Third Edition Organic Chemistry Janice Gorzynski Smith
Periodic Table of the Elements Group number→1A 8 Key H 67 1.0079 He 2 Atomic numbe Ho Symbol 3A 4A 7A 164.92 Atomic weight An element B c 型 ● 三 N 3B 48 5B 6B 7B 8B 8B 8B 1B 29 T Y Co N 兰 7 S 三 型 Rh Ca 2 n·T 5日 7 2 2 27 28 2B4 Lanthanides 6 Ce Nd Pm Sm Gd Tb Ho Er Tm b Lu 器 50 97 94 95 97 8 00 101 102 Actinide Th Pa Am Bk Es Fm Md 310359 24 25j
Period number Group number Lanthanides Actinides Key 1 1 1 H Hydrogen 1.0079 67 Ho Holmium 164.9303 86 Rn Radon (222) 54 Xe Xenon 131.29 36 Kr Krypton 83.80 18 Ar Argon 39.948 10 Ne Neon 20.1797 53 I Iodine 126.9045 35 Br Bromine 79.904 17 Cl Chlorine 35.4527 9 F Fluorine 18.9984 34 Se Selenium 78.96 16 S Sulfur 32.066 8 O Oxygen 15.9994 15 P Phosphorus 30.9738 7 N Nitrogen 14.0067 6 C Carbon 12.011 2 He Helium 4.0026 2 3 Li Lithium 6.941 3 11 Na Sodium 22.9898 4 19 K Potassium 39.0983 5 2 3 4 5 37 Rb Rubidium 85.4678 6 55 Cs Cesium 132.9054 7 87 Fr Francium (223) 4 Be Beryllium 9.0122 12 Mg Magnesium 24.3050 20 Ca Calcium 40.078 38 Sr Strontium 87.62 56 Ba Barium 137.327 88 Ra Radium (226) 21 Sc Scandium 44.9559 3B 4B 5B 6B 7B 8B 8B 8B 1B 2B 39 Y Yttrium 88.9059 22 Ti Titanium 47.88 40 Zr Zirconium 91.224 72 Hf Hafnium 178.49 104 Rf Rutherfordium (267) 23 V Vanadium 50.9415 41 Nb Niobium 92.9064 73 Ta Tantalum 180.9479 105 Db Dubnium (268) 24 Cr Chromium 51.9961 42 Mo Molybdenum 95.94 74 W Tungsten 183.84 106 Sg Seaborgium (271) 25 Mn Manganese 54.9380 43 Tc Technetium (98) 76 Os Osmium 190.2 107 Bh Bohrium (272) 26 Fe Iron 55.845 44 Ru Ruthenium 101.07 77 Ir Iridium 192.22 108 Hs Hassium (270) 27 Co Cobalt 58.9332 45 Rh Rhodium 102.9055 78 Pt Platinum 195.08 109 Mt Meitnerium (276) 28 Ni Nickel 58.693 46 Pd Palladium 106.42 79 Au Gold 196.9665 110 Ds Darmstadtium (281) 29 Cu Copper 63.546 47 Ag Silver 107.8682 80 Hg Mercury 200.59 111 Rg Roentgenium (280) 3A 4A 5A 6A 7A 8A 30 Zn Zinc 65.41 48 Cd Cadmium 112.411 81 Tl Thallium 204.3833 112 – — (285) 31 Ga Gallium 69.723 13 Al Aluminum 26.9815 49 In Indium 114.82 50 Sn Tin 118.710 82 Pb Lead 207.2 83 Bi Bismuth 208.9804 114 – — (289) 84 Po Polonium (209) 6 58 Ce Cerium 140.115 7 6 7 6 7 90 Th Thorium 232.0381 59 Pr Praseodymium 140.9076 91 Pa Protactinium 231.0359 60 Nd Neodymium 144.24 92 U Uranium 238.0289 61 Pm Promethium (145) 93 Np Neptunium (237) 62 Sm Samarium 150.36 94 Pu Plutonium (244) 63 Eu Europium 151.964 95 Am Americium (243) 64 Gd Gadolinium 157.25 96 Cm Curium (247) 65 Tb Terbium 158.9253 97 Bk Berkelium (247) 66 Dy Dysprosium 162.50 98 Cf Californium (251) 67 Ho Holmium 164.9303 99 Es Einsteinium (252) 68 Er Erbium 167.26 100 Fm Fermium (257) 69 Tm Thulium 168.9342 101 Md Mendelevium (258) 70 Yb Ytterbium 173.04 102 No Nobelium (259) 71 Lu Lutetium 174.967 103 Lr Lawrencium (260) 75 Re Rhenium 186.207 116 – — (293) 5 B Boron 10.811 14 Si Silicon 28.0855 32 Ge Germanium 72.64 33 As Arsenic 74.9216 51 Sb Antimony 121.760 52 Te Tellurium 127.60 85 At Astatine (210) 57 La Lanthanum 138.9055 89 Ac Actinium (227) 1A 2A Atomic number Name An element Symbol Atomic weight Periodic Table of the Elements 113 – — (284) 115 – — (288) smi75625_endppFRONT.indd 2 12/2/09 10:14:16 AM
COMMON FUNCTIONAL GROUPS ype of Compound General Structure Example Functional Group Type of Compound General Structure Example Functional Grour chiode Aromatic compound phenyl group R-OH nadoggoep cate eabS9op CH°ScH -COOR R-H CHaCHa R--R CHa-Q-CHa ao X Keton eat9rog .:D halo oup tril R-CaN CHa-CxN: gnSvop -CC- H-C=C-H R--R CHa--CH 8 R-别 Amine 品 am -COSR Anhydride ga具具
