Solomons Organic Chemistry Solution Manual - Chapter 3

P1: PBU/OVY JWCL234-03
P2: PBU/OVY
QC: PBU/OVY
T1: PBU
Printer: Bind Rite December 8, 2009 21:29
JWCL234-Solomons-v1
AN INTRODUCTION TO ORGANIC REACTIONS AND THEIR MECHANISMS: ACIDS AND BASES
SOLUTIONS TO PROBLEMS
F
3.1 (a) CH3
F
+
+ F Cl
CH3
O H
+
B F F Cl
(b) CH3
Cl
Al Cl
Cl
CH3
Cl
Al Cl Cl
F (c) CH3 O CH3 + F

3.2 (a) Lewis base (b) Lewis acid (c) Lewis base (d) Lewis base (e) Lewis acid (f) Lewis base
F
+
CH3
O CH3
B F F
H
3.3 CH3
F + F Lewis acid B F CH3
H N
+
F B F
N CH3
CH3
Lewis base
3.4 (a) K a =
[H3 O+ ][HCO2 ] = 1.77 104 [HCO2 H]
Let x = [H3 O+ ] = [HCO2 ] at equilibrium then, 0.1 x = [HCO2 H] at equilibrium but, since the K a is very small, x will be very small and 0.1 x
0.1 35
CONFIRMING PAGES
P2: PBU/OVY
QC: PBU/OVY
T1: PBU
JWCL234-Solomons-v1
36
AN INTRODUCTION TO ORGANIC REACTIONS AND THEIR MECHANISMS
Therefore, (x)(x) = 1.77 104 0.1 x 2 = 1.77 105 x = 0.0042 = [H3 O+ ] = [HCO2 ] [H3 O+ ] 100 0.1 [HCO2 ] 100 0.1
(b) % Ionized = =
or
.0042 100 = 4.2% 0.1
3.5 (a) p K a = log 107 = (7) = 7 (b) p K a = log 5.0 = 0.669 (c) Since the acid with a K a = 5 has a larger K a , it is the stronger acid. 3.6 When H3 O+ acts as an acid in aqueous solution, the equation is H3 O+ + H2 O and K a is [H2 O][H3 O+ ] = [H2 O] [H3 O+ ] The molar concentration of H2 O in pure H2 O, that is [H2 O] = 55.5; therefore, K a = 55.5 Ka = The p K a is p K a = log 55.5 = 1.74 H2 O + H3 O+
H
3.7
(a)
(c)
HO (b)
O O
(d)
3.8 The p K a of the methylaminium ion is equal to 10.6 (Section 3.6C). Since the p K a of the anilinium ion is equal to 4.6, the anilinium ion is a stronger acid than the methylaminium ion, and aniline (C6 H5 NH2 ) is a weaker base than methylamine (CH3 NH2 ). 3.9
+ O
NH2 O
NH3 O O Na+ O
3.10 R
C O
+ H
Na+
C O OH
+ HO
C OH
CONFIRMING PAGES
P2: PBU/OVY
QC: PBU/OVY
T1: PBU
JWCL234-Solomons-v1
ACIDS AND BASES
37
3.11 (a) Negative. Because the atoms are constrained to one molecule in the product, they have to become more ordered. (b) Approximately zero. (c) Positive. Because the atoms are in two separate product molecules, they become more disordered. 3.12 (a) If K eq = 1 then, log K eq = 0 = G = 0 (b) If K eq = 10 then, log K eq = 1 = G 2.303 RT G = (2.303)(0.008314 kJ mol1 K1 )(298 K) = 5.71 kJ mol1 S = 0 G 2.303 RT
(c) G = H T S G = H = 5.71 kJ mol1 if
3.13 Structures A and B make equal contributions to the overall hybrid. This means that the carbon-oxygen bonds should be the same length and that the oxygens should bear equal negative charges.
O CH3 C O A
O CH3 B C O
O CH3 C
O hybrid
3.14 (a) CHCl2 CO2 H would be the stronger acid because the electron-withdrawing inductive effect of two chlorine atoms would make its hydroxyl proton more positive. The electronwithdrawing effect of the two chlorine atoms would also stabilize the dichloroacetate ion more effectively by dispersing its negative charge more extensively. (b) CCl3 CO2 H would be the stronger acid for reasons similar to those given in (a), except here there are three versus two electron-withdrawing chlorine atoms involved. (c) CH2 FCO2 H would be the stronger acid because the electron-withdrawing effect of a uorine atom is greater than that of a bromine atom (uorine is more electronegative). (d) CH2 FCO2 H is the stronger acid because the uorine atom is nearer the carboxyl group and is, therefore, better able to exert its electron-withdrawing inductive effect. (Remember: Inductive effects weaken steadily as the distance between the substituent and the acidic group increases.) 3.15 All compounds containing oxygen and most compounds containing nitrogen will have an unshared electron pair on their oxygen or nitrogen atom. These compounds can, therefore, act as bases and accept a proton from concentrated sulfuric acid. When they accept a proton, these compounds become either oxonium ions or ammonium ions, and having become ionic, they are soluble in the polar medium of sulfuric acid. The only nitrogen compounds that do
CONFIRMING PAGES
P2: PBU/OVY
QC: PBU/OVY
T1: PBU
JWCL234-Solomons-v1
38
not have an electron pair on their nitrogen atom are quaternary ammonium compounds, and these, already being ionic, also dissolve in the polar medium of concentrated sulfuric acid.
methanol
3.16 (a) CH3O
Stronger acid pKa = 16

