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Alkynes are molecules that incorporate a CC triple

bond.
10.1 Alkynes
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -1
Chapter 9
2
Introduction
Alkynes contain a triple bond.
General formula is C
n
H
2n-2
.
Two elements of unsaturation for each
triple bond.
Some reactions resemble the reactions of
alkenes, like addition and oxidation.
Some reactions are specific to alkynes.

Given the presence of two pi bonds and their associated
electron density, alkynes are similar to alkenes in their
ability to act as a nucleophile.






Converting pi bonds to sigma bonds generally makes a
molecule more stable. WHY?
10.1 Alkynes
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -3
Chapter 9
4
Acetylene is the simplest alkyne.
It is used in blow torches and as a precursor for the synthesis
of more complex alkynes.
More than 1000 different alkyne natural products have
been isolated.
One example is histrionicotoxin,
which can be isolated from South
American frogs, and is used on
poison-tipped arrows by South
American tribes.

10.1 Alkyne Uses
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -5
An example of a synthetic alkyne is ethynylestradiol.
Ethynylestradiol is the active
ingredient in many birth control
pills.

The presence of the triple bond increases the potency
of the drug compared to the natural analog.
How do you think a CC triple bond affects the
molecules geometry? Its rigidity? Its intermolecular
attractions?
10.1 Alkyne Uses
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -6
Alkynes are named using the same procedure we used in
Chapter 4 to name alkanes with minor modifications:
1. Identify the parent chain, which should include the CC triple
bond.
2. Identify and name the substituents.
3. Assign a locant (and prefix if necessary) to each substituent, giving
the CC triple bond the lowest number possible.
4. List the numbered substituents before the parent name in
alphabetical order. Ignore prefixes (except iso) when ordering
alphabetically.
5. The CC triple bond locant is placed either just before the parent
name or just before the -yne suffix.
10.2 Alkyne Nomenclature
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -7
Alkynes are named using the same procedure we used
in Chapter 4 to name alkanes with minor
modifications:
1. Identify the parent chain, which should include the CC
triple bond.





2. Identify and name the substituents.
10.2 Alkyne Nomenclature
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -8
Alkynes are named using the same procedure we used
in Chapter 4 to name alkanes with minor
modifications:
3. Assign a locant (and prefix if necessary) to each substituent.
giving the CC triple bond the lowest number possible.





The locant is ONE number, NOT two. Although the triple
bond bridges carbons 2 and 3, the locant is the
lower of those two numbers.
10.2 Alkyne Nomenclature
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -9
Alkynes are named using the same procedure we used
in Chapter 4 to name alkanes with minor
modifications:
4. List the numbered substituents before the parent name in
alphabetical order. Ignore prefixes (except iso) when
ordering alphabetically.
5. The CC triple bond locant is placed either just before the
parent name or just before the -yne suffix.
10.2 Alkyne Nomenclature
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -10
In addition to the IUCAP naming system, chemists
often use common names that are derived from the
common parent name acetylene.




You should also be aware of the terminology below.


Practice with SKILLBUILDER 10.1.
10.2 Alkyne Nomenclature
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -11
Name the molecule below.






Recall that when triple bonds are drawn, their angles
are 180.
10.2 Alkyne Nomenclature
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -12
Chapter 9
13
Nomenclature: IUPAC
Find the longest chain containing the triple
bond.
Change -ane ending to -yne.
Number the chain, starting at the end closest
to the triple bond.
Give branches or other substituents a number
to locate their position.
Chapter 9
14
Chapter 9
15
Examples of Nomenclature
All other functional groups, except ethers and
halides have a higher priority than alkynes.

If there is a tie between a double bond and triple bond
the double bond gets the lower number but name ends with yne
Nomenclature
Chapter 9
17
Physical Properties
Nonpolar, insoluble in water.
Soluble in most organic solvents.
Boiling points are similar to alkane of same
size.
Less dense than water.
Up to four carbons, gas at room temperature.
Chapter 9
18
Acetylene
Acetylene is used in welding torches.
In pure oxygen, temperature of flame reaches
2800C.
It would violently decompose to its elements,
but the cylinder on the torch contains crushed
firebrick wet with acetone to moderate it.

