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Appendix
A
pKa Values for Selected
Compounds
Compound
pKa
HI
–10
HBr
–9
H2SO4
–9
Compound
Br
pKa
COOH
4.0
+OH
CH3
C
CH3
SO3H
HCl
–7
–7
+
[(CH3)2OH]
–3.8
[CH3OH2]+
–2.5
H3O
+
C
0.0
NH2
CF3COOH
0.2
CCl3COOH
0.6
+
O2N
NH3
1.3
H3PO4
2.1
FCH2COOH
2.7
ClCH2COOH
2.8
BrCH2COOH
2.9
ICH2COOH
3.2
HF
3.2
COOH
+
+
NH3
4.3
4.5
4.6
NH3
CH3COOH
4.8
(CH3)3CCOOH
5.0
+
CH3
NH3
5.1
5.2
+
N
H
+
CH3O
NH3
5.3
H2CO3
6.4
H2S
7.0
O2N
OH
SH
3.4
3.8
HCOOH
Br
COOH
1.0
Cl2CHCOOH
O2N
COOH
CH3O
–1.2
+OH
CH3
CH3
–1.7
CH3SO3H
4.2
COOH
–7.3
CH3
O
7.1
7.8
O
8.9
3.9
H
A-1
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Appendix A
A-2
pKa Values for Selected Compounds
Compound
pKa
Compound
pKa
HC –
–N
9.1
CH3OH
15.5
Cl
OH
9.4
H2O
15.7
CH3CH2OH
16
NH4+
9.4
CH3CONH2
16
H3NCH2COO–
9.8
CH3CHO
17
(CH3)3COH
18
10.0
–O
(CH3)2C –
19.2
CH3CO2CH2CH3
24.5
10.2
HC –
– CH
CH3C –
–N
25
25
HCO3–
10.2
CHCl3
25
CH3NO2
10.2
CH3CON(CH3)2
30
H2
35
NH3
38
CH3NH2
40
+
OH
CH3
OH
NH2
OH
10.3
CH3CH2SH
10.5
+
10.6
[(CH3)3NH]
O
O
OEt
CH3
41
H
43
10.7
H
[CH3NH3]+
10.7
+
NH3
CH2 –
– CHCH3
43
– CH2
CH2 –
44
10.7
H
[(CH3)2NH2]
+
CF3CH2OH
O
46
10.7
CH4
50
12.4
CH3CH3
50
O
EtO
OEt
13.3
H
H
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15
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Appendix
B
Nomenclature
Although the basic principles of nomenclature are presented in the body of this text, additional
information is often needed to name many complex organic compounds. Appendix B concentrates on three topics:
• Naming alkyl substituents that contain branching
• Naming polyfunctional compounds
• Naming bicyclic compounds
Naming Alkyl Substituents That Contain Branching
Alkyl groups that contain any number of carbons and no branches are named as described in Section 4.4A: change the -ane ending of the parent alkane to the suffix -yl. Thus the seven-carbon
alkyl group CH3CH2CH2CH2CH2CH2CH2 – is called heptyl.
When an alkyl substituent also contains branching, follow a stepwise procedure:
[1] Identify the longest carbon chain of the alkyl group that begins at the point of attachment
to the parent. Begin numbering at the point of attachment and use the suffix -yl to indicate
an alkyl group.
1
2
3
1
4
Start numbering here.
4 C’s in the chain
butyl group
2
3
5
4
Start numbering here.
5 C’s in the chain
pentyl group
[2] Name all branches off the main alkyl chain and use the numbers from Step [1] to designate
their location.
methyl groups at C1 and C3
methyl group at C3
1
2
3
4
3-methylbutyl
1
2
3
5
4
1,3-dimethylpentyl
A-3
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Appendix B
Nomenclature
A-4
[3] Set the entire name of the substituent in parentheses, and alphabetize this substituent name
by the first letter of the complete name.
C1 of the six-membered ring
(3-methylbutyl)cyclohexane
1-(1,3-dimethylpentyl)-2-methylcyclohexane
• Alphabetize the d of dimethylpentyl before the m of methyl.
