Organic Chemistry

William H. Brown Christopher S. Foote Brent L. Iverson

7-1

Alkynes

Chapter 7

7-2

Nomenclature
IUPAC:

use the infix -yn- to show the presence of a carbon-carbon triple bond
4 3 2 1 1 2 3 4 5 6 7

1 2 3 4 5

3-Methyl-1-bu tyn e

6,6-D imethyl-3-hep tyn e

1,6-Hep tadiyne

Common

names: prefix the substituents on the triple bond to the word acetylene
IUPAC name: 2-Butyne 1-Buten-3-yne Common name: D imethylacetylene V inylacetylene
7-3

Cycloalkynes
Cyclononyne

is the smallest cycloalkyne isolated

it is quite unstable and polymerizes at room temp the C-C-C bond angle about the triple bond is approximately 155, indicating high angle strain

Cyclon on yne

7-4

Physical Properties
Similar

to alkanes and alkenes of comparable molecular weight and carbon skeleton

Name Eth yne Propyne 1-Butyne 2-Butyne 1-Pentyne 1-He xyne 1-Octyne 1-De cyne Melting Point Formula ( C) -81 HC CH CH 3 C CH -102 CH 3 CH2 C CH -126 -32 CH 3 C CCH3 CH 3 ( CH2 ) 2 C CH -90 CH 3 ( CH2 ) 3 C CH CH 3 ( CH2 ) 5 C CH CH 3 ( CH2 ) 7 C CH -132 -79 -36 Boiling Point ( C) -84 -23 8 27 40 71 125 174 Density at 20C (g/mL) (a gas) (a gas) (a gas) 0.691 0.690 0.716 0.746 0.766

7-5

Acidity
The

pKa of acetylene and terminal alkynes is approximately 25, which makes them stronger acids than ammonia but weaker acids than alcohols (Section 4.1)
terminal alkynes react with sodium amide to form alkyne anions
H-C C-H + p Ka 25 (S tronger acid) NH2 H-C C:- + NH3 p K a 38 (Weaker acid)

7-6

Acidity
terminal alkynes can also be converted to alkyne anions by reaction with sodium hydride or lithium diisopropylamide (LDA)
Na H Sodium hydride
+

[( CH3 ) 2 CH] 2 N Li Lith ium diisoprop ylamide (LDA)

because water is a stronger acid than terminal alkynes, hydroxide ion is not a strong enough base to convert a terminal alkyne to an alkyne anion
HC CH + OH p Ka 25 W(eaker acid) HC
-9. 3 C- + H2 O Keq = 10 pK a 15.7 (Stronger acid)

7-7

Alkylation of Alkyne Anions

Alkyne

anions are both strong bases and good nucleophiles They participate in nucleophilic substitution reactions with alkyl halides to form new C-C bonds to alkyl groups; they undergo alkylation
because alkyne anions are also strong bases, alkylation is practical only with methyl and 1 halides with 2 and 3 halides, elimination is the major reaction
Br HC C- Na+ + S od ium acetylide H Bromocyclohexane elimination (Ch 9) HC CH + + Na+ Br
-

Acetylene Cycloh exene

7-8

Alkylation of Alkyne Anions

alkylation of alkyne anions is the most convenient method for the synthesis of terminal alkynes
HC C - Na+ + Sodium acetylid e Br 1-Bromob utane 1-Hexyne + Na+ Br-

alkylation can be repeated and a terminal alkyne can be converted to an internal alkyne
CH3 CH2 C C- Na+ + CH3 CH2 -Br Sodiu m bu tyn ide Bromoethan e CH3 CH2 C CCH2 CH3 3-Hexyne + Na+ Br-

7-9

Preparation from Alkenes

Treatment

of a vicinal dibromoalkane with two moles of base, most commonly sodium amide, results in two successive dehydrohalogenation reactions (removal of H and X from adjacent carbons) and formation of an alkyne
CH3 CH=CHCH3 + Br2 2-Buten e CH2 Cl2 Br Br CH3 CH-CHCH3 + 2 NaNH2 Sodiu m amid e NH3 ( l) -33o C

CH3 C CCH3 2-Bu tyn e

2 NaBr

2 NH 3

7-10

Preparation from Alkenes

for a terminal alkene to a terminal alkyne, 3 moles of base are required
CH3 ( CH2 ) 3 CH = CH 2 1-He xene CH3 ( CH2 ) 3 C C N a
-

Br2

Br Br CH3 ( CH2 ) 3 CH -CH2 1,2-Dibromohe xane

+

3 N aN H2 - 2 HBr

H2 O

CH3 ( CH2 ) 3 C CH 1-He xyne

Sodium s alt of 1-hexyne

7-11

Preparation from Alkenes

a side product may be an allene, a compound containing adjacent carbon-carbon double bonds, C=C=C
R
R

C C C H X H RCC= CR R N a N H2 - HBr R An allene H RCC CR R An alkyne

A haloalkene (a vinylic halide)

