Organic Chemistry

1352 Pages·2013·503.34 MB·English

by  Janice Gorzynski Smith

Periodic Table of the Elements
Group number-1A
BA
1 I Key
Period H H2 e
number__. 1
H1y.d0r0og7e9n LAtomic numbe"r -- "~'*H6""7o "-'-·- _Symbol Helium 1
2A 3A 4A SA 6A 7A 4.0026
Holmium
L3 i B4 e - Atom;, we;ght B5 C6 N7 08 F9 N10e
2 2
An element
Lithium Beryllium Boron Carton Nitrogen Oxygen Fluorine Neon
6.941 9.0122 ---- 10.811 12.011 14.0067 15.9994 18.9984 20.1797
N11a M12g A13l S14i p15 s16 C17l A18r
3 3
Sodium Magnesium Aluminum Silicon Phosphorus Sulfur Chlorine Argon
22.9898 24.3050 3B 4B 5B 6B 7B 8B 8B 8B 1B 2B 26.9815 28.0855 30.9738 32.066 35.4527 39.948
K19 C20a S21c T22i V23 C24r M25n F26e C27o N28i C29u Z30n G31 a G32e A33s S34e ' B35r K36r
4 4
PolaSSlum Calcium Scandjum Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
39.0983 40,078 44.9559 47.88 50.9415 51.9961 54 9380 55.845 58.9332 58.693 63.546 65.41 69.723 72.64 74.9216 78.96 79.904 83.80
R37b S38r y39 Z40r N41b M42o T43c R44u R45h P46d A47g C48d I4n9 S5n0 S51b T52e 5I3 X54e
5 5
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
85.4678 87.62 88.9059 91.224 92.9064 95.94 (98) 101.07 102 9055 106.42 107.8682 112.411 114.82 118 710 121.760 127.60 126,9045 131.29
C55s B56a L57a H72 f T73a w74 R75e O76s I7r7 P78t A79u H80g T81l P82b B83i P84o A85t R86n
6 6
Cesium Barium Lanthanum Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury Thallium Lead Bismuth Polonium Astatine Radon
132.9054 137.327 138.9055 178.49 180.9479 183.84 186.207 190.2 192.22 195.08 196.9665 200.59 204.3833 207.2 208.9804 (209) (210) (222)
F87r R88a A89c R104f D10b5 S10g6 B10h7 H108s M109t O110s R111g C11n2 -113 F114l -115 L116v -117 -118
7 - - - - 7
Francium Radium Actinium Ruthe~ordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roen!~ Copemicium Flerovium Uvermorium
(223) (226) (227) (267) (268) (271) (272) (270) (276) (281) (280) (285) (284) (289) (288) (293) (294) (294)
' \
..
C58e P59r N60d P6m1 S6m2 E63u G64d T65b D66y H67o E68r T6m9 Y70b L71u
Lanthanides 6 6
Cerium Praseodymium Neodymium Promethium Samarium Europium Gado~nlum Terllium Dysprosium Holmium Erbium Thulium Ytterllium Lutetium
140.115 140.9076 144.24 (145) 150.36 151.964 157.25 158 9253 162.50 164.9303 167.26 168.9342 173.04 174.967
T90h P91a u92 N93p P94u A9m5 C9m6 B97k C98f E99s F1m00 M101d N102o L10r3
Actinides 7 7
Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Calilornium Einsteinium Fermium Mendelevium Nobelium lawrencium
232.0381 231.0359 238.0289 (237) (244) (243) (247) (247) (251) (252) (257) (258) (259) (260)
COMMON FUNCTIONAL GROUPS
Type of Compound General Structure Example Functional Group Type of Compound General Structure Example Functional Group
:o: :o: 0 0
Acid II II
,,c..._.. - ,,c.._.. -COCI Aromatic compound phenyl group
chloride
R s:;1: CHa s:;1:
:o: :o:
Alcohol R-O.. H CH3- QH -OH Carboxylic II ll -COOH
hydroxy group acid ,,c..._.. carboxy group
R OH cH,,c' oH
3 .•
:o: :o: :o: :o:
II II II II
Aldehyde C C C=O Ester ,,c, .. -COOR
R,, ' H CH; ' H carbonyl group R OR cH3,, c' o•• cH 3
-- -OR
Alkane R-H CH3CH3 Ether R-Q-R CH3-Q-CH3 alkoxy group
'
H H :o: :o:
\ I \ I II II C=O
Alkene C=C C=C double bond Ketone C C
I \ I \ R,, ' R CH; ' CH3 carbonyl group
H H
Alkyl halide (X = RF, -CXl,: Br, I) CH3-$[: halo- gxro up Nitrile R-C=N: CH3-C=N: cya-Cno= gNro up
