TEST1:
Alkanes, alkenes, dienes, bond polarization, optical isomerism
1. Give systematic names
C
C
C
C C
C
C
C
C C
C
C C
C C
C
C
C C
C C C C C C C C C C C C C C C C C C C C C C C C C
C
C C
C
C
C C
C
C
C
C
C
C
C C
C C
C
C C C C C C C C C C C C C C C C C C C C C C
C
C C
C
C
C C
C
C
C
C
Me
C
C
C
C C
C
Bu
C
C
C C C C C
C C C C
C
Me
C
C
C C
C
C
C
C
C
C C
C
C C C
C C C C C C C C C C C C C C
C
C C
C
C
C
C
C C
C
C C C C C
C
C
C
C
C C C C C C
C
C
C
C
2. Draw energy diagram for the rotation of 1-chloro-2-methylpropane about the C-1–C-2 bond showing the relative
height of energy minima and maxima together with the corresponding conformations (Newman projections)!
3. Draw energy diagram for the rotation of 2-methylbutane about the C-2–C-3 bond showing the relative height of
energy minima and maxima together with the corresponding conformations (Newman projections)!
4. Which method can be used to differentiate enantiomers?
a. melting point b. boiling point c. direction of rotation d. value of rotation
e. absolute configuration f. solubility in water g. solubility in chloroform
h. solubility in (+)-2-chloropentane i. solubility in (+)-2-chloropentane
j. solubility in (–)-2-chloropentane
5. What are the simplest alcohols, which can correspond to the following equations?
R
CH
oxidation
R'
OH
optically active
R
C
R'
R
R'
oxidation
OH
O
optically inactive
CH
optically active
R
C
R'
O
optically active
6. There are 4 isomers of dimethylcyclopropane.
a) Write the structural formula of each isomer!
b) Which of the four show optical activity?
c) Which are meso compounds?
d) Having a mixture containing 1 mol of each isomer and performing fractional distillation,
how many fractions can be collected? Give the composition of each fraction!
7. The reaction of buta-1,3-diene with bromine at room temperature yields 1,4-dibromobut-2-ene. Determine if it is the
product of kinetic or thermodynamic control. Interpret! Draw the structure of the other isomer and the energy diagram
of the reaction!
8. Halogenation of isobutane (Reactions)+Draw the energy diagram of the reaction and interpret product distributions!
9. The reaction of buta-1,3-diene with HBr (Reactions)+Draw the energy diagram of the reaction and interpret!
10. The reaction of propene with HBr (Reactions)+Draw the energy diagram of the reaction and interpret product
distribution!
11. Draw the structure of the alkenes, which can be transformed to following alcohols by acid-catalyzed hydration.
ethanol, butan-2-ol, 2-methylpropan-2-ol, 2-methylpropan-1-ol, butan-1-ol
12. Give an interpretation for the strained structure of cyclopropane!
13. Draw the Fischer projection of the following compounds
(R)-2-chloropentane
(S)-CH3CHDOH
(R)-2-methylpentan-3-ol
14. Draw the structural formula of the following compounds with the lowest possible carbon numbers, which are
chiral! a) alkane (two isomers) b) dibromoalkane c) monoalkohol d) alkene e) allene
15. Determine the absolute configuration of the following compounds! (detailed step-by-step method)
1
CH3
OH
OH
COOH
CH2
CH2
CD2
CH2
CH2
Me C NH2
OH
CH2
CH2Br
CH3CH2 C CH2SH CH2 CH C CCl3 Cl CH2 C H
CH2
CH2
CH2
Br C NH2 Me C H
CH2
CDH
CH2
CH2OH
OH
CH2OH
OCH3
CH3
OMe
16. Explain why the boat conformation of cyclohexane is characterized by an energy maximum (draw stereo structure
and Newman projection)!
