smi75625_endppFRONT.indd 2
Periodic Table of the Elements
Group number 1A 8A
1 Key
Period 2
number 1 H 67 He 1
Hydrogen
Atomic number Symbol
Ho
1.0079 Helium
2A 3A 4A 5A 6A 7A 4.0026
3 4 Holmium 5 6 7 8 9 10
Name Atomic weight
Li Be B C N O F Ne
164.9303
2 2
An element
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
6.941 9.0122 10.811 12.011 14.0067 15.9994 18.9984 20.1797
11 12 13 14 15 16 17 18
3 Na Mg Al Si P S Cl Ar 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
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr 4
Potassium Calcium Scandium 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
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe 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
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
6 Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn 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)
87 88 89 104 105 106 107 108 109 110 111 112 113 114 115 116
7 Fr Ra Ac Rf Db Sg Bh Hs Mt Ds Rg – – – – – 7
Francium Radium Actinium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium — — — — —
(223) (226) (227) (267) (268) (271) (272) (270) (276) (281) (280) (285) (284) (289) (288) (293)
58 59 60 61 62 63 64 65 66 67 68 69 70 71
Lanthanides 6 Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu 6
Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium 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
90 91 92 93 94 95 96 97 98 99 100 101 102 103
Actinides 7 Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr 7
Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium
232.0381 231.0359 238.0289 (237) (244) (243) (247) (247) (251) (252) (257) (258) (259) (260)
12/2/09 10:14:16 AM
, COMMON FUNCTIONAL GROUPS
Type of Compound
Acid
General Structure
O
Example
O
Functional Group Type of Compound General Structure Example Functional Group
Organic Chemistry
C C –COCl Aromatic compound phenyl group
chloride R Cl CH3 Cl
Third Edition
–OH O O
Alcohol R OH CH3 OH Carboxylic –COOH
hydroxy group acid C C carboxy group
R OH CH3 OH
O O O O
Aldehyde C C C O Ester C C –COOR
R H CH3 H carbonyl group R OR CH3 OCH3
–OR
Alkane R H CH3CH3 –– Ether R O R CH3 O CH3 alkoxy group
H H O O
C O
Alkene C C C C double bond Ketone C C carbonyl group
R R CH3 CH3
H H
Alkyl halide
R X
(X = F, Cl, Br, I)
CH3 Br –X
halo group
Nitrile R C N CH3 C N –C N
cyano group
Janice Gorzynski Smith
University of Hawai’i at Ma-noa
Alkyne C C H C C H triple bond Sulfide R S R CH3 S CH3 –SR
alkylthio group
O
O –CONH2,
Amide C H (or R) –CONHR, Thiol R SH CH3 SH –SH
R N C
CH3 NH2 –CONR2 mercapto group
H (or R)
O O
Amine R NH2 or CH3 NH2 –NH2 Thioester C C –COSR
R2NH or R3N amino group R SR CH3 SCH3
O O O O O O
Anhydride C C C C C C
R O R CH3 O CH3 O
TM
smi75625_fm_00i-xxxiv.indd i 11/17/09 11:21:07 AM
, About the Author
Janice Gorzynski Smith was born in Schenectady, New York, and grew up following
the Yankees, listening to the Beatles, and water skiing on Sacandaga Reservoir. 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
For Megan Sarah gibberellic acid.
Following her postdoctoral work, Jan joined 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 Ma- noa, 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: Matthew and Zachary, age 14 (margin photo on page 163); Jenna, a student at
Temple University’s Beasley School of Law; and Erin, an emergency medicine physician and
co-author of the Student Study Guide/Solutions Manual for this text. 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 Hawaiian quilting.
The author (far right) and her family from the left: husband Dan,
and children Zach, Erin, Jenna, and Matt.