7-12

Allene
Allene:

a compound containing a C=C=C group

the simplest allene is 1,2-propadiene, commonly named allene

7-13

Allenes
most allenes are less stable than their isomeric alkynes, and are generally only minor products in alkyne-forming dehydrohalogenation reactions
CH2 =C=CH2 CH2 =C=CHCH3 CH3 C CH CH3 C CCH3 H 0 = -6.7 kJ (-1.6 kcal)/mol H 0 = -16.7 kJ (-4.0 kcal)/mol

7-14

Addition of X2
Alkynes

add one mole of bromine to give a dibromoalkene

addition shows anti stereoselectivity
CH3 C CCH3 + Br2 CH3 COOH, LiBr anti addition H3 C C C Br

2-Butyne

Br CH3 (E)-2,3-Dibromo-2-b utene

7-15

Addition of X2
the intermediate in bromination of an alkyne is a bridged bromonium ion
Br Br
H3 C C C CH3

Br C H3 C C CH3 H3 C Br C

Br C CH3

H3 C C Br C

Br CH3

7-16

Addition of HX
Alkynes

undergo regioselective addition of either 1 or 2 moles of HX, depending on the ratios in which the alkyne and halogen acid are mixed
Br CH3 C CH
Propyne

Br HBr CH3 CCH 3

Br 2,2-Dibromopropane

HBr

CH3 C= CH 2
2-Bromopropene

7-17

Addition of HX
the intermediate in addition of HX is a 2 vinylic carbocation
CH3 C CH + H-Br + CH3 C=CH2 + A 2 vin ylic carbocation Br

reaction of the vinylic cation (an electrophile) with halide ion (a nucleophile) gives the product
+ CH 3 C=CH2 + Br Br CH 3 C=CH2 2-Bromopropen e

7-18

Addition of HX
in the addition of the second mole of HX, Step 1 is reaction of the electron pair of the remaining pi bond with HBr to form a carbocation of the two possible carbocations, the favored one is the resonance-stabilized 2 carbocation
Br H CH3 C CH2 Br faster s low er + CH3 C CH2 Br Br + CH3 C CH2 Br H H CH3 C CH2 + Br Br CH3 CCH3 Br H

1 Carb ocation

Resonance-stabilized 2 carbocation

7-19

Hydroboration
Addition

of borane to an internal alkyne gives a trialkenylborane

addition is syn stereoselective
+ BH3 3-Hexyne THF B R R A trialkenylboran e (R = cis- 3-hexenyl group ) H

7-20

Hydroboration
to prevent dihydroboration with terminal alkynes, it is necessary to use a sterically hindered dialkylborane, such as (sia)2BH
B-H

D i-sec -isoamylboran e [(sia)2 BH]

treatment of a terminal alkyne with (sia)2BH results in stereoselective and regioselective hydroboration
H + ( sia ) 2 BH 1-Octyne B( sia ) 2 H An alk en ylborane

7-21

Hydroboration
Treating

an alkenylborane with H2O2 in aqueous NaOH gives an enol

1 . BH3 2 . H2 O 2 , NaOH H OH O

Ke q = 6.7 x 106 2-Buten-2-ol (an enol) 2-Butanone (a ketone) (for keto-enol tautomerism)

2-Butyne

enol: a compound containing an OH group on one carbon of a carbon-carbon double bond an enol is in equilibrium with a keto form by migration of a hydrogen from oxygen to carbon and the double bond from C=C to C=O keto forms generally predominate at equilibrium keto and enol forms are tautomers and their interconversion is called tautomerism 7-22

Hydroboration
hydroboration/oxidation of an internal alkyne gives a ketone
1 . BH 3 2 . H 2 O 2 , N a OH 3-Hexyne O

3-Hexanone

hydroboration/oxidation of a terminal alkyne gives an aldehyde

1 . ( sia) 2 BH 2 . H2 O2 , NaOH

1-Octyne

OH H H A n enol Octanal

O H

7-23

Addition of H2O: hydration

In

the presence of sulfuric acid and Hg(II) salts, alkynes undergo addition of water
H2 SO4 OH CH3 C= CH 2 1-Propen-2-ol (an enol) O CH3 CCH 3 Propanone (Acetone)

CH3 C CH + H2 O Hg SO 4 Propyne

7-24

Addition of H2O: hydration

Step 1: attack of Hg2+ (an electrophile) on the triple bond (a nucleophile) gives a bridged mercurinium ion

Step 2: attack of water (a nucleophile) on the bridged mercurinium ion intermediate (an electrophile) opens the three-membered ring
Hg + C H3 C H O H + H3 C C H
+

Hg C C H H

7-25

Addition of H2O: hydration

Step 3: proton transfer to solvent gives an organomercury enol
H O H H3 C + C C O+ H H H O Hg + H3 C C H C H Hg
+

