Synthesis of Alkynes

Objectives
1. Draw the structures for alkynes
2. Describe how alkynes are prepared
3. Enumerate the general and specific
reactions of alkynes
 Alkynes: Addition Reactions
 The principal reaction of the alkynes is addition
across the triple bond to form alkanes. These
addition reactions are analogous to those of the
alkenes.
 Hydrogenation.
 Alkynes undergo catalytic hydrogenation with the
same catalysts used in alkene hydrogenation:
platinum, palladium, nickel, and rhodium.
 Hydrogenation proceeds in a stepwise fashion,
forming an alkene first, which undergoes further
hydrogenation to an alkane.
 Alkynes: Addition Reactions
• 1. Catalytic Hydrogenation
• The catalytic addition of hydrogen to 2-butyne not only serves as an
example of such an addition reaction, but also provides heat of
reaction data that reflect the relative thermodynamic stabilities of
these hydrocarbons
• Since alkynes are thermodynamically less stable than alkenes,
addition reactions is more exothermic and relatively faster.
• The catalytic hydrogenation, the usual Pt and Pd hydrogenation
catalysts are so effective in promoting addition of hydrogen to both
double and triple carbon-carbon bonds.
• Lindlar's catalyst, prepared by deactivating (or poisoning) a
conventional palladium catalyst by treating it with lead acetate and
quinoline, permits alkynes to be converted to alkenes without further
reduction to an alkane.
R-C≡C-R + H2 & Lindlar catalyst ——> cis R-CH=CH-R

R-C≡C-R + 2 Na in NH3 (liq) ——> trans R-CH=CH-R + 2 NaNH2

 Alkynes: Addition Reactions
• 2. Addition by Electrophilic Reagents
 Although these electrophilic additions to alkynes are sluggish,
they do take place and generally display Markovnikov Rule
 In the last example, 1,2-diodoethene does not suffer further
addition inasmuch as vicinal-diiodoalkanes are relatively
unstable.,
 Alkynes: Addition Reactions
• 2. Addition by Electrophilic Reagents
 Why are the reactions of alkynes with electrophilic reagents
more sluggish than the corresponding reactions of alkenes?
 alkynes are generally more exothermic than additions to alkenes,
and there would seem to be a higher π-electron density about the
triple bond ( two π-bonds versus one ).
 Two factors are significant in explaining this apparent paradox.
 First, although there are more π-electrons associated with the
triple bond, the sp-hybridized carbons exert a strong attraction for
these π-electrons, which are consequently bound more tightly to
the functional group than are the π-electrons of a double bond.
This is seen in the ionization potentials of ethylene and acetylene.

Acetylene HC≡CH + Energy ——> [HC≡CH •(+) + e(–) ΔH = +264 kcal/mole

Ethylene H2C=CH2 + Energy ——> [H2C=CH2] •(+) + e(–) ΔH = +244 kcal/mole
Ethane H3C–CH3 + Energy ——> [H3C–CH3] •(+) + e(–) ΔH = +296 kcal/mole
Alkynes: Addition Reactions
• 2. Addition by Electrophilic Reagents
 Two factors are significant in explaining this
apparent paradox.
 A second factor is presumed to be the stability of the
carbocation intermediate generated by sigma-bonding of a
proton or other electrophile to one of the triple bond carbon
atoms. This intermediate has its positive charge localized
on an unsaturated carbon, and such vinyl cations are less
stable than their saturated analogs.
 Alkynes: Addition Reactions
• Despite these differences, electrophilic additions to
alkynes have emerged as exceptionally useful synthetic
transforms. For example, addition of HCl, acetic acid
and hydrocyanic acid to acetylene give respectively the
useful monomers vinyl chloride, vinyl acetate and
acrylonitrile, as shown in the following equations. Note
that in these and many other similar reactions transition
metals, such as copper and mercury salts, are effective
catalysts.
Alkynes: Addition Reactions
3. Hydration of Alkynes and Tautomerism
 As with alkenes, the addition of water to alkynes requires a
strong acid, usually sulfuric acid, and is facilitated by mercuric
sulfate. However, unlike the additions to double bonds which
give alcohol products, addition of water to alkynes gives ketone
products ( except for acetylene which yields acetaldehyde ).
 The explanation for this deviation lies in enol-keto
tautomerization. The initial product from the addition of water to
an alkyne is an enol (a compound having a hydroxyl substituent
attached to a double-bond), and this immediately rearranges to
the more stable keto tautomer.
Alkynes: Addition Reactions
3. Hydration of Alkynes and Tautomerism
 Tautomers are defined as rapidly interconverted
constitutional isomers, usually distinguished by a different
bonding location for a labile hydrogen atom (colored red
here) and a differently located double bond. The
equilibrium between tautomers is not only rapid under
normal conditions, but it often strongly favors one of the
isomers
 Alkynes: Addition Reactions
3. Hydration of Alkynes and Tautomerism
 Two factors have an important influence on the enol-
keto tautomerizations described here.
 The first is the potential energy difference between the
tautomeric isomers. This factor determines the position of
the equilibrium state.
 The second factor is the activation energy for the
interconversion of one tautomer to the other. This factor
determines the rate of rearrangement

