Appendlces

APPENDIX I.

SU BSTITUTIVE NOM ENCLATU RE

OF ORGANIC COMPOUNDS
The substitutive name of an organic compound is based on its principal group and principal
chain.
T\re principal group is assigned according to the following priorities:

il

tl

ll

-C-OH

(carborylic acid)

>

-C-O-C-

-C-X

(anhydride)

>

il

-C-OR

(ester)

o
il

(acid halide)

>

ll

-C-NR2

(amide)

>

-C-$

(nitrile)

>

il

-C-H

(aldehyde)

>

o
ll

-C-

(ketone)

TI.rc principal chain

>

-OH

(alcohol, phenol)

>

-SH

(thiol) >

-NRz

(amine)

is identifiedby applying the following criteria in order until a decision

can be made.

1. Maximum number of substituents corresponding to the principal group

2. Maximum number of double and triple bonds considered together
3. Maximum length
4. Maximum number of substituents cited as prefixes

A-1

A,-2

APPE

Dtc

ES

A principal chain is numbered by applying the following criteria in order until there is no
ambiguity. Where multiple numbers are possible, comparisons are made at the first point of
difference.

l.

Lowest number for the principal group cited as a suffix-that is, the group on which the

name is based
2. Lowest numbers for multiple bonds, with double bonds having priority over triple bonds

in case of ambiguity

3. Lowest numbers for other substituents, taking into account the "first point of difference"
rule (p. 62, rule 8)
4. Lowest number for the substituent named as a prefix that is cited first in the name

The name ts constructed starting with the hydrocarbon corresponding to the principal
chain.

1. Cite the principal group by its suffix and number; its number is the last one cited in the
name.

2. lf there is no principal group, name the compound as a substituted hydrocarbon.

3. Cite the names and numbers of the other substituents in alphabetical order at the begin,
ning of the name.
These lists cover most of the cases cited in the text. (See Study Problems 8.1-8.3,
pp.328-331, for illustrations.) For a more complete discussion of nomenclature, see Nomenclature of Organic Chemistry, 1979 Edition, by the International Union of Pure and Applied
Chemistry, published by Pergamon Press.
In 1993, the IUPAC released A Guide to IUPAC Nomenclature of Organic Compounds
Recommendations 1993, by R. Panico, W. H. Powell, and Jean-Claude Richer (senior editor),
Blackwell Science. This publication advocated one major change that affects the nomenclature of relatively simple compounds. This change involves the way that principal groups are
cited. The 1993 Recommendations cite the principal group or multiple bond position with a
number preceding the suffix itself, whereas the 1979 Recommendarlons (followed in this text)
cite the principal group or multiple bond position with a number preceding the hydrocarbon
name. These differences are best illustrated by example.

H:C-CHCH2CHTCH-3
1

97 9

99

Recornrtendatio

ns

3 Recornntendations:

HOCH2CH2CH2CH2CHT

HOCH2CH2CH2CH:CH:

-pentene

1-pentanol

4-penten- l -ol

pent- l -ene

pentan- l -ol

pent-4-en- l -ol

The 1993 Recommendationshave not yet been generally adopted. Thus, names that adhere

to either set of recommendations are acceptable.

APPENDIX II. INFRARED ABSORPTIONS OF ORGANIC COMPOUNDS

This table presents a summary of the important infrared absorptions discussed in this text. For
more detailed tables, the reader may wish to consult more specialized texts, such as Infrared
Absorption spectroscopy, by Koji Nakanishi and Philippa H. Solomon, San Francisco:
Holden-Day, 1977; or Organic Structure Analysis, by Philip Crews, Jaime Rodriguez, and
Marcel Jaspars, 1998, Oxford University Press, Chapter 8.

APPENDIX II. INFRARED ABSORPTIONS OF ORGANIC

Typeofabsorption FrEquency,Gm-r(lntensity)*

COMPOUNDS A.3

Comment

Alkanes

stretch

C-H

2850-3000

(m)

occurs in all compounds with aliphatic

C-H

bonds

C-O

bonds:

Alkenes

C:C

stretch
t

-CH:CHz
C:

640 (m)

16ss (m)

CHr

1660-1025

others

:C-H

stretch

:C-H

bend

(w)

not observed if alkene

is symmetrical

3000-31 00 (m)

910-990

-CH:CHz

(s)

C:CH,

8e0

\/C:C
/\

960-980

(s)

\/
/\

675-730

(s\

\/C:C
/\

800-8a0

(s)

(s)

HH
r-f
L-L

position is highly variable

Alcohols and Phenols

O-H stretch
C-O stretch

3200-3400

(s)

1050-1 250

(s)

also present in other compounds with

ethers, esters, etc.