(b) CH3CH2O
H Stronger base (from NaH)
CH3O Weaker base
H2 Weaker acid pKa = 35
Stronger acid pKa = 16

(c) H
NH2 Stronger base (from NaNH2)
ethanol
CH3CH2O Weaker base
NH3 Weaker acid pKa = 38
CH2CH3
hexane
NH2
CH3CH3 Weaker acid pKa = 50
H Stronger acid pK a = 38 H
(d) H
+
Stronger base (from CH3CH2Li)
Weaker base
NH2
liq. NH3
NH3 Weaker base
NH3 Weaker acid pKa = 38
H Stronger acid pK a = 9.2 (from NH4Cl)
Stronger base (from NaNH2)
(e) H
Stronger acid pK a = 15.7
Stronger base [from (CH3)3CONa]
Weaker base
OC(CH3)3
H2O
+ HOC(CH3)3 Weaker acid p K a = 18
(f) No appreciable acid-base reaction would occur because HO is not a strong enough base to remove a proton from (CH3 )3 COH. 3.17 (a) HC
CH CNa
+ + + +
NaH D2O D2O NaH T2O +
hexane
HC HC
CNa CD
+ + +
H2 NaOD LiOD + + H2 NaOT + LiOD
(b) HC
(c) CH3CH2Li (d) CH3CH2OH (e) CH3CH2ONa
hexane hexane
CH3CH2D
CH3CH2ONa CH3CH2OT
(f ) CH3CH2CH2Li
D2O
hexane
CH3CH2CH2D
CONFIRMING PAGES
P2: PBU/OVY
QC: PBU/OVY
T1: PBU
JWCL234-Solomons-v1
ACIDS AND BASES
39
Problems
Brnsted-Lowry Acids and Bases
(the amide ion) 3.18 (a) NH2
(d) H
(the ethynide ion)
(b) H (c) H
(the hydroxide ion)
(e) CH3O
(the methoxide ion)
(the hydride ion)
(f ) H2O (water)
3.19
> NH2 H > H
> CH3O
> H2O
3.20 (a) H2 SO4 (b) H3 O+ (c) CH3 NH3 +
(d) NH3 (e) CH3 CH3 (f) CH3 CO2 H
3.21 H2 SO4 > H3 O+ > CH3 CO2 H > CH3 NH3 + > NH3 > CH3 CH3
Lewis Acids and Bases
Cl
3.22 (a) CH3CH2
Cl
AlCl3 Lewis acid
CH3CH2
Cl
Al Cl Cl
Lewis base
F (b) CH3 Lewis base CH3 (c) CH3 Lewis acid C+ CH3 Lewis base + H2O CH3 OH + BF3 Lewis acid CH3 O H CH3 C CH3 OH2
+ +
B F F
CONFIRMING PAGES
P2: PBU/OVY
QC: PBU/OVY
T1: PBU
JWCL234-Solomons-v1
40
Curved-Arrow Notation 3.23 (a) CH3
OH
CH3
O H H
(b) CH3
NH2 +
Cl
CH3
N H
Cl
H (c) H
3.24 (a)
H C C H O BF3 + BF3
+ O BF3 +
H + H F
+
H C C H H + F
(b)
O O
+ BF3
(c)
O H
H + H
Cl O
H Cl
(d)
H + CH3CH2CH2CH2
Li
Li+ + CH3CH2CH2CH3
O
3.25 (a) CH3CH2
O O H +
CH3CH2
C O
+H
O (b) C6H5 S O O H +
C6H5
S O
+ H
(c) No appreciable acid-base reaction takes place because CH3CH2ONa is too weak a base to remove a proton from ethyne. (d) H C C H +
CH2CH3 (from LiCH2CH3)