Chapter 9
19
Synthesis of Acetylene
Heat coke with lime in an electric furnace to
form calcium carbide.
Then drip water on the calcium carbide:
lime
This reaction was used to produce light for miners lamps and for the stage.
C C aO 3
+
+ C aC
2
C O
H C C H
C a( O H )
2
C aC
2
+ 2 H
2
O +
Chapter 9
20
Molecular Structure of Acetylene
Triple-bonded carbons have sp hybrid orbitals.
A sigma bond is formed between the carbons by overlap
of the sp orbitals.
Sigma bonds to the hydrogens are formed by using the
second sp orbital.
Since the sp orbitals are linear, acetylene will be a linear
molecule.


Chapter 9
21
Bond Lengths
Triple bonds are shorter than double or single
bonds because of the two pi overlapping orbitals.
Chapter 9
22
Acidity Table
Chapter 9
23
Acidity of Alkynes
Terminal alkynes, are more acidic than other
hydrocarbons due to the higher s character of the sp
hybridized carbon.
Terminal alkynes can be deprotonated quantitatively
with strong bases such as sodium amide (
-
NH
2
).
Hydroxide and alkoxide bases are not strong enough
to deprotonate the alkyne quantitatively.
Recall that terminal alkynes have a lower pK
a
than
other hydrocarbons.




Acetylene is 19 pK
a
units more acidic than ethylene,
which is 10
19
times stronger.
Does that mean that terminal alkynes are strong acids?
10.3 Alkyne Acidity
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -24
Because acetylene (pK
a
=25) is still much weaker than
water (pK
a
=15.7), a strong base is needed to make it
react.



Recall from Chapter 3 that we used the acronym ARIO
to rationalize differences in acidity strengths.
Use ARIO to explain why acetylene is a stronger acid than
ethylene which is stronger than ethane.
10.3 Alkyne Acidity
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -25
Use ARIO to rationalize the equilibria below.







A bases conjugate acid pK
a
must be greater than 25 for
it to be able to deprotonate a terminal
alkyne.
10.3 Alkyne Acidity
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -26
Chapter 9
27
Chapter 9
28
Formation of Acetylide Ions
H
+
can be removed from a terminal alkyne by
sodium amide, NaNH
2
.





The acetylide ion is a strong nucleophile that can
easily do addition and substitution reactions.
Acidity of Terminal Alkynes
NaOH can not be used to deprotonate C-H of terminal alkyne

NaNH
2
is a stronger base than NaOH
Other bases that can be used to deprotonate C-H of terminal
alkyne
Like alkenes, alkynes can also be prepared by
elimination.
10.4 Preparation of Alkynes
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -31
Such eliminations usually occur via an E2 mechanism:
GEMINAL dihalides can be used.



VICINAL dihalides can also be used.



E2 requires anti-periplanar geometry.
10.4 Preparation of Alkynes
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -32
Often, excess equivalents of NaNH
2
are used to shift
the equilibrium toward the elimination products.





NH
2
1-
is quite strong, so if a terminal alkyne is
produced, it will be deprotonated.
That equilibrium will greatly favor products.
10.4 Preparation of Alkynes
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -33
A proton source is needed to produce the alkyne.




Predict the products in the example below.



Practice with CONCEPTUAL CHECKPOINT
10.7.
10.4 Preparation of Alkynes
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -34
Like alkenes, alkynes can readily undergo
hydrogenation.
Two equivalents of H
2
are
consumed for each
alkynealkane conversion.

The cis alkene is produced as an intermediate. WHY
cis?

10.5 Reduction of Alkynes
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -35
Chapter 9
36
Catalytic Hydrogenation of Alkynes
Two molecules of hydrogen can add across the triple bond
to form the corresponding alkane.
A catalyst such as Pd, Pt, or Ni needs to be used for the
reaction to occur.
Under these conditions the alkyne will be completely
reduced; the alkene intermediate cannot be isolated.
A deactivated or poisoned catalyst can be used to
selectively react with the alkyne.



Lindlars catalyst and P-2 (Ni
2
B complex) are common
examples of a poisoned catalysts.
10.5 Reduction of Alkynes
Poisoned Catalyst
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -37
Is this a syn or anti addition?








