Organic Chemistry

ABCT2423

Alkynes
Dr. Chau Ming SO
Office: Y843
Email: bccmso@polyu.edu.hk
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 Handout for “ALKYNES”

IUPAC Nomenclature of Alkynes

Acidity of Hydrocarbons
Alkylation of Acetylene and Terminal Alkynes
Preparation of Alkynes by "Double Dehydrohalogenation"
Hydrogenation of Alkynes to Alkanes
Lindlar Catalyst: Partial Hydrogenation (Alkynes to
Alkenes)
Hydration of Alkynes

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 Nomenclature

• Acetylene and ethyne are both acceptable

IUPAC names for HC CH
• Higher alkynes are named in much the same
way as alkenes except using an -yne suffix
instead of -ene.

HC CCH3 HC CCH2CH3
Propyne 1-Butyne or But-1-yne
(CH3)3CC CCH3

4,4-Dimethyl-2-pentyne or 4,4-Dimethyl-pent-2-yne
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 Handout for “ALKYNES”

IUPAC Nomenclature of Alkynes

Acidity of Hydrocarbons
Alkylation of Acetylene and Terminal Alkynes
Preparation of Alkynes by "Double Dehydrohalogenation"
Hydrogenation of Alkynes to Alkanes
Lindlar Catalyst: Partial Hydrogenation (Alkynes to
Alkenes)
Hydration of Alkynes

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 The Reaction of Acid with Base
• Brønsted Acids and Bases

• A smaller value of pKa indicates a stronger acid

• Any substances providing Hydrogen (H+) are acids

stronger acid weaker acid

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 Sodium Acetylide

• Sodium amide is a strong base

NaNH2 + HC CH NaC CH + NH3

.. – .. –
H2N : + H C CH H2N H + :C CH
stronger acid weaker acid
pKa = 26 pKa = 36

• Ammonia is a weaker acid than acetylene.

The position of equilibrium lies to the right.
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 Acidity of Hydrocarbons
• In general, hydrocarbons are exceedingly
weak acids, but acetylene is not nearly as
weak as alkanes or alkenes.

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 Acidity of Hydrocarbons
• Electrons in an orbital with more s character are closer
to the nucleus and more strongly held.

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 Handout for “ALKYNES”

IUPAC Nomenclature of Alkynes

Acidity of Hydrocarbons
Alkylation of Acetylene and Terminal Alkynes
Preparation of Alkynes by "Double Dehydrohalogenation"
Hydrogenation of Alkynes to Alkanes
Lindlar Catalyst: Partial Hydrogenation (Alkynes to
Alkenes)
Hydration of Alkynes

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 Alkylation of
Acetylene and Terminal Alkynes

– SN2
H—C C: + R X H—C C—R + : X–

• The alkylating agent is an alkyl halide, and

the reaction is nucleophilic substitution.
• The nucleophile is sodium acetylide or the
sodium salt of a terminal (monosubstituted)
alkyne.

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 Example: Alkylation of Acetylene

NaNH2
HC CH HC CNa
NH3

CH3CH2CH2CH2Br

HC C CH2CH2CH2CH3

(70-77%)
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 Example: Dialkylation of Acetylene

H—C C—H
1. NaNH2, NH3
2. CH3CH2Br
Limitation
• Effective ONLY
CH3CH2—C C—H with primary alkyl
halides
1. NaNH2, NH3
2. CH3Br • Secondary and
tertiary alkyl halides
undergo elimination
CH3CH2—C C—CH3

(81%) 12
 Acetylide Ion as a Base
• E2 predominates over SN2 when alkyl
halide is secondary or tertiary.

–
H—C C: H C

C X
E2

H—C C —H + C C + : X–
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 Handout for “ALKYNES”

IUPAC Nomenclature of Alkynes

Acidity of Hydrocarbons
Alkylation of Acetylene and Terminal Alkynes
Preparation of Alkynes by "Double Dehydrohalogenation"
Hydrogenation of Alkynes to Alkanes
Lindlar Catalyst: Partial Hydrogenation (Alkynes to
Alkenes)
Hydration of Alkynes

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 Preparation of Alkynes by
"Double Dehydrohalogenation"

H X H H

C C C C

H X X X

Geminal dihalide Vicinal dihalide

• The most frequent applications are in

preparation of terminal alkynes.
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Geminal dihalide  Alkyne

(CH3)3CCH2—CHCl2

1. 3NaNH2, NH3
2. H2O

(CH3)3CC CH
(56-60%)

Why 3NaNH2 is required?

