http://create.mcgraw-hill.com Copyright by The McGraw-Hill Companies, Inc. All rights reserved. Printed in the United States of America. Except as permitted under the United States Copyright Act of 1976, no part of this publication may be reproduced or distributed in any form or by any means, or stored in a database or retrieval system, without prior written permission of the publisher. This McGraw-Hill Create text may include materials submitted to McGraw-Hill for publication by the instructor of this course. The instructor is solely responsible for the editorial content of such materials. Instructors retain copyright of these additional materials. ISBN-10: ISBN-13: 192071128118201161802611 Contents 1. Structure and Bonding 1 2. Acids and Bases 33 3. Introduction to Organic Molecules and Functional Groups 57 4. Alkanes 75 5. Stereochemistry 111 6. Understanding Organic Reactions 139 7. Alkyl Halides and Nucleophilic Substitution 159 8. Alkyl Halides and Elimination Reactions 193 9. Alcohols, Ethers, and Epoxides 223 10. Alkenes 257 11. Alkynes 287 12. Oxidation and Reduction 309 13. Mass Spectrometry and Infrared Spectroscopy 337 14. Nuclear Magnetic Resonance Spectroscopy 351 15. Radical Reactions 373 16. Conjugation, Resonance, and Dienes 397 17. Benzene and Aromatic Compounds 421 18. Electrophilic and Aromatic Substitution 443 19. Carboxylic Acids and the Acidity of the O-H Bond 479 20. Introduction to Carbonyl Chemistry 501 21. Aldehydes and Ketones — Nucleophilic Addition 535 22. Carboxylic Acids and Their Derivatives — Nucleophilic Acyl Substitution 567 23. Substitution Reactions of Carbonyl Compounds at the a Carbon 603 24. Carbonyl Condensation Reactions 631 25. Amines 659 26. Carbon-Carbon Bonding-Forming Reactions in Organic Synthesis 693 27. Carbohydrates 715 28. Amino Acids and Proteins 751 29. Lipids 785 30. Synthetic Polymers 801 Credits S .1 tructure and Bonding: Chapter 1 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 1 A .2 cids and Bases: Chapter 2 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 3 I .3 ntroduction to Organic Molecules and Functional Groups: Chapter 3 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 75 A .4 lkanes: Chapter 4 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 57 S .5 tereochemistry: Chapter 5 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 1 U .6 nderstanding Organic Reactions: Chapter 6 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 931 A .7 lkyl Halides and Nucleophilic Substitution: Chapter 7 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 951 A .8 lkyl Halides and Elimination Reactions: Chapter 8 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 391 A .9 lcohols, Ethers, and Epoxides: Chapter 9 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 32 A .01 lkenes: Chapter 10 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 752 A .1 lkynes: Chapter 11 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 782 O .21 xidation and Reduction: Chapter 12 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 903 M .31 ass Spectrometry and Infrared Spectroscopy: Chapter 13 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 73 N .41 uclear Magnetic Resonance Spectroscopy: Chapter 14 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 153 R .51 adical Reactions: Chapter 15 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 373 C .61 onjugation, Resonance, and Dienes: Chapter 16 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 793 B .71 enzene and Aromatic Compounds: Chapter 17 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 124 E .81 lectrophilic and Aromatic Substitution: Chapter 18 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 34 C .91 arboxylic Acids and the Acidity of the O-H Bond: Chapter 19 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 974 20. Introduction to Carbonyl Chemistry: Chapter 20 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 501 21. Aldehydes and Ketones — Nucleophilic Addition: Chapter 21 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 535 22. Carboxylic Acids and Their Derivatives — Nucleophilic Acyl Substitution: Chapter 22 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 