Organic Chemistry

1293 Pages·2016·52.22 MB·english

by  Craig B. Fryhle

This page intentionally left blank
18VIIIA 2 HeHelium4.0026 10 NeNeon20.180 18 ArArgon39.948 36 KryptonrK83.798 54 XeXenon131.29 86 RnRadon(222) 118 Uuo (294)
m
17VIIA 9 FinerFluo18.998 17 ClinerChlo35.453 35 BrBromine79.904 53 IIodine126.90 85 AtAstatine(210) 117 Uus (294) 71 LuLutetium174.97 103 Lrwrenciua(262)
L
m
16VIA 8 OOxygen15.999 16 SSulfur32.065 34 SeSelenium78.96 52 eTiumrelluT127.60 84 oPoloniumP(209) 116 LvLivermoriu(293) 70 YbYtterbium173.04 102 NoNobelium(259)
S 15AV 7 NNitrogen14.007 15 PusrPhospho30.974 33 AsArsenic74.922 51 SbynAntimo121.76 83 BiuthmBis208.98 115 Uup (288) 69 TmThulium168.93 101 MdviumeMendel(258)
ENT 14AVI 6 CCarbon12.011 14 SiSilicon28.086 32 GemaniumrGe72.64 50 SnTin118.71 82 PbLead207.2 114 FlFlerovium(289) 68 ErErbium167.26 100 FmmiumreF(257)
LEM 13IIIA 5 BBoron10.811 13 AlumnAlumi26.982 31 GaGallium69.723 49 InIndium114.82 81 TlThallium204.38 113 Uut (284) 67 HoHolmium164.93 99 EsEinsteinium(252)
ELE OF THE UPAC recommendations:s Service group notation: 101211VIIIBIIBIB 302928 ZnCuNiZincCopperelckNi65.40963.54658.693 484746 PdCdAgCadmiumervSilalladiumP112.41107.87106.42 788079 HguAPtnPlatiyrMercuGoldum200.59196.97195.08 110112111 CnRgDsCoperniciumRoentgeniumDarmstadtium(285)(272)(281) 656664 DyTbGdDysprosiumerbiumTGadolinium162.50158.93157.25 989796 CfBkCmniumrofCalieliumkrBeiumrCu(251)(247)(247)
TAB IAbstract 9VIIIB 27 CoCobalt58.933 45 RhRhodium102.91 77 IridiumrI192.22 109 MtiumrMeitne(268) 63 EuEuropium151.96 95 AmiciumrAme(243)
DIC Chemical 8VIIIB 26 FeIron55.845 44 RuRuthenium101.07 76 OsOsmium190.23 108 HsHassium(277) 62 SmiumrSama150.36 94 PuPlutonium(244)
PERIO 6 CCarbon 12.011 67VIBVIIB 2524 MnCrManganeseChromium54.93851.996 4342 TcMoechnetiumTumnMolybde(98)95.94 7574 WReRheniumungstenT186.21183.84 107106 BhSgiumrBohSeaborgium(264)(266) 6160 PmNdPromethiumNeodymium(145)144.24 9392 UNpNeptuniumaniumrU(237)238.03
Atomic number Symbol Name (IUPAC)Atomic mass 54VBIVB 2322 VTianadiumVTitanium50.94247.867 4041 NbZrNiobiumZirconium92.90691.224 7273 HfaTantalumTHafnium180.95178.49 104105 DbRfDubniumordiumfRuther(262)(261) 5958 CePriumrCeaseodymiumrP140.12140.91 9091ThaPiumrThoProtactinium232.04231.04
3IIIB 21 ScScandium44.956 39 YiumrYtt88.906 57 *LaumnLantha138.91 89 #AcActinium(227) iesrSe e iesrSe e
