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Answers to Problems

Chapter 2 (Structural Theory)

2.1 Structure (a) not (b). 2.2 Linear. 2.3 (a) Expect zero; (b) Expect NF3  NH3.
2.4 d, e.

Chapter 4 (Types of Reactions of Organic Compounds)

4.1 (a) CH3OH  CH3NH2; (b) CH3SH  CH3OH; (c) H3O  NH4. 4.2 (a) H3O;
(b) NH4; (c) H2S; (d) H2O.

4.3 Aprotic b, c, e, g, j, k, l

4.4 (a) (CH3)4 N cation is more

hydrophobic than NH4 . (b) by increasing the size of the alkyl group.

Chapter 5A.I (Introduction to Alkanes)

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is

5A.I.2 No. 5A.I.3 van der Waals repulsion between large methyls. 5A.I.9 (a) and
(b) C3H8; (c) CH3  CH2CH2D and CH3CHDCH3. 5A.I.10 (a) 3, (b) 4 (c) 2, (d) 1. 5A.I.11
(b) RX should be 1. 5A.I.13 (a) 44% 1-Cl, 56% 2-Cl; (b) 64% 1, 36% 3; (c) 55% 1, 45%; 3;
(d) 21% 1-Cl, 53% 2-Cl, 26% 3-Cl; (e) 28% 1-Cl-2-Me, 23% 2-Cl-2-Me, 35% 2-Cl-3-Me, 14%
1-Cl-3-Me; (f) 45% 1-Cl-2,2,3-triMe, 25% 3-Cl-2,2,3-triMe, 30% 1-Cl-2,3,3-triMe; (g) 33%
1-Cl-2,2,4-triMe, 28% 3-Cl-2,2,4-triMe, 18% 4-Cl-2,2,4-triMe, 22% l-Cl-2,4,4-triMe.
5A.I.14 (a) 4% 1-Br, 96% 2-Br; (b) 0.6% 1, 99.4% 3; (c) 0.3% 1.99.7% 3; (d) 1% 1-Br,
66% 2-Br, 33% 3-Br; (e) 0.3% 1-Br-2-Me, 90% 2-Br-2-Me, 9% 2-Br-3-Me, 0.2% 1-Br-3-Me;
(f) 0.6% 1-Br-2,2,3-triMe, 99% 3-Br-2,2,3-triMe, 0.4% 1-Br 2,3,3-triMe; (g) 0.5% 1-Br-2,2,4triMe, 9% 3-Br-2,2,4-triMe, 90% 4-Br-2,2,4-triMe, 0.3% 1-Br2,4,4-triMe. 5A.I.15 40:1.
5A.I.16 1.15:1. 5A.I.21 2,2-dimethylhexane.

Chapter 5A.II (Stereoisomerism)

sh

5AII.1 (a) 39.0; (b) 2.4; (c) 0.6 5AII.2 Use a shorter or longer tube, measure rotation
5AII.3 Mirror images. 5AII.5 3, 2, 1, 5AII.9 (b) Neither active; one is a chiral other is a
racemic modification, 5AII.11 (a) 4; (c) none. 5AII.13 c,d,e.g., 5AII.15 1.01.

Chapter 5B.II (Stereochemistry)

5BII.1 trans is resolvable. 5BII.3 (a) 0 kcal; (b) 2.7 kcal; (c) 5.4 kcal (3.6 from methylmethyl interaction); (d) 0 kcal; (e) 0 kcal; (f) 3.6 kcal. 5BII.4 (b) 3.6 kcal. 5BII.5 (a) cis  trans;
(b) trans  cis; (c) 1.8 kcal mol1 in each case. 5BII.6 Resolvable: b. d Meso: C (e, f do not
contain Chiral centers ). 5BII.7 (a) e; (b) a; (c) c. f; (d) d; (e) b; (f) none. 5BII.8 Pairs of
enantinomers: a, b, c, d. No meso compounds. None are nonresolvable racemic modification.
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Organic Chemistry 7e by Robert Thornton Morrison, Robert Neilson Boyd, and S. K. Bhattacharjee

Chapter 5C (Aromatic Hydrocarbons and Aromaticity)

5C.1 (a) 5.6 kcal; (b) 26.8 kcal. 5C.2 (a) 824.1 kcal; (b) 35.0 kcal greater. 5C.7 ortho
+6 C; meta 7 C, para:  87 C 5C.10
BF4 .
CH3
A

+
H3C

H
DG CH3
H H

5C.11 (a) CH3CHCl; (b) CH3CH2; (c) CH3CH2; (e)

(h) inductive; (i) resonance.