Practice with CONCEPTUAL CHECKPOINT 10.9.
10.5 Reduction of Alkynes
Poisoned Catalyst
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -38
Chapter 9
39
Hydrogenation with Lindlars
Catalyst
The catalyst used for the hydrogenation reaction is partially
deactivated (poisoned), the reaction can be stopped after the
addition of only one mole of hydrogen.
The catalyst used is commonly known as Lindlar's catalyst and it is
composed of powdered barium sulfate, coated with palladium
poisoned with quinoline.
The reaction produces alkenes with cis stereochemistry.

Chapter 9
40
Mechanism
Both substrates, the hydrogen and the alkyne, have to be
adsorbed on the catalyst for the reaction to occur.
Once adsorbed, the hydrogens add to the same side of the
double bond (syn addition) giving the product a cis
stereochemistry.

Reduction with H
2
gives syn addition.
Dissolving metal conditions can give anti addition
producing the trans alkene.


Ammonia has a boiling point of 33C, so the
temperature for these reactions must remain very low.
Why cant water be used as the solvent?
10.5 Reduction of Alkynes
Dissolving Metal Reductions
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -41
Chapter 9
42
Reduction of Alkynes with Metal
Ammonia
To form a trans alkene, two hydrogens must be
added to the alkyne anti stereochemistry, so this
reduction is used to convert alkynes to trans
alkenes.
Chapter 9
43
Reduction of Alkynes with Metal
Ammonia
Use dry ice to keep ammonia liquid.
As sodium metal dissolves in the ammonia,
it loses an electron.
The electron is solvated by the ammonia,
creating a deep blue solution.
N H
3
+ Na
+
N a
+
N H
3
e
-
Chapter 9
44
Mechanism of Metal Reduction
Step 1: An electron adds to the alkyne, forming a radical
anion.
Step 2: The radical anion is protonated to give a radical.
Step 3: An electron adds to the alkyne, forming an
anion.
Step 4: Protonation of the anion gives an alkene.
Mechanismstep 1:
Note the single-barbed and double-barbed (fishhook)
arrows.
Why does Na metal so readily give up an electron?
10.5 Reduction of Alkynes
Dissolving Metal Reductions
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -45
Mechanismstep 1:


Why is the first intermediate called a RADICAL ANION?
The radical anion adopts a trans configuration to
reduce repulsion.
10.5 Reduction of Alkynes
Dissolving Metal Reductions
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -46
Mechanismstep 2 and 3:








Draw the product for step 3 of the mechanism.
10.5 Reduction of Alkynes
Dissolving Metal Reductions
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -47
Mechanismstep 4:







Do the pK
a
values for NH
3
and the alkene favor the
proton transfer?
10.5 Reduction of Alkynes
Dissolving Metal Reductions
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -48
Predict the product(s) for the following reactions.







Practice with CONCEPTUAL CHECKPOINT 10.10.
10.5 Reduction of Alkynes
Dissolving Metal Reductions
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -49
Chapter 9
50
Familiarize yourself with the reagents necessary to
manipulate alkynes.






Practice with CONCEPTUAL CHECKPOINT 10.11.
10.5 Reduction of Alkynes
Summary
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -51
Like alkenes, alkynes also undergo hydrohalogenation.






Draw the final product for the reaction above.
Do the reactions above exhibit Markovnikov
regioselectivity?
10.6 Hydrohalogenation of Alkynes
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -52
Modeled after the hydrohalogenation of alkenes, you might
expect alkynes to react by the same mechanism.







Yet, the mechanism above does not explain all observed
phenomena:
A slow reaction rate
3
rd
order overall rate law
Vinylic carbocations are especially unstable
10.6 Hydrohalogenation of Alkynes
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -53
Kinetic studies on the hydrohalogenation of an alkyne
suggest that the rate law is 1
st
order with respect to
the alkyne, and 2
nd
order with respect to HX.




What type of collision would result in such a rate law?
Unimolecular, bimolecular, or termolecular?
10.6 Hydrohalogenation of Alkynes
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -54






Reaction rate is generally slow for termolecular
collisions. WHY?
Considering the polarizability of the alkyne, does the
mechanism explain the regioselectivity?
May involve multiple competing mechanisms.
10.6 Hydrohalogenation of Alkynes
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -55
Peroxides can be used in the hydrohalogenation of
alkynes to promote anti-Markovnikov addition just like
with alkenes.



