Organic Chemistry Carboxylic Acids and Derivatives Worksheets

CHM2211COrganic Chemistry I
Chapter 20 Core Concepts Part 1
Name:
Date:
Chapter 20: Carboxylic Acids and Derivatives
1. Carboxylic Acids
a. Nomenclature
i. Monoacids
4-ethoxybenzoic acid
O
HO
Decanoic Acid
CO2H
ii. Diacids
Malonic Acid
O
OH
HO
O
O
HO
Succinic Acid
O
OH
b. Physical Properties – dimer formation
What type of IMF do you associate with carboxylic acids?
c. Acidity of H of carboxylic acid – Write and balanced equation and mechanism for the
reaction of acetic acid with water.
d. Synthesis
i. Grignard with CO2 and H3O+
Starting with benzene synthesize benzoic acid using a grignart.
ii. Hydrolysis of CN
Starting with pentane synthesize pentanecarboxylic acid
iii. Oxidation of sidechain on benzene
Write a reaction for the synthesis of Benzoic acid from Cumene.
iv. Cleavage of alkynes
Write a reaction for the synthesis of 2 moles of acetic acid from 2-butyne.
CHM2211C
Organic Chemistry I
Chapter 20 Core Concepts Part 2
Name:
Date:
Chapter 20: Carboxylic Acids and Derivatives
e. Reactions
i. Reduction with LiAlH4, H2O – Primary Alcohol formation
Starting with benzoic acid synthesize benzyl alcohol using LiAlH4, H2O. Also write the mechanism
ii. Fischer Esterificaiton – ROH and H3O+
Write a balanced equation and mechanism for the reaction of benzoic acid and methanol. Each step is
in equilibrium.
iii. SOCl2 – Acid Chloride formation
Write a balanced equation and mechanism for the formation of Benzoyl Chloride from Benzoic Acid
iv. Decarboxylation of beta keto acids – Draw the product for the following reaction
O
O
Heat
OH
v. Decarboxylation of beta dicarboxylic acids – Draw the products for the following
reaction.
O
Heat
OH
HO
O
CHM2210C
Organic Chemistry I
Chapter 21 Core Concepts Part 1
Name:
Date:
Chapter 21: Enolates
1. Enolates
a. Enolate formation
i. Draw the mechanism for the formation of the enolate formed from the reaction
of acetone and sodium hydroxide.
ii. Draw the mechanism for the formation of an enol formed from the reaction of
acetone and hydronium and water.
b. Aldol Condensation
i. Draw the mechanism for the above reaction.
c. Intramolecular Aldol Condensation
d. Claisen Condensation
O
2CH3COEt
Ethyl ethanoate
(Ethyl acetate)
O
O
CH3CCH2COEt + EtOH
2. H 2O, HCl
Ethyl 3-oxobutanoate Ethanol
(Ethyl acetoacetate)
–
1. EtO Na
+
i. Draw the mechanism for the above reaction.
e. Dieckmann Condensation
O
EtO
–
OEt
O
Diethyl hexanedioate
(Diethyl adipate)
1. EtO Na
+
2. H 2 O, HCl
O
O
OEt
+
Ethyl 2-oxocyclopentanecarboxylate
EtOH
i. Draw the mechanism for the above reaction.
CHM2210C
Organic Chemistry I
Chapter 21 Core Concepts Part 2
Name:
Date:
Chapter 21: Enolates
f. Acetoacetic Ester Synthesis
i. Show the synthesis of Ethyl acetate from Acetic Acid. (Think backwards!)
ii. Using a Claisen condensation show the synthesis of Ethyl acetoacetate from
ethyl acetate.
O
O
CH3CCH2 COEt
Ethyl acetoacetate
(Acetoacetic ester)
O
CH3CCH2 R A monosubstituted
acetone
O
CH3CCHR
R’
A disubstituted
acetone
3
iii. Form the following compound using Acetoacetic Ester Synthesis starting with
acetic acid.
O
g. Malonic Ester Synthesis
i. In the space below synthesize diethyl malonate from malonic acid.
4
O
O
EtOCCH2COEt
Diethyl malonate
(Malonic ester)
i.
