Study guide solutions manual to accompany organic chemistry (3e) janice gorzynski smith

Study guide solutions manual to accompany organic chemistry (3e) janice gorzynski smith Study guide solutions manual to accompany organic chemistry (3e) janice gorzynski smith Study guide solutions manual to accompany organic chemistry (3e) janice gorzynski smith Study guide solutions manual to accompany organic chemistry (3e) janice gorzynski smith Study guide solutions manual to accompany organic chemistry (3e) janice gorzynski smith Study guide solutions manual to accompany organic chemistry (3e) janice gorzynski smith

http://create.mcgraw-hill.com Copyright 2011 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: 1121180612 ISBN-13: 9781121180611 Contents Structure and Bonding Acids and Bases 33 Introduction to Organic Molecules and Functional Groups 57 Alkanes 75 Stereochemistry 111 Understanding Organic Reactions 139 Alkyl Halides and Nucleophilic Substitution 159 Alkyl Halides and Elimination Reactions 193 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 iii Credits Structure and Bonding: Chapter from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith Acids and Bases: Chapter from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 33 Introduction to Organic Molecules and Functional Groups: Chapter from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 57 Alkanes: Chapter from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 75 Stereochemistry: Chapter from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 111 Understanding Organic Reactions: Chapter from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 139 Alkyl Halides and Nucleophilic Substitution: Chapter from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 159 Alkyl Halides and Elimination Reactions: Chapter from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 193 Alcohols, Ethers, and Epoxides: Chapter from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 223 10 Alkenes: Chapter 10 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 257 11 Alkynes: Chapter 11 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 287 12 Oxidation and Reduction: Chapter 12 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 309 13 Mass Spectrometry and Infrared Spectroscopy: Chapter 13 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 337 14 Nuclear Magnetic Resonance Spectroscopy: Chapter 14 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 351 15 Radical Reactions: Chapter 15 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 373 16 Conjugation, Resonance, and Dienes: Chapter 16 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 397 17 Benzene and Aromatic Compounds: Chapter 17 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 421 18 Electrophilic and Aromatic Substitution: Chapter 18 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 443 19 Carboxylic Acids and the Acidity of the O-H Bond: Chapter 19 from Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 479 iv 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 v Smith: Study Guide/ Solutions Manual to accompany Organic Chemistry, Third Edition Structure and Bonding © The McGraw−Hill Companies, 2011 Text Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition Structure and Bonding 1–1 C Chhaapptteerr 11:: SSttrruuccttuurree aanndd B Boonnddiinngg