2IIA 4 BeyliumrBe9.0122 12 MgMagnesium24.305 20 CaCalcium40.078 38 SrStrontium87.62 56 BaiumrBa137.33 88 RaRadium(226) anthanid Actinid #
L
*
1IA 1 HHydrogen1.0079 3 LILithium6.941 11 NaSodium22,990 19 KotassiumP39.098 37 RbRubidium85.468 55 CsCesium132.91 87 FranciumrF(223)
Table 3.1 RelaTive STRengTh of SelecTed acidS and TheiR conjugaTe baSeS
conjugate
acid approximate pK base
a
Strongest acid HSbF < −12 SbF− Weakest base
6 6
HI −10 I−
H2SO4 −9 HSO−4
HBr −9 Br−
HCl −7 Cl−
C6H5SO3H −6.5 C6H5SO−3
(CH3)2O+H −3.8 (CH3)2O
(CH3)2C=O+H −2.9 (CH3)2C=O
+
(CH3)OH2 −2.5 CH3OH
H3O+ −1.74 H2O
HNO3 −1.4 NO−3 In
ngth CHFF3CO2H 03..128 CF−F3CO−2 creas
creasing acid stre CCCHC662HHHHC3355CCOCNOO3OH2C+32HHH2COCH3 44469.....267301355 CCCHC66HCHHH33O55CC−3CNOOOH−2C−−22HCOCH3 ing base strength
In NH+4 9.2 NH3
C6H5OH 9.9 C6H5O−
HCO− 10.2 CO2−
3 3
CH3NH+3 10.6 CH3NH2
H2O 15.7 HO−
CH3CH2OH 16 CH3CH2O−
(CH3)3COH 18 (CH3)3CO−
CH3COCH3 19.2 −CH2COCH3
HC≡CH 25 HC≡C−
C6H5NH2 31 C6H5NH−
H2 35 H−
(i-Pr)2NH 36 (i-Pr)2N−
NH3 38 −NH2
CH=CH 44 CH=CH−
2 2 2
Weakest acid Strongest base
CH3CH3 50 CH3CH−2
Organic Chemistry
T.W. Graham SolomonS
University of South Florida
CraiG B. Fryhle
Pacific Lutheran University
SCoTT a. Snyder
University of Chicago
12e
For Annabel and Ella. TWGS
For my mother and in memory of my father. CBF
For Cathy and Sebastian. SAS
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Structure image from the RCSB PDB (www.rcsb.org) of 1FKB (Van Duyne, G. D., Standaert, R. F., Schreiber, S. L.,
Clardy, J. C. (1992) Atomic Structure of the Ramapmycin Human Immunophilin Fkbp-12 Complex, J. Amer. Chem. Soc.
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Library of Congress Cataloging-in-Publication Data
Names: Solomons, T. W. Graham, author. | Fryhle, Craig B. | Snyder, S. A. (Scott A.)
Title: Organic chemistry.
Description: 12th edition / T.W. Graham Solomons, Craig B. Fryhle, Scott A.
Snyder. | Hoboken, NJ : John Wiley & Sons, Inc., 2016. | Includes index.
Identifiers: LCCN 2015042208 | ISBN 9781118875766 (cloth)
Subjects: LCSH: Chemistry, Organic—Textbooks.
Classification: LCC QD253.2 .S65 2016 | DDC 547—dc23 LC record available at http://lccn.loc.gov/2015042208
ISBN 978-1-118-87576-6
Binder-ready version ISBN 978-1-119-07725-1
The inside back cover will contain printing identification and country of origin if omitted from this page. In
addition, if the ISBN on the back cover differs from the ISBN on this page, the one on the back cover is correct.