Which product is E and which is Z?
The process proceeds through a free radical
mechanism that we will discuss in detail in Chapter 11.
Practice with CONCEPTUAL CHECKPOINT 10.13.
10.6 Hydrohalogenation of Alkynes
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -56
Chapter 9
57
Addition of HX
One mole of HCl, HBr, and HI add to alkynes to form vinyl
halides.
If two moles of HX is added, product is a geminal dihalide.
The addition of HX is Markovnikov and will produce a
geminal dihalide.
Chapter 9
58
Mechanism of Hydrogen Halide
Addition
The triple bonds abstract a proton from the hydrogen
halide forming a vinyl cation.
The proton adds to the least substituted carbon.
The second step of the mechanism is the attack by the
halide.
Chapter 9
59
Anti-Markovnikov Addition of
Hydrogen Bromide to Alkynes
By using peroxides, hydrogen bromide can be added to a
terminal alkyne anti-Markovnikov.
The bromide will attach to the least substituted carbon
giving a mixture of cis and trans isomers.

Like alkenes, alkynes can also undergo acid catalyzed
Markovnikov hydration.
The process is generally catalyzed with HgSO
4
to
compensate for the slow reaction rate that results
from the formation of vinylic carbocation.




10.7 Hydration of Alkynes
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -60
HgSO
4
catalyzed hydration involves the mercury (II) ion
interacting with the alkyne.
Can you imagine what that interaction might look like
and how it will increase the rate of reaction for the
process?




Why is the intermediate called an enol?
10.7 Hydration of Alkynes
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -61
The enol/ketone TAUTOMERIZATION generally cannot
be prevented and favors the ketone greatly.





TAUTOMERS are constitutional isomers that rapidly
interconvert. How is that different from resonance?
Practice with SKILLBUILDER 10.3.
10.7 Hydration of Alkynes
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -62
Chapter 9
63
Hydration of Alkynes
Mercuric sulfate in aqueous sulfuric acid
adds HOH to one pi bond with a
Markovnikov orientation, forming a vinyl
alcohol (enol) that rearranges to a ketone.
Hydroborationoxidation adds HOH with
an anti-Markovnikov orientation, and
rearranges to an aldehyde.

Chapter 9
64
Mercuric Ion Catalyzed Hydration of
Alkynes
Water can be added across the triple bond in a reaction
analogous to the oxymercurationdemercuration of alkenes.
The hydration is catalyzed by the mercuric ion.
In a typical reaction, a mixture of mercuric acetate in
aqueous sulfuric acid is used.
The addition produces an intermediate vinyl alcohol (enol)
that quickly tautomerizes to the more stable ketone or
aldehyde.
Chapter 9
65
Mechanism of Mercuric Ion
Catalyzed Hydration
The electrophilic addition of mercuric in (Hg
+2
) creates a
vinyl carbocation.
Water attacks the carbocation and after deprotonation,
forms an organomercurial alcohol.
Hydrolysis of the alcohol removes the mercury, forming a
vinyl alcohol commonly referred to as enol.
Chapter 9
66
KetoEnol Tautomerism
Enols are not stable and they isomerize to the
corresponding aldehyde or ketone in a process
known as keto-enol tautomerism.

Chapter 9
67
Hydroboration-oxidation for alkynes proceeds through
the same mechanism, as for alkenes, giving the anti-
Markovnikov product.
It also produces an enol that will quickly tautomerize.



In this case, the tautomerization is catalyzed by the
base (OH
-
) rather than by an acid.
10.8 Hydroboration-Oxidation
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -68
In general, we can conclude
that a C=O double bond is
more stable than a C=C
double bond. WHY?
10.8 Hydroboration-Oxidation
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -69
After the BH
2
and H groups have been added across
the C=C double bond, in some cases, an undesired
second addition can take place.





To block out the second unit of BH
3
from reacting with
the intermediate, bulky borane reagents are
often used.
10.8 Hydroboration-Oxidation
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -70
Some bulky borane reagents are shown below.







