CHE-302 Review
Nomenclature
Syntheses
Reactions
Mechanisms
Spectroscopy
Aromatic Hydrocarbons (Electrophilic Aromatic Substitution)
Spectroscopy (infrared & H-nmr)
Arenes
Aldehydes & Ketones
Carboxylic Acids
Functional Derivatives of Carboxylic Acids
Acid Chlorides, Anhydrides, Amides, Esters
Carbanions
Amines & Diazonium Salts
Phenols
Mechanisms:
Electrophilic Aromatic Substitution
Nitration
Sulfonation
Halogenation
Friedel-Crafts Alkylation & Acylation
Nucleophilic Addition to Carbonyl
Nucleophilic Addition to Carbonyl, Acid Catalyzed
Nucleophilic Acyl Substitution
Nucleophilic Acyl Substitution, Acid Catalyzed
Aromatic Hydrocarbons
hydrocarbons
aliphatic
alkanes alkenes alkynes
aromatic
Aliphatic compounds: open-chain compounds and ring
compounds that are chemically similar to open-chain
compounds. Alkanes, alkenes, alkynes, dienes, alicyclics,
etc.
Aromatic compounds: unsaturated ring compounds that
are far more stable than they should be and resist the
addition reactions typical of unsaturated aliphatic
compounds. Benzene and related compounds.
Nomenclature for benzene:
monosubstituted benzenes:
Special names:
CH3
toluene
CO2H
benzoic acid
NH2
OH
aniline
phenol
SO3H
benzenesulfonic acid
NO2
CH3
Br
Br
Cl
Br
o-dibromobenzene
1,2-dibromobenzene
m-chloronitrobenzene
p-bromotoluene
3-chloro-1-nitrobenzene
4-bromotoluene
If more than two groups on the ring, use numbers!
NH2
Br
Br
Br
Br
Br
Br
1,2,4-tribromobenzene
2,4,6-tribromoaniline
Electrophilic Aromatic Substitution (Aromatic compounds)
Ar-H = aromatic compound
1. Nitration
Ar-H
+ HNO3, H2SO4  Ar-NO2 + H2O
2. Sulfonation
Ar-H + H2SO4, SO3  Ar-SO3H + H2O
3. Halogenation
Ar-H + X2, Fe  Ar-X + HX
4. Friedel-Crafts alkylation
Ar-H + R-X, AlCl3  Ar-R + HX
Friedel-Crafts alkylation (variations)
a) Ar-H + R-X, AlCl3  Ar-R + HX
b) Ar-H + R-OH, H+  Ar-R + H2O
c) Ar-H + Alkene, H+  Ar-R
increasing reactivity
Common substituent groups and their effect on EAS:
-NH2, -NHR, -NR2
-OH
-OR
-NHCOCH3
-C6H5
-R
-H
-X
-CHO, -COR
-SO3H
-COOH, -COOR
-CN
-NR3+
-NO2
ortho/para directors
meta directors
If there is more than one group on the benzene
ring:
1. The group that is more activating (higher
on “the list”) will direct the next
substitution.
2. You will get little or no substitution
between groups that are meta- to each
other.
“Generic” Electrophilic Aromatic Substitution mechanism:
RDS
2)
Y+Z-
+
1)
Y
+
H
Z-
Y
H
+
Z-
Y
+
HZ
Mechanism for nitration:
H3O+
1) HONO2 + 2 H2SO4
+
2)
NO2+
RDS
2 HSO4- + NO2+
+
NO2
H
NO2
3)
H
NO2
+ H+
Mechanism for sulfonation:
1)
H3O+
2 H2SO4
RDS
2)
+ SO3
+
HSO4-
+
SO3
SO3H
3)
SO3H
4)
SO3- + H3O+
SO3-
+
H+
SO3H
+ H2O
Mechanism for halogenation:
1)
Cl-Cl-AlCl3
Cl2 + AlCl3
RDS
+
2)
Cl
Cl-Cl-AlCl3
+ AlCl4-
H
Cl
3)
H
+
AlCl4-
Cl
+ HCl + AlCl3
Mechanism for Friedel-Crafts alkylation:
1)
R-X
+
FeX3
R
RDS
+ R
2)
+
FeX4R
H
R
3)
H
+ FeX4-
R
+
HX
+ FeX3
Mechanism for Friedel-Crafts with an alcohol & acid
1)
R-OH
2)
ROH2+
+
H+
ROH2+
R
+ R
3)
+ H2O
RDS
R
H
R
4)
H
R
+ H+
Mechanism for Friedel-Crafts with alkene &
acid:
1)
+
C C
H+
R
RDS
R
+ R
2)
H
R
3)
R
+
H+
H
electrophile in Friedel-Crafts alkylation = carbocation
Arenes
alkylbenzenes
alkenylbenzenes
alkynylbenzenes
etc.
Alkylbenzenes, nomenclature:
Special names
CH3
CH3
CH3
CH3
CH3
CH3
CH3
toluene
o-xylene
m-xylene
p-xylene
others named as “alkylbenzenes”:
H3C
CH
CH3
isopropylbenzene
CH3
H2C
CH2
H2
CH3
C
CH
CH3
n-propylbenzene
isobutylbenzene
H2
C CH3
C CH3
H2
o-diethylbenzene
n-butylbenzene
Use of phenyl
C6H5- = “phenyl”
CH2CH2
2-methyl-3-phenylheptane
1,2-diphenylethane
do not confuse phenyl (C6H5-) with benzyl (C6H5CH2-)
Alkenylbenzenes, nomenclature:
Special name
CH=CH2
styrene
Rest are named as substituted alkenes
CH2CH=CH2
3-phenylpropene
(allylbenzene)
(Z)-1-phenyl-1-butene
Alkylbenzenes, syntheses:
1. Friedel-Crafts alkylation
2. Modification of a side chain:
a) addition of hydrogen to an alkene
b) reduction of an alkylhalide
i) hydrolysis of Grignard reagent
ii) active metal and acid
c) Corey-House synthesis
Alkynylbenzenes, nomenclature:
C CH
phenylacetylene
phenylethyne
5-phenyl-2-hexyne
Friedel-Crafts alkylation
+
CH2=CHCH3,
CH3
CH
CH3
H+
+ CH3CH2-OH, H+
CH2
CH3
isopropylbenzene
ethylbenzene
CH3
CH3
+
CH3
H3C C CH3
Br
AlCl3
p-tert-butyltoluene
H3C C CH3
CH3
Friedel-Crafts limitations:
a) Polyalkylation
b) Possible rearrangement
c) R-X cannot be Ar-X
d) NR when the benzene ring is less reactive
than bromobenzene
e) NR with -NH2, -NHR, -NR2 groups
Modification of side chain:
+
H2, Ni
Br
+
Sn, HCl
ethylbenzene
Br
+
Mg; then H2o
Alkylbenzenes, reactions:
1. Reduction
2. Oxidation
3. EAS
a) nitration
b) sulfonation
c) halogenation
d) Friedel-Crafts alkylation
4. Side chain
free radical halogenation
COOH
+
KMnO4, heat
COOH
COOH
+
KMnO4, heat
+
2 CO2
Alkylbenzenes, EAS
CH2CH3
HNO3, H2SO4
CH2CH3
NO2
CH2CH3
+
NO2
H2SO4, SO3
-R is electron
releasing.
