Exercise Sheet 1: Functional groups in Organic Chemistry.
b
1- Classify the ten molecules shown below according to the functional group and write the
number of the molecule on the corresponding box:
Exercise Sheet 1: Functional groups in Organic Chemistry. b
2- Recognize and name the functional groups in the following molecules of biological
interest:
3- Complete the next puzzle as a “Sudoku”1 of 9x9, divided in 3x3 sub-sections. The idea is
to complete each row, column and sub-section with the numbers 1 to 9, referring to 9
functional groups.
1
Sudoku Home Page: https://sudoku.com
Exercise Sheet 1: Functional groups in Organic Chemistry. b
4- Write the structural molecule for each case:
a) An alcohol and ether with the molecular formula C4H10O
b) An aldehyde and ketone with the molecular formula C3H6O
c) A carboxylic acid and ester with molecular formula C3H6O2
d) An amine with molecular formula C3H9N
e) An amide with molecular formula C3H7NO
5- The Krebs Cycle (a metabolic pathway)
is a chain of chemical reactions that forms
part of the cellular respiration in aerobic
cells. This cycle, also known as Citric
acid cycle or tricarboxylic acid cycle is
part of a catabolic pathway that oxidizes
carbone hydrates, fatty acids and amino
acids to CO2, producing energy in the
form of reducing power (NADH and
FADH2) and ATP2.
Identify and name the functional
groups in the molecules involved in
the Krebs cycle.
6- Name the functional group and carbon
hybridization of the molecules given below:
2
The oxidative metabolism of carbohydrates, fatty acids and proteins is frequently divided in three stages, being
the Krebs Cycle the second stage. In the first stage the carbons of these macromolecules form two carbon
molecules called acetyl-CoA, which includes the catabolic pathway for certain amino acids, beta-oxidation of fatty
acids and glycolysis. The third stage is the oxidative phosphorylation, in which the reducing power (NADH and
FADH2) is used for ATP synthesis. The Krebs cycle also provides precursors for many biomolecules, such as
amino acids. Therefore, it is considered an amphibolic pathway, indicating that it functions as catabolic and
anabolic pathways at the same time.
Exercise Sheet 2: General introduction to organic chemistry. . b
Organic molecule properties. b
1- For each structure, choose which bond best fits the description:
i) The C–C bond is longer in: H–C≡C–CH2–CH3 ii) The C–C bond is shorter in: H3C–C≡C–CH2–CH=CH2
iii) The C–H bond is longer in: iv) The C–H bond is shorter in:
2- Predict the bond lengths for the following chemical compounds:
i) 1-Hexen-5-yne ii) 3-Hexen-1-yne
a) For the compound (i) explain the difference in distance between H–C1, H–C4 and H–C6.
b) Explain the difference in distance C2–C3 between compounds (i) and (ii).
3- For the following compounds, complete the Lewis structures and designate the formal
charge for C, N and O.
4- a) Classify the following substituents according to their inductive effect (+I or -I):
b) Classify the following substituents according to their resonant effect (+M or -M):
5- From each group of resonance structures, designate which one will contribute the most to
the resonance hybrid and explain why.
Exercise Sheet 3: General introduction to organic chemistry. . b
Organic molecule properties. b
1- The compounds shown below have the following dipole moments:
Explain why the value of the dipole moment in b) is higher than a).
2- Given the following compounds:
i) (CH3)2NH ii) CH3CH2F iii) (CH3)3N iv) (CH3)2CO v) CH3OCH2CH2OH
a) Draw structures showing the hydrogen bonds (if there are any) that are expected to be in
the pure compounds in liquid state.
b) Indicate which ones can establish hydrogen bonds with water and explain why.
3- Predict the solubility order in water for the following compounds. Explain.
a) Methanol: CH3OH b) Methanoic acid: c) Toluene:
4- a) For compounds (A-H), identify which ones, in pure liquid state, follow these statements:
i) The compound can establish exclusively intramolecular hydrogen bonds.
ii) The compound can establish exclusively intermolecular hydrogen bonds.
iii) The compound can establish intramolecular and intermolecular hydrogen bonds.
iv) The compound can not establish hydrogen bonds.