Alkynes

C:C

stretch

-C-H

2100-2200
3300

stretch

(m)

not present or weak in many internal alkynes

present in 1-alkynes only

(s)

Aromatic Compounds
rh

500, t 600 (s)

C:C

stretch

C-H

bend

650-750

strong; (m)

(s)

1660-2000 (w)

overtone
*(s)

two absorptions

medium; (w)

weak.
(Table continues)

A-4

APPENDTcES

Type of

absorption

Frequency, cm-l

(lntensity)*

Comment

Aldehydes

C:O

stretch
ordinary

a,p-unsaturated
benzaldehydes

C-H

1720-1725 (s)
1680-1690 (s)
1700 (s)

zz20 (m)

stretch

Kctones

C:O

stretch

(s)

ordinary

1710-171 5

d,&unsaturatd
ketones

l67G-168O (s)
1680-1690 (s)

aryl

increases with decreasing ring size (Table 2t .3,

p.996)

Carborylic Acids

C:O

stretch
ordinary

t 710 (s)

benzoic

1680-1690

(s)

2400-3000

(s)

O-H

acids

stretch

very broad
Esterc and Lactonet

C:O

stretch

1735-1745

(s)

increases with decreasing ring size (Table 21.3,

p.996)
Acid Chlorides

C:O

stretch

1800

(s)

a second weaker band sometimes observed

r

at

700-1 750

Anhydrides

C:O

stretch

two bands; increases with decreasing ring size

1760,1820 (s)

in cyclic anhydrides

Amldesand Lactams

C:O

stretch

165G1655

(s)

increases with decreasing ring size (Table 21.3,

p.996)

N-H bend

1640

N-H

3200-3400 (m)

stretch

(s)

doublet absorption observed for some

primary amides

Nitriles

C-N

stretch

2200-2250 (m)

stretch

3200-337s (m)

Amines

N-H
*(s)

strong; (m)

medium; (w)

weak.

several absorptions sometimes observed,

especially for primary amines

APPENDIX III. PROTON NMR CHEMICAL SHIFTS IN ORGANIC

COMPOUNDS A-5

APPENDIX III. PROTON NMR CHEMICAL SHIFTS

IN ORGANIC COMPOUNDS
This appendix is subdivided into a table of chemical shifts for protons that are pa rt of functtonal
groups and a table of chemical shifts for protons that are adjacenfto functional groups.

A.

Protons within Functional Groups

Chemical shift, ppm

Group

tl
-C-C-H
tl
\/r-a
\_-\/\

0
4.7

-1

.5

ll

-c-H

9-1

-O-H

Chemical shift, ppm

Group

tl

4.6-5.7

-C-N-H

7.s-9.5

varies with solvent and

with acidity of O-H

-c-NH-

0.s-1.5

-c-c-H

/Y*

1.7-2.s

GNH-

6.5-8.5

2.s-3.s

B. Protons Adjacent to Functional Groups

In this table, a range of chemical shifts is given for protons in the general environment
I

H-C-G
in which G is a group listed in column 1, and the two other bonds are to carbon or hydrogen.
The remaining columns give the approximate chemical shifts for methyl protons (H3C-G),
methylene protons (-CH2-G), and methine protons (-CH-G), respectively. The shifts
in the following table are typical; some variation with structure of a few tenths of a ppm can be
expected. The chemical shifts of methine protons are usually further downfield than those of
methylene protons, which are further downfield than methyl protons. Each additional carbon
substitution increases the chemical shift by 0.3-1.0 ppm.