Activates to
EAS and directs
ortho/para
CH2CH3
SO3H
CH2CH3
+
SO3H
Br2, Fe
CH2CH3
Br
CH2CH3
+
Br
CH3Cl, AlCl3
CH2CH3
CH3
CH2CH3
+
CH3
Alkylbenzenes, free radical halogenation in side chain:
Benzyl free radical
CH2CH3
+
Cl2, heat
CHCH3
Cl
91%
CH2CH3
+
only
CH2CH2-Cl
9%
CHCH3
Br
Br2, heat
+
Alkenylbenzenes, syntheses:
1. Modification of side chain:
a) dehydrohalogenation of alkyl halide
b) dehydration of alcohol
c) dehalogenation of vicinal dihalide
d) reduction of alkyne
(2. Friedel-Crafts alkylation)
Alkenylbenzenes, synthesis modification of side chain
KOH(alc)
CHCH3
Br
CH=CH2
styrene
H+, heat
CHCH3
OH
Zn
CHCH2
Cl Cl
H2, Pd-C
C CH
Alkenylbenzenes, reactions:
1.
Reduction
2.
Oxidation
3.
EAS
4.
Side chain
a) add’n of H2
j) oxymercuration
b) add’n of X2
k) hydroboration
c) add’n of HX
l) addition of free rad.
d) add’n of H2SO4
m) add’n of carbenes
e) add’n of H2O
n) epoxidation
f) add’n of X2 & H2O
o) hydroxylation
g) dimerization
p) allylic halogenation
h) alkylation
q) ozonolysis
i) dimerization
r) vigorous oxidation
Alkenylbenzenes, reactions: reduction
CH=CH2
+
CH=CH2 +
H2, Ni
CH2CH3
o
H2, Ni, 250 C, 1,500 psi
CH2CH3
H
Alkenylbenzenes, reactions oxidation
CH=CH2
KMnO4
CHCH2
OHOH
KMnO4
CH=CH2
COOH
+
CO2
CH=O
+
O=CH2
heat
1. O3
CH=CH2
2. Zn, H2O
Alkenylbenzenes, reactions EAS?
electrophilic addition
CH=CH2
electrophilic aromatic substitution
alkenes are more reactive with electrophiles than aromatic rings!
CH=CH2
+
Br2, Fe
CHCH2
Br Br
CH=CHCH3
H2O, H+
CHCH2CH3
OH
Br2, H2O
Br
CHCHCH3
OH
1. H2O, Hg(OAc)2
2. NaBH4
CHCH2CH3
OH
1. (BH3)2
2. H2O2, NaOH
CH2CHCH3
OH
HBr, perox.
CH=CHCH3
CH2CHCH3
Br
polymer.
CHCH2
CH=CH2
n
polystyrene
CH2N2, hv
CH=CHCH3
PBA
CH=CHCH3
O
CH=CHCH3
H
C C
H
CH3
+
CH=CHCH2-Br
Br2, heat
KMnO4
CH3
H
OH
HO
H
+
CH3
HO
H
H
OH
(E)-1-phenylpropene
100 syn-oxidation; make a model!
Alkynylbenzenes, syntheses:
Dehydrohalogenation of vicinal dihalides
Br2
CH=CH2
Br
CHCH2
Br
1. KOH
C CH
2. NaNH2
KOH(alc)
H
C CH3
Br
H2
C CH3
CH2=CH2
HF
Alkynylbenzenes, reactions:
1. Reduction
2. Oxidation
3. EAS
4. Side chain
a) reduction
e) as acids
b) add’n of X2
f) with Ag+
c) add’n of HX
g) oxidation
d) add’n of H2O, H+
Alkynylbenzenes, reactions: reduction
C C CH3
C C CH3
+
2 H2, Ni
+
(xs) H2, Ni
heat & pressure
+
Li, NH3
CH2CH2CH3
Anti-
+
H2, Pd-C
Syn-
Alkynylbenzenes, reactions: oxidation
O3; then Zn, H2O
KMnO4
COOH
C C CH3
KMnO4, heat
+
HOOCCH3
Alkynylbenzenes, reactions EAS?
electrophilic addition
C CH
electrophilic aromatic substitution
alkynes are more reactive with electrophiles than aromatic rings!
C CH
+
Br2, Fe
Br
C=CH
Br
Alkynylbenzenes, reactions: side chain:
Br2
Br
C=CH
Br
2 Br2
Br Br
C C H
Br Br
C C CH3
HBr
C=CH2
Br
2 HBr
Br
CCH3
Br
H2O, H+
C CH
O
CCH3
Na
C C-Na+
C CH
Ag+
C C-Ag+
C CH
Ag+
C CCH3
NR, not terminal
Aldehydes and Ketones
Nomenclature:
Aldehydes, common names:
Derived from the common names of carboxylic acids;
drop –ic acid suffix and add –aldehyde.
CH3CH2CH2CH=O
butyraldehyde
CH3
CH3CHCH=O
isobutyraldehyde
(α-methylpropionaldehyde)
Aldehydes, IUPAC nomenclature:
Parent chain = longest continuous carbon chain containing
the carbonyl group; alkane, drop –e, add –al. (note: no
locant, -CH=O is carbon #1.)
CH3CH2CH2CH=O
butanal
H2C=O
methanal
CH3
CH3CHCH=O
2-methylpropanal
CH3CH=O
ethanal
Ketones, common names:
Special name:
H3C
O
C
CH3
acetone
“alkyl alkyl ketone” or “dialkyl ketone”
O
CH3CH2CCH3
ethyl methyl ketone
O
CH3CH2CCH2CH3
diethyl ketone
O
CH3CCH2CH2CH3
methyl n-propyl ketone
(o)phenones:
O
R C
Derived from common name of carboxylic acid, drop –ic
acid, add –(o)phenone.