H3 O

Step 4: tautomerism of the enol gives the keto form

H3 C C C HO H Enol form Hg
+

O CH3 -C-CH2 -Hg + Keto form

7-26

Addition of H2O: hydration

Step 5: proton transfer to the carbonyl oxygen gives an oxonium ion +
O + H O H + CH3 -C-CH2 -Hg+ H O CH3 -C-CH2 -Hg+ + H2 O: H

Steps 6 and 7: loss of Hg2+ gives an enol; tautomerism of the enol gives the ketone
H+ O CH3 -C-CH2 -Hg+ Hg
2+

O + CH3 -C=CH2 (enol form)

O CH3 -C-CH3 (Keto form)

7-27

Reduction
Treatment

of an alkyne with hydrogen in the presence of a transition metal catalyst, most commonly Pd, Pt, or Ni, converts the alkyne to an alkane
CH3 C CCH3 + 2 H2 2-Butyne Pd, Pt, or Ni 3 atm CH3 CH2 CH2 CH3 Butane

7-28

Reduction
With

the Lindlar catalyst, reduction stops at addition of one mole of H2

this reduction shows syn stereoselectivity
CH3 C CCH3 + H2 2-Butyne Lin dlar catalyst H3 C C C CH3

H H cis -2-Buten e

7-29

Hydroboration - Protonolysis
Addition

of borane to an internal alkyne gives a trialkenylborane

addition is syn stereoselective
+ BH3 3-Hexyne THF B R R A trialkenylboran e (R = cis- 3-hexenyl group ) H

treatment of a trialkenylborane with acetic acid results in stereoselective replacement of B by H

O + 3 CH3 COH R R A trialkenylborane H B H H cis -3-Hexene + ( CH3 COO) 3 B

7-30

Dissolving Metal Reduction

Reduction

of an alkyne with Na or Li in liquid ammonia converts an alkyne to an alkene with anti stereoselectivity
R R R' + 2 Na NH3 (l) H H + 2 NaNH2 R' H 2 Na NH3 ( l) 4-Octyn e H trans -4-Octen e

7-31

Dissolving Metal Reduction

Step 1: a one-electron reduction of the alkyne gives a radical anion
R-C C-R + N a R-C C-R + N a+ An alkenyl radical anion

Step 2: the alkenyl radical anion (a very strong base) abstracts a proton from ammonia (a very weak acid)

R N H H C R C H + N H H

R- C

C-R + H

An alk enyl rad ical

Amide ion

7-32

Dissolving Metal Reduction

Step 3: a second one-electron reduction gives an alkenyl anion this step establishes the configuration of the alkene a trans alkenyl anion is more stable than its cis isomer
Na + R

C C

Na+ +

C C

R H An alkenyl anion

Step 4: a second acid-base reaction gives the trans alkene

R H N H + H C R C H H N H + H C R C H R

Amide ion

A t rans alken e7-33

Organic Synthesis
A

successful synthesis must

provide the desired product in maximum yield have the maximum control of stereochemistry and regiochemistry do minimum damage to the environment (it must be a green synthesis)
Our

strategy will be to work backwards from the target molecule

7-34

Organic Synthesis
We

analyze a target molecule in the following ways

the carbon skeleton: how can we put it together. Our only method to date for forming new a C-C bond is the alkylation of alkyne anions (Section 7.5) the functional groups: what are they, how can they be used in forming the carbon-skeleton of the target molecule, and how can they be changed to give the functional groups of the target molecule

7-35

Organic Synthesis
We

use a method called a retrosynthesis and use an open arrow to symbolize a step in a retrosynthesis
target molecule starting materials

Retrosynthesis:

a process of reasoning backwards from a target molecule to a set of suitable starting materials

7-36

Organic Synthesis
Target

molecule: cis-3-hexene
d is connect here

cis- 3-Hexene

3-Hexyne
-

:C C:

2 CH3 CH2 Br

Acetylide dian ion

Bromoeth ane

7-37

Organic Synthesis
starting materials are acetylene and bromoethane
HC CH Acetylene 1 . NaNH2 2 . CH3 CH2 Br 1-Butyne 3 . NaNH2 4 . CH3 CH2 Br 5 . H2 Lin dlar catalyst

3-Hexyne

cis- 3-Hexene

7-38

Organic Synthesis
Target

molecule: 2-heptanone

An acid-catalyzed h yd ration of th is alkyne gives a mixture of 2-heptan on e and 3-heptanone O 2-Hep tanone HC C An acid-catalyzed hydration of this alkyne gives 2-heptan on e 1-Heptyne
-

2-Heptyne

+ Br 1-Bromopentane

Acetylide anion

7-39

Organic Synthesis
starting materials are acetylene and 1-bromopentane
HC CH 1 . NaNH2 2 . Br 1-Hep tyne O 3 . H2 O H2 SO4 , HgSO4 2-Heptanone

7-40

Alkynes
End Chapter 7
7-41