The rapidity with which enol-keto tautomerization occurs suggests that the activation
energy for this process is low.
Alkynes: Addition Reactions
4. Hydroboration Reactions
 Diborane reacts readily with alkynes, but the formation of
substituted alkene products leaves open the possibility of
a second addition reaction.
 Consequently, large or bulky electrophilic reagents add
easily to the triple-bond, but the resulting alkene is
necessarily more crowded or sterically hindered and
resists further additions.
Alkynes: Addition Reactions
5. Oxidations
 Reactions of alkynes with oxidizing agents such as
potassium permanganate and ozone usually result in
cleavage of the triple-bond to give carboxylic acid
products. A general equation for this kind of
transformation follows. The symbol [O] is often used
in a general way to denote an oxidation.

RC≡CR' + [O] ——> RCO2H + R'CO2H

https://www2.chemistry.msu.edu/faculty/reusch/virttxtjml/addyne1.htm
 H H
| |
—C—C— + 2 KOH  — C  C — + KX + H2O
| | heat
X X

CH3CH2CHCH2 + KOH; then NaNH2  CH3CH2CCH

Br Br

“ + 2 KOH, heat
 X2 1. KOH
alkene vicinal dihalide alkyne
2. NaNH2

Br2
CH3CH=CH2 CH3CHCH2 1. CH
KOH
CCH
3

Br Br 2. NaNH2
Synthesis of propyne from propane

Br2, heat
CH3CH2CH3 CH3CH2CH2-Br + CH3CHCH3
Br
KOH(alc)

CH3CHCH2 CH3CH=CH2
Br2
Br Br

KOH
NaNH2
CH3CH CH CH3C CH
Br
2. coupling of metal acetylides with 1o/CH3 alkyl halides

R-CC-Na+ + R´X  R-CC-R´ + NaX

a) SN2
b) R´X must be 1o or CH3X

CH3CC-Li+ + CH3CH2-Br  CH3CCCH2CH3

note: R-X must be 1o or CH3 to get SN2!

CH3 CH3
CH3C C Na + CH3CCH3 CH3C CH2
Br
+
3o alkyl halide
CH3C CH
E2 elimination!
Reactions, alkynes:

1. addition of H2 (reduction)
2. addition of X2
3. addition of HX
4. addition of H2O, H+
5. as acids
6. Ag+
7. oxidation
1. Addition of H2

H H
| |
— C  C — + 2 H2, Ni  —C—C—
| |
H H

alkane

requires catalyst (Ni, Pt or Pd)

HCCH + 2 H2, Pt  CH3CH3

[ HCCH + one mole H2, Pt  CH3CH3 + CH2=CH2 +

HCCH ]

H
\ /
Na or Li C=C anti-
NH3(liq) / \
H
—CC—
\ /
H2, Pd-C C=C syn-
Lindlar catalyst / \
H H
 CH3 H
\ /
Na or Li C=C anti-
NH3(liq) / \
H CH3

trans-2-butene
CH3CCCH3

H H
\ /
H2, Pd-C C=C syn-
Lindlar catalyst / \
CH3 CH3

cis-2-butene
2. Addition of X2

X X X
| | |
— C C— + X2  — C = C — + X2  — C — C —
| | |
X X X

Br Br Br
CH3CCH + Br2  CH3C=CH + Br2  CH3-C-CH
Br Br Br
3. Addition of hydrogen halides:
H H X
| | |
— C C— + HX  — C = C — + HX  — C — C —
| | |
X H X

a) HX = HI, HBr, HCl

b) Markovnikov orientation

Cl
CH3CCH + HCl  CH3C=CH2 + HCl  CH3CCH3
Cl Cl
4. Addition of water. Hydration.
O

— C  C — + H2O, H+, HgO  — CH2 — C—

H OH
—C=C—
“enol” keto-enol
tautomerism

Markovnikov orientation.
5. As acids. terminal alkynes only!

a) with active metals

CH3CCH + Na  CH3CC-Na+ + ½ H2 

b) with bases

CH3CCH + CH3MgBr  CH4 + CH3C CMgBr

SA SB WA WB
acid strength:

CH4 < NH3 < HCCH < ROH < H2O < HF

HC CH + NaOH  NR ( H2O = stronger acid! )

CH3CH2CCH + LiNH2  NH3 + CH3CH2CC-Li+

SA WA
7. Oxidation

KMnO4

R-CC-R´ hot KMnO4 RCOOH +

HOOCR´
carboxylic acids

O3; then Zn, H2O

CH3CH2CCCH3 + KMnO4 
CH3CH2COOH +

HOOCCH3

CH3CCH + hot KMnO4 

CH3COOH + CO2

CH3CCCH3 + O3; then Zn, H2O 

2 CH3COOH
Alkynes

Nomenclature

Syntheses
1. dehydrohalogenation of vicinal dihalide
2. coupling of metal acetylides with 1o/CH3X