A-6

APPENDTcES

Chemical shift of
Chemical shift

H3C-G, ppm

Group, G

of

Chemical shift

-CH'-G,

of

ppm

I
I

-CH-G,ppm

0.2

-H
-CR,

0.9

1.2

1.4

-F

4.3

4.5

4.8

-cl

3.0

3.4

4.0

-Br

2.7

3.4

4.1

-l

2"2

3.2

4.2

1.8

2.4

2.3

2.2

2.8

-CR:CRz
:
(R

H, alkyl)

-C_CR

(R

- alkyl, H)

RO-

(R

alkyl, H)

3.3 (R

3.s (R

alkyl)
H)

RO-

(R

aryl)

3.7

4.0

4.6

RS-

(R

alkyl, H)

2.4

2.6

3.0

o
tl

R-C-

2.1 (R
2.6 (R

3.6 (R
3.8 (R

-: alkyl)
aryl)

alkyl)
aryl)

2.4 (R
2.7 (R

alkyl)
aryl)

2.6 (R
3.4 (R

alkyl)
aryl)

o
tl

RO-C(R
- alkyl, H)
o
ll

R-C-O(R

alkyl, H)

4.1
(R

o
ll

R2N-C(R

alkyl, H)

o
tl

R-C-N-

2.8

(R

alVl,

H)

-NR,
(R : alkyl, H)

-Nn
I\J
R

- alkyl, H)
N:C-

(R

3.1

5.0
alkyl, aryl)

(R

alkyl, aryl)

APPENDIX IV. 13C NMR CHEMICAL SHIFTS IN ORGANIC

COMPOUNDS A-7

APPENDIx Iv. 13C NMR CHEMICAL SHIFTS

IN ORGANIG GOMPOUNDS
This section is divided into a table of chemical shifts for carbons within functional groups and
a table of chemical shifts for alkyl carbons adjacent to functional groups. A typical range of
shifts is siven for each case.

A. Chemical Shifts of Carbons within Functional

Group

Groups

Chemical shift range' PPm

B-23

-CH,

20-30

-CHrI

-CH-

21

-33

17

-29

-cI

\tC:C

/\

a-r
\--

05-1 50*

66-93*

\-

G-

25-1 50"

o
ll

tc

200-220

-.-

o
tl

.CrO.R

R: H, alkyl

r 70-1

80

o
il

,c--NaR

H, alkyl

165-175

-C-N

110-120

*Alkyl substitution typically increases chemical shift.

B. Ghemical Shifts of Garbons ediacent to runctional Groups

In most cases, alkyl substitution on the carbon increases chemical shift. Methyl carbons will
have shifts in the low end ofthe range; tertiary and quaternary carbons will have shifts in the
upper end of the range.

A-8

APPENDTcES

Group

Chemical shift of carbon in

- CI

R,C:CR-

14-40

HC-C-

8-28

29-45

F-

B3-9

clBr-

32-6s

t-

5-42

HO-

62-70

RO-

alkyl,H

70-79

o
ll

R-C-

R-alkyl,H

43-50

o
il

RO-C- R-alkyl,H
RrN-

R-alkyl,H

N-C-

33-44
41-51
53-60

(R:H)
(R

alkyl)

16-28

APPENDIX V. SUMMARY OF SYNTHETIC METHODS

The following methods are listed in order of their occurence in the text; the section reference
follows each reaction in parentheses. Thus, a review at any point in the text is possible by considering the methods listed for earlier sections.
Don't forget that in many cases, a method can be applied to compounds containing more
than one functional group. Thus, catalytic hydrogenation can be used to convert phenols into
alcohols, but it is listed under "Synthesis of Alkanes and Aromatic Hydrocarbons" because

the actual transformation is the formation of

groups from
groups; the presence of the --{H group is incidental.
Reaction summaries for each chapter are found in the Study Guide.

-CHr-CHr-

A. Synthesis of Alkanes

-CH:CH-

and Aromatic Hydrocarbons

1. Catalytic hydrogenation of alkenes (4.9A)

2. Protonolysis of Grignard or related reagents (8.88)

3. Cyclopropane formation by the addition of carbenoids to alkenes (Simmons-Smith reaction;9.8B)

4.
5.
6.
7.

Catalytic hydrogenation of alkynes (14.6A)

Friedel{rafts alkylation of aromatic compounds (16.48)

Catalytic hydrogenation of aromatic compounds (16.6)
Stille reaction of aryl triflates and aryl- or alkylstannanes to form substituted aromatic
hydrocarbons (18.10B)

APPENDIX V. SUMMARY OF SYNTHETIC

METHODS A.9

8. Wolff-Kishner or Clemmensen reductions of aldehydes or ketones (19.12)

9. Reaction of aryldiazonium salts with hypophosphorous acid (23.10A)

B. synthesis of Alkenes
l. B-Elimination reactions of alkyl halides or sulfonates

(9.5, 10.3A,

17

.38)

2.