CH2CH2Cl; (f) CH3CHCl;

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Chapter 6A [Alkenes: Structure and Preparation (Elimination)]

6A.5 (g) None. 6A.8 (a) 2.05; (b) 1.02 mol HCl : 1 mol DCl. 6A.9 (g) None. 6A.10 iBu  n-Pr  Et (W neopentyl). 6A.13 Anion unsolvated, highly basic. 6A.16 Unsolvated
F|, very basic. 6A.17 Principal base is t-butonol. 6A.19 Step (3) is slower than the reverse
of (2). 6A.21 (c) 1-Butene 649.8, cis-2-butene 648.1, trans-2-butene 647.1; (d) 1-Pentene
806.9, cis-2-pentene 805.3, trans-2-pentene 804.3. 6A.22 (a) H3O; HBr; (b) HBr; (c) HBr.
6A.24 (a) Nucleophilic substitution by H2O; (b) SN2; (c) SN1. 6A.28 (a) Et  i-Pr  t-Bu;
(b) i-Pr OEt 19.8 kcal, t-Bu OEt 32.9 kcal. 6A.28 (a) Isopropylmethylether.

Chapter 6B [Alkenes: Dienes (Conjugation and Resonance)]

6B.1 React with relatively scarce HCl, with a minimum Eact of 15 kcal. 6B.2 1-Chloro2-butene and 3-Chloro-l-butene. 6B.7 One and a half bonds effectively prevent rotation
between configurations. 6B.10 (a) 5060 kcal. 6B.11 l,3-Hexadiene. 6B.13 Addition to an
allylic radical.

Chapter 7 (Alkynes)

7.5 H goes to terminal C. 7.6 (a) Calcium acetylide. (b) Acetylene gas is evolved.

Chapter 8 [Alkyl Halides (Nucleophilic Substitutions, SN Reactions)]

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8.1 1: 4; 2 : three; 3: one. 8.5 Starting bromide 63% optical purity; expect alcohol of 6.5, same purity. 8.6 Optical purity of final product 13% that of the reactant;
13% inversion, 87% racemisation; or 43.5% frontside attack, 56.5% backside attack.
8.9 (a) 1.9%; (b) 16.4%; (c) 66.2%; (d) 95.1%; (e) 99.0%. 8.12 Unsolvated F| very basic.
8.14 (a) Transition state more stabilized; (b) reactants more stabilized.

Chapter 9 [Aryl Halides Nucleophilic Aromatic Substitution (SNAr Reactions)]

sh

9.3 (b) Nucleophilic aromatic substitution; (c) electron withdrawal.

Chapter 10 (Alcohols and Ethers)

10.3 (a) Leucine isopentyl alcohol: isoleucine active amyl alcohol
10.5 Electron withdrawing groups increase acid strength. 10.7 Free radical chlorination of
neopentane. 10.9 complete inversion. 10.11 (a) Configuration of () ether same as ()
alcohol; (b) Maximum rotation is 19.5 10.12 Complete inversion.
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Organic Chemistry 7e by Robert Thornton Morrison, Robert Neilson Boyd, and S. K. Bhattacharjee

Chapter 11 (Phenols)
11.4 (a) the OSO3H group is displaced by electrophilic reagents, in this case of nitronium ion.
11.5 Sulfonation is reversible: rate vs equilibrium control. 11.6 Phenol, HONO, 78 C;
HNO3. 11.8 (a) Sulfate ion weak base, good leaving group; (b) alkyl sulfonates.