iv
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, Contents in Brief Contents
Prologue 1 Preface xviii
1 Structure and Bonding 6 Acknowledgments xxiii
2 Acids and Bases 54 List of How To’s xxv
List of Mechanisms xxvii
3 Introduction to Organic Molecules and Functional Groups 81
List of Selected Applications xxx
4 Alkanes 113
5 Stereochemistry 159
6 Understanding Organic Reactions 196 Prologue 1
7 Alkyl Halides and Nucleophilic Substitution 228 What Is Organic Chemistry? 1
8 Alkyl Halides and Elimination Reactions 278 Some Representative Organic Molecules 2
9 Alcohols, Ethers, and Epoxides 312 Ginkgolide B—A Complex Organic Compound from the Ginkgo Tree 4
10 Alkenes 358
11 Alkynes 399
12 Oxidation and Reduction 426 1 Structure and Bonding 6
13 Mass Spectrometry and Infrared Spectroscopy 463 1.1 The Periodic Table 7
14 Nuclear Magnetic Resonance Spectroscopy 494 1.2 Bonding 10
15 Radical Reactions 538 1.3 Lewis Structures 12
16 Conjugation, Resonance, and Dienes 571 1.4 Lewis Structures Continued 17
1.5 Resonance 18
17 Benzene and Aromatic Compounds 607
1.6 Determining Molecular Shape 23
18 Electrophilic Aromatic Substitution 641
1.7 Drawing Organic Structures 27
19 Carboxylic Acids and the Acidity of the O – H Bond 688
1.8 Hybridization 32
20 Introduction to Carbonyl Chemistry; Organometallic Reagents;
1.9 Ethane, Ethylene, and Acetylene 36
Oxidation and Reduction 721
1.10 Bond Length and Bond Strength 40
21 Aldehydes and Ketones—Nucleophilic Addition 774
1.11 Electronegativity and Bond Polarity 42
22 Carboxylic Acids and Their Derivatives—Nucleophilic Acyl Substitution 825
1.12 Polarity of Molecules 44
23 Substitution Reactions of Carbonyl Compounds at the α Carbon 880 1.13 L-Dopa—A Representative Organic Molecule 45
24 Carbonyl Condensation Reactions 916 Key Concepts 46
25 Amines 949 Problems 47
26 Carbon–Carbon Bond-Forming Reactions in Organic Synthesis 1002
27 Carbohydrates 1027
28 Amino Acids and Proteins 1074 2 Acids and Bases 54
29 Lipids 1119 2.1 Brønsted–Lowry Acids and Bases 55
30 Synthetic Polymers 1148 2.2 Reactions of Brønsted–Lowry Acids and Bases 56
Appendices A-1 2.3 Acid Strength and pKa 58
Glossary G-1 2.4 Predicting the Outcome of Acid–Base Reactions 61
2.5 Factors That Determine Acid Strength 62
Credits C-1
2.6 Common Acids and Bases 70
Index I-1
2.7 Aspirin 71
2.8 Lewis Acids and Bases 72
Key Concepts 74
Problems 75
v vi
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Periodic Table of the Elements
Group number 1A 8A
1 Key
Period 2
number 1 H 67 He 1
Hydrogen
Atomic number Symbol
Ho
1.0079 Helium
2A 3A 4A 5A 6A 7A 4.0026
3 4 Holmium 5 6 7 8 9 10
Name Atomic weight
Li Be B C N O F Ne
164.9303
2 2
An element
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
6.941 9.0122 10.811 12.011 14.0067 15.9994 18.9984 20.1797
11 12 13 14 15 16 17 18
3 Na Mg Al Si P S Cl Ar 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
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr 4
Potassium Calcium Scandium 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
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe 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
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
6 Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn 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)
87 88 89 104 105 106 107 108 109 110 111 112 113 114 115 116
7 Fr Ra Ac Rf Db Sg Bh Hs Mt Ds Rg – – – – – 7
Francium Radium Actinium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium — — — — —
(223) (226) (227) (267) (268) (271) (272) (270) (276) (281) (280) (285) (284) (289) (288) (293)
58 59 60 61 62 63 64 65 66 67 68 69 70 71
Lanthanides 6 Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu 6
Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium 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
90 91 92 93 94 95 96 97 98 99 100 101 102 103
Actinides 7 Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr 7
Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium
232.0381 231.0359 238.0289 (237) (244) (243) (247) (247) (251) (252) (257) (258) (259) (260)
12/2/09 10:14:16 AM
, COMMON FUNCTIONAL GROUPS
Type of Compound
Acid
General Structure
O
Example
O
Functional Group Type of Compound General Structure Example Functional Group
Organic Chemistry
C C –COCl Aromatic compound phenyl group
chloride R Cl CH3 Cl
Third Edition
–OH O O
Alcohol R OH CH3 OH Carboxylic –COOH
hydroxy group acid C C carboxy group
R OH CH3 OH
O O O O
Aldehyde C C C O Ester C C –COOR
R H CH3 H carbonyl group R OR CH3 OCH3
–OR
Alkane R H CH3CH3 –– Ether R O R CH3 O CH3 alkoxy group
H H O O
C O
Alkene C C C C double bond Ketone C C carbonyl group
R R CH3 CH3
H H
Alkyl halide
R X
(X = F, Cl, Br, I)
CH3 Br –X
halo group
Nitrile R C N CH3 C N –C N
cyano group
Janice Gorzynski Smith
University of Hawai’i at Ma-noa
Alkyne C C H C C H triple bond Sulfide R S R CH3 S CH3 –SR
alkylthio group
O
O –CONH2,
Amide C H (or R) –CONHR, Thiol R SH CH3 SH –SH
R N C
CH3 NH2 –CONR2 mercapto group
H (or R)
O O
Amine R NH2 or CH3 NH2 –NH2 Thioester C C –COSR
R2NH or R3N amino group R SR CH3 SCH3
O O O O O O
Anhydride C C C C C C
R O R CH3 O CH3 O
TM
smi75625_fm_00i-xxxiv.indd i 11/17/09 11:21:07 AM
, About the Author
Janice Gorzynski Smith was born in Schenectady, New York, and grew up following
the Yankees, listening to the Beatles, and water skiing on Sacandaga Reservoir. 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
For Megan Sarah gibberellic acid.
