and look
More informationAlpha Substitution and Condensations of Enols and Enolate Ions. Alpha Substitution
Alpha Substitution and ondensations of Enols and Enolate Ions hap 23 W: 27, 28, 30, 31, 37, 39, 42-44, 47, 51, 54-56 Alpha Substitution Replacement of a hydrogen on the carbon adjacent to the carbonyl,
More informationSubstitution and Elimination reactions
PART 3 Substitution and Elimination reactions Chapter 8. Substitution reactions of RX 9. Elimination reactions of RX 10. Substit n/elimin n of other comp ds 11. Organometallic comp ds 12. Radical reactions
More informationReactions at α-position
Reactions at α-position In preceding chapters on carbonyl chemistry, a common reaction mechanism observed was a nucleophile reacting at the electrophilic carbonyl carbon site NUC NUC Another reaction that
More informationAugust 10, Prospective Chemistry 5511 Students. SUBJECT: Course Syllabus for Chemistry 5511 Fall 2011
TO: FROM: Prospective Chemistry 5511 Students Peter Gaspar August 10, 2011 SUBJECT: Course Syllabus for Chemistry 5511 Fall 2011 Chemistry 5511 Mechanistic Organic Chemistry is the first semester of a
More information1/4/2011. Chapter 18 Aldehydes and Ketones Reaction at the -carbon of carbonyl compounds
Chapter 18 Aldehydes and Ketones Reaction at the -carbon of carbonyl compounds The Acidity of the Hydrogens of Carbonyl Compounds: Enolate Anions Hydrogens on carbons to carbonyls are unusually acidic
More informationN_HW1 N_HW1. 1. What is the purpose of the H 2 O in this sequence?
N_HW1 N_HW1 Multiple Choice Identify the choice that best completes the statement or answers the question. There is only one correct response for each question. 1. What is the purpose of the H 2 O in this
More informationSubstitution α to a carbonyl center: Enol and enolate chemistry
Chapter 11 Organic Reaction Mechanisms, Part 2: Substitutions at Aliphatic Centers and Thermal Isomerizations/Rearrangements 11.1 Tautomerization Substitution α to a carbonyl center: Enol and enolate chemistry
More informationConjugated Systems & Pericyclic Reactions
onjugated Systems & Pericyclic Reactions 1 onjugated Dienes from heats of hydrogenation-relative stabilities of conjugated vs unconjugated dienes can be studied: Name 1-Butene 1-Pentene Structural Formula
More informationSeptember [KV 804] Sub. Code: 3804
September 2009 [KV 804] Sub. Code: 3804 (Regulations 2008-2009) (Candidates admitted from 2008-2009 onwards) Paper IV PHARMACEUTICAL ORGANIC CHEMISTRY Time : Three hours Maximum : 70 marks Answer All questions
More informationThis syllabus is printed on both sides of each page in the hard-copy version.