Note: each statement may include
between zero and three compounds.
b) Show the hydrogen bonds that
have compound F with water.
c) Between compound E and
compound J: which one has a higher
boiling point?
5- The structure of lynestrenol, which is a compound found in some contraceptives is
showed below:
Identify in the structure an example of each one of the following bonds or atoms:
a) A highly polarized covalent bond.
b) A poorly polarized covalent bond.
c) A carbon atom with sp hybridization.
d) A carbon atom with sp2 hybridization.
e) A carbon atom with sp3 hybridization.
f) A bond between atoms with different hybridization
g) A primary, secondary and tertiary carbon atom
h) A quaternary carbon atom
Exercise Sheet 3: General introduction to organic chemistry. . b
Organic molecule properties. b
6- Write the resonance structures of the following compounds, indicating in each case which
is the most stable and why.
7- Compare the stability of each pair of organic ions:
Exercise Sheet 4: Conformations and Stereochemistry. b
1- Represent the three-dimensionally conformational study for ethane and butane.
2- Represent the next compound: 2-Chloro-3-methylbutane in Sawhorse projection and
Newman projection.
a) Represent the possible conformations resulting from variation of the dihedral angle
Cl-C2-C3 between 0° and 360° with increments of 60°.
b) Predict and visualize which one is the conformer.
3- a) Analyze the conformations of cyclohexane.
b) Identify the unfavorable 1,3-diaxial interactions in the chair conformation and the
1,4-pseudoaxial interactions in the boat conformation.
4- Represent for each compound all possible conformations and identify the conformer:
a) Methylcyclohexane.
b) t-Butylcyclohexane.
5- Represent the following compounds in their corresponding projections for each case.
6- Represent the balanced conformations of the following compounds, identifying which one
is the most stable:
a) cis-1,2-Dimethylcyclohexane. b) trans-1,2-Dichlorehexane.
c) d)
7- Indicate the stereochemical relationship between the following pair of compounds and the
absolute configuration of their chiral carbons:
Exercise Sheet 4: Conformations and Stereochemistry. b
8- Formulate the next compound according to the given stereochemistry, indicating if it is
optically active or not: (2S,3R)-2,3-Dimethoxybutane.
9- Complete the following projections.
a) (R,S)-1,2-Dibromo-1,2-diphenylethane
b) (2R,3S)-3-Bromo-2-butanol
c) Do the mentioned compounds present optical activity? Explain why.
10- Complete the boxes as indicated in each case:
Exercise Sheet 4: Conformations and Stereochemistry. b
11- (EXAM) a) Classify the pairs of compounds into one of the following groups: conformers,
enantiomers, diastereomers, pair of meso compounds (one for each group).
b) Explain why compound C1 is more soluble in water than A1.
12- (EXAM) a) Identify the relation between compound (A) and each one of the other given
compounds. Classify them as: equals, epimers, functional isomers, positional isomers.
b) Decide the absolute configuration of the chiral carbons from compound (A).
c) Explain whether the compound (A) is capable of dissolving in water. Show the type of
interaction that this compound can establish with this solvent.
d) Considering compound (A) and compound (*), which one has a higher boiling point?
Explain.
13- From a stereochemical point of view, analyze the compounds shown below:
i) Bromochloroiodomethane
ii) 2-Bromo-3-fluorobutane
iii) 2,3-Dibromobutane
Exercise Sheet 5: Alkanes and cycloalkanes. Isomerism, .. b
terminology, reactions and physical properties. b
1- a) Name the following compounds using IUPAC terminology:
b) Write the structure of:
iii) 6,6-Diethyl-2-methyl-4-propyloctane
iv) 5-(1-Ethyl-1-methylpropyl)-5-propylnonane
2- Identify if these structures correspond to 2,4-dimethyloctane or an isomer:
3- Write all possible isomers using the following formula: C4H10, C4H9Br y C3H6O2. Classify
the isomers in: chain isomers, position isomers or function isomers.