O
C
benzophenone
H3C
O
C
acetophenone
Ketones: IUPAC nomenclature:
Parent = longest continuous carbon chain containing the
carbonyl group. Alkane, drop –e, add –one. Prefix a locant
for the position of the carbonyl using the principle of lower
number.
O
CH3CH2CCH3
O
CH3CH2CCH2CH3
2-butanone
3-pentanone
O
CH3CCH2CH2CH3
2-pentanone
Aldehydes, syntheses:
1. Oxidation of 1o alcohols
2. Oxidation of methylaromatics
3. Reduction of acid chlorides
Ketones, syntheses:
1. Oxidation of 2o alcohols
2. Friedel-Crafts acylation
3. Coupling of R2CuLi with acid chloride
Aldehydes synthesis 1) oxidation of primary alcohols:
RCH2-OH
+
K2Cr2O7, special conditions  RCH=O
RCH2-OH
+
C5H5NHCrO3Cl
 RCH=O
(pyridinium chlorochromate)
[With other oxidizing agents, primary alcohols  RCOOH]
Aldehyde synthesis: 2) oxidation of methylaromatics:
O
H3C
C O
C O
H3C
CH O
CH3
+ CrO3, (CH3CO)2O
Br
Br
geminal diacetate
CHO
H2O, H+
Br
p-bromobenzaldehyde
Aromatic aldehydes only!
Aldehyde synthesis: 3) reduction of acid chloride
R
O
C
LiAlH(O-t-Bu)3
Cl
lithium aluminum hydride tri-tert-butoxide
O
LiAlH(O-t-Bu)3
Cl
isovaleryl chloride
R
O
C
H
O
H
isovaleraldehyde
Ketone synthesis: 1) oxidation of secondary alcohols
H
O
OH
NaOCl
cyclohexanone
cyclohexanol
OH
CH3CHCH3
isopropyl alcohol
K2Cr2O7
H3C
O
C
CH3
acetone
Ketone synthesis:
2) Friedel-Crafts acylation
AlCl3
RCOCl, AlCl3 + ArH
O
CH3CH2CH2C
Cl
+
AlCl3
O
R C Ar
O
CH3CH2CH2C
butyrophenone
Aromatic ketones (phenones) only!
+ HCl
Ketone synthesis:
3) coupling of RCOCl and R2CuLi
O
RCOCl + R'2CuLi
C
R
R'
O
O
Cl
+
(CH3CH2)2CuLi
lithium diethylcuprate
Isobutyryl chloride
2-Methyl-3-pentanone
Aldehydes & ketones, reactions:
1) Oxidation
2) Reduction
3) Addition of cyanide
4) Addition of derivatives of ammonia
5) Addition of alcohols
6) Cannizzaro reaction
7) Addition of Grignard reagents
8) (Alpha-halogenation of ketones)
9) (Addition of carbanions)
nucleophilic addition to carbonyl:

O
C

+
Y Z
OY
C
Z
Mechanism: nucleophilic addition to carbonyl
1)
O
C
2)
O
C
Z
Z
O
C
Z
Y
OY
C
Z
RDS
+
+
Mechanism: nucleophilic addition to carbonyl, acid catalyzed
1)
O
C
2)
OH
C
3)
OH
C
ZH
+
OH
C
H
OH
C
ZH
RDS
+
HZ
OH
C
Z
+
H
1) Oxidation
a) Aldehydes (very easily oxidized!)
CH3CH2CH2CH=O
+ KMnO4, etc. 
CH3CH2CH2COOH
carboxylic acid
CH3CH2CH2CH=O + Ag+  CH3CH2CH2COO- + Ag
Silver mirror
Tollen’s test for easily oxidized compounds like aldehydes.
(AgNO3, NH4OH(aq))
b) Methyl ketones:
R
O
C
CH3
+
OI-
R
O
C
O-
+
CHI3
iodoform
Yellow ppt
test for methyl ketones
O
CH3CH2CH2CCH3
2-pentanone
+ (xs) NaOI
CH3CH2CH2CO2- + CHI3
2) Reduction:
a) To alcohols
O
C
H2, Ni
NaBH4 or LiAlH4
then H+
OH
C
H
H2, Pt
H
O
OH
cyclopentanol
cyclopentanone
O
C CH3
acetophenone
1. NaBH4
2. H+
OH
CHCH3
1-phenylethanol
Reduction
b) To hydrocarbons
O
C
NH2NH2, OH-
O
C
Zn(Hg), HCl
CH2
Wolff-Kishner
Clemmensen
CH2
3) Addition of cyanide
O
C
1. CN-
OH
C
CN
cyanohydrin
2. H+
+
O + NaCN; then H
OH
CN
4) Addition of derivatives of ammonia
O
+ H2N G
(H+)
+ H2O
N G
O
H2N NH2
H2N OH
hydrazine
hydroxylamine
NH2
H2N N
H
semicarbazide
O2N
H2N HN
H2N HN
NO2
phenylhydrazine
2,4-dinitrophenylhydrazine
CH2 CHO
+ H2NOH
CH2 CH NOH
hydroxylamine
an oxime
phenylacetaldehyde
H+
O
O
+
H2NHNCNH2
O
NHNCNH2
semicarbazide
cyclohexanone
CH3CH2CH2CH2CHO
pentanal
a semicarbazone
+ NH2 NH
phenylhydrazine
CH3CH2CH2CH2CH N NH
a phenylhydrazone
5) Addition of alcohols
O
C
+ ROH, H+
OH
C
OR
OR
C
OR
hemiacetal
acetal
(xs) EtOH, H+
CH2CHO
OEt
CH2 CH
OEt
acetal
O
(xs) CH3OH, dry HCl
OCH3
OCH3
ketal
6) Cannizzaro reaction. (self oxidation/reduction)
a reaction of aldehydes without α-hydrogens
COO-
CH2OH
CHO
conc. NaOH
+
Br
Br
conc. NaOH
H2C=O
CH3OH + HCOO-
Br
Formaldehyde is the most easily oxidized aldehyde. When
mixed with another aldehyde that doesn’t have any alphahydrogens and conc. NaOH, all of the formaldehyde is
oxidized and all of the other aldehyde is reduced.