TO: FROM: Prospective Chemistry 5511 Students Peter Gaspar August 13, 2010 SUBJECT: Course Syllabus for Chemistry 5511 Fall 2010 Chemistry 5511 Mechanistic Organic Chemistry is the first semester of a
More informationLecture 3: Aldehydes and ketones
Lecture 3: Aldehydes and ketones I want to start by talking about the mechanism of hydroboration/ oxidation, which is a way to get alcohols from alkenes. This gives the anti-markovnikov product, primarily
More informationCHM 292 Final Exam Answer Key
CHM 292 Final Exam Answer Key 1. Predict the product(s) of the following reactions (5 points each; 35 points total). May 7, 2013 Acid catalyzed elimination to form the most highly substituted alkene possible
More informationChapter 4. Reactions of alkenes. Addition reactions Carbocations Selectivity of reactions
Chapter 4 Reactions of alkenes Addition reactions Carbocations Selectivity of reactions Prob 47 p192. Give the reagents that would be required (including catalyst). Ch 4 #2 Electrophilic addition Ch 4
More informationChapter 19. Carbonyl Compounds III Reaction at the α-carbon
Chapter 19. Carbonyl Compounds III Reaction at the α-carbon There is a basic hydrogen (α hydrogen) on α carbon, which can be removed by a strong base. 19.1 The Acidity of α-hydrogens A hydrogen bonded
More informationEthers. Chapter 14: Ethers, Epoxides, & Sulfides. General Formula: Types: a) Symmetrical: Examples: b) Unsymmetrical: Examples: Physical Properties:
Chamras Chemistry 106 Lecture Notes Examination 1 Materials Chapter 14: Ethers, Epoxides, & Sulfides Ethers General Formula: Types: a) Symmetrical: Examples: b) Unsymmetrical: Examples: Physical Properties:
More informationInorganic Chemistry GARY L. MIESSLER DONALD A. TARR. St. Olaf College Northfield, Minnesota
Inorganic Chemistry GARY L. MIESSLER DONALD A. TARR St. Olaf College Northfield, Minnesota Contents PREFACE xiii 1 INTRODUCTION TO INORGANIC CHEMISTRY 1 1-1 What Is Inorganic Chemistry? 1 1-2 Contrasts
More informationModule No and Title. PAPER No: 5 ; TITLE : Organic Chemistry-II MODULE No: 25 ; TITLE: S E 1 reactions
Subject Chemistry Paper No and Title Module No and Title Module Tag 5; Organic Chemistry-II 25; S E 1 reactions CHE_P5_M25 TABLE OF CONTENTS 1. Learning Outcomes 2. Introduction 3. S E 1 reactions 3.1
More informationLecture Topics: I. Electrophilic Aromatic Substitution (EAS)
Reactions of Aromatic Compounds Reading: Wade chapter 17, sections 17-1- 17-15 Study Problems: 17-44, 17-46, 17-47, 17-48, 17-51, 17-52, 17-53, 17-59, 17-61 Key Concepts and Skills: Predict and propose
More informationAdvanced Organic Chemistry
D. A. Evans, G. Lalic Chem 530A Chemistry 530A Advanced Organic Chemistry Lecture notes part 8 Carbanions Organolithium and Grignard reagents Organocopper reagents 1. Direct metalation 2. From radical
More informationLecture Notes Chem 51C S. King. Chapter 20 Introduction to Carbonyl Chemistry; Organometallic Reagents; Oxidation & Reduction
Lecture Notes Chem 51C S. King Chapter 20 Introduction to Carbonyl Chemistry; rganometallic Reagents; xidation & Reduction I. The Reactivity of Carbonyl Compounds The carbonyl group is an extremely important
More informationAldehydes & Ketones LEVEL I. Phenol (enol form) Phenol is aromatic, so equiulibrium is shifted to the right hand side. b) O
Subjective Problems Aldehydes & Ketones LEVEL I 1. a) 2,4cyclohexadiene-1-one (keto form) Phenol (enol form) Phenol is aromatic, so equiulibrium is shifted to the right hand side. b) Base This ketone is
More informationCOURSE UNIT DESCRIPTION. Dept. Organic Chemistry, Vilnius University. Type of the course unit
Course unit title Organic Chemistry II Lecturer(s) Rimantas Vaitkus COURSE UNIT DESCRIPTION Department Dept. Organic Chemistry, Vilnius University Cycle First Type of the course unit Mode of delivery Period
More informationCourse Goals for CHEM 202
Course Goals for CHEM 202 Students will use their understanding of chemical bonding and energetics to predict and explain changes in enthalpy, entropy, and free energy for a variety of processes and reactions.