• Number the ring to give the lower number to the first substituent
alphabetically: place the dimethylpentyl group at C1.
Naming Polyfunctional Compounds
Many organic compounds contain more than one functional group. When one of those functional
groups is halo (X – ) or alkoxy (RO – ), these groups are named as substituents as described in
Sections 7.2 and 9.3B. To name other polyfunctional compounds, we must learn which functional group is assigned a higher priority in the rules of nomenclature. Two steps are usually
needed:
[1] Name a compound using the suffix of the highest priority group, and name other
functional groups as substituents. Table B.1 lists the common functional groups in order of
decreasing priority, as well as the prefixes needed when a functional group must be named
as a substituent.
[2] Number the carbon chain to give the lower number to the highest priority functional group,
and then follow all other rules of nomenclature. Examples are shown in Figure B.1.
Polyfunctional compounds that contain C – C double and triple bonds have characteristic suffixes
to identify them, as shown in Table B.2. The higher priority functional group is assigned the
lower number.
Increasing priority
Table B.1 Summary of Functional Group Nomenclature
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Functional group
Suffix
Substituent name (prefix)
Carboxylic acid
-oic acid
carboxy
Ester
-oate
alkoxycarbonyl
Amide
-amide
amido
Nitrile
-nitrile
cyano
Aldehyde
-al
– O) or formyl ( – CHO)
oxo ( –
Ketone
-one
oxo
Alcohol
-ol
hydroxy
Amine
-amine
amino
Alkene
-ene
alkenyl
Alkyne
-yne
alkynyl
Alkane
-ane
alkyl
Ether
—
alkoxy
Halide
—
halo
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A-5
Appendix B
Nomenclature
Figure B.1
NH2
Examples of nomenclature of
polyfunctional compounds
2
3
O
CN
highest priority
1 H
COOH
OH
3-amino-2-hydroxybutanal
higher priority
o-cyanobenzoic acid
Name as a derivative of an aldehyde since
CHO is the highest priority functional group.
Name as a derivative of benzoic acid since
COOH is the higher priority functional group.
O
highest priority
O
4
NH2
higher priority
H
1 OCH
3
O
O
methyl 4-oxohexanoate
OCH3
4-formyl-3-methoxycyclohexanecarboxamide
Name as a derivative of an ester since
COOR is the higher priority functional group.
Name as a derivative of an amide since
CONH2 is the highest priority functional group.
Table B.2 Naming Polyfunctional Compounds with C– C Double and Triple Bonds
Functional groups
Suffix
– C and OH
C–
enol
Example
Start numbering here.
OH
5-methyl-4-hexen-1-ol
C–
– C + C–
– O (ketone)
enone
Start numbering here.
O
(4E )-4-hepten-3-one
– C + C–
C–
–C
enyne
Start numbering here.
HC CCH2CH2CH CH2
1-hexen-5-yne
Naming Bicyclic Compounds
Bicyclic ring systems—compounds that contain two rings that share one or two carbon atoms—
can be bridged, fused, or spiro.
bridged ring
fused ring
spiro ring
• A bridged ring system contains two rings that share two non-adjacent carbons.
• A fused ring system contains two rings that share a common carbon–carbon bond.
• A spiro ring system contains two rings that share one carbon atom.
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Appendix B
Nomenclature
A-6
Fused and bridged ring systems are named as bicyclo[x.y.z]alkanes, where the parent alkane
corresponds to the total number of carbons in both rings. The numbers x, y, and z refer to the
number of carbons that join the shared carbons together, written in order of decreasing size. For
a fused ring system, z always equals zero, because the two shared carbons are directly joined
together. The shared carbons in a bridged ring system are called the bridgehead carbons.
1 C joining the bridgehead C’s
C
C
C
C
C
8 C’s in the ring system
3 C’s joining the bridgehead C’s
C
2 C’s joining the bridgehead C’s
Name: bicyclo[3.2.1]octane
bicyclooctane
C
C
10 C’s in the ring system
C
C
C
C
C
4 C’s joining the common C’s
C
No C’s join the shared C’s at the ring fusion.