567 23. Substitution Reactions of Carbonyl Compounds at the a Carbon: Chapter 23 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 603 24. Carbonyl Condensation Reactions: Chapter 24 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 631 25. Amines: Chapter 25 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 659 26. Carbon-Carbon Bonding-Forming Reactions in Organic Synthesis: Chapter 26 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 693 27. Carbohydrates: Chapter 27 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 715 28. Amino Acids and Proteins: Chapter 28 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 751 29. Lipids: Chapter 29 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 785 30. Synthetic Polymers: Chapter 30 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 801 Smith: Study Guide/ 1. Structure and Bonding Text © The McGraw−Hill Solutions Manual to Companies, 2011 accompany Organic Chemistry, Third Edition Structure and Bonding 1–1 CCChhhaaapppttteeerrr 111::: SSStttrrruuuccctttuuurrreee aaannnddd BBBooonnndddiiinnnggg Important facts • The general rule of bonding: Atoms strive to attain a complete outer shell of valence electrons (Section 1.2). H “wants” 2 electrons. Second-row elements “want” 8 electrons. nonbonded electron pair H C N O X X = F, Cl, Br, I Usual number of bonds 1 4 3 2 1 in neutral atoms Number of nonbonded 0 0 1 2 3 electron pairs The sum (# of bonds + # of lone pairs) = 4 for all elements except H. • Formal charge (FC) is the difference between the number of valence electrons of an atom and the number of electrons it “owns” (Section 1.3C). See Sample Problem 1.4 for a stepwise example. number of number of electrons formal charge = – Definition: valence electrons an atom "owns" Examples: C C C • C shares 8 electrons. • Each C shares 6 electrons. • C shares 6 electrons. • C "owns" 4 electrons. • Each C "owns" 3 electrons. • C has 2 unshared electrons. • FC = 0 • FC = +1 • C "owns" 5 electrons. • FC = 1 • Curved arrow notation shows the movement of an electron pair. The tail of the arrow always begins at an electron pair, either in a bond or a lone pair. The head points to where the electron pair “moves” (Section 1.5). O O Move an electron pair to O. H C N H H C N H A B Use this electron pair to form a double bond. • Electrostatic potential plots are color-coded maps of electron density, indicating electron rich and electron deficient regions (Section 1.11). Smith: Study Guide/ 1. Structure and Bonding Text © The McGraw−Hill Solutions Manual to Companies, 2011 accompany Organic Chemistry, Third Edition Chapter 1–2 The importance of Lewis structures (Sections 1.3, 1.4) A properly drawn Lewis structure shows the number of bonds and lone pairs present around each atom in a molecule. In a valid Lewis structure, each H has two electrons, and each second-row element has no more than eight. This is the first step needed to determine many properties of a molecule. Geometry [linear, trigonal planar, or tetrahedral] (Section 1.6) 2 3 Lewis structure Hybridization [sp, sp , or sp ] (Section 1.8) Types of bonds [single, double, or triple] (Sections 1.3, 1.9) Resonance (Section 1.5) The basic principles: • Resonance occurs when a compound cannot be represented by a single Lewis structure. • Two resonance structures differ only in the position of nonbonded electrons and bonds. • The resonance hybrid is the only accurate representation for a resonance-stabilized compound. A hybrid is more stable than any single resonance structure because electron density is delocalized. O O O CH3CH2 C CH3CH2 C CH3CH2 C delocalized charges O O O delocalized bonds resonance structures hybrid The difference between resonance structures and isomers: • Two isomers differ in the arrangement of both atoms and electrons. • Resonance structures differ only in the arrangement of electrons. O O O CH3 C CH3CH2 C CH3CH2 C O CH3 O H O H isomers resonance structures Geometry and hybridization The number of groups around an atom determines both its geometry (Section 1.6) and hybridization (Section 1.8). o Number of Geometry Bond angle ( ) Hybridization Examples groups 2 linear 180 sp