4- Write the majority products obtained in the next halogenation reactions under homolytic
cleavage conditions:
5- The reaction between 2,3-Dimethyl-2-Butene and bromine that is catalyzed by light gives
two compounds (A) and (B). Propose a mechanism to obtain these products.
6- In proteins, amino acids establish different types of
attractive interactions: ionic interactions, hydrogen
bonds, dipole-dipole interactions and Van der
Waals interactions, among others (shown as
dotted lines in the image). Identify each one of
the interactions previously mentioned.
Exercise Sheet 6: Alkenes and alkynes. Isomerism, terminology,. b
reactions, physical properties and stereochemistry. b
1- Name the following compounds according to IUPAC and identify the hybridization for each
carbon atom.
2- Isoprene, which is an essential structure of many natural compounds, has the following
IUPAC name: 2-methyl-1,3-butadiene. Write its structural formula.
3- Identify if these alkenes correspond to a Z or E configuration.
4- Order the following substituents according to Cahn-Ingold-Prelog rules from higher to
lower priority:
5- For the next reactions, choose the correct product and explain why.
6- Starting from an alkene of your choice, designate the reagents and reaction conditions to
form each of the following compounds:
Propose a mechanism for compound b). Which difference is present between this
mechanism and the mechanism from Exercise 2?
Exercise Sheet 6: Alkenes and alkynes. Isomerism, terminology,. b
reactions, physical properties and stereochemistry. b
7- Given the next reactions:
a) Complete the products.
b) Write the mechanisms to obtain (D) and (E).
8- a) Identify the position isomers of butene. Show in which ones isomery cis/trans is present
b) Explain why a trans alkene can't be transformed into a cis alkene.
c) Explain the difference in water solubility between fumaric acid and maleic acid.
d) Write the dipole moment (module, direction and sense) for both compounds.
9- Write the products (A-D) for the next reactions, and the mechanisms to obtain A, B and D.
Exercise Sheet 7: Alkyl halides. b
1- Represent three-dimensionally the following mechanisms:
2- Given the next reactions upon compound (A):
Formulate the structures of the obtained products and propose the corresponding
mechanisms. Specify if they keep the deuterium atom (D).
3- Given the following reactions:
a) Write the structures for both products and the mechanism to obtain compound A.
b) Establish the absolute configurations of the chiral carbons for the reagents and products.
c) Write whether the products are optically active or not.
d) Establish the stereochemical relation between A and B.
Exercise Sheet 7: Alkyl halides. b
4- (EXAM) a) Classify the next reactions according to their mechanism in SN1, SN2, E1, E2.
b) Write the mechanism for the reactions with (*).
5- a) Which of the following bromide halides will react faster in a SN2?
b) Which of the previous bromide halides will react faster in an E1?
c) Classify the following carbocations in order from higher to lower stability:
d) Between the structures shown below, identify which one belongs to this reaction:
Exercise Sheet 7: Alkyl halides. b
e) Which one is the main product of the following reaction?
f) Radical chlorination (Cl2, hυ) is not selective. Which of the following compounds will
experience the most selective monochlorination?
6- For the compounds represented ahead, indicate whether they would react preferably
under SN1 (EtOH, Δ) or SN2 (KI/Acetone, Room temperature) conditions.
Write the products and the mechanisms of each process.
Exercise Sheet 8: Aromatic compounds. b
1- Pyridine and furan are heterocyclic compounds that classify as
aromatic, as they chemically behave as benzene.
Indicate the electronic distribution that explains this similarity.
2- For an SEAr reaction, the reactive order and orientation for these
compounds are:
aniline (ortho and para orientation) > benzene > nitrobenzene (meta orientation).
Explain these statements.
3- For the next synthetic sequence, indicate the products A - E. Write the mechanism for A → B
4- Plan a synthetic sequence to obtain each of the following products, with good performance,
using as starting material ethylbenzene and the organic and inorganic reagents considered
necessary. o-nitrobenzoic acid; p-nitrobenzoic acid; m-nitrobenzoic acid.
5- (EXAM) a) For each one of the statements in the first column, choose a substituent from
the second column (X) that fits the description of the compound on the right.