+
hexane
+ CH3CH3
(e) CH3
CH2
CH2CH3
hexane
CH3
CH2
+ CH3CH3
(from LiCH2CH3)
CONFIRMING PAGES
P2: PBU/OVY
QC: PBU/OVY
T1: PBU
JWCL234-Solomons-v1
ACIDS AND BASES
41
Acid-Base Strength and Equilibrium 3.26 Because the proton attached to the highly electronegative oxygen atom of CH3 OH is much more acidic than the protons attached to the much less electronegative carbon atom.
3.27 CH3CH2
liq. NH3
CH3CH2
+H
3.28 (a) p K a = log 1.77 104 = 4 0.248 = 3.75 (b) K a = 1013 3.29 (a) HB is the stronger acid because it has the smaller p K a . (b) Yes. Since A is the stronger base and HB is the stronger acid, the following acid-base reaction will take place.
A + H B Stronger Stronger base acid pKa =10
B A H + Weaker Weaker acid base pKa = 20
3.30 (a) C6H5 then
C C
C C
H + NaNH2 Na+ + T2O H + NaH
ether
C6H5 C6H5 CH3
C C
C C
Na+ + NH3 T + NaOT
C6H5 (b) CH3 then CH3
CH CH3 CH CH3
CH CH3
O Na+ + H2
O Na+ + D2O
CH3
CH CH3
D + NaOD
(c) CH3CH2CH2OH + NaH then CH3CH2CH2O Na+ + D2O

3.31 (a) CH3 CH2 OH > CH3 CH2 NH2 > CH3 CH2 CH3
+ CH3CH2CH2O Na + H2
CH3CH2CH2OD + NaOD
Oxygen is more electronegative than nitrogen, which is more electronegative than carbon. The O-H bond is most polarized, the N-H bond is next, and the C-H bond is least polarized. (b) CH3 CH2 O < CH3 CH2 NH < CH3 CH2 CH2 The weaker the acid, the stronger the conjugate base.
CONFIRMING PAGES
P2: PBU/OVY
QC: PBU/OVY
T1: PBU
JWCL234-Solomons-v1
42
3.32 (a) CH3C
CH > CH3CH
CH2 > CH3CH2CH3
(b) CH3CHClCO2H > CH3CH2CO2H > CH3CH2CH2OH (c) CH3CH2OH2 > CH3CH2OH > CH3OCH3
+ 3.33 (a) CH3NH3 < CH3NH2 < CH3NH +
(b) CH3O < CH3NH < CH3CH2 (c) CH3C C < CH3CH CH < CH3CH2CH2
General Problems 3.34 The acidic hydrogens must be attached to oxygen atoms. In H3 PO3 , one hydrogen is bonded to a phosphorus atom:
O H O P O H O
3.35 (a) H
O O H H O P O H O +
C O H
C O O

O H
O (b) H C O
+ CH3
C O
O CH3
O (c) H C O
O O CH3 H H C O H +
CH3
(d) H
CH3
I CH3
CH3 + I
CH3 Cl CH2 C + Cl CH3 + H
(e) H
CH2
C CH3
CONFIRMING PAGES
P2: PBU/OVY
QC: PBU/OVY
T1: PBU
JWCL234-Solomons-v1
ACIDS AND BASES
43
3.36 (a) Assume that the acidic and basic groups of glycine in its two forms have acidities and basicities similar to those of acetic acid and methylamine. Then consider the equilibrium between the two forms:
O C
H O
N H Stronger base
CH2
Stronger acid
H Weaker acid
Weaker base
We see that the ionic form contains the groups that are the weaker acid and weaker base. The equilibrium, therefore, will favor this form. (b) The high melting point shows that the ionic structure better represents glycine. 3.37 (a) The second carboxyl group of malonic acid acts as an electron-withdrawing group and stabilizes the conjugate base formed (i.e., HO2 CCH2 CO2 ) when malonic acid loses a proton. [Any factor that stabilizes the conjugate base of an acid always increases the strength of the acid (Section 3.11C).] An important factor here may be an entropy effect as explained in Section 3.10. (b) When O2 CCH2 CO2 H loses a proton, it forms a dianion, O2 CCH2 CO2 . This dianion is destabilized by having two negative charges in close proximity. 3.38 HB is the stronger acid. 3.39
log Keq pKa pKa pKa
= = = =
H T S 6.3 kJ mol1 (298 K)(0.0084 kJ mol1K1) 3.8 kJ mol1 log Ka = pKa = G 2.303RT G = 2.303RT 3.8 kJ mol 1 = (2.303)(0.008314 kJ mol1K1)(298 K) = 0.66
3.40 The dianion is a hybrid of the following resonance structures:

O O
O C
CH2
If we mentally fashion a hybrid of these structures, we see that each carbon-carbon bond is a single bond in three structures and a double bond in one. Each carbon-oxygen bond is a double bond in two structures and a single bond in two structures. Therefore, we would expect all of the carbon-carbon bonds to be equivalent and of the same length, and exactly the same can be said for the carbon-oxygen bonds.
CONFIRMING PAGES
P2: PBU/OVY
QC: PBU/OVY
T1: PBU
JWCL234-Solomons-v1
44
Challenge Problems 3.41 (a) A is CH3 CH2 S C is CH3 CH2 SCH2 CH2 O E is OH

B is CH3 OH D is CH3 CH2 SCH2 CH2 OH
(b) CH3CH2
H + CH3
CH3CH2 CH3CH2
S S
+ CH3 CH2CH2
O O
CH3CH2
S + CH2 CH2 O S CH2CH2 O
CH3CH2
+ H
H S CH2CH2 O H + H O
CH3CH2
3.42 (a) CH3(CH2)8OD + CH3(CH2)8Li
CH3(CH2)8O Li + + CH3(CH2)8 D
Hexane could be used as solvent. Liquid ammonia and ethanol could not because they would compete with CH3 (CH2 )8 OD and generate mostly non-deuterio-labelled CH3 (CH2 )7 CH3 . (b) NH2 + CH3C
CH
NH3 + CH3C
Hexane or liquid ammonia could be used; ethanol is too acidic and would lead to CH3 CH2 O (ethoxide ion) instead of the desired alkynide ion.
(c) HCl +
NH2
NH3 + Cl
Hexane or ethanol could be used; liquid ammonia is too strong a base and would lead to NH4 + instead of the desired anilinium ion.
3.43 (a,b)
O C H N CH3 CH3 H
O C
N CH3
CH3
The uncharged structure on the left is the more important resonance form. (c) Since DMF does not bind with (solvate) anions, their electron density remains high and their size small, both of which make nucleophiles more reactive.
CONFIRMING PAGES
P2: PBU/OVY
QC: PBU/OVY
T1: PBU
JWCL234-Solomons-v1
ACIDS AND BASES
45
3.44 (a)
O
+
O (b)
O (c) H3C O C H3C CH2 + D2O H3C C CH3 + NH2 H3C
O C CH2 O C CH2D + OD + NH3
3.45 The most acidic hydrogen atoms in formamide are bonded to the nitrogen atom. They are acidic due to the electron-withdrawing effect of the carbonyl group and the fact that the resulting conjugate base can be stabilized by resonance delocalization of the negative charge into the carbonyl group. The electrostatic potential map shows deep blue color near the hydrogen atoms bonded to the nitrogen atom, consistent with their relative acidity.
QUIZ
3.1 Which of the following is the strongest acid? (a) CH3 CH2 CO2 H (b) CH3 CH3 (c) CH3 CH2 OH (d) CH2 CH2
3.2 Which of the following is the strongest base? (a) CH3 ONa (b) NaNH2 (c) CH3 CH2 Li (d) NaOH (e) CH3 CO2 Na
3.3 Dissolving NaNH2 in water will give: (a) A solution containing solvated Na+ and NH2 ions. (b) A solution containing solvated Na+ ions, OH ions, and NH3 . (c) NH3 and metallic Na. (d) Solvated Na+ ions and hydrogen gas. (e) None of the above.
CONFIRMING PAGES
P2: PBU/OVY
QC: PBU/OVY
T1: PBU
JWCL234-Solomons-v1
46
3.4 Which base is strong enough to convert (CH3 )3 COH into (CH3 )3 CONa in a reaction that goes to completion? (a) NaNH2 (b) CH3 CH2 Na (c) NaOH (d) CH3 CO2 Na
(e) More than one of the above. 3.5 Which would be the strongest acid? (a) CH3 CH2 CH2 CO2 H (d) CH2 FCH2 CH2 CO2 H (b) CH3 CH2 CHFCO2 H (e) CH3 CH2 CH2 CH2 OH (c) CH3 CHFCH2 CO2 H
3.6 Which would be the weakest base? (a) CH3 CO2 Na (b) CF3 CO2 Na (c) CHF2 CO2 Na (d) CH2 FCO2 Na
3.7 What acid-base reaction (if any) would occur when NaF is dissolved in H2 SO4 ? 3.8 The p K a of CH3 NH3 + equals 10.6; the p K a of (CH3 )2 NH2 + equals 10.7. Which is the stronger base, CH3 NH2 or (CH3 )2 NH? 3.9 Supply the missing reagents.
(a) CH3CH2C CH +
hexane
CH3CH2C (b)
Li
+ CH3CH3
CH3CH2C
CD + LiOD
3.10 Supply the missing intermediates and reagents.
(a) CH3Br + 2 Li (b) + LiBr
CH3 CH3CHCH2OT + LiOT