Printed in the United States of America
10 9 8 7 6 5 4 3 2 1
Brief Contents
1 The Basics Bonding and Molecular Structure 1
2 Families of Carbon Compounds Functional Groups, Intermolecular Forces, and Infrared (IR)
Spectroscopy 55
3 Acids and Bases An Introduction to Organic R eactions and Their Mechanisms 104
4 Nomenclature and Conformations of Alkanes and Cycloalkanes 144
5 Stereochemistry Chiral Molecules 193
6 Nucleophilic Reactions Properties and Substitution Reactions of Alkyl Halides 240
7 Alkenes and Alkynes I Properties and Synthesis. Elimination Reactions of Alkyl Halides 282
8 Alkenes and Alkynes II Addition Reactions 337
9 Nuclear Magnetic Resonance and Mass Spectrometry Tools for Structure Determination 391
10 Radical Reactions 448
11 Alcohols and Ethers Synthesis and Reactions 489
12 Alcohols from Carbonyl Compounds Oxidation–Reduction and O rganometallic Compounds 534
13 Conjugated Unsaturated Systems 572
14 Aromatic Compounds 617
15 Reactions of Aromatic Compounds 660
16 Aldehydes and Ketones Nucleophilic Addition to the C arbonyl Group 711
17 Carboxylic Acids and Their Derivatives Nucleophilic Addition–Elimination at the Acyl Carbon 761
18 Reactions at the α Carbon of Carbonyl Compounds Enols and Enolates 811
19 Condensation and Conjugate Addition Reactions of Carbonyl Compounds More
Chemistry of Enolates 849
20 Amines 890
21 Transition Metal Complexes Promoters of Key Bond-Forming Reactions 938
22 Carbohydrates 965
23 Lipids 1011
24 Amino Acids and Proteins 1045
25 Nucleic Acids and Protein Synthesis 1090
GloSSary GL-1
index I-1
anSWerS To SeleCTed ProBlemS can be found at www.wiley.com/college/solomons
iii
Contents
1 2
The Basics Families of Carbon
BONDING AND Compounds
MOLECuLAR
FuNCTIONAL GROuPS,
STRuCTuRE 1
INTERMOLECuLAR FORCES, AND
1.1 Life and the Chemistry of Carbon INFRARED (IR) SPECTROSCOPy 55
Compounds—We Are Stardust 2
2.1 H ydrocarbons: Representative Alkanes, Alkenes,
The ChemiSTry oF… Natural Products 3 Alkynes, and Aromatic Compounds 56
1.2 Atomic Structure 3 2.2 Polar Covalent Bonds 59
1.3 Chemical Bonds: The Octet Rule 5 2.3 Polar and Nonpolar Molecules 61
1.4 HoW To Write Lewis Structures 7 2.4 Functional Groups 64
1.5 Formal Charges and HoW To Calculate Them 12 2.5 Alkyl Halides or Haloalkanes 65
1.6 I somers: Different Compounds that Have the Same 2.6 Alcohols and Phenols 67
Molecular Formula 14
2.7 Ethers 69
1.7 HoW To Write and Interpret Structural Formulas 15
The ChemiSTry oF… Ethers as General
1.8 Resonance Theory 22 Anesthetics 69
1.9 Quantum Mechanics and Atomic Structure 27 2.8 Amines 70
1.10 Atomic Orbitals and Electron Configuration 28 2.9 Aldehydes and Ketones 71
1.11 Molecular Orbitals 30 2.10 Carboxylic Acids, Esters, and Amides 73
1.12 The Structure of Methane and Ethane: 2.11 Nitriles 75
sp3 Hybridization 32
2.12 S ummary of Important Families of Organic
The ChemiSTry oF… Calculated Molecular Models: Compounds 76
Electron Density Surfaces 36
2.13 P hysical Properties and Molecular Structure 77
1.13 T he Structure of Ethene (Ethylene):
The ChemiSTry oF… Fluorocarbons and Teflon 81
sp 2 Hybridization 36
2.14 Summary of Attractive Electric Forces 85
