Acetylene Organic Chemistry CHE 275 Chapter 9 Alkynes

Industrial preparation of acetylene is by dehydrogenation of ethylene CH3CH3 H2C CH2 800C 1150C H2C HC CH2 + H2 CH + H2

cost of energy makes acetylene a more expensive industrial chemical than ethylene

Naturally Occurring Alkynes

Some alkynes occur naturally. For example, O CH3(CH2)10C C(CH2)4COH
HN OH

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

Tariric acid: occurs in seed of a Guatemalan plant

Histrionicotoxin: defensive toxin in the poison dart frogs of Central and South America

4,4-Dimethyl-2-pentyne or 4,4-Dimethylpent-2-yne

Physical Properties of Alkynes

Structure
linear geometry for acetylene 120 pm C C

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

106 pm

106 pm

CH3

121 pm C C

146 pm

106 pm

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

sp Hybridization in Acetylene
Mix together (hybridize) the 2s orbital and one of the three 2p orbitals 2p 2p

2sp

2s

sp Hybridization in Acetylene
Mix together (hybridize) the 2s orbital and one of the three 2p orbitals 2p

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.

Each carbon has two half-filled sp orbitals available to form bonds.

2sp

Bonds in Acetylene
One of the two bonds in acetylene is shown here. The second bond is at right angles to the first.

Bonds in Acetylene
This is the second of the two bonds in acetylene.

Electrostatic Potential in Acetylene

Comparison of Ethane, Ethylene, and Acetylene

Ethane CC distance CH distance HCC angles CC BDE 153 pm 111 pm 111.0 368 kJ/mol 410 kJ/mol sp3 25% 62 Ethylene 134 pm 110 pm 121.4 611 kJ/mol 452 kJ/mol sp2 33% 45 Acetylene 120 pm 106 pm 180 820 kJ/mol 536 kJ/mol sp 50% 26

The region of highest negative charge lies above and below the molecular plane in ethylene.

The region of highest negative charge encircles the molecule around its center in acetylene.

CH BDE hybridization of C % s character pKa

Acidity of Acetylene and Terminal Alkynes

Acidity of Hydrocarbons
In general, hydrocarbons are exceedingly weak acids Compound HF pKa 3.2 15.7 36 45 60

H2O NH3 H2C CH2

CH4

Acidity of Alkynes
Alkynes are not nearly as weak acids as alkanes or alkenes Compound HF H2O HC CH pKa 3.2 15.7 26 36 45 60

Carbon: Hybridization and Electronegativity

C pKa = 60 H H C C pKa = 26 C C H H+ + C H+ + C : : H+ + C C C : sp sp3 sp2

pKa = 45

NH3 H2C CH2

CH4

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

Sodium Acetylide
Objective: Prepare a solution containing sodium acetylide NaC CH

Sodium Acetylide
No. Hydroxide is not a strong enough base to deprotonate acetylene. .. : HO .. + .. HO .. H + :C CH

CH

Will treatment of acetylene with NaOH be effective? NaOH + HC CH NaC CH + H2O

weaker acid pKa = 26

stronger acid pKa = 15.7

In acid-base reactions, the equilibrium lies to the side of the weaker acid.

Sodium Acetylide
Solution: Use a stronger base. Sodium amide is a stronger base than sodium hydroxide. NaNH2 + HC CH NaC CH + NH3 .. H2N: + H C CH .. H2N H + :C CH

Interactive Question
Which one of the following is the strongest acid? A) water B) ammonia C) 1-butene D) 1-butyne

stronger acid pKa = 26

weaker acid pKa = 36

Ammonia is a weaker acid than acetylene. The position of equilibrium lies to the right.