Crossed Cannizzaro:
CH=O
CH2OH
+ H2C=O
conc. NaOH
+ HCOO-
OCH3
OH
vanillin
OCH3
OH
7) Addition of Grignard reagents.
O
C
+ RMgX
O MgBr
+ H2O
C
R
O MgBr
C
R
OH
+ Mg(OH)Br
C
R
larger alcohol
Planning a Grignard synthesis of an alcohol:
a) The alcohol carbon comes from the carbonyl
compound.
b) The new carbon-carbon bond is to the alcohol carbon.
O
C
+
+ RMgX
H
New carbon-carbon bond
OH
C
R
HX
ROH
Mg
RX
RMgX
H2O
R´OH
ox.
-C=O
larger
alcohol
CH3
HBr
CH3
CH3CHCH2OH
CH3CHCH2Br
Mg
CH3
CH3CHCH2MgBr
H+
K2Cr2O7
CH3CH2OH
CH3CH=O
special cond.
CH3
CH3CHCH2CHCH3
OH
4-methyl-2-pentanol
Carboxylic Acids
Carboxylic acids, syntheses:
1. oxidation of primary alcohols
RCH2OH + K2Cr2O7  RCOOH
2. oxidation of arenes
ArR + KMnO4, heat  ArCOOH
3. carbonation of Grignard reagents
RMgX + CO2  RCO2MgX + H+ 
RCOOH
4. hydrolysis of nitriles
RCN + H2O, H+, heat  RCOOH
1. oxidation of 1o alcohols:
CH3CH2CH2CH2-OH
+
CrO3  CH3CH2CH2CO2H
n-butyl alcohol
1-butanol
CH3
CH3CHCH2-OH
isobutyl alcohol
2-methyl-1-propanol`
butyric acid
butanoic acid
+ KMnO4 
CH3
CH3CHCOOH
isobutyric acid
2-methylpropanoic acid
2. oxidation of arenes:
CH3
KMnO4, heat
COOH
toluene
CH3
benzoic acid
COOH
KMnO4, heat
HOOC
H3C
terephthalic acid
p-xylene
H2
C CH3
ethylbenzene
KMnO4, heat
COOH
benzoic acid
note: aromatic
acids only!
3. carbonation of Grignard reagent:
Mg
R-X
H+
CO2
RMgX
RCO2MgX
RCOOH
Increases the carbon chain by one carbon.
CO2 H+
Mg
CH3CH2CH2-Br
n-propyl bromide
RMgX +
O
C
O
CH3CH2CH2MgBr
O
R C
O-
CH3CH2CH2COOH
butyric acid
H+
+
+
MgX
O
R C
OH
4. Hydrolysis of a nitrile:
H2O, H+
R-CN
R-CO2H
heat
H2O, OH-
R-CN
R-CO2- + H+  R-CO2H
heat
R-X + NaCN  R-CN + H+, H2O, heat  RCOOH
1o alkyl halide
Adds one more carbon to the chain.
R-X must be 1o or CH3!
carboxylic acids, reactions:
1. as acids
2. conversion into functional derivatives
a)  acid chlorides
b)  esters
c)  amides
3. reduction
4. alpha-halogenation
5. EAS
as acids:
a) with active metals
RCO2H + Na  RCO2-Na+ + H2(g)
b) with bases
RCO2H + NaOH  RCO2-Na+ + H2O
c) relative acid strength?
CH4 < NH3 < HCCH < ROH < HOH < H2CO3 < RCO2H < HF
d) quantitative
HA + H2O  H3O+ + AKa = [H3O+] [A-] / [HA]
ionization in water
2. Conversion into functional derivatives:
a)  acid chlorides
O
R C
OH
SOCl2
O
R C
Cl
or PCl3
orPCl5
CO2H + SOCl2
O
CH3CH2CH2 C
OH
COCl
PCl3
O
CH3CH2CH2 C
Cl
b)  esters
“direct” esterification:
RCOOH + R´OH  RCO2R´ + H2O
-reversible and often does not favor the ester
-use an excess of the alcohol or acid to shift equilibrium
-or remove the products to shift equilibrium to completion
“indirect” esterification:
RCOOH + PCl3  RCOCl + R´OH  RCO2R´
-convert the acid into the acid chloride first; not reversible
c)  amides
“indirect” only!
RCOOH + SOCl2  RCOCl + NH3  RCONH2
amide
O
PCl3
OH
3-Methylbutanoic acid
O
NH3
Cl
O
NH2
Directly reacting ammonia with a carboxylic acid results in an
ammonium salt:
RCOOH + NH3  RCOO-NH4+
acid
base
3. Reduction:
RCO2H + LiAlH4; then H+  RCH2OH
1o alcohol
LiAlH4
H+
CH3CH2CH2CH2CH2CH2CH2COOH
Octanoic acid
(Caprylic acid)
CH3CH2CH2CH2CH2CH2CH2CH2OH
1-Octanol
Carboxylic acids resist catalytic reduction under normal
conditions.
RCOOH + H2, Ni  NR
4. Alpha-halogenation: (Hell-Volhard-Zelinsky reaction)
RCH2COOH + X2, P  RCHCOOH + HX
X
α-haloacid
X2 = Cl2, Br2
CH3CH2CH2CH2COOH
+
Br2,P
pentanoic acid
COOH
Br2,P
NR (no alpha H)
CH3CH2CH2CHCOOH
Br
2-bromopentanoic acid
5. EAS: (-COOH is deactivating and meta- directing)
CO2H
HNO3,H2SO4
NO2
CO2H
CO2H
H2SO4,SO3
SO3H
CO2H
benzoic acid
Br2,Fe
Br
CH3Cl,AlCl3
NR
Functional Derivatives of Carboxylic Acids
O
R C
Cl
acid chloride
O
R C
O
R C
O
anhydride
O
R C
NH2
amide
O
R C
OR'
ester
R may be H or Ar
Nomenclature: the functional derivatives’ names are derived from the
common or IUPAC names of the corresponding carboxylic acids.