Column I Column II (X)
a) X gives electrons by inductive effect but neither donates nor accepts electrons –OH
by resonance.
b) X accepts electrons for inductive and resonance effects. –Br
c) X deactivates the ring and lead ortho/para in SEAr reactions . –CH2CH3
d) X accepts electrons by inductive effect, gives electrons by resonance effect and –NO2
activates the ring.
b) Choose which would be (X) for this following case.
Propose a mechanism that explains the reaction.
6- a) Propose structures for aromatic compounds that fits the next formula: C7H9N,
C6H3Cl2Br, C4H3NO3.
b) Calculate the DU (Degree of Unsaturation) for nitrobenzene and benzonitrile.
Exercise Sheet 8: Aromatic compounds. b
7- (EXAM) Given the following compounds (A - F), explain briefly:
a) Which one(s) would be more reactive than benzene in relation to nitration?
b) Which one(s) go through substitution in the meta position of the ring when treated with Br2
in presence of Fe?
c) Choose a compound from part (a) and describe the nitration mechanism.
8- Given the following reactions upon compound C:
a) Write the conditions needed to obtain compounds D, E and F.
b) Classify each reaction according to the mechanism involved in this process.
Propose a reaction mechanism to obtain E from C.
Exercise Sheet 9: Alcohols, phenols and ethers. b
1- Name the following compounds according to IUPAC:
2- For the next compounds, analyze the capacity to establish inter and intramolecular
hydrogen bonds: a) 4-hydroxybenzoic acid b) 2-hydroxybenzoic acid
3- Indicate the products of the next reactions:
4- Identify the structure for the following compounds (A - C) using the provided information:
a) Compound (A) is optically inactive, with molecular formula C4H10O, does not experience
oxidation with CrO3/H2SO4 but releases hydrogen when treated with Na.
b) Compound (B) is optically inactive, with molecular formula C4H10O, does not experience
oxidation with CrO3/H2SO4 nor release hydrogen when treated with Na.
c) Compound (C) is optically active, with molecular formula C4H10O, and does experience
oxidation with CrO3/H2SO4.
Exercise Sheet 9: Alcohols, phenols and ethers. b
5- The reactivity for aliphatic alcohols differs from that of aromatic (phenols) alcohols.
Indicate for each case whether there is a reaction or not. If affirmative, then write the
obtained products.
6- Formulate an alcohol and the corresponding oxidant to use as reagents in an oxidation
reaction to obtain: 3-ethyl-2,2-dimethylpentanoic acid.
7- Explain the following statements related to alcohols:
a) The boiling point for butane is - 0.5 °C, meanwhile for n-propanol (with similar molecular
weight) is 97°C.
b) The alcohols with 1 - 4 carbon atoms have great solubility in water.
8- Propose the reaction for n-propanol with each reagent:
a) K2Cr2O7/H2SO4/Δ
b) Na(s)
c) H2SO4(c)/Δ
d) HCl(c)
9- Complete these reactions with the main organic product:
Exercise Sheet 9: Alcohols, phenols and ethers. b
10- Which compound(s) would be the product(s) of the following reaction?
11- Identify the structure for the following compounds (A - C) using the provided information:
Compound (A) with the molecular formula C6H6O, experiences deprotonation when treated
with Na, and it undergoes an SN2 reaction with CH3Br to produce compound (B). Compound
(B) when treated with HNO3 (c)/H2SO4 (c) mainly generates compound (C), with formula:
C7H7NO3.
12- Propose a synthetic pathway for the next compounds, using phenol as reagent:
a) 2-bromo-4-methylphenol b) p-nitrophenol c) p-isopropylphenol
13- complete the reactions with the main organic product:
Exercise Sheet 10: Carboxylic acids and derivatives. Part I b
1- Name the following compounds according to IUPAC and indicate stereochemistry if
corresponds:
2- The following reactivity order of carboxylic acid derivatives against nucleophiles is known:
Acetic anhydride > methyl acetate > acetic acid
Explain these statements.
3- Study theoretically the following mechanism, predicting atomic charges, bond lengths and
geometries.
4- i) Complete the next reactions, showing the mechanisms from parts a) and b):
ii) Indicate the reaction conditions to obtain 1-propanol from propanoic acid.