Acid-catalyzed dehydration of alcohols ( I 0' I )

3. Catalytic hydrogenation of alkynes (gives cis-alkenes when used with internal alkynes;

14.6A)

4. Reduction of alkynes with alkali metals in liquid ammonia (gives trans-alkenes when
used with internal alkenes; 14.68)

5.
6.
7.
8.
9.

Diels-Alder reactions of dienes and alkenes to give cyclic alkene s (15 .3 , 2'7 .3)
Heck reaction of aryl halides and alkenes to give aryl-substituted alkenes (18.6A)
Suzuki coupling of aryl or vinylic halides with aryl or vinylic boronic acids (18.68)

Alkene metathesis (18.6C)

Wittig reaction of aldehydes and ketones ( 19. l3)
10. Aldol condensation reactions ofaldehydes orketones to give a,B-unsaturated aldehydes
or ketones (22.4)
11. Hofmann elimination of quaternary ammonium hydroxides (23.8)

c.

Synthesis of Alkynes
1. Alkylation of acetylenic anions with alkyl halides or sulfonates (14.78)
of alkyl dihalides or vinylic halides (18.2)

2. B-Elimination reactions

D. Synthesis of Alkyl, Aryl, and Vinylic Halides

1. Addition of hydrogen halides to alkenes (4.7, 15.44)

2. Addition of halogens to alkenes to give vicinal dihalides (5.2)

3. Peroxide-promoted addition of HBr to alkenes (5.6)

4. Addition of halogens or HBr to alkynes (14.4)

5. Synthesis of dihalocyclopropanes by the addition of dihalomethylene to alkenes (9.8A)
6. Reaction of alcohols with HBr, thionyl chloride, or phosphorus tribromide (10.2, 10.3D,
17.1)

7. Reaction of sulfonate esters or other alkyl halides with halide ions (10.3,{, 17.4)
8. Halogenation of aromatic compounds (16.4A)
9. Allylic and benzylic bromination of alkenes or aromatic hydrocarbons (17.2)

10. a-Halogenation of aldehydes, ketones, or carboxylic acids (22.34,C)

1

l.

Synthesis of aryl halides by the reaction of cuprous chloride, cuprous bromide, or potassium iodide with aryldiazonium salts (Sandmeyer and related reactions; 23.10A)

E. Synthesis of Grignard Reagents and Related

Organometallic ComPounds

1. Reaction of alkyl or aryl halides with metals (8.8A)

2. Preparation of lithium dialkylcuprates by the reaction of alkyllithium reagents with

cuprous halides (1 1.4C)

3. Preparation of acetylenic Grignard reagents by the metal-hydrogen exchange

4. Preparation of alkyl- and arylstannanes by the reaction of

trialkylstannyl chlorides

(I

8.98)

(L4.7

A)

Grignard reagents with

A-

APPENDTcES

F. Synthesis of Alcohols

and Phenols

(Syntheses apply only to alcohols unless noted otherwise.)

l.

Acid-catalyzed hydration ofalkenes (used industrially, but generally not a good labora-

tory method;4.9B)
2. Synthesis ofhalohydrins from alkenes (5.2B)

3. Oxymercuration-reduction of alkenes (5.4A)

4. Hydroboration-oxidation of alkenes (5.4B)
5. Ring-opening reactions of epoxides (1 l.4A,B)
6. Reaction of ethylene oxide with Grignard reagents (1 l.4C)
7. Reaction of epoxides with lithium organocuprates (l l.4C)
8. Reduction of aldehydes orketones (19.8,22.9,24.8D)
9. Reactionof aldehydesorketoneswithGrignardorrelatedreagents (19.9,22.10A)
10. Reduction of carboxylic acids to primary alcohols (20. 10)
l. Reduction of esters to primary alcohols (2I.9A)
12. Reaction of esters with Grignard or related reagents (21.10A)
13. Aldol addition reactions of aldehydes or some ketones to give B-hydroxy aldehydes or
ketones (22.4)
14. Reaction of diazonium salts with water to give phenols (23. 10A)
15. Synthesisof phenolsbytheClaisenreanangementof allylicarylethers (27.4B)
1

c.