Acid chloride Alcohol R Cl O C CH3 NH2 O R N C H (or R) O C H (or R) HR O C 3 HCH O C –COCl Amide Anhydride –CONH2, –CONHR, –CONR2 –OH hydroxy group Carboxylic acid –COOH carboxy group –OR alkoxy group 3 ClCH O C Type of Compound General Structure Example Functional Group Type of Compound General Structure Example Functional Group R OH CH3 OH Alkane R H CH – – 3CH3 Ether Alkyl halide Alkene double bond Aromatic compound phenyl group Aldehyde carbonyl group C O carbonyl group C O cyano group –C N C C H H H H C C Alkyne C C CH C H triple bond Nitrile Amine –NH2 amino group (X = F, Cl, Br, I) R X –X halo group CH3 Br NH2 R or R2NH or R3N CH3 NH2 R R O C O C O O C O C CH3 CH3 O O C O C O OHR O C R R O CH3 O CH3 –SR alkylthio group Sulfide R R S CH3 O C OH Ester –COSR –COOR ORR O C CH3 O C OCH3 RR O Ketone C CH3 O C CH3 Thioester CR N CH3 S CH3 –SH mercapto group Thiol R SH R O C SR CH3 O C SCH3 CH3 SH 3 CCH N COMMON FUNCTIONAL GROUPS smi75625_endppFRONT.indd 3 12/2/09 10:14:16 AM
About the Author Janice Gorzynski Smith was bom in Schene sted in che ell Unive from Harvard Unive sity under the din 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 Hawal I in the n and her family move there permanently ntly a faculty member at the Unr received the Char r chemistry lecture and lab courses.In 2003 sides in Hawaii with her husband Dar four children:Matthew and Zacha eI6P.She a a.a student at Temple University's Beasley School of Law:and cy medicine physician and co-author of the Smudent 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
iv 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 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 chemistry 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’tmiss courses” in a survey by Boston magazine. After spending two sabbaticals amidst the natural 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. smi75625_fm_00i-xxxiv.indd iv 11/17/09 11:21:09 AM
Contents in Brief Prologue 1 1 Structure and Bonding 6 2 Acids and Bases 54 Introduction to Organic Molecules and Functional Groups 81 Alkanes 113 5 Stereochemistry 159 6 Understanding organic Reactions 196 1 Alkyl Halides and Nucleophilic Substitution 228 8 Alkyl Halides and Elimination Reactions 278 9 Alcohols,Ethers,and Epoxides 312 10 Alkenes 358 426 Mass Spectrometry and Infrared Spectroscopy 463 14 Nuclear Magnetic Resonance Spectroscopy 494 15 Radical Reactions 538 1617 Conjugation,Resonance,and Dienes 571 Benzene and Aromatic Compounds 607 18 Electrophilic Aromatic Substitution 641 19 Carboxylic Acids and the Acidity of the O-H Bond 688 20 batcenncateelc I Ch mistry;Organometallic Reagents Aldehydes and Keto -Nucleophilic Addition 774 22 Carboxylic Acids and Their Derivatives-Nucleophilic Acyl Substitution 82 2 Substitution Reactions of Carbonyl Compounds at the a Carbon 880 24 Carbonyl Condensation Reactions 916 Amines 949 Carbon-Carbon Bond-Forming Reactions in Organic Synthesis 1002 Carbohydrates 1027 28 Amino Acids and Proteins 1074 29 Lipids 1119 30 Synthetic Polymers 1148 Appendices A-1 Glossary G-1 Credits C-1 Index 1-1
v Contents in Brief Prologue 1 1 Structure and Bonding 6 2 Acids and Bases 54 3 Introduction to Organic Molecules and Functional Groups 81 4 Alkanes 113 5 Stereochemistry 159 6 Understanding Organic Reactions 196 7 Alkyl Halides and Nucleophilic Substitution 228 8 Alkyl Halides and Elimination Reactions 278 9 Alcohols, Ethers, and Epoxides 312 10 Alkenes 358 11 Alkynes 399 12 Oxidation and Reduction 426 13 Mass Spectrometry and Infrared Spectroscopy 463 14 Nuclear Magnetic Resonance Spectroscopy 494 15 Radical Reactions 538 16 Conjugation, Resonance, and Dienes 571 17 Benzene and Aromatic Compounds 607 18 Electrophilic Aromatic Substitution 641 19 Carboxylic Acids and the Acidity of the O–H Bond 688 20 Introduction to Carbonyl Chemistry; Organometallic Reagents; Oxidation and Reduction 721 21 Aldehydes and Ketones—Nucleophilic Addition 774 22 Carboxylic Acids and Their Derivatives—Nucleophilic Acyl Substitution 825 23 Substitution Reactions of Carbonyl Compounds at the α Carbon 880 24 Carbonyl Condensation Reactions 916 25 Amines 949 26 Carbon–Carbon Bond-Forming Reactions in Organic Synthesis 1002 27 Carbohydrates 1027 28 Amino Acids and Proteins 1074 29 Lipids 1119 30 Synthetic Polymers 1148 Appendices A-1 Glossary G-1 Credits C-1 Index I-1 smi75625_fm_00i-xxxiv.indd v 11/17/09 11:21:09 AM