IIm mppoorrttaanntt ffaaccttss • The general rule of bonding: Atoms strive to attain a complete outer shell of valence electrons (Section 1.2) H “wants” electrons Second-row elements “want” electrons nonbonded electron pair H C N O X Usual number of bonds in neutral atoms Number of nonbonded electron pairs 0 X = F, Cl, Br, I The sum (# of bonds + # of lone pairs) = 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 Definition: Examples: formal charge number of valence electrons C C • C shares electrons • C "owns" electrons • FC = • = – number of electrons an atom "owns" C • Each C shares electrons • Each C "owns" electrons • FC = +1 • C shares electrons • C has unshared electrons • C "owns" 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) Move an electron pair to O O H C N H A O H C N H 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/ Structure and Bonding Text Study Guide/Solutions Manual to accompany: Organic Chemistry, 3rd Edition Solutions Manual to accompany Organic Chemistry, Third Edition © The McGraw−Hill Companies, 2011 Chapter 1–2   TThhee iim mppoorrttaannccee ooff LLeew wiiss ssttrruuccttuurreess ((SSeeccttiioonnss 11 33,, 11 44)) 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 [linear, trigonal planar, or tetrahedral] (Section 1.6) Geometry Hybridization Lewis structure [sp, sp2, or sp3] (Section 1.8) Types of bonds [single, double, or triple] (Sections 1.3, 1.9)  R Reessoonnaannccee ((SSeeccttiioonn 11 55)) 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 O delocalized charges CH3CH2 C 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 CH3 C O CH3CH2 C O CH3 isomers CH3CH2 C O H O H resonance structures  G Geeoom meettrryy aanndd hhyybbrriiddiizzaattiioonn The number of groups around an atom determines both its geometry (Section 1.6) and hybridization (Section 1.8) Number of groups Geometry Bond angle (o) Hybridization Examples linear trigonal planar tetrahedral 180 120 109.5 sp sp2 sp3 BeH2, HCCH BF3, CH2=CH2 CH4, NH3, H2O Smith: Study Guide/ Solutions Manual to accompany Organic Chemistry, Third Edition Structure and Bonding © The McGraw−Hill Companies, 2011 Text Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition Structure and Bonding 1–3

D Drraaw wiinngg oorrggaanniicc m moolleeccuulleess ((SSeeccttiioonn 11 77)) • Shorthand methods are used to abbreviate the structure of organic molecules CH3 H = CH3 C C C H H CH3 skeletal structure • CH3 CH3 (CH3)2CHCH2C(CH3)3 = 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 C H H H H H H HH C C C H H H H H HH Each drawing has two solid lines, one wedge, and one dashed line

B Boonndd lleennggtthh • 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 weakest bond C C C C Increasing bond strength C C shortest C–C bond strongest bond Smith: Study Guide/ Structure and Bonding Text Study Guide/Solutions Manual to accompany: Organic Chemistry, 3rd Edition Solutions Manual to accompany Organic Chemistry, Third Edition © The McGraw−Hill Companies, 2011 Chapter 1–4 • Sigma () bonds are generally stronger than
bonds (Section 1.9) C C strong m bond C C stronger m bond weaker / bond C C stronger m bond weaker / bonds   EElleeccttrroonneeggaattiivviittyy aanndd ppoollaarriittyy ((SSeeccttiioonnss 11 1111,, 11 1122)) • 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  D Drraaw wiinngg LLeew wiiss ssttrruuccttuurreess:: A A sshhoorrttccuutt Chapter 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 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 Smith: Study Guide/ Solutions Manual to accompany Organic Chemistry, Third Edition 30 Synthetic Polymers 807 © The McGraw−Hill Companies, 2011 Text Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition Synthetic Polymers 30–7 30.15 O HOOC + a O b O COOH H2N H O O HO NH + O NH2 O NH2 c N N H2N(CH2)6NH2 H2O H H H N N OH HO N N H H O O O 30.16 H OH2 O C + OH [1] C OCH3 CH3O2C CH3O2C H OCH3 O OH [2] CH3O2C C OCH3 + O + H O H H2O HO OH [3] OH CH3O2C H OH2 C OCH3 OCH2CH2OH OH CH3O2C C OCH3 [4] OCH2CH2OH H H O O+ OH H H OH2 CH3O2C + C OCH3 OCH2CH2OH CH3O2C [5] O CH2CH2OH + CH3OH [6] O O O O Repeat for all ester bonds CH3O2C O CH2CH2OH O + H OH2 30.17 O OH HO O HO O OH O O O This compound is less suitable than either nylon 6,6 or PET for use in consumer products because esters are more easily hydrolyzed than amides, so this polyester is less stable than the polyamide nylon This polyester has more flexible chains than PET, and this translates into a less strong fiber 808 Smith: Study Guide/ 30 Synthetic Polymers Text Study Guide/Solutions Manual to accompany: Organic Chemistry, 3rd Edition Solutions Manual to accompany Organic Chemistry, Third Edition © The McGraw−Hill Companies, 2011 Chapter 30–8 30.18 O C6H5O C OH H A OC6H5 C6H5O C OH OC6H5 OH C6H5O C OC6H5 H A C6H5O C OC6H5 OH O OH O H + A A HO OH A O H C6H5O C OH H C6H5O C O C6H5O C OC6H5 OH O O OH O OH + HA + C6H5OH + A Repeat this process for all other CO bonds O O O C O O O + C6H5OH 30.19 O HO OH 1,4-dihydroxybenzene + O O O O Cl O epichlorohydrin (excess) O OH n A H2N NH2 OH OH O NH O O HN O n OH OH O O NH HN O O OH B n OH Smith: Study Guide/ Solutions Manual to accompany Organic Chemistry, Third Edition 30 Synthetic Polymers 809 © The McGraw−Hill Companies, 2011 Text Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition Synthetic Polymers 30–9 30.20 HO AlCl3 O H O OH OH OH OH OH H OH H AlCl3 + resonance structures resonance-stabilized carbocation AlCl3 OH HO AlCl3 OH + AlCl3 + H2O 30.21 HO OH OH OH R H2C=O = R H+ R CH2 cardinol OH R 30.22 Chemical recycling of HDPE and LDPE is not easily done because these polymers are both long chains of CH2 groups joined together in a linear fashion Since there are only C–C bonds and no functional groups in the polymer chain, there are no easy methods to convert the polymers to their monomers This process is readily accomplished only when the polymer backbone contains hydrolyzable functional groups 30.23 a Combustion of polyethylene forms CO2 + H2O b Combustion of polyethylene terephthalate forms CO2 + H2O c These reactions are exothermic d HDPE and PET must be separated from poly(vinyl chloride) prior to incineration because combustion of hydrocarbons (like HDPE) and oxygen-containing organics (like PET) releases only CO2 + H2O into the atmosphere Poly(vinyl chloride) also contains Cl atoms bonded to a hydrocarbon chain On combustion this forms HCl, which cannot be released directly into the atmosphere, making incineration of halogen-containing polymers more laborious and more expensive 30.24 OH a O O OH O H O O b OH H2N O N N H O O 810 Smith: Study Guide/ 30 Synthetic Polymers Text Study Guide/Solutions Manual to accompany: Organic Chemistry, 3rd Edition Solutions Manual to accompany Organic Chemistry, Third Edition © The McGraw−Hill Companies, 2011 Chapter 30–10 30.25 Draw the polymer formed by chain-growth polymerization as in Answer 30.2 COCH3 COCH3 COCH3 F F F F F F F O a c F OCH3 CH3O b C CH3CH2O2C NH O d C CH2 NH N H OCH3 CH2 NH O O CO2CH2CH3 CO2CH2CH3 30.26 Draw the copolymers a CN and d CN and n n Cl b Cl and Cl Cl c e Ph and n n CN and CN n 30.27 a CO2Et CO2Et CO2Et CO2Et CN b CN c CN O H N N H O H2N OH O C(CH3)3 d and O O O C(CH3)3 C(CH3)3 O e O O O HO O OH or O O O f O O O O O O Cl Cl and HO OH Smith: Study Guide/ Solutions Manual to accompany Organic Chemistry, Third Edition 30 Synthetic Polymers © The McGraw−Hill Companies, 2011 Text Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition Synthetic Polymers 30–11 30.28 = a CO2Et CO2Et CO2Et = b CN c n CO2Et CN CN O H N N H n O H N = O n C(CH3)3 O d O C(CH3)3 O = n C(CH3)3 O e O O = O O O O f O n O O O O = O O O n 30.29 An isotactic polymer has all Z groups on the same side of the carbon backbone A syndiotactic polymer has the Z groups alternating from one side of the carbon chain to the other An atactic polymer has the Z groups oriented randomly along the polymer chain a c b Cl Cl Cl CN CN CN CN Ph Ph Ph 30.30 OH CCl3 from ethylene oxide n 30.31 O H2N a NH2 and HO2C CO2H H N H N O Ph Ph 811 812 Smith: Study Guide/ 30 Synthetic Polymers Text Study Guide/Solutions Manual to accompany: Organic Chemistry, 3rd Edition Solutions Manual to accompany Organic Chemistry, Third Edition © The McGraw−Hill Companies, 2011 Chapter 30–12 H N O b O C N and N C O HO OH O O O N H O O O COCl c and HO OH COCl O O H N O d N H O e HO OH and Cl O Cl O O O f HO COOH O 30.32 CN Ph ABS 30.33 H2N NH2 O a N H + N H O HO O Quiana OH O ClOC b COCl H2N + NH2 O O N H Nomex N H Smith: Study Guide/ Solutions Manual to accompany Organic Chemistry, Third Edition 30 Synthetic Polymers 813 © The McGraw−Hill Companies, 2011 Text Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition Synthetic Polymers 30–13 30.34 O H N O O O H N N H H N O O O N H H N N H Kevlar O N H 30.35 O O O O O O H N O O O n polyester A O n nylon 6,6 PET T g = < oC Tm = 50 oC Tg = 70 oC Tm = 265 oC N H n Tg = 53 oC Tm = 265 oC a Polyester A has a lower Tg and Tm than PET because its polymer chain is more flexible There are no rigid benzene rings so the polymer is less ordered b Polyester A has a lower Tg and Tm than nylon 6,6 because the N–H bonds of nylon 6,6 allow chains to hydrogen bond to each other, which makes the polymer more ordered c The Tm for Kevlar would be higher than that of nylon 6,6 because in addition to extensive hydrogen bonding between chains, each chain contains rigid benzene rings This results in a more ordered polymer 30.36 O O O O O O A dibutyl phthalate O O Diester A is often used as a plasticizer in place of dibutyl phthalate because it has a higher molecular weight, giving it a higher boiling point A should therefore be less volatile than dibutyl phthalate, so it should evaporate from a polymer less readily 814 Smith: Study Guide/ 30 Synthetic Polymers Text Study Guide/Solutions Manual to accompany: Organic Chemistry, 3rd Edition Solutions Manual to accompany Organic Chemistry, Third Edition © The McGraw−Hill Companies, 2011 Chapter 30–14 30.37 Initiation: (CH3)3CO [1] OC(CH3)3 [2] (CH3)3CO (CH3)3CO + Propagation: (CH3)3CO [3] (CH3)3CO (CH3)3CO new C–C bond Repeat Step [3] over and over to form gutta-percha Termination: [4] 30.38 H F [1] O F3B H H F [2] Ph + F B O Ph + F3B OH H [3] 1,2-H shift H a highly resonance-stabilized carbocation Ph Ph [4] Ph + Repeat Steps [3] and [4] A Ph new C–C bond Ph Ph Ph A is the major product formed due to the 1,2-H shift (Step [3]) that occurs to form a resonance-stabilized carbocation B is the product that would form without this shift Ph A major product B 30.39 H F3B O CN C N
+ H H F3B O CN C This carbocation is unstable because it is located next to an electron-withdrawing CN group that bears a