Synthesis of Glycols
I. Acid-catalyzed hydrolysis

of epoxides (I L4B)

2. Reaction of alkenes with osmium tetroxide or alkaline potassium permanganate (11.5)

H. Synthesis of Etherg Acetals, and Sulfides

l. Alkylation of alkoxides, phenoxides, or thiolates with alkyl halides

or alkyl sulfonates

(Williamson synthesis; I l.l A, 18.78, 24.7)

2. Alkoxymercuration-reduction of alkenes ( 1 I . 18)

3. Acid-catalyzed dehydration of alcohols ( I 1. I C)

4. Acid-catalyzed addition of alcohols to alkenes ( I I . I C)
5. Reaction of epoxides with alkoxides and alcohols (11.4A,B)
6. Reaction of 2- and 4-nitroaryl halides with alkoxides (18.4)
7

Acetal formation by the acid-catalyzed reaction of alcohols with aldehydes or ketones

(r9.104,24.6)

8. Conjugate addition of thiols to d,B-unsaturated carbonyl compounds (22.8A)

l.

Synthesis of Epoxides
I . Oxidation of alkenes with peroxycarboxylic acids ( 1 l .2A)
2. Cyclization of halohydrins ( I I .2B)
3. Asymmetric epoxidation of allylic alcohols (11.10)

J.

Synthesis of Disulfides
1. Oxidation of rhiols (10.9,26.8)

APPENDIX V. SUMMARY OF SYNTHETIC

METHODS 4.11

K. Synthesis of Aldehydes
1. Ozonolysis of alkenes (of limited utility because carbon-carbon bonds are broken; 5.5)
2. Oxidation of primary alcohols (10.6A)
3. Oxidative cleavage of glycols (of limited utility because carbon--carbon bonds are broken; 11.5B, 24.8C)

4. Hydroboration--oxidation of alkynes ( 14.58)

5. Oxidation of allylic and benzylic alcohols with MnO, (Sec. 17.54)
6. Reduction of acid chlorides (21.9D).
7. Aldol addition reactions of aldehydes to give B-hydroxy aldehydes (22.4)
8. Aldol condensation reactions ofaldehydes to give a,B-unsaturated aldehydes (22.4)
9. Synthesis of aldoses from other aldoses by the Kiliani-Fischer synthesis (24.9) and the
Ruff degradation (24. 10)

L.

Synthesis of Ketones

l. Ozonolysis of alkenes (of limited utility because carbon-carbon bonds are broken; 5.5)
2. Oxidation of secondary alcohols (10.6A)
3. Oxidative cleavage of glycols (of limited utility because carbon--carbon bonds are broken; 11.5B)

4.
5.
6.
7.
8.
9.

Mercuric-ion catalyzed hydration of alkynes (14.5A)

Friedel-Crafts acylation of aromatic compounds (16.4F)
Oxidation of phenols to quinones (18.8)
Reaction of acid chlorides with lithium dialkylcuprates (21.10B)
Aldol condensation reactions of ketones to give a,B-unsaturated ketones (22.4)
Claisen and Dieckmann condensation reactions of esters to give B-keto esters (22.5A,

B)
10. Crossed Claisen condensation reactions of esters to give B-diketones (22.5C)
I l. Acetoacetic ester synthesis (22.7C)
12. Conjugate addition reactions of a,B-unsaturated ketones (22.8), including the addition
of lithium dialkylcuprate reagents (22.lOB)

M. Synthesis of Sulfoxides and Sulfones

l.

Oxidation of sulfides (11.8)

N. Synthesis of carboxylic and Sulfonic Acids

(Syntheses apply only to carboxylic acids unless noted otherwise.)

l. Ozonolysis of alkenes (of limited utility because carbon--carbon bonds are broken; 5.5)
2. Oxidation of primary alcohols (10.6B)
3. Oxidation of thiols to sulfonic acids (10.9)
4. Sulfonation of aromatic compounds to give arylsulfonic acids (16.4D, 20.6)
5. Side-chain oxidation of alkylbenzenes (17.5)
6. Oxidation of aldehydes (19.14)
7. Reaction of Grignard or related reagents with carbon dioxide (20.6)
8. Hydrolysis of carboxylic acid derivatives, especially nitriles (21.7 , 2l .ll, 26.7)
9. Haloform reaction of methyl ketones (of limited utility because carbon--carbon bonds
are broken; 22.38)

A-12

APPENDTcES

10. Malonic ester synthesis (22.64,26.48)

11. Strecker synthesis of a-amino acids (26.4C)

O. Synthesis of Esters
1. Reaction of alcohols and phenols with sulfonyl chlorides (for sulfonate esters; 10.3,4',
18.10B)

2.
3.
4.
5.
6.
7.
8.