17. Draw the structural formula of the following compounds and indicate which can be separated into optically active
isomers. When isomerism does not exist, give the corresponding symmetry element.
a) CHFClBr b) CHDClBr c) 2,3-dimethylpentane d) cis-1,2-dimethylcyclobutane e) 2-chloropropane f) butan-2-ol
g) methylcyclohexane h) trans-1,2-dibromoethylene i) 3,3-dimethylpentane j) chloroacetone k) 1,1-dibromoallene
l)1,3-dibromoallene
18. Draw conformational equilibrium for each compound and indicate the more stable chair conformer!
a) ethylcyclohexane b) cis-1,2-dimethylcyclohexane c) trans-1,2-dimethylcyclohexane
19. Which of the isomeric C8H18 compounds has a single monochloro derivative?
20. Draw the structural formula of the C8H18 meso compound 
21. Rank the following substituents using the Cahn-Ingold-Prelog convention!
CH2Br, CCl3, CH=CH2, CN, CH2NH2
22. Determine the absolute configuration of each asymmetric carbon of the following compound (detailed step-by-step
method). Determine whether it shows optical activity. Give explanation!
COOH
H C OH
H C OH
COOH
23. Draw the structural formula of the products formed after hydrogenation of the following compounds! Give the
isomeric relationship and the method for their separation!
(R)
CH3 CH2
C CH3
CH3 CH C CH3
O
HO
O
24. Indicate bond polarizations in the following compounds/ions and give the corresponding symbols!
C
Br
C
C O
C
C OH
C
MgHlg
C
NH2
Si
C
C
O
N
N
25. Draw resonance hybrids for the following compounds/ions indicate bond polarization (give symbols if possible)!
CH2 CH
CH2 CH
Reactions:
H3C
CH CH2
CH2
H
N
C
H
H
H
H
..
O:
C
H
H
H
H
H
C
C
..
O
..
N
H
H
OH
C
C
H
N:
H
O
CH2 CH
H
C
..
N
C
H
Cl
H
H2C
..
C
H
1–16
Important terms
conformation, conformer, chiral compound, prochiral compound, chiral center, racemic mixture, meso compound,
configuration, retention, inversion, racemization, resolution, enantiomers, asymmetric synthesis, molecular asymmetry,
diastereoisomerism, nucleophile, electrophile, degree of oxidation, tertiary/secondary/primary carbon, addition,
elimination, substitution, functional group, isomerism, homologous series, atomic orbital, angular (Baeyer) strain,
torsional (Pitzer) strain, tautomerization, molecularity
2
TEST2
Aromatic compounds
1. Prepare the following compounds from benzene using the necessary reagents:
a) m-toluenesulfonic acid b) m-bromobenzoic acid c) p-bromobenzoic acid
d) p-chloroacetophenone
e) o-chloroacetophenone
f) m-nitrobenzoic acid
g) 3-isopropylbenzenesulfonic acid
h) m-chloroacetophenone
i) p-nitrobenzyl bromide
j) 3-nitroisopropylbenzene
2. Prepare the following compounds from toluene using the necessary reagents:
a) o-bromobenzoic acid b) m-bromobenzoic acid c) p-nitrobenzyl bromide d) m-nitrobenzoic acid
3. Draw the structure of the following compounds and rank them according to their reactivity in aromatic electrophilic
substitution!
a) aniline, benzaldehyde, chlorobenzene, benzene
b) phenol, benzene, 2-aminoacetophenone, benzoic acid
c) toluene, acetophenone, acetanilide, o-dinitrobenzene
d) nitrobenzene, phenol, benzene, toluene
e) aniline, o-nitrobenzaldehyde, bromobenzene, toluene
f) phenol, benzene, acetanilide, benzoic acid
4. Give the mechanism of aromatic SE reactions using, as example, i. nitration, ii. bromination, iii. sulfonation iv.
Friedel–Crafts alkylation with tert-butyl chloride, v. Friedel–Crafts acylation with acetyl chloride. Show the formation
of the electrophile and draw the detailed structure (resonance formulae) of the  complex! Draw detailed energy
diagram of the reaction!
5. Write equations and interpret the following:
i) in Friedel–Crafts alkylations polysubstituted products are often formed. In contrast, polyacylation in Friedel–
Crafts acylation does not occur;
ii) catalytic amount of Lewis acid is sufficient in alkylations, whereas acylation requires the use of stoichiometric
quantity.