Acid chlorides: change –ic acid to –yl chloride
O
C
Cl
O
CH3CH2CH2C
Cl
butanoyl chloride
butyryl chloride
benzoyl chloride
Anhydrides: change acid to anhydride
O
H3C C
O
H3C C
O
ethanoic anhydride
acetic anhydride
O
O
O
phthalic anhydride
O
O
O
maleic anhydride
Amides: change –ic acid (common name) to –amide
-oic acid (IUPAC) to –amide
O
CH3CH2CH2C
NH2
butanamide
butyramide
O
C
NH2
benzamide
Esters: change –ic acid to –ate preceded by the name of the alcohol group
O
CH3CH2CH2C
O CH3
methyl butanoate
methyl butyrate
O
C
O CH2CH3
ethyl benzoate
Mechanism: Nucleophilic Acyl Substitution
1)
O
+ :Z
R C
W
2)
O
R C W
Z
O
R C W
Z
O
R C + :W
Z
RDS
Mechanism: nucleophilic acyl substitution, acid catalyzed
O
1) R C + H+
W
OH
2) R C
+ :ZH
W
OH
3) R C W
ZH
OH
R C
W
OH
R C W
ZH
RDS
O
R C + HW + H+
Z
Acid Chlorides
Syntheses:
RCOOH +
SOCl2
PCl3
PCl5
O
C
OH
 RCOCl
O
C
Cl
+ SOCl2
benzoic acid
benzoyl chloride
O
O
OH
3-methylbutanoic acid
isovaleric acid
+ PCl3
Cl
3-methylbutanoyl chloride
isovaleryl chloride
Acid chlorides, reactions:
1. Conversion into acids and derivatives:
a) hydrolysis
b) ammonolysis
c) alcoholysis
2. Friedel-Crafts acylation
3. Coupling with lithium dialkylcopper
4. Reduction
acid chlorides: conversion into acids and other
derivatives
Hydrolysis
O
O
H2O
Cl
OH
isovaleryl chloride
3-methylbutanoyl chloride
Ammonolysis
CH3CH2
O
C
Cl
NH3
CH3CH2
propionyl chloride
propanoyl chloride
Alcoholysis
O
C
Cl
benzoyl chloride
isovaleric acid
3-methylbutanoic acid
O
C
NH2
propionamide
propanamide
CH3CH2OH
O
C
OCH2CH3
ethyl benzoate
acid chlorides: Friedel-Crafts acylation
O
R C
Cl
O
R C Ar
AlCl3
+ ArH
+ HCl
phenone
O
CH3CH2CH2C Cl
+
butyryl chloride
O
CH3CH2CH2C Cl
butyryl chloride
CH3
AlCl3
toluene
+
O
CH3CH2CH2C
CH3
p-methylbutyrophenone
AlCl3
NO2
No reacton
+ ortho-
acid chlorides: coupling with lithium dialkylcopper
O
R C
Cl
+ R'2CuLi
O
R C R'
ketone
O
C
Cl
O
C CH2CH2CH3
+ (CH3CH2CH2)2CuLi
lithium di-n-propylcopper
benzoyl chloride
O
C
Cl
isobutyryl chloride
butyrophenone
O
+
2CuLi
lithium diisopropylcopper
2,4-dimethyl-3-pentanone
acid chlorides: reduction to aldehydes
O
R C
Cl
LiAlH(t-BuO)3
O
LiAlH(t-BuO)3
C
Cl
O
R C
H
O
C
H
mechanism, nucleophilic acyl substitution by hydride :H-
1)
2)
O
R C
Cl
O
R C Cl
H
+ :H
O
R C Cl
H
O
R C
H
+ Cl
RDS
Anhydrides, syntheses:
Buy the ones you want!
Anhydrides, reactions:
1) Conversion into carboxylic acids and derivatives.
a) hydrolysis
b) ammonolysis
c) alcoholysis
2) Friedel-Crafts acylation
O
COOH
O
+ H2O
COOH
O
phthalic anhydride
(CH3CO)2O
+ NH3
acetic anhydride
O
O
+ CH3CH2OH
O
succinic anhydride
phthalic acid
O
+
CH3 C
NH2
acetamide
O
CH3 C
ONH4
ammonium acetate
O
CH2COCH2CH3
CH2COH
O
ethyl hydrogen succinate
2) anhydrides, Friedel-Crafts acylation.
(RCO)2O + ArH
(CH3CO)2O +
acetic anhydride
AlCl3
O
O
R C Ar + R C
OH
phenone
CH3
AlCl3
O
H3C C
CH3 + CH3CO2H
p-methylacetophenone
toluene
O
O
+
O
phthalic anhydride
AlCl3
O
C
C OH
O
o-benzoylbenzoic acid
Amides, synthesis:
Indirectly via acid chlorides.
O
R C
OH
SOCl2
O
R C
Cl
NH3
O
R C
NH2
[ carboxylic acids form ammonium salts when reacted directly with ammonia ]
CH3CH2CH2CO2H
PCl3
butyric acid
PCl5
COOH
benzoic acid
O
CH3CH2CH2C
Cl
butyryl chloride
O
C
Cl
NH3
NH3
benzoyl chloride
O
CH3CH2CH2C
NH2
butyramide
O
C
NH2
benzamide
Amides, reactions.
1) Hydrolysis.
O
R C
NH2
H2O, H+ or OHheat
CH3
O
+ H2O
CH3CHCH2C
NH2
isovaleramide
O
R C
OH
H+
heat
CH3
O
CH3CHCH2C
OH
isovaleric acid
Esters, syntheses:
1) From acids
RCO2H + R’OH, H+
RCO2R’ + H2O
2) From acid chlorides and anhydrides
RCOCl + R’OH
RCO2R’ + HCl
3) From esters (transesterification)
RCO2R’ + R”OH, H+
RCO2R” + R’OH
RCO2R’ + R”ONa
RCO2R” + R’ONa
“Direct” esterification is reversible and requires use of
LeChatelier’s principle to shift the equilibrium towards the
products. “Indirect” is non-reversible.
O
C
H+
OH
isovaleric acid
+ CH3CH2OH
ethyl alcohol
O
C
O
+ H2O
ethyl isovalerate
SOCl2
O
C
Cl
+ CH3CH2OH
ethyl alcohol
isovaleryl chloride
O
C
O
ethyl isovalerate
+ HCl
In transesterification, an ester is made from another ester by
exchanging the alcohol function.