Acid-catalyzed esterification of carboxylic acids with primary or secondary alcohols

(20.8A, 24;t,26.5)
Alkylation of carboxylic acids with diazomethane (20.88)
Alkylation of carboxylate salts with alkyl halides (20.8B)
Reaction of acid chlorides, anhydrides, or esters with alcohols and phenols (21.8,24.7)
Claisen and Dieckmann condensation reactions of esters to give B-keto esters (22.54.,8)
Alkylation of ester enolate ions; includes malonic ester synthesis, acetoacetic ester synthesis, and direct alkylation (22.7)
Conjugate addition reactions of a,B-unsaturated esters (22.8,22.108)

P. Synthesis of Anhydrides
1. Reaction of carboxylic acids with dehydrating agents (20.98)

2. Reaction of acid chlorides with carboxylate salts (21.8A)

Q. synthesis of Acid chlorides

1. Reaction of carboxylic or sulfonic acids with thionyl chloride, phosphorus pentachloride, or related reagents (20.9A')

2. Synthesis of sulfonyl halides by chlorosulfonation of aromatic compounds (20.9A)

R. Synthesis of Amides
1. Reaction of acid chlorides, anhydrides, or esters with amines (21.8,23.7C,26.5)
2. Condensation of amines and carboxylic acids with dicyclohexylcarbodiimide (26.6)

S. Synthesis of Nitriles
l.

Formation of cyanohydrins from aldehydes and some ketones (19.7A,8,24.9)

2. Reaction of alkyl halides or alkyl sulfonates with cyanide ion (21. I i )

3. Conjugate addition of cyanide ion to a,B-unsaturated carbonyl compounds (22.8A)
4. Reaction of cuprous cyanide with aryldiazonium salts (23.10A)

T.

Synthesis of Amines
1. Reductionof amides (21.98)
2. Reduction of nitriles to primary amines (21.9C)
3. Direct alkylation of ammonia or amines (of limited utility because of the possibility of
over-alkylation; 23.7 A, 26.4 A)
4. Reductive amination of aldehydes and ketones (23.78)
5. Aromatic substitution reactions of aniline derivatives (23.9)
6. Gabriel synthesis of primary amines (23.ll{)
7. Reduction of nitro compounds (23.11B)

APPENDIX V. SUMMARY OF SYNTHETIC

METHODS A-13

8. Pd-catalyzed amination of aryl halides and triflates (23.11C)

9. Curtius and Hofmann reuurangements (23.1lD)

U. Synthesis of Nitro Compounds

1. Nitration of aromatic compounds (16.4C, 18.9)

APPENDIX VI. REACTIONS USED TO FORM

CARBON-CARBON BONDS
Reactions that form carbon-carbon bonds have central importance in organic chemistry, because these reactions can be used to form carbon chains or rings. These reactions are listed in
the order in which they are discussed in the text. The section reference follows each reaction

in parentheses.

l.

Cyclopropane formation by addition ofcarbenes or carbenoids to alkenes (9.8)

2. Reaction of Grignard reagents with ethylene oxide (1 1.4C)

3. Reaction of epoxides with lithium organocuprates (11.4C)
Reaction of acetylenic anions with alkyl halides or sulfonates (14.78)
Diels-Alder reactions (15.3,21 .3)
Friedel-Crafts alkylation (16.4E) and acylation reactions (16.4F)
The Heck reaction of alkenes with aryl halides (18.5F)
Suzuki coupling of aryl or vinylic halides with aryl or vinylic boronic acids ( I 8.68)
Alkene metathesis (18.6C)
10. The Stille reaction of organostannanes with aryl triflates (18.9B)
I 1 . Cyanohydrin formation (19.7 , 24.9, 26.4C)
12. Reaction of Grignard and related reagents with aldehydes and ketones (19.9)
13. Wittig alkene synthesis (19.13)
14. Reaction of Grignard and related reagents with aldehydes and ketones (20.6)
15. Reaction of Grignard and related reagents with esters (21 .10A)
16. Reaction of lithium dialkylcuprates with acid chlorides (21.10B)
17. Reaction of cyanide ion with alkyl halides or sulfonates (21.11)
18. Aldol addition and condensation reactions (22.4)
19. Claisen and related condensation reactions (22.5)
20. Malonic ester synthesis (22.7 4,26.48)
21. Alkylation of ester enolate ions with alkyl halides or sulfonates (22.78)
22. Acetoacetic ester synthesis (22.7C)
23. Conjugate-addition reactions of cyanide ion (22.8A) or enolate ions (22.8C) to a,B-unsaturated carbonyl compounds
24. Conjugate addition of lithium dialkylcuprate reagents to c,B-unsaturated carbonyl compounds (22.108)
25. Reaction of aryldiazonium salts with cuprous cyanide (23.1 0A)
26. Formation of rings by electrocyclic reactions (27 .2)
27. Claisen realrangement (27 .48)