BeH2, HCCH 2 3 trigonal planar 120 sp BF3, CH2=CH2 3 4 tetrahedral 109.5 sp CH4, NH3, H2O Study Guide/Solutions Manual to accompany: Organic Chemistry, 3rd Edition Smith: Study Guide/ 1. Structure and Bonding Text © The McGraw−Hill Solutions Manual to Companies, 2011 accompany Organic Chemistry, Third Edition Structure and Bonding 1–3 Drawing organic molecules (Section 1.7) • Shorthand methods are used to abbreviate the structure of organic molecules. CH3 H CH3 = CH3 C C C CH3 = (CH3)2CHCH2C(CH3)3 H H CH3 skeletal structure isooctane condensed structure • A carbon bonded to four atoms is tetrahedral in shape. The best way to represent a tetrahedron is to draw two bonds in the plane, one in front, and one behind. Four equivalent drawings for CH4 H H H H H H C C C C H H H H H H H H H H Each drawing has two solid lines, one wedge, and one dashed line. BBBooonnnddd llleeennngggttthhh • Bond length decreases across a row and increases down a column of the periodic table (Section 1.6A). C H > N H > O H H F < H Cl < H Br Increasing bond length Increasing bond length • Bond length decreases as the number of electrons between two nuclei increases (Section 1.10A). CH3 CH3 < CH2 CH2 < H C C H Increasing bond length • Bond length increases as the percent s-character decreases (Section 1.10B). Csp H Csp2 H Csp3 H Increasing bond length • Bond length and bond strength are inversely related. Shorter bonds are stronger bonds (Section 1.10). longest C–C bond shortest C–C bond weakest bond C C C C C C strongest bond Increasing bond strength Smith: Study Guide/ 1. Structure and Bonding Text © The McGraw−Hill Solutions Manual to Companies, 2011 accompany Organic Chemistry, Third Edition Chapter 1–4 • Sigma () bonds are generally stronger than bonds (Section 1.9). C C C C C C 1 strong m bond 1 stronger m bond 1 stronger m bond 1 weaker / bond 2 weaker / bonds Electronegativity and polarity (Sections 1.11, 1.12) • Electronegativity increases across a row and decreases down a column of the periodic table. • A polar bond results when two atoms of different electronegativity are bonded together. Whenever C or H is bonded to N, O, or any halogen, the bond is polar. • A polar molecule has either one polar bond, or two or more bond dipoles that reinforce. DDDrrraaawwwiiinnnggg LLLeeewwwiiisss ssstttrrruuuccctttuuurrreeesss::: AAA ssshhhooorrrtttcccuuuttt Chapter 1 devotes a great deal of time to drawing valid Lewis structures. For molecules with many bonds, it may take quite awhile to find acceptable Lewis structures by using trial-and-error to place electrons. Fortunately, a shortcut can be used to figure out how many bonds are present in a molecule. Shortcut on drawing Lewis structures—Determining the number of bonds: [1] Count up the number of valence electrons. [2] Calculate how many electrons are needed if there were no bonds between atoms and every atom has a filled shell of valence electrons; i.e., hydrogen gets two electrons, and second-row elements get eight. [3] Subtract the number obtained in Step [2] from the sum obtained in Step [1]. This difference tells how many electrons must be shared to give every H two electrons and every second-row element eight. Since there are two electrons per bond, dividing this difference by two tells how many bonds are needed. To draw the Lewis structure: [1] Arrange the atoms as usual. [2] Count up the number of valence electrons. [3] Use the shortcut to determine how many bonds are present. [4] Draw in the two-electron bonds to all the H’s first. Then, draw the remaining bonds between other atoms making sure that no second-row element gets more than eight electrons and that you use the total number of bonds determined previously. [5] Finally, place unshared electron pairs on all atoms that do not have an octet of electrons, and calculate formal charge. You should have now used all the valence electrons determined in the first step. Example: Draw all valid Lewis structures for CH3NCO using the shortcut procedure. [1] Arrange the atoms. H • In this case the arrangement of atoms is implied by the way the structure is H C N C O drawn. H Study Guide/Solutions Manual to accompany: Organic Chemistry, 3rd Edition