More informationChapter 8: Ethers and Epoxides. Diethyl ether in starting fluid
Chapter 8: Ethers and Epoxides Diethyl ether in starting fluid 8.1 Nomenclature of Ethers Ethers are usually named by giving the name of each alkyl or aryl group, in alphabetical order, followed by the
More informationREACTION AND SYNTHESIS REVIEW
REACTION AND SYNTHESIS REVIEW A STUDENT SHOULD BE ABLE TO PREDICT PRODUCTS, IDENTIFY REACTANTS, GIVE REACTION CONDITIONS, PROPOSE SYNTHESES, AND PROPOSE MECHANISMS (AS LISTED BELOW). REVIEW THE MECHANISM
More informationDetailed Course Content
Detailed Course Content Chapter 1: Carbon Compounds and Chemical Bonds The Structural Theory of Organic Chemistry 4 Chemical Bonds: The Octet Rule 6 Lewis Structures 8 Formal Charge 11 Resonance 14 Quantum
More informationChapter 20: Carboxylic Acids
1 Chapter 20: Carboxylic Acids I. Introduction: Carboxylic acid structure: Classification of carboxylic acids: A carboxylic acid donates protons by the heterocyclic cleavage of the O-H bond, generating
More informationChapter 19 Carboxylic Acids
Carboxylic acids have the formula RCO2H. Nomenclature Chapter 19 Carboxylic Acids For the parent alkane, drop the terminal e and add the suffix oic acid. The parent alkane is the longest continuous chain
More informationEthers can be symmetrical or not:
Chapter 14: Ethers, Epoxides, and Sulfides 175 Physical Properties Ethers can be symmetrical or not: linear or cyclic. Ethers are inert and make excellent solvents for organic reactions. Epoxides are very
More informationPhysical organic chemistry
Physical organic chemistry Second edition Neil S. Isaacs Foreword to first edition Foreword to second edition Symbols and abbreviations Mechanistic designations vi i ix xxvi i xxvii r Models of chemical
More informationCHEM 330. Topics Discussed on Oct 5. Irreversible nature of the reaction of carbonyl enolates with the electrophiles discussed on Oct 2
CEM 330 Topics Discussed on ct 5 Irreversible nature of the reaction of carbonyl enolates with the electrophiles discussed on ct 2 Kinetic control in an irreversible reaction: the product that is obtained
More information75. A This is a Markovnikov addition reaction. In these reactions, the pielectrons in the alkene act as a nucleophile. The strongest electrophile will
71. B SN2 stands for substitution nucleophilic bimolecular. This means that there is a bimolecular rate-determining step. Therefore, the reaction will follow second-order kinetics based on the collision
More information1. What is the major organic product obtained from the following sequence of reactions?
CH320 N N_HW1 Multiple Choice Identify the choice that best completes the statement or answers the question. There is only one correct response for each question. Carefully record your answers on the Scantron
More informationCHEM Chapter 23. Carbonyl Condensation Reactions (quiz) W25
CHEM 2425. Chapter 23. Carbonyl Condensation Reactions (quiz) W25 Student: 1. Which of the following statements about Aldol reactions with either aldehydes or ketones is true? Equilibrium favors the starting
More informationOrganic Chemistry Lecture 2 - Hydrocarbons, Alcohols, Substitutions
ALKANES Water-insoluble, low density C-C single bonds Higher MW -> higher BP, higher MP Branching -> lower BP, higher MP Forms cycloalkanes which can have ring strain Cyclohexane: chair vs. boat configuration
More information18.8 Oxidation. Oxidation by silver ion requires an alkaline medium