4.
5.
6.
7.
8.
9.

A-14

APPENDTcES

APPENDIX VII. TYPICAT AGIDITIES AND BASIGITIES

OF ORGANIC FUNCTIOIIIAI GROUPS

A. Acldlties of Groups That lonlze to Glve Anionlc Gonlugate Bases

Functional group

Structure of
conjugate base

Structure*

o
ll

sulfonic acid

tl

R-5-O-H

R-S-O-

ll

<

1 (strong acid)

il

0
tl

ll

carboxylic acid

Typical pK"

R-C-O-H
*

R-C-O-

3-5

phenol

xkJro-H'

*00-t

9-1

thiol

R-S-H

R-5-

9-'l

OH

sulfonamide

ill
R-S-N-R

il_

R- S-N-R

ll

tl

amide

OH
ill
R-C-N-R

alcohol

R-O-H

o
o

lt_

R_C-N-R

15-19

OH

aldehyde, ketone

lll
R-C-CRz

15-17

ll-

R-C-CR2

HO

17-20

ester

ttl
R2C-C-OR

R2C-C-OR

alkyne

R-C-C-H

R-C:C-

tl

H
I

nitrile

R2C-C-N

R'C-C-N

25

amine

R2N-H

RrN-

32

alkene

\/C:C
/\

\r
/\-rRR
lE-ls

benzylic alkyl

group
alkane

Ar-CR2

Ar-C

R3C-H

RrC-

*ln the structures, R : alkyl or H.The acidic hydrogen is shown in red.

tX a general ring substituent group.
-

R,

42

55-60

APPENDIX VII. TYPICAL ACIDITIES AND BASICITIES OF ORGANIC FUNCTIONAL

GROUPS A-'I 5

B. Basicities of Groups That Protonate to Give Cationic

Gonjugate Acids

One should be careful to distinguish between the behavior of a particular functional group as
an acid and the same functional group as a base. For example, when an alcohol acid acts as an
acid, it loses the RO-H proton to form an alkoxide (see the table in part A of this section.)
When it acts as a base,it gains a proton to form ROHr. These are very different processes with
different pK" values. When we discuss the acidity of an alcohol, the relevant pK^ is that for the
alcohol itself (see the table in part A). This same pK" describes the basicity of the alkoxide,
RO-, which is the conjugate base of the alcohol. When we discuss the basicity of the alcohol
itself, the relevant pK" is the value for the acidity of RdHr, given in the following table.

Functional

group

Structur*,*

Structure of
conjugate acid*,*
+

alkylamine

R,N

R3N-

pyridine

1l*
xu

O*+-H
xX-l

aromatic

Typical conjugate-

".ia

p4

9-1

(,,-

amine

x1-l,FNRt
*o/H

o
tl

R-C-NR2

amide

tl

R-C-NR2
H

R-O-R

alcohol, ether

R-O-R
+

*o/H

o
ester, carboxylic

tl

R-C-OR

acid

phenol, aromatic ethert

-2 to -3

ll

R-C-OR

-6 to -7

*kJao*
H

thiol,

su

R-S-

lfide

R-S-R
+

*o/H

ketone
*ln the structures, R :

tl

R-C-R

aldehyde,

+X

-6 to -7

il

R-C-R

-7

alkyl or H. In the conjugate acid, the acidic hydrogen is shown in red.

= a general ring substituent group.

TA phenol or aromatic ether can be protonated on a ring carbon

ifthe resulting carbocation can be strongly stabilized

by the substituent groups.