Exercise Sheet 10: Carboxylic acids and derivatives. Part I b
5- It is known that an unknown compound (I) has the following characteristics:
i) It has the molecular formula: C7H14O.
ii) Deviates polarized light.
iii) When treated with con SOCl2 / Py (pyridine), followed by a reaction with KCN it produces
compound (II), with the molecular formula: C8H13N.
iv) When (II) is treated under hydrolysis conditions (NaOH/heat), 2-((1R, 3R)-3-methylcyclopentyl)
acetic acid is obtained.
a) Write structures (I) and (II) explaining your justification. Indicate the mechanisms involved in
part iii).
b) Explain the purpose of the Py (pyridine) in the first reaction of part iii).
Exercise Sheet 11: Carboxylic acids and derivatives. Part II b
1- Name the following compounds according to IUPAC and indicate stereochemistry if
corresponds:
2- Complete the following sequence of reactions:
3- Compound A with the formula C7H5N is heated in an acid medium to generate compound
B with the formula C7H6O2. B reacts with thionyl chloride to obtain compound C, which is
very reactive. Compound C is treated with D, with molecular formula C2H6O, which
generates compound E. Note: compound B may be obtained through oxidation with KMnO4
and heat starting from propylbenzene.
a) Write the structures (A - E).
b) Write all the reactions involved.
4- Compound A with the formula C7H11NO2 can be any of the following products:
Is it known that compound A deviates polarized light and X ray diffraction experiments
indicate that this compound has a C–N bond of 1.17 Å.
Data of average length bonds: C–N = 1.47 Å, C=N = 1.28 Å, C≡N = 1.16 Å.
a) Identify which structure corresponds to compound A.
b) What happens when A is treated in an acidic-aqueous medium and heat?
Exercise Sheet 11: Carboxylic acids and derivatives. Part II b
5- N-(4-hydroxyphenyl)ethanamide, also known by its common name paracetamol, is an
analgesic and antipyretic used to treat mild to moderate pain and fever, and is prepared
industrially (in its last step) by a selective acetylation which is shown below:
a) Explain the mechanism to obtain paracetamol.
b) Why is it said to be a selective acetylation? Explain.
Exercise Sheet 12: Amines. Acid-base. b
1- Classify the following structures as primary, secondary or tertiary amines, and name them
according to IUPAC.
2- The compound 4-methylpiperidine has a higher boiling point than N-methylpiperidine.
Explain why.
3- a) Design a synthetic pathway to obtain o-bromoiodobenzene starting from aniline.
b) Indicate how to prepare m-isopropylnitrobenzene from cumene (isopropylbenzene).
4- Organize the acidity of the following compounds in increasing order: cyclohexanol,
phenol, p-nitrophenol and benzoic acid. Explain your rearrangement.
5- Predict the acidity order of the following compounds: cyclohexanol, phenol,
2,4-dinitrophenol. Explain your rearrangement.
6- Explain the acidity order of these compounds:
7- Explain the following statements:
a) 4-Methoxypyridine is more basic than Pyridine.
b) Aniline is more basic than p-Bromoaniline.
c) The basicity of B is lower than A.
8- (EXAM) a) The amino acid Alanine (2-aminopropanoic acid) can adopt two enantiomeric
forms. Explain why and formulate both enantiomers.
b) Alanine has great solubility in both dilute HCl and dilute NaOH. Explain using reactions
these solubilities.
c) The boiling point of the ethyl ester from alanine (ethyl 2-aminopropanoate) is lower than
the boiling point of alanine. Explain why
d) When alanine reacts with another amino acid, for example, glycine (2-aminoethanoic acid)
it produces an amide bond known as peptide bond. Draw the type of bond with the functional
groups involved in its structure, as well as the process.
Exercise Sheet 12: Amines. Acid-base. b
9- (EXAM) The nitrogen atom from the aniline is
significantly less reactive as a nucleophile than the
nitrogen atom from an aliphatic primary aniline.
Explain this observation.