Chapter 12 (Aldehydes and Ketones Nucleophilic Addition)

12.2 (a) Acetic acid, propionic acid and n-butyric acids; (b) Adipic acid. 12.3 (a) 1;
(b) 1, Cl; (d) 2 (both active); (e) 2; (f) no change. 12.4 Semicarbazone formation
reversible; rate control vs equilibrium control. 12.9 Internal crossed Comnizzaro
reaction. 12.13 A, PhCH2CH2CHO: B, PhCH2CH2CH2OH; C, PhOCHPCHCH2OH.
12.15 (d)OCH2OCHO

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CN
Orion

OCH2OCHO

COOMe

Acryloid,

OCH2OC(CH3)O

COOMe

Lucite, phlexiglas

12.18 All less stable than I. 12.l9 An amide. 12.20 Two successive nucleophilic
addition. 12.21 Two successive nucleophilic addition. 12.22 B, CH3CH (CH2COOH)2;
D,
-ketocaproic acid. E. CH3COCH2CH2CH (COOC2H5)2; F, PhCH(CH2COPh)2;H,
CH2PCH  CH(COOH)CH2CH2COOH; I, Etooe. CHPC(COOEt) CH(COOEt)  COCH3 J.
HOOC  CHPC(COOH)CH2COOH. 12.23 (a) K. CH2PC(COOEt)2; C, glutaric acid.
12.27 (c) can not form iminium ions. 12.28 1,4-Diphyenyl-l, 3-butadiene  maleic anhydride; l,3-Butadiene  2-cyclopentenone; 2 moles of 1,3-butadiene. 12.29 (a) 3-Ethoxy-1,
3-pentadiene + p-benzoquinone; (b) 5-methoxy-2-methyl-l,4-benzoquinone + 1,3-butadiene.
12.30 This is one case in which enol is more stable than the Keto. 12.31 (a) Ease of oxidation; (b) ease of reduction. 12.32 p-Nitrosophenol undergoes Ketoenol tantomerization
to give the mono oxime.

Chapter 13 (Carboxylic Acids)

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13.1 91 at 110 C, 71 at 156 C; association occurs even in the vapour phase, decreasing as
temperature increases. 13.2 (b) 2-Methyldecanoic acid: (c) 2,2-dimethyldodecanoic acid;
(d) ethyl-n-octyl malonate n C8H17CH(COOEt)2. 13.3 (b) 2-Methylbutanoic acid.
13.4 (a) p-Bromobenzoic acid; (b) p-bromophenylacetic acid. 13.7 (a) F  Cl  Br  I;
(b) electron withdrawing. 13.12 To prevent generation of HCN. 13.17 (a) Cyclic diester;
(b) cyclic anhydride.

sh

Chapter 14 (Functional Derivatives of Carboxylic Acids Nucleophilic Acyl Substitution)

14.3 (a) Cis. Acid; the only one that can form cyclic anhydride. 14.4 G. naphthalene.
14.5 Final products is l-phenylnaphthalene. 14.5 Final product is 1-phenylnaphthalene. 14.7 O-(p-totuyl) benzoic acid. 14.8 The product, O  HOOC  C6H4 
COOR, has an acidic handle. 14.12 (a) Cyclic double ester; (b) linear polyester by step
reaction polymerization. 14.15 Basicity of leaving Cl  RCOO  RO  NH2 14.16
Structure II. 14.20 (a) Formic acid. 14.21 l-Octadeconol and 1-butanol. 14.24 Linear
sp-carbon. 14.25. Urea, CaCO3, NH3. 14.26 (b) Nucleophilic addition.
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Organic Chemistry 7e by Robert Thornton Morrison, Robert Neilson Boyd, and S. K. Bhattacharjee
{

14.27 (a) RCOCl; (b) RCOO NH4 , RCONH2, RCN, amides of low molecular weights,
amines. 14.28 (a) 102; (c) 4; (d) no. 14.29 (a) Two, 97; (b) S.E = mol.wt/number of ester
groups per molecule.