CH3
O
+ HO CHCH3
CH3CH2CH2C
OCH3
methyl butanoate
O
+
CH3CH2CH2C
OCH3
H+
isopropyl alcohol
CH2ONa
O
CH3
+ CH3OH
CH3CH2CH2C
O CHCH3
isopropyl butanoate
O
CH3CH2CH2C
O
benzyl alcohol
methyl butanoate
benzyl butanoate
+
CH2
CH3ONa
Esters, reactions:
1) Conversion into acids and derivatives
a) hydrolysis
b) ammonolysis
c) alcoholysis
2) Reaction with Grignard reagents
3) Reduction
a) catalytic
b) chemical
4) Claisen condensation
O
C
OH
O
H2O; H+ or OHC
OCH2CH3 heat
+ CH3CH2OH
ethyl benzoate
CH3 O
CH3CHC
O CH3
CH3 O
CH3CHC
NH2
NH3
+ CH3OH
methyl isobutyrate
H+
O
CH3C
OCH2CH3
ethyl acetate
+
OH
O
CH3C
O
cyclopentyl acetate
+ CH3CH2OH
Esters, reaction with Grignard reagents
O
R C
+ R'MgX
O R''
H2O
OH
R C R'
R'
3o alcohol
nucleophilic
acyl substitution
O
R C R'
ketone
nucleophilic
addition
+ R'MgX
+ R''OH
O
CH3CH2CH2C
+
MgBr
OCH3
methyl butanoate
phenyl magnesium bromide
H2O
OH
CH3CH2CH2C
1,1-diphenyl-1-butanol
Esters, reduction
a) catalytic
O
+ H2, Ni
R
NR
O R'
O
R
H2, CuO, CuCr2O4
O R'
150o, 5000 psi
O
LiAlH4
RCH2OH + R'OH
b) chemical
R
H+
RCH2OH + R'OH
O R'
O
O
H2, CuO, CuCr2O4
150o,
5000 psi
phenyl propanoate
+
OH
isobutyl alcohol isopropyl alcohol
isopropyl isobutyrate
O
CH3CH2C
O
OH
OH
1. LiAlH4
2. H+
CH3CH2CH2OH
n-propyl alcohol
+
phenol
Carbanions
|
— C: –
|
The conjugate bases of weak acids,
strong bases, excellent
nucleophiles.
1. Alpha-halogenation of ketones
OH- or H+
O
C C
H
+ X2
O
C C
X
+ HX
 -haloketone
X2 = Cl2, Br2, I2
H3C
O
C
CH3
acetone
+ Br2, NaOH
H3C
O
C
CH2Br
 -bromoacetone
+
NaBr
Carbanions. The conjugate bases of weak acids;
strong bases, good nucleophiles.
1. enolate anions
2. organometallic compounds
3. ylides
4. cyanide
5. acetylides
Aldehydes and ketones: nucleophilic addition
O
C
+ YZ
OY
C
Z
Esters and acid chlorides: nucleophilic acyl substitution
O
C
W
+ Z
O
C
Z
+ W
Alkyl halides: SN2
R X
+ Z
R Z + X
Carbanions as the nucleophiles in the above reactions.
2. Carbanions as the nucleophiles in nucleophilic
addition to aldehydes and ketones:
a) aldol condensation
“crossed” aldol condensation
b) aldol related reactions (see problem 21.18
on page 811)
c) addition of Grignard reagents
d) Wittig reaction
a) Aldol condensation. The reaction of an aldehyde or ketone
with dilute base or acid to form a beta-hydroxycarbonyl product.
CH3CH=O
acetaldehyde
OH
CH3CHCH2CH O
3-hydroxybutanal
O
CH3CCH3
acetone
OH O
CH3CCH2CCH3
CH3
dil. NaOH
dil. NaOH
4-hydroxy-4-methyl-2-pentanone
dil. NaOH
CH3CH=O
acetaldehyde
OH
CH3CHCH2CH O
3-hydroxybutanal
+ H2O
OH
CH2CH=O + CH3CH O
O
CH3CHCH2CH O
+ H2O
nucleophilic addition by enolate ion.
Crossed aldol condensation:
If you react two aldehydes or ketones together in an
aldol condensation, you will get four products. However, if
one of the reactants doesn’t have any alpha hydrogens it can be
condensed with another compound that does have alpha
hydrogens to give only one organic product in a “crossed”
aldol.
NaOH
CH3CH2CH O + H2C O
CH O
CH3CHCH2 OH
N.B. If the product of the aldol condensation under basic
conditions is a “benzyl” alcohol, then it will spontaneously
dehydrate to the α,β-unsaturated carbonyl.
CH=O + CH3CH2CH2CH=O
OH
CHCHCH=O
CH2
CH3
dil OH-
-H2O
CH=CCH=O
CH2
CH3
d) Wittig reaction (synthesis of alkenes)
1975 Nobel Prize in Chemistry to Georg Wittig
R
C O + Ph3P=C R'
ylide
CH2CH=O
Ph = phenyl
O R
C C R'
PPh3
+ Ph3P=CH2
R
C C R'
+ Ph3PO
CH2CH=CH2 + Ph3PO
3. Carbanions as the nucleophiles in nucleophilic acyl
substitution of esters and acid chlorides.
a) Claisen condensation
a reaction of esters that have alpha-hydrogens in basic
solution to condense into beta-keto esters
CH3COOEt
ethyl acetate
NaOEt
O
CH3CCH2COOEt + EtOH
ethyl acetoacetate
Mechanism for the Claisen condensation:
CH3COOEt
NaOEt
O
CH3CCH2COOEt + EtOH
OEt
CH2CHOOEt
CH3
O
C
OEt
CH3
O
C OEt
CH2COOEt
nucleophilic acyl substitution by enolate anion
Crossed Claisen condensation:
NaOEt
COOEt + CH3COOEt
O
C CH2COOEt
ethyl benzoate
OEt
HCOOEt + CH3CH2COOEt
ethyl formate
O
H C CHCOOEt
CH3
Carbanions II
Carbanions as nucleophiles in SN2 reactions with alkyl
halides.
a) Malonate synthesis of carboxylic acids
b) Acetoacetate synthesis of ketones
c) 2-oxazoline synthesis of esters/carboxylic acids
d) Organoborane synthesis of acids/ketones
e) Enamine synthesis of aldehydes/ketones
O
C OEt
CH2
C OEt
O
Na
O
C OEt
Na CH
C OEt
O
RX
O
C OEt
R CH
C OEt
O
H+,H2O
heat
diethyl malonate
O
C OH
R CH
C OH
O
heat
-CO2
Na
R CH2COOH
O
C OEt R'X
R C
C OEt
O
O
C OEt
R C R'
C OEt
O
H+,H2O
heat
O
C OH
R C R'
C OH
O
-CO2
heat
R CHCOOH
R'
O
C OEt
Na
CH2
C CH3
O
O
C OEt
RX
Na CH
C CH3
O
O
C OEt
R CH
C CH3
O
H+,H2O
heat
ethyl acetoacetate
heat
-CO2
O
R CH2CCH3
Na
O
C OEt R'X
R C
C CH3
O
O
C OEt
R C R'
C CH3
O
O
C OH
R CH
C CH3
O
H+,H2O
heat
O
C OH
-CO2
R C R'
heat
C CH3
O
O
R CHCCH3
R'
Amines
(organic ammonia)
:NH3
:NH2R or RNH2
1o amine
:NHR2 or R2NH
2o amine
:NR3
3o amine
NR4+
or R3N
(R may be Ar)
4o ammonium salt
NB amines are classified by the class of the nitrogen, primary
amines have one carbon bonded to N, secondary amines have
two carbons attached directly to the N, etc.
