Copyright exists

UNIVERSITY OF PRETORIA

DEPARTMENT OF CHEMISTRY

DATE: 10/05/2018 TOTAL MARKS: 60

TOTAL TIME: 90 min

Internal Examiners: Dr D Riley & Dr M Nkwelo

External Examiner: Dr N October

CHM 215
SEMESTER TEST 2
ORGANIC CHEMISTRY

Surname and Initials Student number

Memo
Signature

Question Marks Examiner

1 3
2 12
3 18
Total
4 27
60

General Instructions:
1. Answer both Sections directly on the question papers. If an answer is not given in the space provided, clearly
indicate location. Cancel answers that should not be marked with pen.
2. Final answers should be given in blue or black pen.
3. Cell phones must be switched off.,
4. Use line structures where structures are required, unless specified otherwise.

Page 1 of 10
Question 1 (3 marks)

1.1 Provide IUPAC names for the following compound: (3)

(4S, 2E)-2-pentene-1,4-diol or (4S,2E)-4-hydroxy-2-penten-1-ol

Question 2 (12 marks)

2.2 Consider the following reactions and based on the intermediates formed in step 1, rank the
given compounds according to their increasing reactivity. Fully explain. (NB: Do not give the final
products.) (8)

Page 2 of 10
2.3 Purine occurs commonly in the structure of DNA. Using the template given below, show an
atomic orbital drawing of the π and lone pair electrons of purine. (4)

Page 3 of 10
Question 3 (18 marks)

3.1 Use suitable diagrams and curly arrows to show electron movement to explain why aniline is
ortho-, para- directing. (9)

Page 4 of 10
3.2 Aniline when nitrated affords the unexpected meta-product as the major product.

(a) Show mechanistically how the electrophile (+NO2) is generated (3)

(b) Explain mechanistically how the ortho, para directing aniline affords the meta-substituted
product as the major product when doing a nitration? (6)

Page 5 of 10
Question 4 (27 marks)

4.1 The following alkylation of benzene does not give product A as the major product.

a) Give the line structures of products B and C and show mechanistically how both form. (9)
b) Show a synthetic approach (no mechanism) detailing how you might obtain only product A
as the major product. (3)

Page 6 of 10
4.2 Propose a synthetic route for the following conversion. Assume that solvents and any other
reagents are available. Show all steps complete with reagents and products. Mechanisms are not
required. (6)

Page 7 of 10
4.3 Propose a synthetic route for the preparation of benzoic acid from benzene. Assume that solvents
and any other reagents are available. Show all steps complete with reagents and products.
Mechanisms are not required. (5)

Page 8 of 10
4.4 Show the major product formed in each of the following EAS reactions; where appropriate
justify your choice. (4)

Page 9 of 10
 CHM 215 Organic Reagents Data Sheet

Alkylating agents (R = alkyl, phenyl, etc) Halogenating agents

 Grignard:  X2, CCl4 (X = Cl, Br)
1. RX (X = Cl, Br, I)  X2, H2O (X = Cl, Br)
2. Mg, dry ether  X2, hν
3. H2O or H3O+  NBS, aq DMSO or DMSO (aq)
 Grignard in carboxylation:  HX (X = Cl, Br, I)
1. RX (X = Cl, Br, I)  HX (X = Cl), ZnCl2
2. Mg, dry ether  PBr3, ether
3. CO2  SOCl2, pyridine
4. H3O+

Hydrating agents Dehydrating agents

 H2O, H+ or H3O+  Conc. acid, e.g. H3PO4 or H2SO4
 1. BH3, THF  POCl3, pyridine
2. H2O2, HOˉ

Hydrohalogenating agents Dehydrohalogenating agents

 HX (X = Cl, Br, I)  ROˉ or HOˉ

Oxidising agents Reducing agents

 1. OsO4 Tollens:  H2, Pd/C or PtO2
2. NaHSO3 1. Ag2O  1. NaBH 4, CH3OH
 KMnO4, H2O, HOˉ NH4OH (2. H2O or H3O+) (optional)
 1. CH3CO3H 2. H3O+  1. LiAlH4, dry ether
2. H3O+ or HOˉ 2. H2O or H3O+
 1. O3  1. DIBAL-H, -78○C
2. Zn, H2O or Me2S 2. H2O
 CrO3, H2SO4 (aq) (Jones’ reagent)
 Na2Cr2O7 or K2Cr2O7 , H2SO4 (aq) = (H2CrO4)
 PCC (C5H6N+ClCrO3ˉ), CH2Cl2

Electrophilic aromatic substitution reagents Carboxylic acid derivatization reagents

 X2, FeX3 with X = Cl, Br  PBr3, ether
 I2, CuCl2 or HNO3  SOCl2, pyridine
 HNO3 (c), H2SO4 (c)  R’OH, H2SO4 (c)
 SO3, H2SO4 (c) or H2SO4 (c)  R’OH, pyridine
 RCl, AlCl3  1. NH3 or NH2R or NHR2 2. ∆ > 100 oC
 ROH, BF3, ∆ or alkene + H2SO4  NaOH, H2O
 RC(O)Cl, AlCl3  1. NaOH 2. R’X
Benzene side chain reactions reagents Hydrolysis reagents / Deprotection reagents
[Note: Reducing agents (see also top right)]  H3O+, ∆ or H2O, H+, ∆
 RC(O)Cl, base (specify!) or (H3CC(O))2O  H2O, HOˉ, ∆
 H2SO4 (aq), ∆ or H2SO4, steam
 Br2, hν or ∆
 NBS, hν or ROOR
 KMnO4, ∆ and 1. KMnO4, HOˉ, ∆ 2. H3O+
 1. Fe, HCl
2. HOˉ
 1. Sn, HCl
2. HOˉ
 1. SnCl2, H3O+
2. HOˉ
 Zn (Hg), HCl, ∆
 NH2NH2, HOˉ, ∆

Other reagents Other reagents

 In• or Rad•  NC¯  N3¯
 Na (s) or K (s) or NaH or NaNH2  RCO2¯  HCC:¯
 ROˉ, ROH  ROH
 HS¯ or RS¯  H2O
 HOˉ
Note: Specify symbols such as R, X, etc.!
Functional groups in order of decreasing priority according to IUPAC rules:
Funksionele groepe in afnemende prioriteitsorde volgens IUPAC reëls:

carboxylic acid > carboxylic acid derivative>aldehyde>ketone>alcohol>phenol>thiol>

amine>alkene>alkyne>alkane>>ether; halide; nitro; sulfide
karboksielsuur > karboksielsuurderivaat>aldehied>ketoon>alkohol>fenol>tiol> amien>alkeen>alkyn

Page 10 of 10