(Table continues)

'

A-16

APPENDTcES

Functionalgroup StructutE*

of
conlugateacid
Structure

Typlcal conjugate'

acidpK.

atkene

RRRI
\:./
/\/l
i'RRR

\-l-*

-8 to -ro

nitrile

R-C: N

R-C-fi-H

- 10

*ln the structures,

alkyl or H.

Credlts
2.10
Figure 2.11
Figure

Photo copyright @ by Stan Honda/Getty Images.

The source of the historical ice-core CO, data is D. M. Etheridge, Division of

Atmospheric Research, Australian Commonwealth Scientific and Industrial Research Organization (CSIRO). The source of the data in the inset is C. D. Keeling of the Scripps Institute of
Oceanography, and the National Oceanic and Atmospheric Administration (NOAA).

2.12 Photo copyright @ by Jenna Wagner/iStockphoto.com

Figure 2.14 The photo of methane digesters is courtesy of Mark Stoermann, Fair
Figure

Oaks

Farms. The methanogen in the inset is copyright @ by T. J. Beveridge/Getty Images.

6.18 Reprinted with permission from G. B. Kauffman and R. D. Myers, Journal

Chemical Education (L975), 52,777 . Copyright @ by the American Chemical Society.

Figure

of

9.7 Photo courtesy of Tira Bunyaviroch, M.D., and R. Edward Coleman, M.D.
Reprinted with permission from the Journal of Nuclear Medicine (20O6), 47, 251. Copyright
@ by the Society of Nuclear Medicine.
Figure

Figure 12.17 Mass spectra courtesy of Dr. Karl V. Wood and the Purdue University Mass
Spectrometry Center.

Figure 12.18 Adapted from F. W. Mclafferty, Interpretation of Mass Spectra. Copyright

1977 by the Benjamin-Cummings Publishing Company. Used with permission.

Figure 13.23 DEPT-NMR spectrum of camphor, courtesy of John Kozlowski, Purdue University.

Figure 13.19 Reprinted with permission from F. A. Bovey, Chemical and Engineering
News, August 30, 1965. Copyright @ by the American Chemical Society

Figure L3.26 Courtesy of Dr. Paul J. Keller, Barrow Neurological Institute.

Figure

14.7

Photo copyright @ by Marc Loudon.

26.5

Mass spectrum courtesy of Prof. Richard Gibbs and Animesh Aditya of Purdue
Dr.
Karl V. Wood, and the Purdue University Mass Spectrometry Center.
University,

Figure

Figures 25.5,26.13,26.15, and 26.16 are based on coordinates obtained from the Protein
Data Bank, operated by the Research Collaboratory for Structural Biology (RCSB), supported
by the National Science Foundation (NSF), the National Institute of General Medical Sciences
(NIGMS), the Office of Science, Department of Energy (DOE), the National Library of Medicine (NLM), the National Cancer Institute (NCI), the National Center for Research Resources
(NCRR), the National Institute of Biomedical Imaging and Bioengineering (NIBIB), the National Institute of Neurological Disorders and Sffoke (NINDS), and the National Institute of
Diabetes and Digestive and Kidney Diseases (NIDDK). We gratefully acknowledge the assistance of Prof. Markus Lill, Purdue University, in obtaining the images.

c-1

C-2

cREDrrs

Figure

26.16

Coordinates courtesy of Abbott Laboratories.

IR Spectra Adapted fromthe Aldich@ Library of FT-IR Specta, Charles

J. Pouchert, Editor. Copyright@ 1997 by the Aldrich Chemical Company, and used with permission. These
spectra are found in Figures 12.4, 12.7 , 12.10, l2.Il, 12.12, 12.t3, P12.26, P12.27, P12.32,
P 12.33, P 13.24, r4.4, r4.5, P 14.3 5, t6.r, 19.3, 20.2, 21 .2, 21.3, and 23.1.

Mass Spectra Mass spectra not separately acknowledged in the foregoing credits are from
the EPA-NIH Mass Spectral Data Base, published by the National Bureau of Standards,
United States Department of Commerce, and used with permission. These spectra are found
in Figures I2.l 4-12. 16, P 12.37, P 13.V1, P 1 6.55a, 19.7, ard P 19.64.
LIV

Spectra UV

spectra were obtained by the author.

IttMR Spectra We gratefully acknowledge the cooperation of the Purdue Magnetic Resonance Laboratory and the able assistance of Dr. Tony Thompson in obtaining the spectra.