6. Interpret the effect of the substituent (orientation, effect on rate) in SE-Ar reactions of nitrobenzene/ phenol/aniline
(indicate and give symbols for bond polarization and draw mesomeric structures)!
7. Give the three conditions necessary to have aromatic structures. Analyze the structure of cyclopentadiene/
cycloheptatriene whether they satisfy these conditions! Transform them to aromatic derivatives!
8. Determine the stabilization (resonance) energy of benzene using the following data: 130 kJ/mol, 240 kJ/mol. What
kind of data are these? Interpret all calculations!
Organic halides, hydroxy compounds
9. Draw the structural formulae of the following compounds and rank them according to their reactivity in S N2/SN1
reactions!
2-chloro-2-methylbutane, 1-chloropentane, 1-iodopentane, vinyl chloride
iodobenzene, tert-butyl chloride, 1-chloropentán, 1-iodopentane
vinyl chloride, 1-chlorobutane, 2-bromobutane, 1-iodopentane
bromobenzene, benzyl chloride, 2-chlorobutane, 1-bromopentane
benzyl chloride, 2-fluoropentane, sec-butyl bromide, iodobenzene
tert-butyl chloride, propyl chloride, isobutyl chloride, 2-chlorobutane
10. Write conformational equilibriums and on the basis of information for E2 eliminations interpret the following
observations. Use appropriate chair conformations for interpretation!
i) why are 2 products formed in reaction a) and why not in equal amounts,
ii) why is it that only one product is formed in reaction b),
iii) what is the reason for the rate difference?
a)
Me
Me
Cl
Me
KOH, EtOH
Me KOH, EtOH
Cl
slow
+
fast
25%
Me
b)
75%
11. Draw the energy diagram of SN2/SN1/E2/E1 reactions and insert structure/formula of the corresponding starting
materials/products/intermediates/transition states. Indicate activation energies and interpret molecularity.
12. Draw the structure of the leaving groups formed in the nucleophilic substitution of the following compounds and
the corresponding conjugate acids. Rank the leaving groups according to their leaving ability.
3
O
R O H
R O S R'
R NH2
O
R F
+
R N N
R Br
+ H
R O
H
+
R NH3
R Cl
R S
R
I
H
13. Interpret the acidity of alcohols/ phenols on the basis of ground-state polarization and stability of the
alcoholate/phenolate anion (indicate and give symbols for bond polarization and draw mesomeric structures)!
14. Give part steps of the following nucleophilic substitution!
Me
H
Et
Et
HCl
OH
(R)-butan-2-ol
Me
Pr
HCl
OH
(R)-3-methylhexan-3-ol
15. Indicate, which statements are true for SN2, SN1, E2 or E1 transformations!
a) takes place via carbocation
g) rearrangement is possible
b) first-order kinetics
h) reaction rate increases with increasing substitution on carbon
c) second-order kinetics
i) reaction rate decreases with increasing substitution on carbon
d) anti elimination
j) pentacoordinate transition state
e) inversion during substitution
k) synchronous process
f) racemization during substitution
Reactions:
23–41
4
TEST3
Nitrogen-containing compounds
1. Interpret the basicity of ammonia and aliphatic/aromatic amines in the gas phase and in aqueous solution
considering electronic factors and solvation. How basicity is the interpreted? Indicate and name bond polarizations and
draw mesomeric structures when necessary; show formulae for the effect of solvation)! Use also graphical
representation!
2. Give the synthesis of aromatic diazonium salts and interpret the reasons for using the acid in high excess!
3. Write the reaction of diazo coupling! Give reaction type, discuss the electrophilic nature of the diazonium ion (draw
resonance structures) and interpret the necessity, character and role of the substituents!
4. Interpret the facile racemization of chiral amines (draw structures)!
Carbonyl compounds, carboxylic acids
5. Interpret the changes in reactivity of aliphatic and aromatic carbonyl compounds in AN reactions induced by
substitution (indicate and name bond polarization and draw mesomeric structures when necessary)!
6. Most AN reactions of carbonyl compounds are equilibrium process. Exceptions are reductions (hydride addition)
and addition of the Grignard reagent. Write the first step of each reaction and interpret!