Chapter 15 (Amines)

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15.2 R; undergoes inversion. 15.6 Rearrangement is intramolecular. 15.7 N2

is leaving group. 15.8 Goes with reaction, since only cis-amino acids can form lactams.
{
|
15.10 (CH3)3 N O B F3. 15.15 Attack at acylcarbon less hindered than at sulfur; sulfonate better leaving group than carboxylate. 15.16 Free amine is much more reactive.
|
15.18 Leaving groups Cl|  H2O  OH. 15.22 (a) Electrondelocalization makes diazonium ion more electrophilic. 15.25. (a) 2-bromo-4-hydroxy-3,4-dimethyl azobenzene.
15.27 (a) That unknown is 2; (b) separate, acidify aqueous solution.

Chapter 16 (Heterocyclic Compounds)

16.1 B, [OCH(COOEt) COCH3]2. 16.3 OCOOH deactivates ring. 16.4 Two units of
starting materials linked at the 5-position through a OCH2-group. 16.5 Sodium furoate and
furfuryl alcohol (Cannizzaro). 16.10 Hygrine,2-acetonyl ON-methyl pyrrolidine,hygrinic acid,
N-methyl-2-pyrrolidine carboxylic acid. 16.11 para orientation controlled by activating NH2
group. 16.14 Amine  i-mine  nitrile; sp3  sp2  sp. 16.18 Piperidine, a secondary
amine, would itself be acylated. 16.22 (f) None.

Chapter 17B (Spectroscopy and Structure)

{

17B.1 (CH3)3C ; CH2PCHOCH2; CH3CH2; CH2PCH.

17B.4. (a) CH3COH2CH3
(b) CH3 CH CH2 CH3
|
OH

 CH , CH CH CH
 CH ; (b) Ph C .
17B.8. I signal. 17B.20 (a) CH3CH
3
3
2
3
3

Chapter 18E (Stereoselectivity and Stereospecificity in Organic Synthesis)

is

18E.1 Enantiomeric, a, c, d; identical, b.

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Chapter 20 [Molecular Orbitals; Orbital Symmetry (Pericyclic Reactions)]

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20.1 (a) Conclosure; I or III trans; II cis; (b) dis closure; I or III cis-;
II trans. 20.2 (a) 1; two p-clectrons; (b) 4n  2; dis (thermal); (c)4n, con (thermal);
(d) cation, 4n, con (thermal). 20.3 (a) Dis opening; (b) disclosure; con opening; dis closure;
(d) con opening (4e). disclosure (6e); (e) dis-opening of cation (2e), then combination with
water; (f) protonated ketone like a pentadienyl cation, with 4 p electrons; con closure.
20.4. Via the cyclobutene, with con closure and openings. 20.5 (a) cis-3,6-Dimethylcyclohexene;
[4 + 2]; (c) phenyls are cis-to each other (syn addition) and cis-to the anhydride bridge
(endo reaction); (d), (e), (f) all are tetramethyl cyclobutanes; in D one CH3 is trans to the other
three. 20.6. (a) Diels-Alder; retro-Diels-Alder; (b) endo not exo. 20.7 (a) [4  2], not [6  2];
(b) photochemical (intramolecular) supra-supra [2  2]; (c) supra-supra [6  4); (d) supra-supra
[8  2]; (e) supra-supra [14  2]. 20.8. (a) supra [1, 5]H to either face of trigonal carbon;
b [1, 5]D, not [1, 3]D; (c) [1,3]C (supra) with inversion at migrating carbon.
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Organic Chemistry 7e by Robert Thornton Morrison, Robert Neilson Boyd, and S. K. Bhattacharjee

Chapter 22B [Macromolecules (Polymers and Polymerization)]

22B.1 (a) Amide; (b) amide; 6-aminohexanoic acid; (c) ether; ethylene oxide;
(d) chloroalkene; 2-chloro-1,3-butadiene; (e) chloroalkane; 1, l-dichloro ethene. 22B.2 1,2and 1,4-addition. 22B.3 Polymer is transfer agent. 22B.5 (a) Chain transfer.