4 C’s joining the common C’s
Name: bicyclo[4.4.0]decane
bicyclodecane
Rings are numbered beginning at a shared carbon, and continuing around the longest bridge
first, then the next longest, and so forth.
Start numbering here.
8
7
6
1
Start numbering here.
7
1
6
2
5 4
5
4
2
3
3
3,3-dimethylbicyclo[3.2.1]octane
7,7-dimethylbicyclo[2.2.1]heptane
Spiro ring systems are named as spiro[x.y]alkanes where the parent alkane corresponds to the
total number of carbons in both rings, and x and y refer to the number of carbons that join the
shared carbon (the spiro carbon), written in order of increasing size. When substituents are present, the rings are numbered beginning with a carbon adjacent to the spiro carbon in the smaller
ring.
6
7
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5
3
4
8
2
1
Start numbering here.
10 C’s in the ring system
8 C’s in the ring system
Name: spiro[4.5]decane
Name: 2-methylspiro[3.4]octane
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Appendix
C
Bond Dissociation Energies
for Some Common Bonds
[A– B → A• + •B]
Bond
∆Ho kJ/mol
(kcal/mol)
H – Z bonds
H– F
569
(136)
H – Cl
431
(103)
H – Br
368
(88)
H– I
297
(71)
H – OH
498
(119)
H– H
435
(104)
F– F
159
(38)
Z – Z bonds
Cl – Cl
242
(58)
Br – Br
192
(46)
I– I
151
(36)
HO – OH
213
(51)
CH3 – H
435
(104)
CH3CH2 – H
410
(98)
CH3CH2CH2 – H
410
(98)
(CH3)2CH – H
397
(95)
(CH3)3C – H
381
(91)
– CH – H
CH2 –
435
(104)
HC –
– C– H
CH2 –
– CHCH2 – H
523
(125)
364
(87)
C6H5 – H
460
(110)
C6H5CH2 – H
356
(85)
CH3 – CH3
368
(88)
CH3 – CH2CH3
356
(85)
– CH2
CH3 – CH –
385
(92)
CH3 – C –
– CH
489
(117)
R – H bonds
R – R bonds
A-7
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Appendix C
Bond Dissociation Energies for Some Common Bonds [A – B → A• + •B]
Bond
∆Ho kJ/mol
(kcal/mol)
456
(109)
A-8
R – X bonds
CH3 – F
CH3 – Cl
351
(84)
CH3 – Br
293
(70)
CH3 – I
234
(56)
CH3CH2 – F
448
(107)
CH3CH2 – Cl
339
(81)
CH3CH2 – Br
285
(68)
CH3CH2 – I
222
(53)
(CH3)2CH – F
444
(106)
(CH3)2CH – Cl
335
(80)
(CH3)2CH – Br
285
(68)
(CH3)2CH – I
222
(53)
(CH3)3C – F
444
(106)
(CH3)3C – Cl
331
(79)
(CH3)3C – Br
272
(65)
(CH3)3C – I
209
(50)
R – OH bonds
CH3 – OH
389
(93)
CH3CH2 – OH
393
(94)
CH3CH2CH2 – OH
385
(92)
(CH3)2CH – OH
401
(96)
(CH3)3C – OH
401
(96)
– CH2
CH2 –
635
(152)
HC –
– CH
–
O– C–
–O
837
(200)
535
(128)
O2
497
(119)
Other bonds
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Appendix
D
Reactions That Form
Carbon–Carbon Bonds
Section
Reaction
11.11A
SN2 reaction of an alkyl halide with an acetylide anion, –C –
– CR
11.11B
Opening of an epoxide ring with an acetylide anion, –C –
– CR
15.14
Radical polymerization of an alkene
16.12
Diels–Alder reaction
18.5
Friedel–Crafts alkylation
18.5
Friedel–Crafts acylation
20.10
Reaction of an aldehyde or ketone with a Grignard or organolithium reagent
20.13A
Reaction of an acid chloride with a Grignard or organolithium reagent
20.13A
Reaction of an ester with a Grignard or organolithium reagent
20.13B
Reaction of an acid chloride with an organocuprate reagent
20.14A
Reaction of a Grignard reagent with CO2
20.14B
Reaction of an epoxide with an organometallic reagent
20.15
Reaction of an α,β-unsaturated carbonyl compound with an organocuprate reagent
