CHEM 110

Block 4: Functional Groups 1

Lecture 2 – Alkynes, Aromatics
Dr Kaitlin Beare
(CHEM110@auckland.ac.nz)
The pre-reading for this lecture covered:

Alkynes
How to make them

Aromatic compounds
Resonance
Naming

(We’ll do the pre-reading exercise later)

 2.1 Reactions of Alkynes

2.1.1 Hydrogenation
Reagent(s) used depends on the number of mole equivalents of H2 to be
added, and the required stereochemistry of the H2 addition.

(Z)-pent-2-ene (E)-pent-2-ene
Practice Question
What is reagents are required for the following transformations?

(a)

(b)
2.1.2 Electrophilic addition of HX and X2

• Markownikoff’s rule followed for HX addition.

• Reaction can be stopped after addition of one
mole equivalent of reagent.
• Anti stereochemistry of addition is observed.
2.1.3 Addition of water – hydration

(Reagent: aq. H2SO4/HgSO4)

Note:
1. Addition of only one mole equivalent of water
occurs.
2. For all alkynes, except ethyne, the product(s) is(are)
ketones.

Example O
aq. H2SO4 CH3CCH3
CH3C CH HgSO4
2.1.3 Addition of water – hydration …

OH
Presuming Markownikoff addition expect
formation of: H3CC CH2 enol (unstable)

This is a tautomeric equilibrium. The O

species involved are tautomers.
CH3CCH3 keto compound
2.1.4 Formation of alkynide anions
The hydrogen on a terminal alkyne sp carbon is
weakly acidic and can be removed with a strong
base. The carbon nucleophile (alkynide anion)
formed is useful in synthesis for carbon chain
extension.

strong base 1o alkyl halide

NaNH2 CH3CH2Br
RC CH RC C RC C CH2CH3

terminal alkynide
alkyne anion
Practice Question
Which compounds shown to the right would hydrogenate with H2/Pt
at 25 oC?

CH3 CH2CH=CH2

(a) (b) (c)

 3.1 Reactions of Aromatic Compounds

• alkenes undergo addition reactions

• benzene and substituted benzenes usually undergo
substitution reactions.
• aromatic compounds, like benzene, have the extra stability
of 'resonance energy' which essentially 'prevents' aromatic
compounds from doing addition reaction chemistry.

Br2 Br2/FeBr3
Br H Br

H Br
 3.1.1 Prep'n of monosubstituted benzenes

Generally:
H E E+ = electrophile

+ E+ + H+

Electrophilic aromatic substitution

( SEAr )
Mechanism:
+ E+

addition electrophile attack - ‘slow’

H H H H
E
E E E

resonance hybrid
resonance stabilised cation

elimination proton loss - ‘fast’

E
+ H+

Overall: substitution
Note: In the resonance contributors the charge is only in the o- and p-positions
relative to E. The resonance stabilised carbocation intermediates are called
Wheland intermediates.
(a) Generation of electrophiles
The electrophiles are usually formed by catalytic
action. - very reactive

Halogenation
Cl Cl + FeCl3 Cl+ + FeCl4-
No catalyst is needed if a very electron rich aromatic
compound is being halogenated.
Nitration
HNO3 + H2SO4 NO2+ + HSO4- + H2O

Note: The nitro group is

resonance stabilised
Friedel-Crafts acylation
O O
R C X + AlX3 R C + AlX4-
generation of the
electrophile
R C O
R O
1. C

2. - H +
Friedel-Crafts alkylation
R = CH3, CH3CH2, (CH3)2CH
RX + AlX3
X = Cl, Br
Thus: CH3CHCH3
+ AlCl3 1.
Cl CH3 CH3
CH
2. -H+
However in presence of AlCl3:
+ CH3CH2CH2Cl

Why? 1-propyl carbocation is unstable (1o) and it rearranges to the more stable
2o carbocation…