Chapter 9: Alkynes 9.1. Sources of Alkynes.

Acetylene
Industrial preparation of acetylene is by dehydrogenation of ethylene

CH3CH3 H2C CH2

800 800C 1150 1150C

H2C HC

CH2 + H2 CH + H2

Cost of energy makes acetylene a more gy y expensive industrial chemical than ethylene. ethylene.
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9.2. Nomenclature
Acetylene and ethyne are both acceptable IUPAC names for C HC CH Higher alkynes are named in much the same way as alkenes except using an -yne suffix instead yne of -ene.

HC CCH3 Propyne (CH3)3CC

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HC CCH2CH3 1-Butyne y CCH3

2

4,4-Dimethyl4,4-Dimethyl-2-pentyne
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9.3 93 Physical Properties of Alkynes

The physical properties of alkynes are similar to f those of alkanes and alkenes.

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9.4. Structure and Bonding in Alkynes: sp Hybridization

Linear geometry for acetylene 120 pm C C

H 106 pm

106 pm

CH3

121 pm C C

146 pm
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106 pm
4

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Cyclic Alkynes
Cyclononyne is the smallest cycloalkyne stable enough to be stored at room temperature for a reasonable length of time. Cyclooctyne polymerizes on standing.

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Bonding in acetylene is based on sp-hybridization sp hybridization for each carbon

Mix together (h b idi ) th 2 orbital Mi t th (hybridize) the 2s bit l and one of the three 2p orbitals

2p

2p

2sp 2s
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Each carbon has two halffilled sp orbitals available to form s bonds.

6

 and Bonds in Acetylene

Each carbon is connected to a hydrogen by a bond. The two carbons are connected to each other by a bond and two bonds.

Two bonds in acetylene at right angles t each other. i ht l to h th

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 The region of highest negative charge lies above and below the molecular plane in ethylene. ethylene.
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The region of highest negative charge encircles the molecule around its center in acetylene. acetylene.

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Table 9.1. Comparison of ethane, ethylene, and acetylene Ethane CC distance CH distance H C C HCC angles CC BDE CH BDE Hybridization of C % s character pKa
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Ethylene 134 pm 110 pm 121.4 121 4 611 kJ/mol 452 kJ/mol sp2 p 33% 45

Acetylene 120 pm 106 pm 180 180 820 kJ/mol 536 kJ/mol sp p 50% 26
9

153 pm 111 pm 111.0 111 0 368 kJ/mol 410 kJ/mol sp3 p 25% 62
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9.5. Acidity of Acetylene and Terminal Alkynes

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In general, hydrocarbons are exceedingly weak acids

Compound HF
HC CH

p Ka 3.2 16 36 45 60
26

H2O NH3
H2C CH2

CH4

Acetylene is a weak acid, but not nearly as weak as y , y alkanes or alkenes.

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Electronegativity of carbon increases with its s character

C H H C C C C H 10-60 H+ + C : : H+ + C C C C :

sp3 sp2

10-45 10-26

H+ +

sp

Electrons in an orbital with more s character are closer to the nucleus and more strongly held.
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Objective: Prepare a solution containing sodium acetylide.

NaC

CH

Will treatment of acetylene with NaOH be effective?

NaOH + HC

CH

NaC

CH + H2O

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No! Hydroxide is not a strong enough base to y g g deprotonate acetylene. NaOH + HC CH NaC CH + H2O

.. HO: + ..

CH

.. HO ..

H + :C

CH

weaker acid pKa = 26

stronger acid pKa = 16

In acid-base reactions, the equilibrium lies to the id f the th side of th weaker acid. k id
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Solution: Use a stronger base. Sodium amide is a stronger base than sodium hydroxide. NaNH2 + HC CH NaC CH + NH3 H + :C

.. H2N : +

CH

.. H2N

CH

stronger acid pKa = 26

weaker acid pKa = 36

Ammonia is a weaker acid than acetylene. y The position of equilibrium lies to the right.
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9.6. Preparation of Alkynes by Alkylation of Acetylene and T fA t l d Terminal Alk i l Alkynes

There are two main methods for the preparation of alkynes:
Carbon-carbon bond formation: alkylation of acetylene and t lk l ti f t l d terminal alkynes i l lk Functional-group transformations: elimination li i ti

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Alkylation of acetylene and terminal alkynes

HC CH

RC

CH

RC
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CR
17

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Alkylation of acetylene and terminal alkynes

H C C: + R X SN 2 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

HC CH NaNH2 NH3 HC CNa CH3CH2CH2CH2Br

HC

CH2CH2CH2CH3 (70(70-77%)

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Example: Alkylation of a terminal alkyne

(CH3)2CHCH2C CH

NaNH2, NH3 (CH3)2CHCH2C CNa

CH3Br (CH3)2CHCH2C (81%)

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CCH3

Example: Dialkylation of acetylene

HC CH 1. NaNH2, NH3 2. CH3CH2Br CH3CH2C CH 1. NaNH2, NH3 2. CH3Br CH3CH2C
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CCH3
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LIMITATION! Effective only with primary alkyl halides. Secondary and tertiary alkyl halides undergo elimination. g
21

(81%)

E2 predominates over SN2 when alkyl halide is secondary or tertiary

HC C: H C C X E2

HC
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C H +

: X
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9.7. Preparation of Alkynes by Elimination Reactions

Double Dehydrohalogenation
H C H X C X H C X H C X

Geminal dihalide

Vicinal dihalide

The most frequent applications are in preparation of terminal alkynes.