Nomenclature.
Common aliphatic amines are named as “alkylamines”
CH3NH2
methylamine
1o
CH3CH2NHCH3
ethylmethylamine
2o
(CH3)2NH
dimethylamine
2o
CH3CH2CHCH3
NH2
sec-butylamine
1o
(CH3)3N
trimethylamine
3o
CH3
CH3CCH3
NH2
tert-butylamine
1o
NH2
NH2
NH2
NH2
CH3
CH3
o-toluidine
aniline
H3C
N
CH3
m-toluidine
p-toluidine
CH3
H
N
N,N-dimethylaniline
diphenylamine
Amines, syntheses:
1. Reduction of nitro compounds
1o Ar
Ar-NO2 + H2,Ni  Ar-NH2
2. Ammonolysis of 1o or methyl halides
R-X = 1o,CH3
R-X + NH3  R-NH2
3. Reductive amination
avoids E2
R2C=O + NH3, H2, Ni  R2CHNH2
4. Reduction of nitriles
+ 1 carbon
R-CN + 2 H2, Ni  RCH2NH2
5. Hofmann degradation of amides
RCONH2 + KOBr  RNH2
- 1 carbon
1. Reduction of nitro compounds:
NH2
NO2
metal + acid; then OHor H2 + Ni, Pt, or Pd
R NO2
$$$
Chiefly for primary aromatic amines.
R NH2
2. Ammonolysis of 1o or methyl halides.
NH3
R-X
RNH2
R-X
R2NH
o
1o
2
R-X
R3N
3o
R-X
R-X must be 1o or CH3
R4N+X4o salt
CH3CH2CH2CH2Br
NH3
CH3CH2CH2CH2NH2
n-butylamine
3. Reductive amination:
O + NH3
O + RNH2
O + R2NH
Avoids E2
H2, Ni
or NaBH3CN
H2, Ni
CH NH2
1o amine
CH NHR
2o amine
CH NR2
3o amine
or NaBH3CN
H2, Ni
or NaBH3CN
4. Reduction of nitriles
R-CN + 2 H2, catalyst  R-CH2NH2
1o amine
R-X + NaCN  R-CN  RCH2NH2
primary amine with one additional carbon
(R must be 1o or methyl)
CH2Br
benzyl bromide
NaCN
CH2C N
2 H2, Ni
CH2CH2NH2
1-amino-2-phenylethane
5. Hofmann degradation of amides
O
R C
NH2
KOBr
R-NH2
Removes one carbon!
CH3 O
CH3C C
CH3 NH2
OBr
2,2-dimethylpropanamide
CH3
CH3C NH2
CH3
tert-butylamine
Amine, reactions:
1. As bases
2. Alkylation
3. Reductive amination
4. Conversion into amides
5. EAS
6. Hofmann elimination from quarternary
ammonium salts
7. Reactions with nitrous acid
1. As bases
a) with acids
b) relative base strength
c) Kb
d) effect of groups on base strength
2. Alkylation (ammonolysis of alkyl halides)
RNH2
1o
R-X
R2NH
R-X
R3N
3o
o
2
R-X
R4N+X4o salt
SN2: R-X must be 1o or CH3
CH3CH2CH2CH2Br
NH3
CH3CH2CH2CH2NH2
n-butylamine
3. Reductive amination
C O + RNH2
C O + R2NH
H2, Ni
CH NHR
2o amine
CH NR2
3o amine
or NaBH3CN
H2, Ni
or NaBH3CN
4. Conversion into amides
R-NH2 + RCOCl  RCONHR + HCl
1o
N-subst. amide
R2NH + RCOCl  RCONR2 + HCl
2o
R3N
3o
N,N-disubst. amide
+ RCOCl  NR
5. EAS
-NH2, -NHR, -NR2 are powerful activating groups and
ortho/para directors
a) nitration
b) sulfonation
c) halogenation
d) Friedel-Crafts alkylation
e) Friedel-Crafts acylation
f) coupling with diazonium salts
g) nitrosation
a) nitration
NH2
HNO3
TAR!
H2SO4
(CH3CO)2O
NHCOCH3
NH2
NHCOCH3
HNO3
H2O,OH-
H2SO4

NO2
+ ortho-
NO2
b) sulfonation
NH3
NH2
+ H2SO4
SO3
cold H2SO4
NH3 HSO4
c) halogenation
NH2
NH2
Br
Br
polyhalogenation!
+ Br2, aq.
Br
no catalyst needed
use polar solvent
Br
Br2,Fe
Br
HNO3
Br
H2/Ni
H2SO4
NO2
+ ortho-
NH2
e) Friedel-Crafts alkylation
NR with –NH2, -NHR, -NR2
NH2
CH3
+ CH3CH2Br, AlCl3
NR
Do not confuse the above with the alkylation reaction:
NH2
NHCH2CH3
CH3
CH3
+ CH3CH2Br
f) Friedel-Crafts acylation
NR with –NH2, -NHR, -NR2
NH2
CH3
+
O
H3C C
Cl
AlCl3
NR
Do not confuse the above with the formation of amides:
O
NH2
NHCCH3
CH3
CH3
O
+ H3C C
Cl
g) nitrosation
H3C
N
H3C
CH3
N
CH3
NaNO2, HCl
O
N
The ring is sufficiently activated towards EAS to react
with the weak electrophile NO+
h) coupling with diazonium salts  azo dyes
N2 Cl
NH2
NH2
CH3
CH3
+
benzenediazonium
chloride
an azo dye
N
N
6. Hofmann elimination from quarternary hydroxides
step 1, exhaustive methylation  4o salt
step 2, reaction with Ag2O  4o hydroxide + AgX
step 3, heat to eliminate  alkene(s) + R3N
(xs) CH3I
CH3
CH3CH2CH2CH2 N CH3
CH3
CH3CH2CH2CH2 NH2
CH3
CH3CH2CH2CH2 N CH3
CH3
I-
CH3
CH3CH2CH2CH2 N CH3 OH
CH3
Ag2O

I-
CH3
CH3CH2CH2CH2 N CH3 OH- + AgI
CH3
CH3CH2CH=CH2 + (CH3)3N
7. Reactions with nitrous acid
primary amines
R-NH2
N N
+ HONO
NH2
+ HONO
diazonium salt
N2 + mixture of alchols & alkenes
secondary amines
H
N R
O
N
N R
+ HONO
N-nitrosamine
tertiary amines
N R + HONO
R
O
N
N R
R
p-nitrosocompound
Diazonium salts
synthesis
HNO3
NO2
H2SO4
H2, Ni
HONO
N N
benzenediazonium ion
NH2
Diazonium salts, reactions
1. Coupling to form azo dyes
2. Replacements
a) -Br, -Cl, -CN
b) -I
c) -F
d) -OH
e) -H
f) etc.