7. Compare the characteristic reactions of alkenes and carbonyl compounds and interpret equilibrium nature of the
latter!
8. Interpret acidity of enols on the basis of ground-state polarization and stability of the enolate anion (indicate and
name bond polarizations and draw mesomeric structures)!
9. Interpret easy dehydration of aldols (write the reaction)!
10. Interpret easy enolization of pentane-2,4-dione (draw structures)!
11. Give a general definition for the active methylene group. Interpret the acidic character of hydrogens attached to the
-carbon using nitromethane/acetaldehyde as examples (indicate and name bond polarization and draw mesomeric
structures)!
12. Draw the structure of product(s) formed in each cyanohydrin synthesis. Which products are chiral, which show
optical activity, and what is the isomeric relationship of these products? What method can be used to separate the
isomers?
a) acetaldehyde
b) benzaldehyde
c) acetone
d) cyclohexanone
e) (R)- or (S)-glyceraldehyde
f) (R)-2-methylcyclohexanone
13. 2-Methylcyclohexanone and 3-methylcyclohexanone are chiral. One of the compounds undergoes racemization in
the presence of a strong base. Draw the corresponding enol forms and interpret!
14. Which of the following chiral ketones undergo racemization in the presence of a strong base? Draw the
corresponding enol forms and interpret!
CH3
C6H5
*
H5C2 CH C C6H5
O
*
H5C2 C C CH3
CH3O
C2H5
*
H7C3 C
C C6H5
CH3 O
*
H3C C CH C6H5
O CH3
*
C C6H5
CH3
O
H5C2 CH CH2
15. Prepare the following compounds (give reagents and reaction conditions)!
I. from propanal
a) propan-1-ol
b) ethyl methyl ketone
c) butan-2-ol
d) propionic acid
e) dimethyl acetal
f) propanamine
g) cyclic acetal
II. using Grignard reaction (write also the mechanism!)
ethanol, isopropyl alcohol, tert-butyl alcohol, cyclohexanemethanol, diphenylmethanol, butan-2-ol (2 methods)
III. a) iodoform
b) acetaldol
c) acetaldehide cyanohydrin
d) benzenesulfonamide
5
16. Draw the structure of the product formed when acetaldehyde and pentan-3-one are reacted with the following
reagents!
a) NaBH4
b) PhMgBr
c) OH–/ heat
d) KMnO4 (cold or warm)
e) EtOH/H+
+
+
–
f) ethylene glycol /H
g) Ag(NH3)2
h) I2/OH
17. Write the haloform reaction and draw the formula of the following compounds. Which of these give the iodoform
test? Interpret!
isopropyl alcohol, acetophenone, 2-methylcyclohexanone, pentan-3-one, ethanol
Carboxylic acids
18. Interpret the acidity of carboxylic acids on the basis of ground-state polarization and stability of the carboxylate
anion (indicate and name bond polarizations and draw mesomeric structures)!
Reactions:
47–68
6
TEST SCHEDULES
Test1
October 6 / 13
Alkanes, alkenes, dienes, bond polarization, optical isomerism (21 pts)
Consultation: September 30
Test2
October 27/November 10 Aromatic compounds, organic halides, hydroxy compounds (22 pts)
Consultation: October 21
Test3
November 24 / December 1 Nitrogen-containing compounds, carbonyl compounds,
carboxylic acids (22 pts)
Consultation: November 18
General preconditions
To be qualified for exam: 3 successful tests
Conditions: 6 possibilities, any variations. Missed tests are considered to be unsuccessful (one of the six
possibilities is lost).
Passing the tests (minimum requirement): 12 points each
Each successful test can be retaken (improved) once.
Special conditions
An average of 80% (12 mark points out of 15, that is, in mark combinations: 3+4+5, 4+4+4, 2+5+5 or
better) and no missed/failed test has a bonus: exam written test is not required!
However, questions of nomenclature, stereochemistry and definitions are mandatory for everybody in exam.
In exam, each test can be retaken (improved) once.
Internet materials:
http://www2.pharm.u-szeged.hu/test/szerves
tests_1semester
reactions_first
Exam1st
BasicI
folder org1
amolnar@chem.u-szeged.hu
7