10- (EXAM) For the functional group amine:
a) Formulate an amine of natural origin.
b) Indicate whether it is possible for this amine to form intra and intermolecular hydrogen
bonds. If possible, describe examples.
c) Indicate an example for the following reactions:
i) Acetylation of a primary amine.
ii) Formation of imine or shift bases.
iii) Diazotization of aromatic amines.
iv) Classify these amines as acidic, basic or neutral and explain why.
11- (EXAM) a) Arrange the next groups of compounds according to increasing acidity.
Explain the order you choose.
12- Order the following groups of compounds according to their basicity, and explain why.
Exercise Sheet 12: Amines. Acid-base. b
13- Order the following groups of compounds according to their acidity, and explain why.
14- Explain why m-methoxybenzoic acid is stronger than benzoic acid, while
p-methoxybenzoic acid is weaker.
15- Propose a synthetic pathway to obtain compound G starting from
toluene, using organic and inorganic reagents as necessary.
16- Starting from benzene, obtain:
17- Propose a synthetic pathway to obtain the next transformations:
Exercise Sheet 13: Aldehydes and ketones. Grignard reaction. b
1- Name the following compounds according to IUPAC:
2- Explain the next order of aldehyde reactivity towards nucleophiles:
3- For the following reactions, indicate the products A - D, as well as the mechanism to
obtain C.
4- Indicate the products A and B, as well as the mechanism to obtain A.
5- A compound (A) with general formula C8H16 undergoes reductive ozonolysis, producing
two compounds (B) and (C). It is known that compound (B) is optically active and gives a
positive Tollens' test. Compound (C) is known to be optically inactive, gives a negative
Fehling's test, and a positive iodoform test.
Deduce the structures of (A), (B), and (C) that achieve these results.
6- Compound D (C4H8O) reacts with NH2OH giving an oxime as a result. Apart from that, is it
known that when reacts with Grignard reagent (CH3MgBr), a secondary alcohol is obtained
with the molecular formula C5H12O.
Write the structure of compound D explaining the reactions involved.
Exercise Sheet 13: Aldehydes and ketones. Grignard reaction. b
7- (EXAM) Giving 3 isomers A, B and C with the molecular formula C8H8O2.
i) Compound B is reduced to obtain compound E only by LiALH4 treatment, while A and C
react with NaBH4 to generate products D and F respectively.
ii) C gives a positive haloform reaction.
iii) D, E and F react with PCC to give the oxidation products C, G and H respectively.
iv) A, G and H react with Fehling's reagent.
Write the structures A - H, indicating which type of isomers A, B and C are. Briefly explain
your deduction to reach the structures of the compounds involved.
8- (EXAM) Propose the structures for
compounds A - E.
Represent the mechanism to obtain
compound E from compound D.
9- (EXAM) a) Complete the following sequence of reactions:
b) Represent the mechanism to obtain C form B.
c) Which of the following agents (left) would you choose to perform the reactions shown on
the right? Briefly explain your answers.
10- (EXAM) a) Complete the next sequence with products Y, Z and W.
b) Indicate the mechanism to obtain W starting from Z.
Exercise Sheet 13: Aldehydes and ketones. Grignard reaction. b
11- Indicate (if corresponds) the products for the following reactions:
12- Complete with reagents and products the following reactions:
13- (EXAM) a) Complete the sequence of reactions:
b) Indicate the mechanism to transform I in A.
c) Name compound I according to IUPAC.
Exercise Sheet 13: Aldehydes and ketones. Grignard reaction. b
14- (EXAM) a) Acetylsalicylic acid (active principle of Aspirin) introduced by Hoffman in
1898, is the most prescribed analgesic and anti-inflammatory in the world. In the following
diagram a possible synthetic sequence for its production is represented.
Indicate the reagents and products from A to E.
b) Detail the mechanism to obtain salicylic acid from acetylsalicylic acid according to the
figure below:
c) Is acetylsalicylic acid more or less soluble in water than salicylic acid? Explain this
difference in solubility.
15- Indicate in each one of the following compounds which electrostatic interaction/s
(hydrogen bond, van der Waals forces, ionic interactions, dipole-dipole interactions) each of
the following substances has in its pure liquid state.