Preparation of Alkynes
There are two main methods for the preparation of alkynes: Carbon-carbon bond formation alkylation of acetylene and terminal alkynes Functional-group transformations elimination

Alkylation of Acetylene and Terminal Alkynes

HC CH

RC

CH

RC

CR

Alkylation of Acetylene and Terminal Alkynes

HC C: + R X SN2 HC CR + : X HC

Alkylation of Acetylene
CH NaNH2 NH3 HC CNa CH3CH2CH2CH2Br

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. HC C

CH2CH2CH2CH3 (70-77%)

Example: Alkylation of a Terminal Alkyne

(CH3)2CHCH2C CH NaNH2, NH3

Example: Dialkylation of Acetylene

HC CH 1. NaNH2, NH3 2. CH3CH2Br

(CH3)2CHCH2C

CNa

CH3CH2C

CH 1. NaNH2, NH3 2. CH3Br

CH3Br CH3CH2C

(CH3)2CHCH2C (81%)

CCH3

CCH3

(81%)

Interactive Question
Which alkyl halide will react faster with the acetylide ion (HCCNa) in an SN2 reaction? A) bromopropane B) 2-bromopropane C) tert-butyl iodide D) 1-bromo-2-methylbutane

Limitation
Effective only with primary alkyl halides Secondary and tertiary alkyl halides undergo elimination

Acetylide Ion as a Base

E2 predominates over SN2 when alkyl halide is secondary or tertiary C: C C E2 X

Interactive Question
Consider the reaction of each of the following with cyclohexyl bromide. For which one is the ratio of substitution to elimination highest? A) NaOCH2CH3, ethanol, 60C B) NaSCH2CH3, ethanol-water, 25C C) NaNH2, NH3, -33C D) NaCCH, NH3, -33C

HC

HC

C H +

: X

Preparation of Alkynes by Double Dehydrohalogenation

H C H X C X H C X H C X

Geminal dihalide Alkyne

(CH3)3CCH2CHCl2 1. 3 NaNH2, NH3 2. H2O

Geminal dihalide

Vicinal dihalide

(CH3)3CC

CH

The most frequent applications are in preparation of terminal alkynes.

(56-60%)

Geminal dihalide Alkyne

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

Vicinal dihalide Alkyne

CH3(CH2)7CHCH2Br Br 1. 3 NaNH2, NH3 2. H2O CH3(CH2)7C (54%) CH

Interactive Question
In addition to NaNH2, what other base can be used to convert 1,1-dichlorobutane into 1-butyne? A) NaOCH3 B) NaOH C) NaOCH2CH3 D) KOC(CH3)3

Reactions of Alkynes
Acidity (Section 9.5) Hydrogenation (Section 9.9) Metal-Ammonia Reduction (Section 9.10) Addition of Hydrogen Halides (Section 9.11) Hydration (Section 9.12) Addition of Halogens (Section 9.13) Ozonolysis (Section 9.14)

Hydrogenation of Alkynes
RC CR' + 2H2 cat RCH2CH2R'

Heats of Hydrogenation
CH3CH2C CH CH3C CCH3 292 kJ/mol 275 kJ/mol

catalyst = Pt, Pd, Ni, or Rh alkene is an intermediate

Alkyl groups stabilize triple bonds in the same way that they stabilize double bonds. Internal triple bonds are more stable than terminal ones.

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

Lindlar Palladium
H2 cat RCH CHR' H2 cat RCH2CH2R'

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.

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. syn-Hydrogenation occurs; cis alkenes are formed.

Example
CH3(CH2)3C C(CH2)3CH3 + H2 Lindlar Pd CH3(CH2)3 C H (87%) C H (CH2)3CH3

Useful In Industry

Large scale synthesis of vitamin A performed by Hoffman-LaRoche

Partial Reduction
RC CR' RCH CHR' RCH2CH2R'

Example
CH3CH2C CCH2CH3 Na, NH3

Another way to convert alkynes to alkenes is by reduction with sodium (or lithium or potassium) in ammonia. trans-Alkenes are formed.

CH3CH2 C H (82%) C

CH2CH3

Mechanism
Metal (Li, Na, K) is reducing agent; H2 is not involved four steps (1) electron transfer (2) proton transfer (3) (4) electron transfer proton transfer

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

R' + M .

. C

R'

Mechanism
Step (2) Transfer of a proton from the solvent (liquid ammonia) to the anion radical. R R C .. H . C R' .. NH2 H C . C R' H

Mechanism
Step (3): Transfer of an electron from the metal to the alkenyl radical to give a carbanion. R C R R' + M . H C M+ .. C R'

. C

.. : NH2

Mechanism
Step (4) Transfer of a proton from the solvent (liquid ammonia) to the carbanion . H R C H .. C R' .. NH2 R C H C R' H .. : NH2 Suggest efficient syntheses of (E)- and (Z)-2heptene from propyne and any necessary organic or inorganic reagents.