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Geminal dihalide Alkyne

(CH3)3CCH2CHCl2 CCH CHCl 1. 3NaNH2, NH3 2. H2O (CH3)3CC CH

(56(56-60%)

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Geminal dihalide Alkyne

(CH3)3CCH2CHCl2 CCH CHCl (CH3)3CCH CCH ( (CH3)3CC H2O (CH3)3CC CNa CHCl CHCl CH NaNH2, NH3 (slow) NaNH2, NH3 (fast) ( l ) NaNH2, NH3 (slow) N NH

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Vicinal dihalide Alkyne

CH3(CH2)7CHCH2Br Br 1. 3NaNH2, NH3 2. H2O CH3(CH2)7C CH

(54%)
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9.9. Hydrogenation of Alkynes

RC CR CR' + 2H2 cat RCH RCH2CH2R' R

catalyst = Pt, Pd, Ni, or Rh

alkene is an intermediate

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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. bonds are more stable than terminal ones.

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Partial Hydrogenation
RC H2 cat RCH H2 cat RCH2CH2R'

CR'

CHR'

Alkynes could be used to prepare alkenes if a catalyst were available that is active enough to y g catalyze the hydrogenation of alkynes, but not active enough for the hydrogenation of alkenes.

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

There is a catalyst that will catalyze the hydrogenation of alkynes to alkenes, but not that of alkenes to alkanes. It is called the Lindlar catalyst and consists of palladium supported on CaCO3, which has been poisoned with lead acetate and quinoline quinoline. syn-Hydrogenation occurs; cis alkenes are formed.

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CH3(CH2)3C
Lindlar Pd: Pd on CaCO3; Pb(CH3CO2)2 and quinoline added to it.
N

C(CH2)3CH3 + H2 Lindlar Pd

CH3(CH2)3 C H (87%) C

(CH2)3CH3

Quinoline

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9.10. Metal-Ammonia Reduction of Alkynes

Alkynes trans-Alkenes transPartial Reduction

RC

CR CR'

RCH

CHR CHR'

RCH2CH2R' R

Another way to convert alkynes to alkenes is by reduction with sodium (or lithium or potassium) in ammonia. trans-Alkenes are formed.
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Example
CH3CH2C CCH2CH3 Na, NH3 NH CH3CH2 C H (82%) ( )
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H C CH2CH3

Mechanism
Metal ( Na, K) is reducing agent; H2 is not involved. (Li, ) Four steps: (1) Electron transfer (2) P t transfer Proton t f (3) Electron transfer (4) Proton transfer

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Mechanism
Step (1): Transfer of an electron from the metal to the alkyne to give an anion radical.

R' + M .

M+ .. C

. C

R'

Step (2) Transfer of a proton from the solvent (liquid ammonia) to the anion radical radical.

.. C H

. C

R R' .. NH2
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C H

. C

R R'

.. : NH2
35

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Step (3): Transfer of an electron from the metal to the alkenyl radical to give a carbanion.

R C H

. C

R R' + M . H C

M+ .. C R R'

Step (4) Transfer of a proton from the solvent (liquid ammonia) to the carbanion carbanion.

H R C H
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.. NH2

C: R'
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R C H C

.. : NH2

R'

36

 Suggest efficient syntheses of (E)- and (Z)-2- heptene from propyne and any necessary organic or inorganic reagents.

1. NaNH2 2. CH3CH2CH2CH2Br

H2, Lindlar Pd

Na, N NH3

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9.11. Addition of Hydrogen Halides to Alkynes

Follows Markovnikov s Rule Markovnikov's

CH3(CH2)3C

CH

HBr

CH3(CH2)3C Br (60%)

CH2

Alkynes are slightly less reactive than alkenes.

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Termolecular Transition State

.. Br Br : ..

RC .. Br : ..

CH

Observed rate law: rate = k[alkyne][HX]2

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Reaction with two moles of a hydrogen halide yields a geminal dihalide

CH3CH2C CCH2CH3 2 HF HF H CH3CH2 C H F C F CH2CH3

(76%)
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Free-radical addition of HBr occurs when peroxides are present h id t

CH3(CH2)3C CH HBr peroxides CH3(CH2)3CH (79%)
Regioselectivity opposite to Markovnikov's rule.

CHBr CHBr

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9.12. Hydration of Alkynes

Expected reaction:

RC

CR'

+ H2O

H+

RCH

CR' OH

Observed reaction:

enol H+ RCH2CR' O ketone

RC

CR'

+ H2O

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Tautomerism
RCH CR' RCH2CR' O Ketone (keto form)

OH enol

Enols are regioisomers 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. Tautomers are constitutional isomers that equilibrate by migration of an atom or group The equilibrium is called group. tautomerism.
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Mechanism of conversion of enol to ketone

.. :O H + :O H H H : O: H H +O:
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H .. :O H C C +

C H

H .. :O H C C
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Key carbocation intermediate is stabilized by electron delocalization (resonance)

.. :O H C C + .. +O H C C

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Example
CH3(CH2)2C C(CH2)2CH3 H2O, H+ Hg2+ CH3(CH2)2CH O CH3(CH2)2CH2C(CH2)2CH3 (89%)
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via OH C(CH2)2CH3

Markovnikov's rule followed in formation of enol

O CH3(CH2)5C CH H2O, H2SO4 HgSO4 g CH3(CH2)5CCH3 (91%) via OH CH3(CH2)5C
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CH2
47

9.13. Addition of Halogens to Alkynes

Example

Cl HC CCH3 + 2 Cl2 Cl2CH C Cl (63%) CH3

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Addition is anti
CH3CH2 CH3CH2C CCH2CH3 Br2 Br (90%)
Intermediate can be isolated when 1:1 molar ratio is used.

Br C C CH2CH3

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9.14. Ozonolysis of Alkynes

Gives two carboxylic acids by cleavage of triple bond

CH3(CH2)3C
Example

CH

1. O3 O CH3(CH2)3COH (51%) 2. H2O 2 + O

HOC HOCOH

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