O
RCH2COH A monosubstituted
acetic acid
R O
RCHCOH
A disubstituted
acetic acid
Form the following compound using Malonic Ester Synthesis starting with
malonic acid.
O
HO
From
Malonic Acid
5
CHM2210C
Organic Chemistry I
Chapter 21 Core Concepts Part 3
Name:
Date:
Chapter 21: Enolates
h. Michael Reaction
i. In the space below write the mechanism for the two reactions in letter h.
i.
Robinson Annulation
O
O
COOEt
1. NaOEt, EtOH
+
(Michael reaction)
Ethyl 2-oxocyclohex- 3-Buten-2-one
anecarboxylate
(Methyl vinyl
ketone)
O
COOEt
j.
O
(Aldol reaction)
Gilman Reagent – Michael Reaction
O
1. (CH3 )2 CuLi, ether, -78°C
CH3
3-Methyl-2cyclohexenone
2. H2 O, HCl
O
2. NaOEt, EtOH
COOEt
O
CH 3
CH3
3,3-Dimethylcyclohexanone
k. LDA (Lithium Diisopropyl Amide) – Kinetic (excess LDA) vs. Thermodynamic (excess
ketone) Control
i. Write a mechanism for each case above
Excess LDA
Excess ketone
CHM2210C
Organic Chemistry I
Chapter 22 Core Concepts Part 1
Name:
Date:
Chapter 22: Amines
1. Amines
a. Nomenclature
i. Fill in the blank with either the name or the structure of the amine.
Pentylpropylamine
H
N
Cyclopentylamine
Benzylamine
b. Physical Properties
i. What is the major IMF for amines? Draw a diagram to support your answer.
c. Bacisity of Amines – For the following compounds order them from weakest bast to
strongest base: p-methylaniline, p-chloro aniline, aniline, p-aminoaniline, p-nitroaniline.
(hint: look at the pKa of each and the structure of each).
Weakest
Strongest
d. Spectroscopy
IR
Primary amine
Secondary amine
1HNMR
1
e. Synthesis
i. Nitrile to Amine with LiAlH4 – See Carboxylic Acid Derivatives Sheet.
ii. Gabriel Synthesis – Synthesize methylamine using Gabriel Synthesis.
iii. Azide followed by reduction with LiAlH4
+
K N3
Ph CH 2 Cl
Benzyl chloride
–
1. LiAlH4
Ph CH2 N3
2. H2 O
Benzyl azide
Ph CH2 NH 2
Benzylamine
1. Write a mechanism for the formation of benzylamine from benzyl azide.
iv. Reduction of an imine
O
CH3
C
CH3NH2
CH3
+
H
NCH3
CH3
C CH3
1) LiAlH4
2) H2O
NHCH3
CH3
CH CH3
v. Reduction of an amide
O
CH3
NH3
C Cl
O
CH3
C NH2
1) LiAlH4
2) H2O
CH3 CH2 NH2
vi. Reduction of a nitro group
CH3
Zn, HCl
CH3
NO2
CH3CH2OH
NH2
2
CHM2210C
Organic Chemistry I
Chapter 22 Core Concepts Part 2
Name:
Date:
Chapter 22: Amines
vii. Separation of Amine and Neutral Compound
Reaction with acids
• Figure 23.2 Separation and purification of an amine
and a neutral compound.
26
f. Reactions
i. ArNH2 with Nitrous Acid
1
ArNH2 with HNO2
• The -N2+ group of an arenediazonium salt can be
replaced in a regioselective manner by these groups.
40
3
ii. Hofmann Elimination
Hofmann Elimination
• Hofmann elimination: Thermal decomposition of a
quaternary ammonium hydroxide to give an alkene.
• Step 1: Formation of a 4
ammonium hydroxide.
44
iii. Cope Elimination
1. Oxidation of the 3o amine gives an amine oxide.
O
CH2
N
CH 3
H2O2
CH2
CH 3
N
CH 3
CH 3
2. Step 2 is the elimination to yield the alkene.
O
100 oC – 150 oC
CH2
N
CH 3
CH2
+ (CH3)2NOH
CH 3
4
g. Multistep Synthesis – Synthesize the following compound
HO 2C
CO2H
From
Benzene
CO2H
5