1.14 T he Structure of Ethyne (Acetylene): sp
Hybridization 40 The ChemiSTry oF… Organic Templates Engineered to
Mimic Bone Growth 86
1.15 A Summary of Important Concepts that Come from
Quantum Mechanics 43 2.15 I nfrared Spectroscopy: An Instrumental Method
for Detecting Functional Groups 86
1.16 HoW To Predict Molecular G eometry: The Valence
Shell Electron Pair R epulsion Model 44 2.16 Interpreting IR Spectra 90
1.17 Applications of Basic Principles 47 2.17 Applications of Basic Principles 97
[ WHY DO THESE TOPICS MATTER? ] 48 [ WHY DO THESE TOPICS MATTER? ] 97
iv
3 4.3 HoW To Name Alkanes, Alkyl Halides, and Alcohols:
The IuPAC System 148
Acids and Bases 4.4 HoW To Name Cycloalkanes 155
AN INTRODuCTION TO
4.5 HoW To Name Alkenes and Cycloalkenes 158
ORGANIC REACTIONS AND
THEIR MECHANISMS 104 4.6 HoW To Name Alkynes 160
4.7 P hysical Properties of Alkanes and Cycloalkanes 161
3.1 Acid–Base Reactions 105
The ChemiSTry oF… Pheromones: Communication by
3.2 HoW To use Curved Arrows in I llustrating
Means of Chemicals 163
Reactions 107
4.8 Sigma Bonds and Bond Rotation 164
[ A MECHANISM FOR THE REACTION ] Reaction of Water
with Hydrogen Chloride: The use of Curved Arrows 107 4.9 Conformational Analysis of Butane 166
3.3 Lewis Acids and Bases 109 The ChemiSTry oF… Muscle Action 168
3.4 H eterolysis of Bonds to Carbon: 4.10 T he Relative Stabilities of Cycloalkanes: Ring
Carbocations and Carbanions 111 Strain 168
3.5 T he Strength of Brønsted–Lowry Acids 4.11 C onformations of Cyclohexane: The Chair and the
and Bases: K and pK 113 Boat 170
a a
3.6 HoW To Predict the Outcome of Acid–Base The ChemiSTry oF… Nanoscale Motors and Molecular
Reactions 118 Switches 172
3.7 Relationships between Structure and Acidity 120 4.12 S ubstituted Cyclohexanes:
Axial and Equatorial Hydrogen Groups 173
3.8 Energy Changes 123
4.13 D isubstituted Cycloalkanes: Cis–Trans
3.9 The Relationship between the Equilibrium Constant
Isomerism 177
and the Standard Free-Energy Change, ∆G ° 125
4.14 Bicyclic and Polycyclic Alkanes 181
3.10 Acidity: Carboxylic Acids versus Alcohols 126
4.15 Chemical Reactions of Alkanes 182
3.11 The Effect of the Solvent on Acidity 132
4.16 Synthesis of Alkanes and Cycloalkanes 182
3.12 Organic Compounds as Bases 132
4.17 HoW To Gain Structural Information from
3.13 A Mechanism for an Organic Reaction 134
Molecular Formulas and the Index of Hydrogen
[ A MECHANISM FOR THE REACTION ] Reaction of Deficiency 184
tert-Butyl Alcohol with Concentrated Aqueous HCl 134
4.18 Applications of Basic Principles 186
3.14 Acids and Bases in Nonaqueous Solutions 135
[ WHY DO THESE TOPICS MATTER? ] 187
3.15 Acid–Base Reactions and the Synthesis of
Deuterium- and Tritium-Labeled Compounds 136 See SPECIAl TOPIC A, 13C nmr Spectroscopy—a Practical
introduction, in WileyPLUS
3.16 Applications of Basic Principles 137
[ WHY DO THESE TOPICS MATTER? ] 138
5
4
Stereochemistry
CHIRAL MOLECuLES 193
Nomenclature and
5.1 Chirality and Stereochemistry 194
Conformations
5.2 I somerism: Constitutional Isomers
of Alkanes and
and Stereoisomers 195
Cycloalkanes
5.3 Enantiomers and Chiral Molecules 197