Chapter 23 [Symphoria (Anchimeric Assistance)]

23.3 Neighboring trans-Br and trans-I give anchimeric assistance.

Chapter 25 [Lipids (Fats, Steroids, Terpenes, and Prostaglandins)]

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25.1 Decarboxylation. Fatty acids could be precursors of petroleum hydrocarbons.

25.2 Tung oil is high in eleostearic acid (3 double bonds). 25.3 Preserves semiliquidity of
membranes in colder part of body. 25.4 Biological oxidation of fatty acids removes 2 carbons at a time, starting at the carboxyl and I; beta oxidation.

Chapter 26 (Carbohydrates I: Monosaccharides. Carbohydrates II: Disaccharides

and Polysaccharides)

26.1 Formulas I-VIII in page-12. 26.2 (a) 3; (b) 8. 26.3 Glucose  5HIO4 5HCOOH 
HCHO. 26.4. A. Gluconic acid; B, glucitol; C, glucaric acid; D, glucouronic acid. 26.5 Fructose;
Aldose osazone osone 2-ketose. 26.6 Identical in configuration at
C3, C4 and C5. 26.7 Alditol. 26.8 (a) 2 tetroses; (b) 4 pentoses; 8 hexoses; (c) lowest chiral carbon has OH on the right. 26.9 One product (S,S) will be optically active,
one product (meso) optically inactive. 26.10 I ()-allose; II ()-altrose; VI()-idose;
VII()-galactose; VIII()-talose. 26.15 L-family. 26.16 (a) 36.2% a, 63.8% b. 26.18
Acetylation occurs at C1 to give diastereoisomers (anomers). 26.19 (a) Six menbered ring; (b) HCOOH, OHCCHO and HOCH2CHO. 26.20 (a) Six menbered ring;
(b) enantiomer. 26.22 Differ at C1 of reducible glucose unit only. 26.23 2,3,4,6-Tetraand 2,3,6-tri-O-methyl-D-glucose. 26.24 D-glucose and D-erythrose; indicates attachment
to other ring is at C4. 26.26 Some as in 16.22 except for b-linkage in first three formulas.
16.27 D-Galactose and D-erythrose. 26.28 (92.4  52.7)/2 19.9. 26.29 Sucrose is an
a-glucoside. 26.30 Di-O-methyl-L-and D-tartaric acids. 26.31 (0.025%); 3 (0.075%),
(0.225%). 26.32 A poly a-D-glucopyranoside; chain forming unit; attachment at Cl and C6;
chain-linking unit, attachment at C1, C3 and C6; chain terminating unit, attachment at
Cl. 26.33 A poly b-D-xylopyranoside; chain forming unit, attachment at C1 and C4; chain
linking unit, attachment at C1, C3 and C4; chain terminating unit, attachment at C1.

is

Chapter 28 (-Amino Acids and Proteins Molecular Biology)

|

28.1 ONH2  OCOO, proton goes to NH2 to form H3NCHRCOO. 28.2 OCOOH 
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. . 28.4 (a) On acid side; (b) on basic

ONH3; OCOOH gives up proton to form H3NCHRCOO
side; (c) more acidic and more basic than for glyeine. 28.7 4 isomers. 28.11 (a) 22.4 ml; (b)
44.8 ml; (c) no N2. 28.13 Salmine Ala Arg50 Gly4 Ile Pro6 Ser7Va13. 28.14 Same as emperical formula (preceeding problem 18.13). 28.15 70300. 28.16 (a) 16 700; (b) 4. 28.17 A
sulfonamide. which is more resistant to hydrolysis than carboxamide.

28.19 (a) OCOOH CH2OH; (b) OCOOH OCONHNH2 a hydrazide.

28.20 (a) Phe- Val-Asp-Glu-His; (b) His-Leu-Cys-Gly-Ser-His-Len; (c) Tyr-Leu- Val-CysGly-Glu-Arg-Gly-Phe-Phe. 28.21 (a) Cb3-Gly-Ala, SOCl2; Phe; H2, Pd; (b) PhCH2O COCl,
Ala; SOCl2; Gly; H2, Pd. 28.22 In A, polystyrene has a OCH2Cl group attached to rings; in G,
OCH2Br groups.
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