18.8 Oxidation Oxidation by silver ion requires an alkaline medium Test for detecting aldehydes Tollens reagent to prevent precipitation of the insoluble silver oxide, a complexing agent is added: ammonia
More informationChapter 19. Organic Chemistry. Carbonyl Compounds III. Reactions at the a-carbon. 4 th Edition Paula Yurkanis Bruice
Organic Chemistry 4 th Edition Paula Yurkanis Bruice Chapter 19 Carbonyl Compounds III Reactions at the a-carbon Disampaikan oleh: Dr. Sri Handayani 2013 Irene Lee Case Western Reserve University Cleveland,
More informationPAPER No. : Paper-9, Organic Chemistry-III (Reaction Mechanism-2) MODULE No. : Module-10, Hydroboration Reaction CHEMISTRY
Subject Chemistry Paper No and Title Module No and Title Module Tag Paper-9, Organic Chemistry-III (Reaction Mechanism-2) Module-10, Hydroboration Reaction CHE_P9_M10 TABLE OF CONTENTS 1. Learning Outcomes
More informationUNIT 4 REVISION CHECKLIST CHEM 4 AS Chemistry
UNIT 4 REVISION CHECKLIST CHEM 4 AS Chemistry Topic 4.1 Kinetics a) Define the terms: rate of a reaction, rate constant, order of reaction and overall order of reaction b) Deduce the orders of reaction
More informationLecture Notes Chem 51C S. King Chapter 24 Carbonyl Condensation Reactions
Lecture Notes Chem 51C S. King Chapter 24 Carbonyl Condensation Reactions I. Reaction of Enols & Enolates with ther Carbonyls Enols and enolates are electron rich nucleophiles that react with a number
More information1. Radical Substitution on Alkanes. 2. Radical Substitution with Alkenes. 3. Electrophilic Addition
1. Radical Substitution on Alkanes Only Cl and Br are useful at the laboratory level. Alkane reactivity: tertiary > secondary > primary > methyl Numbers below products give their relative yield. Relative
More informationBasic Organic Chemistry Course code : CHEM (Pre-requisites : CHEM 11122)
Basic Organic Chemistry Course code : CHEM 12162 (Pre-requisites : CHEM 11122) Chapter 01 Mechanistic Aspects of S N2,S N1, E 2 & E 1 Reactions Dr. Dinesh R. Pandithavidana Office: B1 222/3 Phone: (+94)777-745-720
More informationGlendale Community College Chemistry 105 Exam. 3 Lecture Notes Chapters 6 & 7
Sevada Chamras, Ph.D. Glendale Community College Chemistry 105 Exam. 3 Lecture Notes Chapters 6 & 7 Description: Examples: 3 Major Types of Organic Halides: 1. Alkyl Halides: Chapter 6 (Part 1/2) : Alkyl
More informationOrganic Chemistry I and II challenge exam
Organic Chemistry I and II challenge exam Dear student: Organic Chemistry I and II at LCSC covers the standard one year organic curriculum and students take the two-semester ACS exam as their spring final.
More informationDouble and Triple Bonds. The addition of an electrophile and a
Chapter 11 Additions to Carbon-Carbon Double and Triple Bonds The addition of an electrophile and a nucleophile to a C-C C double or triple bonds 11.1 The General Mechanism Pi electrons of the double bond
More informationCHEMISTRY. Module No and Title Module-7, Nucleophilic and Free Radical Addition. Reactions of Alkenes
Subject Chemistry Paper No and Title Paper-9, Organic Chemistry-III (Reaction Mechanism-2) Module No and Title Module-7, Nucleophilic and Free Radical Addition Module Tag CHE_P9_M7 TABLE OF CONTENTS 1.
More informationConjugate Addition Reactions 2:02 PM
1 Conjugate Addition vs Direct Addition What is Conjugate Addition? Conjugate addition refers to nucleophilic addition directed to the electrophilic carbon of the C=C (double bond) in a,bunsaturated systems.