4.1 Introduction to Alkanes and Cycloalkanes 145
5.4 M olecules Having One Chirality Center
The ChemiSTry oF… Petroleum Refining 145 are Chiral 198
4.2 Shapes of Alkanes 146 5.5 M ore about the Biological Importance of Chirality 201
v
5.6 HoW To Test for Chirality: Planes of Symmetry 203 [ A MECHANISM FOR THE REACTION ] Mechanism for
the S 1 Reaction 256
5.7 Naming Enantiomers: The R,S-System 204 N
6.11 Carbocations 257
5.8 Properties of Enantiomers: Optical Activity 208
6.12 The Stereochemistry of S 1 Reactions 259
5.9 Racemic Forms 213 N
[ A MECHANISM FOR THE REACTION ] The
5.10 The Synthesis of Chiral Molecules 214
Stereochemistry of an S 1 Reaction 260
N
5.11 Chiral Drugs 216
6.13 Factors Affecting the Rates of S 1 and S 2
N N
The ChemiSTry oF… Selective Binding of Drug Reactions 262
Enantiomers to Left- and Right-Handed Coiled DNA 218
6.14 Organic Synthesis: Functional Group Transformations
5.12 Molecules with More than One Chirality Center 218 using S 2 Reactions 272
N
5.13 Fischer Projection Formulas 224 The ChemiSTry oF… Biological Methylation: A Biological
Nucleophilic Substitution Reaction 273
5.14 Stereoisomerism of Cyclic Compounds 226
[ WHY DO THESE TOPICS MATTER? ] 275
5.15 Relating Configurations through Reactions in
Which No Bonds to the Chirality Center Are
Broken 228 7
5.16 Separation of Enantiomers: Resolution 232
Alkenes and
5.17 C ompounds with Chirality Centers
Alkynes I
Other than Carbon 233
PROPERTIES AND
5.18 C hiral Molecules that Do Not Possess
SyNTHESIS. ELIMINATION REACTIONS
a Chirality Center 233
OF ALKyL HALIDES 282
[ WHY DO THESE TOPICS MATTER? ] 234
7.1 Introduction 283
7.2 The (E )–(Z ) System for Designating Alkene
6 Diastereomers 283
7.3 Relative Stabilities of Alkenes 284
Nucleophilic
7.4 Cycloalkenes 287
Reactions
7.5 Synthesis of Alkenes: Elimination Reactions 287
PROPERTIES AND SuBSTITuTION
7.6 Dehydrohalogenation 288
REACTIONS OF ALKyL HALIDES 240
7.7 The E2 Reaction 289
6.1 Alkyl Halides 241
[ A MECHANISM FOR THE REACTION ] Mechanism for
6.2 Nucleophilic Substitution Reactions 242
the E2 Reaction 290
6.3 Nucleophiles 244
[ A MECHANISM FOR THE REACTION ] E2 Elimination
6.4 Leaving Groups 246 Where There Are Two Axial β Hydrogens 295
6.5 K inetics of a Nucleophilic S ubstitution Reaction: [ A MECHANISM FOR THE REACTION ] E2 Elimination
An S 2 Reaction 246 Where the Only Axial β Hydrogen Is from a Less Stable
N
Conformer 296
6.6 A Mechanism for the S 2 Reaction 247
N
7.8 The E1 Reaction 297
[ A MECHANISM FOR THE REACTION ] Mechanism for
the S 2 Reaction 248 [ A MECHANISM FOR THE REACTION ] Mechanism for
N
the E1 Reaction 298
6.7 Transition State Theory: Free-Energy Diagrams 249
7.9 Elimination and Substitution Reactions Compete
6.8 The Stereochemistry of S 2 Reactions 252
N With Each Other 299
[ A MECHANISM FOR THE REACTION ] The
7.10 Elimination of Alcohols: Acid-Catalyzed
Stereochemistry of an S 2 Reaction 254
N Dehydration 303
6.9 T he Reaction of tert-Butyl Chloride with Water:
[ A MECHANISM FOR THE REACTION ] Acid-Catalyzed
An S 1 Reaction 254
N Dehydration of Secondary or Tertiary Alcohols:
6.10 A Mechanism for the S 1 Reaction 255 An E1 Reaction 306
N
vi