coupling to form azo dyes
N2
G
G
+
an azo dye
G = OH, NH2,
NHR, NR2, etc.
CH3
H3C N
N N
+
N,N-dimethylaniline
N2
SO3H
CH3
H3C N
N N
methyl orange
SO3H
Cl
Br
CN
I
F
H3PO2
NH2
H2O,H+
HBF4
KI
CuCN
CuBr
CuCl
NO2
N2
OH
Phenols
Ar-OH
Phenols are compounds with an –OH group
attached to an aromatic carbon. Although they
share the same functional group with alcohols,
where the –OH group is attached to an
aliphatic carbon, the chemistry of phenols is
very different from that of alcohols.
Nomenclature.
Phenols are usually named as substituted phenols. The
methylphenols are given the special name, cresols. Some other
phenols are named as hydroxy compounds.
CH3
OH
OH
OH
OH
COOH
Br
phenol
m-bromophenol
OH
OH
o-cresol
salicylic acid
OH
COOH
OH
OH
OH
OH
catechol
resorcinol
hydroquinone
p-hydroxybenzoic acid
phenols, syntheses:
1. From diazonium salts
OH
N2
H2O,H+
2. Alkali fusion of sulfonates
SO3 Na
NaOH,H2O
300o
ONa
H+
OH
phenols, reactions:
1. as acids
2. ester formation
3. ether formation
4. EAS
a) nitration
f) nitrosation
b) sulfonation
g) coupling with diaz. salts
c) halogenation
h) Kolbe
d) Friedel-Crafts alkylation
i) Reimer-Tiemann
e) Friedel-Crafts acylation
as acids:
with active metals:
OH
ONa
Na
+ H2(g)
sodium phenoxide
with bases:
CH4 < NH3 < HCCH < ROH < H2O < phenols < H2CO3 < RCOOH < HF
ONa
OH
+ NaOH
SA
SB
+ H2O
WB
WA
2. ester formation (similar to alcohols)
OH
CH3
O
+ CH3CH2C
OH
H+
O
CH3CH2C
O
H3C
O
H3C C
OH
COOH
O
COOH
+ (CH3CO)2O
salicyclic acid
aspirin
+ H2O
3. ether formation (Williamson Synthesis)
Ar-O-Na+ + R-X  Ar-O-R + NaX
note: R-X must be 1o or CH3
Because phenols are more acidic than water, it is possible
to generate the phenoxide in situ using NaOH.
OCH2CH3
OH
+ CH3CH2Br, NaOH
CH3
CH3
4. Electrophilic Aromatic Substitution
The –OH group is a powerful activating group in EAS
and an ortho/para director.
a) nitration
OH
OH
HNO3
O2N
NO2
polynitration!
NO2
OH
OH
OH
dilute HNO3
NO2
+
NO2
b) halogenation
OH
OH
Br2 (aq.)
Br
Br
no catalyst required
use polar solvent
polyhalogenation!
Br
OH
OH
OH
Br2, CCl4
Br
+
non-polar solvent
Br
c) sulfonation
OH
OH
SO3H
H2SO4, 15-20oC
OH
H2SO4, 100oC
SO3H
At low temperature the reaction is non-reversible and the lower Eact orthoproduct is formed (rate control).
At high temperature the reaction is reversible and the more stable paraproduct is formed (kinetic control).
d) Friedel-Crafts alkylation.
OH
OH
+
CH3
H3C C CH3
Cl
AlCl3
H3C C CH3
CH3
e) Friedel-Crafts acylation
OH
OH
O
+
CH3CH2CH2C
AlCl3
Cl
O
Do not confuse FC acylation with esterification:
OH
O
O
+
CH3CH2CH2C
Cl
O
Fries rearrangement of phenolic esters.
OH
O
O
+
CH3CH2CH2C
O
Cl
AlCl3
OH
O
f) nitrosation
OH
OH
HONO
p-nitrosophenol
NO
EAS with very weak electrophile NO+
OH
OH
CH3
CH3
NaNO2, HCl
NO
g) coupling with diazonium salts
(EAS with the weak electrophile diazonium)
N2 Cl
OH
OH
CH3
CH3
+
benzenediazonium
chloride
an azo dye
N
N
h) Kolbe reaction (carbonation)
OH
ONa
+ CO2
COONa
125oC, 4-7 atm.
sodium salicylate
H+
EAS by the weakly
electrophilic CO2

O C O
OH
COOH
salicylic acid
i) Reimer-Tiemann reaction
OH
OH
CHCl3, aq. NaOH
H+
CHO
70oC
salicylaldehyde
The salicylaldehyde can be easily oxidized to salicylic acid
Nomenclature
Syntheses
Reactions
Mechanisms
Spectroscopy
Aromatic Hydrocarbons (Electrophilic Aromatic Substitution)
Spectroscopy (infrared & H-nmr)
Arenes
Aldehydes & Ketones
Carboxylic Acids
Functional Derivatives of Carboxylic Acids
Acid Chlorides, Anhydrides, Amides, Esters
Carbanions
Amines & Diazonium Salts
Phenols
Mechanisms:
Electrophilic Aromatic Substitution
Nitration
Sulfonation
Halogenation
Friedel-Crafts Alkylation & Acylation
Nucleophilic Addition to Carbonyl
Nucleophilic Addition to Carbonyl, Acid Catalyzed
Nucleophilic Acyl Substitution
Nucleophilic Acyl Substitution, Acid Catalyzed