21.9
Cyanohydrin formation
21.10
Wittig reaction to form an alkene
22.18
SN2 reaction of an alkyl halide with NaCN
22.18C
Reaction of a nitrile with a Grignard or organolithium reagent
23.8
Direct enolate alkylation using LDA and an alkyl halide
23.9
Malonic ester synthesis to form a carboxylic acid
23.10
Acetoacetic ester synthesis to form a ketone
24.1
Aldol reaction to form a β-hydroxy carbonyl compound or an α,β-unsaturated
carbonyl compound
24.2
Crossed aldol reaction
24.3
Directed aldol reaction
24.5
Claisen reaction to form a β-keto ester
24.6
Crossed Claisen reaction to form a β-dicarbonyl compound
24.7
Dieckmann reaction to form a five- or six-membered ring
24.8
Michael reaction to form a 1,5-dicarbonyl compound
24.9
Robinson annulation to form a 2-cyclohexenone
25.14
Reaction of a diazonium salt with CuCN
26.1
Coupling of an organocuprate reagent (R2CuLi) with an organic halide (R'X)
26.2
The palladium-catalyzed Suzuki reaction of an organic halide with an organoborane
26.3
The palladium-catalyzed Heck reaction of a vinyl or aryl halide with an alkene
26.4
Addition of a dihalocarbene to an alkene to form a cyclopropane
26.5
Simmons–Smith reaction of an alkene with CH2I2 and Zn(Cu) to form a
cyclopropane
26.6
Olefin metathesis
27.10B
Kiliani–Fischer synthesis of an aldose
28.2B
Alkylation of diethyl acetamidomalonate to form an amino acid
28.2C
Strecker synthesis of an amino acid
30.2
Chain-growth polymerization
30.4
Polymerization using Ziegler–Natta catalysts
A-9
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Appendix
E
Characteristic IR Absorption
Frequencies
Functional group
Wavenumber (cm–1)
• ROH
3600–3200
broad, strong
• RCOOH
3500–2500
very broad, strong
• RNH2
3500–3300
two peaks
• R2NH
3500–3300
one peak
• RCONH2, RCONHR
3400–3200
one or two peaks; N – H
bending also observed at
1640 cm–1
• Csp – H
3300
sharp, often strong
• Csp2 – H
3150–3000
medium
• Csp3 – H
3000–2850
strong
2830–2700
one or two peaks
C–
–C
2250
medium
C–
–N
2250
medium
Bond
Comment
O– H
N– H
C– H
• Csp
2
– H of RCHO
–O
C–
strong
• RCOCl
1800
• (RCO)2O
1800, 1760
two peaks
• RCOOR
1745–1735
increasing ν~ with decreasing
ring size
• RCHO
1730
• R2CO
1715
• R2CO, conjugated
1680
• RCOOH
1710
• RCONH2, RCONHR,
RCONR2
1680–1630
increasing ν~ with decreasing
ring size
increasing ν~ with decreasing
ring size
C–
–C
–N
C–
• Alkene
1650
medium
• Arene
1600, 1500
medium
1650
medium
A-10
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Appendix
F
Characteristic NMR Absorptions
1
H NMR Absorptions
Compound type
Chemical shift (ppm)
Alcohol
1–5
R O H
H
3.4–4.0
R C O
Aldehyde
O
R
C
9–10
H
Alkane
0.9–2.0
RCH3
~0.9
R2CH2
~1.3
R3CH
~1.7
Alkene
H
sp 2 C – H
C C
4.5–6.0
C H
C C
allylic sp 3 C – H
1.5–2.5
Alkyl halide
H
R C F
4.0–4.5
H
R C Cl
3.0–4.0
H
R C Br
2.7–4.0
H
R C I
2.2–4.0
Alkyne
C C H
~2.5
A-11
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Compound type
Chemical shift (ppm)
Amide
O
R
C
7.5–8.5
N H
Amine
0.5–5.0
R N H
H
2.3–3.0
R C N
Aromatic compound
H
sp 2 C – H
C H
benzylic sp 3 C – H
6.5–8
1.5–2.5
Carbonyl compound
O
C
C
H
sp3 C – H on the α carbon
2.0–2.5
Carboxylic acid
O
R
Ether
C
10–12
OH
H