Following her postdoctoral work, Jan joined 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 Ma- noa, 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: Matthew and Zachary, age 14 (margin photo on page 163); Jenna, a student at
Temple University’s Beasley School of Law; and Erin, an emergency medicine physician and
co-author of the Student Study Guide/Solutions Manual for this text. 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 Hawaiian quilting.
The author (far right) and her family from the left: husband Dan,
and children Zach, Erin, Jenna, and Matt.
iv
mi75625_fm_00i-xxxiv.indd iii 11/17/09 11:21:08
smi75625_fm_00i-xxxiv.indd
AM iv 11/17/09 11:21:09 AM
, Contents in Brief Contents
Prologue 1 Preface xviii
1 Structure and Bonding 6 Acknowledgments xxiii
2 Acids and Bases 54 List of How To’s xxv
List of Mechanisms xxvii
3 Introduction to Organic Molecules and Functional Groups 81
List of Selected Applications xxx
4 Alkanes 113
5 Stereochemistry 159
6 Understanding Organic Reactions 196 Prologue 1
7 Alkyl Halides and Nucleophilic Substitution 228 What Is Organic Chemistry? 1
8 Alkyl Halides and Elimination Reactions 278 Some Representative Organic Molecules 2
9 Alcohols, Ethers, and Epoxides 312 Ginkgolide B—A Complex Organic Compound from the Ginkgo Tree 4
10 Alkenes 358
11 Alkynes 399
12 Oxidation and Reduction 426 1 Structure and Bonding 6
13 Mass Spectrometry and Infrared Spectroscopy 463 1.1 The Periodic Table 7
14 Nuclear Magnetic Resonance Spectroscopy 494 1.2 Bonding 10
15 Radical Reactions 538 1.3 Lewis Structures 12
16 Conjugation, Resonance, and Dienes 571 1.4 Lewis Structures Continued 17
1.5 Resonance 18
17 Benzene and Aromatic Compounds 607
1.6 Determining Molecular Shape 23
18 Electrophilic Aromatic Substitution 641
1.7 Drawing Organic Structures 27
19 Carboxylic Acids and the Acidity of the O – H Bond 688
1.8 Hybridization 32
20 Introduction to Carbonyl Chemistry; Organometallic Reagents;
1.9 Ethane, Ethylene, and Acetylene 36
Oxidation and Reduction 721
1.10 Bond Length and Bond Strength 40
21 Aldehydes and Ketones—Nucleophilic Addition 774
1.11 Electronegativity and Bond Polarity 42
22 Carboxylic Acids and Their Derivatives—Nucleophilic Acyl Substitution 825
1.12 Polarity of Molecules 44
23 Substitution Reactions of Carbonyl Compounds at the α Carbon 880 1.13 L-Dopa—A Representative Organic Molecule 45
24 Carbonyl Condensation Reactions 916 Key Concepts 46
25 Amines 949 Problems 47
26 Carbon–Carbon Bond-Forming Reactions in Organic Synthesis 1002
27 Carbohydrates 1027
28 Amino Acids and Proteins 1074 2 Acids and Bases 54
29 Lipids 1119 2.1 Brønsted–Lowry Acids and Bases 55
30 Synthetic Polymers 1148 2.2 Reactions of Brønsted–Lowry Acids and Bases 56
Appendices A-1 2.3 Acid Strength and pKa 58
Glossary G-1 2.4 Predicting the Outcome of Acid–Base Reactions 61
2.5 Factors That Determine Acid Strength 62
Credits C-1
2.6 Common Acids and Bases 70
Index I-1
2.7 Aspirin 71
2.8 Lewis Acids and Bases 72
Key Concepts 74
Problems 75
v vi
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