More information10. Organohalides. Based on McMurry s Organic Chemistry, 7 th edition
10. Organohalides Based on McMurry s Organic Chemistry, 7 th edition What Is an Alkyl Halide An organic compound containing at least one carbonhalogen bond (C-X) X (F, Cl, Br, I) replaces H Can contain
More informationA. Review of Acidity and pk a Common way to examine acidity is to use the Bronsted-Lowry acid-base equation:
1 Chapter 22: Reactions of Enols and Enolates I. Alpha Substitution verview: A. Review of Acidity and pk a Common way to examine acidity is to use the Bronsted-Lowry acid-base equation: Recall that the
More informationCHAPTER 7. Further Reactions of Haloalkanes: Unimolecular Substitution and Pathways of Elimination
CHAPTER 7 Further Reactions of Haloalkanes: Unimolecular Substitution and Pathways of Elimination 7-1 Solvolysis of Tertiary and Secondary Haloalkanes The rate of S N 2 reactions decrease dramatically
More informationAdvanced Organic FOURTH. Part A: Structure and Mechanisms
Advanced Organic FOURTH Chemistry EDITION Part A: Structure and Mechanisms Advanced Organic Chemistry PART A: Structure and Mechanisms PART B: Reactions and Synthesis Advanced Organic Chemistry FOURTH
More informationChapter 18: Ketones and Aldehydes. I. Introduction
1 Chapter 18: Ketones and Aldehydes I. Introduction We have already encountered numerous examples of this functional group (ketones, aldehydes, carboxylic acids, acid chlorides, etc). The three-dimensional
More informationAryl Halides. Structure
Aryl Halides Structure Aryl halides are compounds containing halogen attached directly to an aromatic ring. They have the general formula ArX, where Ar is phenyl, substituted phenyl. X= F,Cl,Br,I An aryl
More informationIntroduction to Organic Chemistry
Introduction to rganic hemistry 59 Introduction to rganic hemistry andout 3 - chanism u u http://burton.chem.ox.ac.uk/teaching.html rganic hemistry J. layden,. Greeves, S. Warren Stereochemistry at a Glance
More informationJEFFERSON COLLEGE COURSE SYLLABUS CHM201 ORGANIC CHEMISTRY II. 5 Credit Hours. Prepared by: Richard A. Pierce. Revised by: Sean Birke October, 2013
JEFFERSON COLLEGE COURSE SYLLABUS CHM201 ORGANIC CHEMISTRY II 5 Credit Hours Prepared by: Richard A. Pierce Revised by: Sean Birke October, 2013 Ms. Linda Abernathy, Math, Science & Business Division Chair
More informationبه نام خدا روشهای سنتز مواد آلی
به نام خدا روشهای سنتز مواد آلی 1 References: 1. Carey, F. A.; Sundberg, R. J. Advanced Organic Chemistry: Reactions and Synthesis (Part B), 5th ed., Springer, 2007. 2. Carey, F. A.; Sundberg, R. J. Advanced
More informationModern Organic Synthesis an Introduction
Modern Organic Synthesis an Introduction G. S. Zweifel M. H. Nantz W.H. Freeman and Company Chapter 1 Synthetic Design 1 What is an ideal or viable synthesis, and how does one approach a synthetic project?
More informationOrganic Chemistry 112 A B C - Syllabus Addendum for Prospective Teachers
Chapter Organic Chemistry 112 A B C - Syllabus Addendum for Prospective Teachers Ch 1-Structure and bonding Ch 2-Polar covalent bonds: Acids and bases McMurry, J. (2004) Organic Chemistry 6 th Edition
More informationChapter 9 Aldehydes and Ketones Excluded Sections:
Chapter 9 Aldehydes and Ketones Excluded Sections: 9.14-9.19 Aldehydes and ketones are found in many fragrant odors of many fruits, fine perfumes, hormones etc. some examples are listed below. Aldehydes
More informationSuggested solutions for Chapter 40
s for Chapter 40 40 PBLEM 1 Suggest mechanisms for these reactions, explaining the role of palladium in the first step. Ac Et Et BS () 4 2 1. 2. K 2 C 3 evision of enol ethers and bromination, the Wittig
More informationREARRANGEMENTS NOTES Mechanistic Aspects of Rearrangements
- 1 - REARRANGEMENTS NOTES Mechanistic Aspects of Rearrangements Nature of the Rearrangement It can vary from being truly stepwise to migration occurring in concert with initial ionisation. These two situations
More informationChem 251 Fall Learning Objectives
Learning Objectives Chapter 8 (last semester) 1. Write an electron-pushing mechanism for an SN2 reaction between an alkyl halide and a nucleophile. 2. Describe the rate law and relative rate of reaction
More informationChapter 11, Part 1: Polar substitution reactions involving alkyl halides
hapter 11, Part 1: Polar substitution reactions involving alkyl halides Overview: The nature of alkyl halides and other groups with electrophilic sp 3 hybridized leads them to react with nucleophiles and
More informationSuggested solutions for Chapter 28
s for Chapter 28 28 PBLEM 1 ow would you make these four compounds? Give your disconnections, explain why you chose them and then give reagents for the. 2 2 Me S Exercises in basic one- group C X disconnections.
More information