3.4–4.0
R C O R
13
C NMR Absorptions
Carbon type
Structure
Chemical shift (ppm)
Alkyl, sp3 hybridized C
C H
5–45
Alkyl, sp3 hybridized C bonded
to N, O, or X
C Z
30–80
Z = N, O, X
Alkynyl, sp hybridized C
C C
65–100
Alkenyl, sp2 hybridized C
C C
100–140
C
120–150
Aryl, sp2 hybridized C
Carbonyl C
C O
160–210
A-12
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Appendix
G
General Types
of Organic Reactions
Substitution Reactions
[1] Nucleophilic substitution at an sp3 hybridized carbon atom
Nu–
nucleophile
R Nu
+
R X
+
a. Alkyl halides (Chapter 7)
R X
b. Alcohols (Section 9.11)
R OH
c. Ethers (Section 9.14)
R OR'
+
HX
HX
+
+
X
–
H2O
+ R' X
R X
+
H2O
X = Br or I
d. Epoxides (Section 9.15)
O
C C
[1] Nu–
OH
[2] H2O
or
HZ
Nu or Z = nucleophile
C C
Nu
(Z)
[2] Nucleophilic acyl substitution at an sp2 hybridized carbon atom
Carboxylic acids and their
derivatives (Chapter 22)
O
R
C
O
Z
+
Nu–
nucleophile
R
C
+
Nu
Z–
Z = OH, Cl, OCOR,
OR', NR'2
[3] Radical substitution at an sp3 hybridized C – H bond
Alkanes (Section 15.3)
R H
+
X2
+
E+
hν or ∆
+
R X
HX
[4] Electrophilic aromatic substitution
Aromatic compounds
(Chapter 18)
H
E
+
H+
electrophile
A-13
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Appendix G
A-14
General Types of Organic Reactions
Elimination Reactions
a Elimination at an sp3 hybridized carbon atom
a. Alkyl halides
(Chapter 8)
C C
+
H X
b. Alcohols
(Section 9.8)
B
base
H B+
+
X
–
new π bond
HA
C C
+
C C
H OH
+
C C
H2O
new π bond
Addition Reactions
[1] Electrophilic addition to carbon–carbon multiple bonds
a. Alkenes
(Chapter 10)
C C
b. Alkynes
(Section 11.6)
C C
+
X Y
+
C C
X Y
X
Y
X
Y
C C
X
Y
[2] Nucleophilic addition to carbon–oxygen multiple bonds
Aldehydes and ketones
(Chapter 21)
O
R
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C
H(R')
+
–
Nu
nucleophile
H2O
OH
R C H(R')
Nu
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Appendix
H
How to Synthesize Particular
Functional Groups
Acetals
• Reaction of an aldehyde or ketone with two equivalents of an alcohol (21.14)
Acid chlorides
• Reaction of a carboxylic acid with thionyl chloride (22.10)
Alcohols
• Nucleophilic substitution of an alkyl halide with –OH or H2O (9.6)
•
•
•
•
•
•
•
•
•
•
•
•
•
Hydration of an alkene (10.12)
Hydroboration–oxidation of an alkene (10.16)
Reduction of an epoxide with LiAlH4 (12.6)
Reduction of an aldehyde or ketone (20.4)
Hydrogenation of an α,β-unsaturated carbonyl compound with H2 + Pd-C (20.4C)
Enantioselective reduction of an aldehyde or ketone with the chiral CBS reagent (20.6)
Reduction of an acid chloride with LiAlH4 (20.7)
Reduction of an ester with LiAlH4 (20.7)
Reduction of a carboxylic acid with LiAlH4 (20.7)
Reaction of an aldehyde or ketone with a Grignard or organolithium reagent (20.10)
Reaction of an acid chloride with a Grignard or organolithium reagent (20.13)
Reaction of an ester with a Grignard or organolithium reagent (20.13)
Reaction of an organometallic reagent with an epoxide (20.14B)
Aldehydes
• Hydroboration–oxidation of a terminal alkyne (11.10)
• Oxidative cleavage of an alkene with O3 followed by Zn or (CH3)2S (12.10)
• Oxidation of a 1° alcohol with PCC (12.12)