Alkyne -C=C- H-C=C-H triple bond Sulfide R-~-R CH3-~-CH3 -SR
alkylthio group
:o:
Amide R ..,Cll ...._N.I. ,,H (or R) cH3_:., coII ,: NH 2 ---CCCOOONNNHHRR22 , , Thiol R- ~H CH3-~H merca-pStoH g roup
H (or R)
:o: :o:
II II
Amine R2RN-HN Hor2 Ro3r N CH3-NH2 ami-nNo Hgr2o up I Thioester R, ,c,~. .R cH3,, c' s.. cH 3 -COSR
:o: :o: :o: :o: 0 0
II II II II 11 II
Anhydride ,,c, .. ,,c ..... CH_.,C,O_.,C,CH ,.....c, ,.....c,
R O R 3 .. 3 0

Organic Chemistry
Fourth Edition
Janice Gorzynski Smith
University of Hawai'i at Manoa
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ORGANIC CHEMISTRY, FOURTH EDITION
Published by McGraw-Hill, a business unit of The McGraw-Hill Companies, Inc., 1221 Avenue of the
Americas, New York, NY 10020. Copyright© 2014 by The McGraw-Hill Companies, Inc. All rights reserved.
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Some ancillaries, including electronic and print components, may not be available to customers outside the
United States.
This book is printed on acid-free paper.
1234567890DOWffiOW109876543
ISBN 978---0---07-340277-2.
MHID 0-07-340277-X
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Library of Congress Cataloging-in-Publication Data
Smith, Janice G.
Organic chemistry / Janice Gorzynski Smith. - 4th ed.
p.cm.
Includes index.
ISBN 978---0---07-340277-2 - ISBN 0-07-340277-X (hard copy: alk. paper) 1. Chemistry, Organic
Textbooks. I. Title.
QD253.2.S63 2014
547-dc23
2012028487
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does not indicate an endorsement by the authors or McGraw-Hill, and McGraw-Hill does not guarantee the
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About the Author
Janice Gorzynski Smith was born in Schenectady, New York. She became interested
in chemistry in high school and went on to major in chemistry at Cornell University, where
she received an A.B. degree summa cum laude. Jan earned a Ph.D. in Organic Chemistry from
Harvard University under the direction of Nobel Laureate E. J. Corey, and she also spent a year
as a National Science Foundation National Needs Postdoctoral Fellow at Harvard. During her
tenure with the Corey group, she completed the total synthesis of the plant growth hormone
gibberellic acid.
Following her postdoctoral work, .Jan jqined the faculty of Mount Holyoke College, where
she was employed for 21 years. During this time she was active in teaching organic chemis
try lecture and lab courses, conducting a research program in organic synthesis, and serving
as department chair. Her organic chemistry class was named one of Mount Holyoke's "Don't
miss courses" in a survey by Boston magazine. After spending two sabbaticals amidst the natu
ral beauty and diversity in Hawai 'i in the 1990s, Jan and her family moved there permanently
in 2000. She is currently a faculty member at the University of Hawai 'i at Manoa, where she
teaches the two-semester organic chemistry lecture and lab courses. In 2003, she received the
Chancellor's Citation for Meritorious Teaching.
Jan resides in Hawai 'i with her husband Dan, an emergency medicine physician. She has
four children and one grandchild. When not teaching, writing, or enjoying her family, Jan bikes,
hikes, snorkels, and scuba dives in sunny Hawai'i, and time permitting, enjoys travel and Hawai
ian quilting.