T2O
(c)
CONFIRMING PAGES

Solomons Organic Chemistry Solution Manual - Chapter 3

Enviado por

Dados do documento

Direitos autorais

Formatos disponíveis

Compartilhar este documento

Compartilhar ou incorporar documento

Opções de compartilhamento

Você considera este documento útil?

Este conteúdo é inapropriado?

Direitos autorais:

Formatos disponíveis

Solomons Organic Chemistry Solution Manual - Chapter 3

Enviado por

Direitos autorais:

Formatos disponíveis

P1: PBU/OVY JWCL234-03

Printer: Bind Rite December 8, 2009 21:29

AN INTRODUCTION TO ORGANIC REACTIONS AND THEIR MECHANISMS: ACIDS AND BASES

F (c) CH3 O CH3 + F

F + F Lewis acid B F CH3

[H3 O+ ][HCO2 ] = 1.77 104 [HCO2 H]

P1: PBU/OVY JWCL234-03

Printer: Bind Rite December 8, 2009 21:29

AN INTRODUCTION TO ORGANIC REACTIONS AND THEIR MECHANISMS

.0042 100 = 4.2% 0.1

P1: PBU/OVY JWCL234-03

Printer: Bind Rite December 8, 2009 21:29

ACIDS AND BASES

(c) G = H T S G = H = 5.71 kJ mol1 if

P1: PBU/OVY JWCL234-03

Printer: Bind Rite December 8, 2009 21:29

AN INTRODUCTION TO ORGANIC REACTIONS AND THEIR MECHANISMS

3.16 (a) CH3O

Stronger acid pKa = 16

H Stronger base (from NaH)

CH3O Weaker base

H2 Weaker acid pKa = 35

Stronger acid pKa = 16

NH2 Stronger base (from NaNH2)

CH3CH2O Weaker base

NH3 Weaker acid pKa = 38

CH3CH3 Weaker acid pKa = 50

Stronger base (from CH3CH2Li)

NH3 Weaker base

NH3 Weaker acid pKa = 38

H Stronger acid pK a = 9.2 (from NH4Cl)

Stronger base (from NaNH2)

Stronger acid pK a = 15.7

Stronger base [from (CH3)3CONa]

+ HOC(CH3)3 Weaker acid p K a = 18

NaH D2O D2O NaH T2O +

H2 NaOD LiOD + + H2 NaOT + LiOD

(c) CH3CH2Li (d) CH3CH2OH (e) CH3CH2ONa

P1: PBU/OVY JWCL234-03

Printer: Bind Rite December 8, 2009 21:29

ACIDS AND BASES

(the ethynide ion)

(the hydroxide ion)

(the methoxide ion)

(the hydride ion)

> NH2 H > H

3.20 (a) H2 SO4 (b) H3 O+ (c) CH3 NH3 +

(d) NH3 (e) CH3 CH3 (f) CH3 CO2 H

Lewis Acids and Bases

AlCl3 Lewis acid

P1: PBU/OVY JWCL234-03

Printer: Bind Rite December 8, 2009 21:29

AN INTRODUCTION TO ORGANIC REACTIONS AND THEIR MECHANISMS

Curved-Arrow Notation 3.23 (a) CH3

CH2CH3 (from LiCH2CH3)

P1: PBU/OVY JWCL234-03

Printer: Bind Rite December 8, 2009 21:29

ACIDS AND BASES

A + H B Stronger Stronger base acid pKa =10

B A H + Weaker Weaker acid base pKa = 20

3.30 (a) C6H5 then

H + NaNH2 Na+ + T2O H + NaH

C6H5 C6H5 CH3

Na+ + NH3 T + NaOT