• Oxidation of a 1° alcohol with HCrO4–, Amberlyst A-26 resin (12.13)
•
•
•
•
•
Reduction of an acid chloride with LiAlH[OC(CH3)3]3 (20.7)
Reduction of an ester with DIBAL-H (20.7)
Hydrolysis of an acetal (21.14B)
Hydrolysis of an imine or enamine (21.12B)
Reduction of a nitrile (22.18B)
Alkanes
• Catalytic hydrogenation of an alkene with H2 + Pd-C (12.3)
• Catalytic hydrogenation of an alkyne with two equivalents of H2 + Pd-C (12.5A)
• Reduction of an alkyl halide with LiAlH4 (12.6)
A-15
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Appendix H
How to Synthesize Particular Functional Groups
A-16
• Reduction of a ketone to a methylene group (CH2)—the Wolff–Kishner or Clemmensen
reaction (18.14B)
• Protonation of an organometallic reagent with H2O, ROH, or acid (20.9)
• Coupling of an organocuprate reagent (R2CuLi) with an alkyl halide, R'X (26.1)
• Simmons–Smith reaction of an alkene with CH2I2 and Zn(Cu) to form a cyclopropane
(26.5)
Alkenes
• Dehydrohalogenation of an alkyl halide with base (8.3)
• Dehydration of an alcohol with acid (9.8)
• Dehydration of an alcohol using POCl3 and pyridine (9.10)
• β Elimination of an alkyl tosylate with base (9.13)
• Catalytic hydrogenation of an alkyne with H2 + Lindlar catalyst to form a cis alkene
(12.5B)
• Dissolving metal reduction of an alkyne with Na, NH3 to form a trans alkene (12.5C)
• Wittig reaction (21.10)
• β Elimination of an α-halo carbonyl compound with Li2CO3, LiBr, and DMF (23.7C)
• Hofmann elimination of an amine (25.12)
• Coupling of an organocuprate reagent (R2CuLi) with an organic halide, R'X (26.1)
• The palladium-catalyzed Suzuki reaction of a vinyl or aryl halide with a vinyl- or arylborane
(26.2)
• The palladium-catalyzed Heck reaction of a vinyl or aryl halide with an alkene (26.3)
• Olefin metathesis (26.6)
Alkyl halides
• Reaction of an alcohol with HX (9.11)
• Reaction of an alcohol with SOCl2 or PBr3 (9.12)
• Cleavage of an ether with HBr or HI (9.14)
• Hydrohalogenation of an alkene with HX (10.9)
• Halogenation of an alkene with X2 (10.13)
• Hydrohalogenation of an alkyne with two equivalents of HX (11.7)
• Halogenation of an alkyne with two equivalents of X2 (11.8)
• Radical halogenation of an alkane (15.3)
• Radical halogenation at an allylic carbon (15.10)
• Radical addition of HBr to an alkene (15.13)
• Electrophilic addition of HX to a 1,3-diene (16.10)
• Radical halogenation of an alkyl benzene (18.13)
• Halogenation α to a carbonyl group (23.7)
• Addition of a dihalocarbene to an alkene to form a dihalocyclopropane (26.4)
Alkynes
• Dehydrohalogenation of an alkyl dihalide with base (11.5)
• SN2 reaction of an alkyl halide with an acetylide anion, –C –– CR (11.11)
Amides
• Reaction of an acid chloride with NH3 or an amine (22.8)
• Reaction of an anhydride with NH3 or an amine (22.9)
• Reaction of a carboxylic acid with NH3 or an amine and DCC (22.10)
• Reaction of an ester with NH3 or an amine (22.11)
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A-17
Appendix H
How to Synthesize Particular Functional Groups
Amines
• Reduction of a nitro group (18.14C)
• Reduction of an amide with LiAlH4 (20.7B)
• Reduction of a nitrile (22.18B)
• SN2 reaction using NH3 or an amine (25.7A)