$
Megan Sarah
Contents in Brief
Prologue 1
1 Structure and Bonding 7
2 Acids and Bases 58
3 Introduction to Organic Molecules and Functional Groups 86
4 Alkanes 120
5 Stereochemistry 166
6 Understanding Organic Reactions 205
7 Alkyl Halides and Nucleophilic Substitution 238
8 Alkyl Halides and Elimination Reactions 288
9 Alcohols, Ethers, and Epoxides 324
10 Alkenes 372
11 Alkynes 416
12 Oxidation and Reduction 444
13 Mass Spectrometry and Infrared Spectroscopy 483
14 Nuclear Magnetic Resonance Spectroscopy 514
15 Radical Reactions 558
16 Conjugation, Resonance, and Dienes 593
17 Benzene and Aromatic Compounds 630
18 Reactions of Aromatic Compounds 665
19 Carboxylic Acids and the Acidity of the O-H Bond 718
20 Introduction to Carbonyl Chemistry; Organometallic Reagents;
Oxidation and Reduction 753
21 Aldehydes and Ketones- Nucleophilic Addition 807
22 Carboxylic Acids and Their Derivatives-Nucleophilic Acyl Substitution 859
23 Substitution Reactions of Carbonyl Compounds at the a Carbon 915
24 Carbonyl Condensation Reactions 954
25 Amines 988
26 Carbor:i-Carbon Bond-Forming Reactions in Organic Synthesis 1042
27 Pericyclic Reactions 1069
28 Carbohydrates 1098
29 Amino Acids and Proteins 1148
30 Lipids 1194
31 Synthetic Polymers 1225
Appendices A-1
Glossary G-1
Credits C-1
Index 1-1
iv
Contents
Prefxaiciei 2.7A spi7r6i n
Acknleodwgmexnxtis 2.8L ewAicsia dnsBd a se7s7
LiosfHto w Tax'xsi v KeCyo nce7p9t s
LiosfMt e chanxivxsim s Probl8e0m s
LiosfSt e leAcptpeldi cxaxtiixo ns
3 IntrodtuoOc rtgiaonni c
Prolog1u e
MolecaunlFdeu sn ctional
WhaItOs r gaCnhiecm istry? Group8s6
SomRee preseOnrtgaaMtnoiilvcee c u2l es
3.1F unctGiroonua8pl7s
OrgaCnhiecm iistnth Mreay r iEnnev iron4m ent
3.2A nO vervoifFe uwn ctGiroonua8pl8s
3.3I ntermoFloercc9ue2ls a r
3.4P hysPircoaple 9r6t ies
1 StrucatnuBdro en di8n g
3.5A pplicVaittiaom1ni0:n2 s
1.1T hPee riToadbil8ce
3.6A ppliocfaS toilounbS iolaip1t0 4y:
1.2B onding 11
3.7A pplicTahCteei Mloelnm :b rane 105
1.3L ewSitsr uct1u3r es
3,8F unctGiroonuaapnlsRd e act1i0v8ity
1.4I some1r8s 3.9B iomole1c1u0les
1.5E xcepttoti hoOenc stR eutl 1e8
KeCyo nce1p1t1s
1.6R esona1n9c e
Probl1e1m3s
1.7D etermMionliencSguh laap2re4
1.8D rawOirngga Sntircu ct2u9r es
1.9H ybridi3z4a tion 4 Alkan1e2s0
1.1E0t haEnteh,y alneAdnc ee,t yl38ene 4.1A lkaneIsn-tArno du12c1tion
1. 11 BonLde ngatnBhdo nSdt ren4g3t h
4.2C ycloal1k25anes
1.1E2l ectronaenBgdoa ntPdio vliat4ry5i ty 4.3A nI ntrodtuoc tion
1.1P3o laorfMi otlye cu4l7e s Nomencl1a2t5u re
1.1L4- DopRae-pAr eseOnrtgaaMtnoiilvcee c 4u8l4e. 4N aming A1l2k6 anes
KeyC once4p9t s 4.5N amiCnygc loal1k3a2n es
Probl5e1m s 4.6C ommoNna me1s3 4
4.7F osFsuiell1 3s5
4.8P hysPircoapleo rfAt likeasn1 e36s
2 AciadnsBd a se5s8
4.9C onformoafAt ciyocAnllsik ca nes-1E3t7h ane
2.1B r0nsteAdc-iLadonswd r y 4.1C0o nformoafBt uitoan1ns4e 1
Base5s9