+ on its C atom This carbocation is difficult to form, so CH2=CHCN is only slowly polymerized under cationic conditions N H H This 2° carbocation is more stable because it is not directly bonded to the electron-withdrawing CN group As a result, it is more readily formed Thus, cationic polymerization can occur more readily Smith: Study Guide/ Solutions Manual to accompany Organic Chemistry, Third Edition 30 Synthetic Polymers 815 © The McGraw−Hill Companies, 2011 Text Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition Synthetic Polymers 30–15 30.40 Initiation: [1] + Bu Li Li+ Bu Ph Ph Repeat Step [2] [2] Propagation: Bu Bu Ph Ph Ph over and over Ph O [3] Termination: O O C O Ph Ph Ph Ph 30.41 The substituent on styrene determines whether cationic or anionic polymerization is preferred When the substituent stabilizes a carbocation, cationic polymerization will occur When the substituent stabilizes a carbanion, anionic polymerization will occur OCH3 a cationic polymerization NO2 b CF3 c anionic polymerization CH2CH3 d anionic polymerization cationic polymerization 30.42 The rate of anionic polymerization depends on the ability of the substituents on the alkene to stabilize an intermediate carbanion: the better a substituent stabilizes a carbanion, the faster anionic polymerization occurs O CN OCH3 O OCH3 O O least most increasing ability to undergo anionic polymerization 30.43 The reason for this selectivity is explained in Figure 9.9 In the ring opening of an unsymmetrical epoxide under acidic conditions, nucleophilic attack occurs at the carbon atom that is more able to accept a
+ in the transition state; that is, nucleophilic attack occurs at the more substituted carbon The transition state having a
+ on a C with an electron-donating CH3 group is more stabilized (lower in energy), permitting a faster reaction [1] O O H OH2 H O + HO H H OH + [4] [2] H2O HO O H H2O Repeat Steps [4] and [5] over and over O HO OH [3] H + H2O [5] HO HO O OH OH + + H3O+ H3O+ 816 Smith: Study Guide/ 30 Synthetic Polymers Text Study Guide/Solutions Manual to accompany: Organic Chemistry, 3rd Edition Solutions Manual to accompany Organic Chemistry, Third Edition © The McGraw−Hill Companies, 2011 Chapter 30–16 30.44 AlCl3 H ClCH2 C Cl H ClCH2 H C Cl AlCl3 H ClCH2 + HO C H H 1,4-cyclohexanediol resonance-stabilized carbocation A OH + AlCl4– Cl AlCl3 H H ClCH2 OH + AlCl3 + HCl CH2 O ClCH2 C O H Repeat CH2 CH2 O O n B 30.45 H N N C O + CH3 OH O C H N CH3 O C O CH3 OH CH3 O H CH3 O H H N CH3 OH + OCH3 O 30.46 (CH3)3CO–OC(CH3)3 a OCH3 OCH3 OCH3 OCH3 Ziegler–Natta catalyst CH3 BuLi (initiator) c O BF3 + H2O d CH2 C CH3 CH2 C CH3 CH2 C O a urethane b N C CO CO CO CH2CH3 CH2CH3 CH2CH3 O CH3 OH Smith: Study Guide/ Solutions Manual to accompany Organic Chemistry, Third Edition 30 Synthetic Polymers 817 © The McGraw−Hill Companies, 2011 Text Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition Synthetic Polymers 30–17 O e –OH O O OH + f OH O OH O O O Cl O O O (excess) n O O g – HO OH OH H2O O O H N h O O O O O O O –OH NH2 O H2O or NH H N i OCN NCO + HO OH O O N H O O O j HO Cl2C=O OH O O 30.47 Polyethylene bottles are resistant to NaOH because they are hydrocarbons with no reactive sites Polyester shirts and nylon stockings both contain functional groups Nylon contains amides and polyester contains esters, two functional groups that are susceptible to hydrolysis with aqueous NaOH Thus, the polymers are converted to their monomer starting materials, creating a hole in the garment 818 Smith: Study Guide/ 30 Synthetic Polymers Text Study Guide/Solutions Manual to accompany: Organic Chemistry, 3rd Edition Solutions Manual to accompany Organic Chemistry, Third Edition © The McGraw−Hill Companies, 2011 Chapter 30–18 30.48 O HO CH2 OH Cl + OH O O CH2 CH2 O O n prepolymer H2N O O NH2 OH OH OH O CH2 CH2 O O O NH n HN NH HN O CH2 O O OH CH2 O OH OH n 30.49 a Poly(vinyl alcohol) cannot be prepared from vinyl alcohol because vinyl alcohol is not a stable monomer It is the enol of acetaldehyde (CH3CHO), and thus it can't be converted to poly(vinyl alcohol) OH OH vinyl alcohol OH poly(vinyl alcohol) b OAc vinyl acetate ROOR radical polymerization –OH OAc OAc poly(vinyl acetate) H2 O hydrolysis + CH3CO2– OH OH poly(vinyl alcohol) O C c OH H H+ OH O O poly(vinyl alcohol) an acetal poly(vinyl butyral) 30.50 NBS h