• Gabriel synthesis (25.7A)
• Reductive amination of an aldehyde or ketone (25.7C)
Amino acids
• SN2 reaction of an α-halo carboxylic acid with excess NH3 (28.2A)
• Alkylation of diethyl acetamidomalonate (28.2B)
• Strecker synthesis (28.2C)
• Enantioselective hydrogenation using a chiral catalyst (28.4)
Anhydrides
• Reaction of an acid chloride with a carboxylate anion (22.8)
• Dehydration of a dicarboxylic acid (22.10)
Aryl halides
• Halogenation of benzene with X2 + FeX3 (18.3)
• Reaction of a diazonium salt with CuCl, CuBr, HBF4, NaI, or KI (25.14A)
Carboxylic acids
• Oxidative cleavage of an alkyne with ozone (12.11)
• Oxidation of a 1° alcohol with CrO3 (or a similar Cr6+ reagent), H2O, H2SO4 (12.12B)
• Oxidation of an alkyl benzene with KMnO4 (18.14A)
• Oxidation of an aldehyde (20.8)
• Reaction of a Grignard reagent with CO2 (20.14A)
• Hydrolysis of a cyanohydrin (21.9)
• Hydrolysis of an acid chloride (22.8)
• Hydrolysis of an anhydride (22.9)
• Hydrolysis of an ester (22.11)
• Hydrolysis of an amide (22.13)
• Hydrolysis of a nitrile (22.18A)
• Malonic ester synthesis (23.9)
Cyanohydrins
• Addition of HCN to an aldehyde or ketone (21.9)
1,2-Diols
• Anti dihydroxylation of an alkene with a peroxyacid, followed by ring opening with –OH or
H2O (12.9A)
• Syn dihydroxylation of an alkene with KMnO4 or OsO4 (12.9B)
Enamines
• Reaction of an aldehyde or ketone with a 2° amine (21.12)
Epoxides
• Intramolecular SN2 reaction of a halohydrin using base (9.6)
• Epoxidation of an alkene with mCPBA (12.8)
• Enantioselective epoxidation of an allylic alcohol with the Sharpless reagent (12.15)
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Appendix H
How to Synthesize Particular Functional Groups
A-18
Esters
• SN2 reaction of an alkyl halide with a carboxylate anion, RCOO– (7.19)
• Reaction of an acid chloride with an alcohol (22.8)
• Reaction of an anhydride with an alcohol (22.9)
• Fischer esterification of a carboxylic acid with an alcohol (22.10)
Ethers
• Williamson ether synthesis—SN2 reaction of an alkyl halide with an alkoxide, –OR (9.6)
• Reaction of an alkyl tosylate with an alkoxide, –OR (9.13)
• Addition of an alcohol to an alkene in the presence of acid (10.12)
• Anionic polymerization of epoxides to form polyethers (30.3)
Halohydrins
• Reaction of an epoxide with HX (9.15)
• Addition of X and OH to an alkene (10.15)
Imine
• Reaction of an aldehyde or ketone with a 1° amine (21.11)
Ketones
• Hydration of an alkyne with H2O, H2SO4, and HgSO4 (11.9)
• Oxidative cleavage of an alkene with O3 followed by Zn or (CH3)2S (12.10)
•
•
•
•
•
•
•
Oxidation of a 2° alcohol with any Cr6+ reagent (12.12, 12.13)
Friedel–Crafts acylation (18.5)
Reaction of an acid chloride with an organocuprate reagent (20.13)
Hydrolysis of an imine or enamine (21.12B)
Hydrolysis of an acetal (21.14B)
Reaction of a nitrile with a Grignard or organolithium reagent (22.18C)
Acetoacetic ester synthesis (23.10)
Nitriles
• SN2 reaction of an alkyl halide with NaCN (7.19, 22.18)
• Reaction of an aryl diazonium salt with CuCN (25.14A)
Phenols
• Reaction of an aryl diazonium salt with H2O (25.14A)
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