4.1A1n I ntrodtuoCc yctliooanl k1a4n4e s
2.2R eactoifBo rn0sn sted-Lowry
4.1C2yc lohex14a5ne
AciadnsBd a se6s0
4.1S3u bstCiytcultoehde 1x4a8nes
2.3A ciSdt reanngpdtK h6 2
a 4.1O4x idaotfAi lokna n1e5s4
2.4P reditchOteui tncgo omfAe c id-Base
4.1L5i pids1- 1P5a6rt
React6i5ons
Key Con1c5e8p ts
2.5F actTohartDs e terAmciiSndte r en6g6t h
Probl1e6m0s
2.6C ommoAnc iadnsBd a se7s6
V
vi Contents
7.5 The Polar Carbon-Halogen Bond 244
5 Stereochemistry 166 7.6 General Features of Nucleophilic
Substitution 245
5.1 Starch and Cellulose 167
7.7 The Leaving Group 246
5.2 The Two Major Classes of
7.8 The Nucleophile 248
Isomers 169
7.9 Possible Mechanisms for Nucleophilic
5.3 Looking Glass Chemistry-Chiral
Substitution 252
and Achiral Molecules 170
7.10 Two Mechanisms for Nucleophilic
5.4 Stereogenic Centers 173
Substitution 253
5.5 Stereogenic Centers in Cyclic Compounds 176
7.11 The SN2 Mechanism 254
5.6 Labeling Stereogenic Centers with R or 5 178
7.12 Application: Useful SN2 Reactions 260
5.7 Diastereomers 183
7.13 The SN 1 Mechanism 262
5.8 Meso Compounds 185
7.14 Carbocation Stability 266
5.9 Rand 5 Assignments in Compounds with Two or
7.15 The Hammond Postulate 268
More Stereogenic Centers 187
7.16 Application: SN 1 Reactions, Nitrosamines, and
5.10 Disubstituted Cycloalkanes 187
Cancer 271
5.11 Isomers-A Summary 189
7.17 When Is the Mechanism SN 1 or SN2? 272
5.12 Physical Properties of Stereoisomers 190
7.18 Vinyl Halides and Ary! Halides 277
5.13 Chemical Properties of Enantiomers 195
7.19 Organic Synthesis 278
KeyConcepts 197
Key Concepts 280
Problems 198
Problems 281
,.
6 Understanding Organic
8 Alkyl Halides ~
Reactions 205
and Elimination t!1I E •.._: ...~ ___ .,. /. 1 :• .;• .,:•; -.
6.1 Writing Equations for Organic
Reactions 288 ,}_.,>~ : -\
Reactions 206 ," . -=·-~. ..' \
6.2 Kinds of Organic Reactions 207 8.1 General Features of .,_' _.,. . ..
Elimination 289
6.3 Bond Breaking and Bond Making 209
8.2 Alkenes-The Products of Elimination
6.4 Bond Dissociation Energy 212
Reactions 291
6.5 Thermodynamics 216
8.3 The Mechanisms of Elimination 294
6.6 Enthalpy and Entropy 218
8.4 The E2 Mechanism 295
6.7 Energy Diagrams 220
8.5 The Zaitsev Rule 299
6.8 Energy Diagram for a Two-Step Reaction
8.6 The El Mechanism 301
Mechanism 222
8.7 SN1 and El Reactions 304
6.9 Kinetics 225
8.8 Stereochemistry of the E2 Reaction 305
6.10 Catalysts 228
8.9 When Is the Mechanism El or E2? 309
6.11 Enzymes 229
8.10 E2 Reactions and Alkyne Synthesis 310
Key Concepts 230
8.11 When Is the Reaction SN 1, SN2, El, or E2? 311
Problems 232
Key Concepts 315
Problems 317
7 Alkyl Halides
and Nucleophilic
Substitution 238 9 Alcohols, Ethers, and
Epoxides 324
7.1 Introduction to Alkyl
Halides 239 9.1 Introduction 325
7.2 Nomenclature 240 9.2 Structure and Bonding 326
7.3 Physical Properties 241 9.3 Nomenclature 327
7.4 Interesting Alkyl Halides 242