Br – OH OH [1] BH3 HO [2] H2O2, –OH OH 1,3-propanediol Smith: Study Guide/ Solutions Manual to accompany Organic Chemistry, Third Edition 30 Synthetic Polymers © The McGraw−Hill Companies, 2011 Text Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition Synthetic Polymers 30–19 30.51 CH3 CH3Cl CH3Cl AlCl3 AlCl3 KMnO4 HOOC CH3 CH3 [1] OsO4 CH2 CH2 HO [2] NaHSO3, H2O COOH terephthalic acid OH ethylene glycol or mCPBA O H2O, –OH OH HO 30.52 OH OH OH OH + CH2 O OH phenol OH Since phenol has no substituents at any ortho or para position, an extensive network of covalent bonds can join the benzene rings together at all ortho and para positions to the OH groups Bakelite OH CH3 OH OH OH OH + CH2 O p-cresol Since p-cresol has a CH3 group at the para position to the OH group, new bonds can be formed only at two ortho positions so that a less extensive three-dimensional network can form 30.53 O a O O
-caprolactone O O polycaprolactone O b O O p-dioxanone O O polydioxanone 819 820 Smith: Study Guide/ 30 Synthetic Polymers Text Study Guide/Solutions Manual to accompany: Organic Chemistry, 3rd Edition Solutions Manual to accompany Organic Chemistry, Third Edition © The McGraw−Hill Companies, 2011 Chapter 30–20 30.54 O O H N O O O O H N N H O H N O O O poly(ester amide) A O H2N O H2N OH NH2 OH HO O OH HO O O the benzyl ester of lysine leucine 30.55 CO2CH2Ph O O OH O O O salicylic acid (2 equiv) + n O + O OH O O benzyl salicylate (2 equiv) CO2H PolyAspirin OH HO Cl Cl O sebacic acid O sebacoyl chloride 30.56 H H N O H2N NH2 N H2N H N N H N N [1] NH2 N O H2N proton transfer N N OH H A [2] NH2 H N N NH2 [3] melamine A H2N H N N N N N N NH2 H2N N N H N NH2 NH2 N N N NH2 N H A H N N NH2 H2N N [5] NH2 [6] H N N NH2 N N NH2 H2N H H N N CH2 N NH2 [4] N H2O H N N H2N N NH2 OH2 A Smith: Study Guide/ Solutions Manual to accompany Organic Chemistry, Third Edition 30 Synthetic Polymers 821 © The McGraw−Hill Companies, 2011 Text Study Guide/Solutions Manual to accompany Organic Chemistry, Third Edition Synthetic Polymers 30–21 30.57 [1] a H re-draw [2] intramolecular H abstraction [3] Repeat Step [2] b Abstraction of the H is more facile than abstraction of the other H's because the H atom that is removed is six atoms from the radical The transition state for this intramolecular reaction is cyclic, and resembles a six-membered ring, the most stable ring size Other H's are too far away or the transition state would resemble a smaller, less stable ring n butyl substituent 30.58 O O H2N O O NH2 H H2N H O N H OH H2N H2N O NH2 H2N O N H N H formaldehyde urea O N N N H2N O N O O N H N N O N O NH2 repeat H2N O N N N NH N NH2 repeat O N N N H CH2 N HN O O N H NH NH2 O NH2 NH2 ... from Study Guide/ Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 57 Alkanes: Chapter from Study Guide/ Solutions Manual to accompany Organic Chemistry, Third Edition by Smith. .. from Study Guide/ Solutions Manual to accompany Organic Chemistry, Third Edition by Smith 479 iv 20 Introduction to Carbonyl Chemistry: Chapter 20 from Study Guide/ Solutions Manual to accompany Organic. .. planar enanthotoxin 11 12 Smith: Study Guide/ Structure and Bonding Text Study Guide/ Solutions Manual to accompany: Organic Chemistry, 3rd Edition Solutions Manual to accompany Organic Chemistry,