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 Geminal dihalide  Alkyne

(CH3)3CCH2—CHCl2
NaNH2, NH3 (slow)
(CH3)3CCH CHCl

NaNH2, NH3 (slow)

(CH3)3CC CH
H2O
NaNH2, NH3 (fast)
(CH3)3CC CNa
• As the terminal product is acidic enough to transfer a
proton to amide anion, one equivalent of base in addition
to the two equivalents required for double
dehydrohalogenation is needed.
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Vicinal dihalide  Alkyne

CH3(CH2)7CH—CH2Br
Br

1. 3NaNH2, NH3
2. H2O

CH3(CH2)7C CH

(54%)
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 Handout for “ALKYNES”

IUPAC Nomenclature of Alkynes

Acidity of Hydrocarbons
Alkylation of Acetylene and Terminal Alkynes
Preparation of Alkynes by "Double Dehydrohalogenation"
Hydrogenation of Alkynes to Alkanes
Lindlar Catalyst: Partial Hydrogenation (Alkynes to
Alkenes)
Hydration of Alkynes

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 Hydrogenation of Alkynes to Alkanes

cat
RC CR' + 2H2 RCH2CH2R'

catalyst = Pt, Pd, Ni, or Rh

• alkene is an intermediate

H2 H2
RC CR' RCH CHR' RCH2CH2R'
cat cat

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 Heats of Hydrogenation

CH3CH2C CH CH3C CCH3

292 kJ/mol 275 kJ/mol

• Alkyl groups stabilize triple bonds in the

same way that they stabilize double bonds.

• Internal triple bonds are more stable than

terminal ones.
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 Handout for “ALKYNES”

IUPAC Nomenclature of Alkynes

Acidity of Hydrocarbons
Alkylation of Acetylene and Terminal Alkynes
Preparation of Alkynes by "Double Dehydrohalogenation"
Hydrogenation of Alkynes to Alkanes
Lindlar Catalyst: Partial Hydrogenation (Alkynes to
Alkenes)
Hydration of Alkynes

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 Lindlar Catalyst: Partial Hydrogenation
(Alkynes to Alkenes)

H2 H2
RC CR' RCH CHR' RCH2CH2R'
cat cat
• Alkynes could be used to prepare alkenes if a
catalyst were available that is active enough to
catalyze the hydrogenation of alkynes, but not
active enough for the hydrogenation of alkenes.

Lindlar Catalyst
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 Lindlar Catalyst

H2 H2
RC CR' RCH CHR' RCH2CH2R'
cat cat

• Lindlar catalyst and consists of palladium

supported on CaCO3, which has been poisoned with
lead acetate and quinoline.

• Catalyze the hydrogenation of alkynes to alkenes,

But not that of alkenes to alkanes.

• syn-Hydrogenation occurs; cis alkenes are

formed.
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 Lindlar Catalyst (Example)

CH3(CH2)3C C(CH2)3CH3 + H2

Lindlar Pd

CH3(CH2)3 (CH2)3CH3

C C
cis alkenes
H H
(87%)
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 Handout for “ALKYNES”

IUPAC Nomenclature of Alkynes

Acidity of Hydrocarbons
Alkylation of Acetylene and Terminal Alkynes
Preparation of Alkynes by "Double Dehydrohalogenation"
Hydrogenation of Alkynes to Alkanes
Lindlar Catalyst: Partial Hydrogenation (Alkynes to
Alkenes)
Hydration of Alkynes

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 Hydration of Alkynes

expected reaction:
H+
RC CR' + H2O RCH CR'

enol OH

observed reaction:
H+
RC CR' + H2O RCH2CR'

ketone O
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 Hydration of Alkynes (Keto-Enol)

RCH CR' RCH2CR'

OH O
enol ketone

• Enols are tautomers of ketones, and exist

in equilibrium with them.
• Keto-enol equilibration is rapid in acidic media.
• Ketones are more stable than enols and
predominate at equilibrium.
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 Example of Alkyne Hydration

CH3(CH2)2C C(CH2)2CH3

H2O, H+ via OH
Hg2+ CH3(CH2)2CH C(CH2)2CH3

CH3(CH2)2CH2C(CH2)2CH3

(89%)
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 Alkyne Hydration (Regioselectivity)

• Markovnikov's rule followed in formation of enol

O
H2O, H2SO4
CH3(CH2)5C CH CH3(CH2)5CCH3
HgSO4
(91%)

via OH

CH3(CH2)5C CH2
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 Alkynes

1. Able to name the alkynes from a given compounds.

2. Understanding the acidity of different
hydrocarbons and alkylation of terminal alkynes.
3. Able to apply the double dehydrohalogenation
reaction to prepare alkynes.
4. Able to apply different reagents to control the
transformation of the alkynes to the desired
alkanes or alkenes.
5. Understanding the keto-enol form of the product
from alkyne hydration reaction regioselectivity.
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