Strategy

Synthesis
1. NaNH2 2. CH3CH2CH2CH2Br

H2, Lindlar Pd

Na, NH3

Retrosynthetic Analysis Interactive Question

What is the structure of Compound Y in the following synthetic sequence?
Write out the reactions in reverse to first

A) pentane B) cis-2-pentene C) trans-2-pentene D) 2-pentyne

Br

Strategies for Synthesis

Problem

Br 2-Bromopentane
Then write out reactions in the forward direction Be sure to look out for incompatabilities Devise a synthesis of 2-bromopentene from acetylene

Retrosynthetic Analysis
Br

Solution

Br +

Na

Problem

Retrosynthetic Analysis
OH

OH 1-Hexanol

Can we synthesize 1-hexanol from acetylene?

Br +

Na

Solution

Addition of HX
CH3(CH2)3C HBr CH CH3(CH2)3C Br (60%) Follows Markovnikov's rule Alkynes are slightly less reactive than alkenes CH2

Termolecular Rate-Determining Step

H .. Br : ..

Two Molar Equivalents of Hydrogen Halide

CH3CH2C CCH2CH3 2 HF

RC .. Br : ..

CH H F C F CH2CH3

CH3CH2

C H

Observed rate law: rate =

k[alkyne][HX]2

(76%)

Free-radical Addition of HBr

HBr CH3(CH2)3CH peroxides (79%) regioselectivity opposite to Markovnikov's rule RC CHBr

Hydration of Alkynes
expected reaction: CR' + H2O H+ RCH CR' OH observed reaction: RC CR' + H2O H+ enol RCH2CR' O ketone

CH3(CH2)3C

CH

Enols
RCH CR' OH enol RCH2CR' O ketone

Mechanism of conversion of enol to ketone

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

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

Mechanism of conversion of enol to ketone

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

Mechanism of conversion of enol to ketone

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

Mechanism of conversion of enol to ketone

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

Key Carbocation Intermediate

Carbocation is stabilized by electron delocalization (resonance)

.. :O C +

H H C

.. +O C

Example of Alkyne Hydration

CH3(CH2)2C C(CH2)2CH3 H2O, H+ Hg2+ CH3(CH2)2CH O CH3(CH2)2CH2C(CH2)2CH3 (89%) via CH3(CH2)5C OH C(CH2)2CH3

Regioselectivity
Markovnikov's rule followed in formation of enol O CH H2O, H2SO4 HgSO4 via OH CH3(CH2)5C CH2 CH3(CH2)5CCH3 (91%)

Mechanism of Hg(II)-Catalyzed Hydration of Alkynes

Hydroboration/Oxidation of Alkynes

Addition of Hg(II) to alkyne gives a vinylic cation Water adds and loses a proton A proton from aqueous acid replaces Hg(II)

BH3 (borane) adds to alkynes to give a vinylic borane Oxidation with H2O2 produces an enol that converts to the ketone or aldehyde Process converts alkyne to ketone or aldehyde with orientation opposite to mercuric ion catalyzed hydration

Addition of Halogens to Alkynes

Cl HC CCH3 + 2 Cl2 Cl2CH C Cl (63%) CH3 CH3CH2C

Addition is anti
CH3CH2 CCH2CH3 Br2 Br (90%) C C CH2CH3 Br

Ozonolysis of Alkynes
gives two carboxylic acids by cleavage of triple bond

Example
CH3(CH2)3C CH 1. O3 2. H2O O CH3(CH2)3COH (51%) + O HOCOH

Summary: Chapter 9
Summary: Chapter 9 9.1 9.2 9.3 9.4 9.5 9.6 9.7 9.8 9.9 Sources of Alkynes Nomenclature Physical Properties of Alkynes sp hybridization Acidity of Alkynes Preparation of Alkynes by Alkylation Preparation of Alkynes by Elimination Reactions of Alkynes Hydrogenation of Alkynes 9.10 9.11 9.12 9.13 9.14

Summary: Chapter 9
Summary: Chapter 9 Dissolving Metal Reductions of Alkynes Addition of HX to Alkynes Hydration of Alkynes Addition of X2 to Alkynes Ozonolysis of Alkynes