Practice with CONCEPTUAL CHECKPOINT 10.20.
10.8 Hydroboration-Oxidation
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -71
Predict products for the following reaction.



Draw the alkyne reactant and reagents that could be
used to synthesize the following molecule.
10.8 Hydroboration-Oxidation
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -72
Markovnikov hydration leads to a ketone.
Anti-Markovnikov hydration leads to an aldehyde.







Practice with SKILLBUILDER 10.4.
10.8 Hydration Regioselectivity
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -73
Alkynes can also undergo halogenation.
Two equivalents of halogen can be added.




You might expect the mechanism to be similar to the
halogenation of alkenes, yet stereochemical evidence
suggests otherwise.
10.9 Alkyne Halogenation
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -74
When one equivalent of halogen is added to an alkyne,
both anti and syn addition is observed.




The halogenation of an alkene undergoes anti addition
ONLY.
The mechanism for alkyne halogenation is not fully
elucidated.
10.9 Alkyne Halogenation
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -75
When alkynes react under ozonolysis conditions, the pi
system is completely broken.






The molecule is cleaved, and the alkyne carbons are
fully oxidized.
Practice with CONCEPTUAL CHECKPOINT
10.25.
10.10 Alkyne Ozonolysis
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -76
Predict the product(s) for the following reaction.
10.10 Alkyne Ozonolysis
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -77
Chapter 9
78
Oxidation of Alkynes
Similar to oxidation of alkenes.
Dilute, neutral solution of KMnO
4
oxidizes
alkynes to a diketone.
Warm, basic KMnO
4
cleaves the triple
bond.
Ozonolysis, followed by hydrolysis, cleaves
the triple bond.
Chapter 9
79
Permanganate Oxidation of Alkynes
to Diketones
Under neutral conditions, a dilute potassium
permanganate solution can oxidize a triple bond into an
diketone.
The reaction uses aqueous KMnO
4
to form a tetrahydroxy
intermediate, which loses two water molecules to produce
the diketone.

Chapter 9
80
Permanganate Oxidation of Alkynes
to Carboxylic Acids
If potassium permanganate is used under basic conditions
or if the solution is heated too much, an oxidative
cleavage will take place and two molecules of carboxylic
acids will be produced.
Chapter 9
81
Ozonolysis
Ozonolysis of alkynes produces carboxylic acids
(alkenes gave aldehydes and ketones).




Used to find location of triple bond in an
unknown compound.

H O C
O
C H
2
C H
3
C H
3
C
O
O H
H
2
O
(2)
O
3
(1)
C H
3
C C C H
2
C H
3 +

Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
7 -82
As acids, terminal alkynes are quite weak.
Yet, with a strong enough base, a terminal alkyne can
be deprotonated and converted into a good
nucleophile.



Which has a higher pK
a
, NH
3
or R-CC-H? WHY?
10.11 Alkylation of Terminal Alkynes
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -83
The alkynide ion can attack a methyl or 1 alkyl halide
electrophile.

Such reactions can be used to develop molecular
complexity.



Alkynide ions usually act as bases with 2 or 3 alkyl
halides to cause elimination rather than
substitution.
10.11 Alkylation of Terminal Alkynes
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -84
Acetylene can be used to perform a double alkylation.


Why will the reaction be unsuccessful if the NaNH
2
and Et-Br
are added together?



Complex target molecules can be made by building a
carbon skeleton and converting functional groups.
Practice with SKILLBUILDER 10.5.
10.11 Alkylation of Terminal Alkynes
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -85
Chapter 9
86
Acetylide Ions in S
N
2 Reactions
One of the best methods for synthesizing substituted
alkynes is a nucleophilic attack by the acetylide ion on an
unhindered alkyl halide.
S
N
2 reaction with 1 alkyl halides lengthens the alkyne
chain.
Unhindered alkyl halides work better in an S
N
2 reaction:
CH
3
X > 1

.
Chapter 9
88
Acetylide Ions as Strong Bases
Acetylide ions are also strong bases. If the S
N
2
reactions is not possible, then an elimination (E2)
will occur.
Chapter 9
89
Show how to synthesize 3-decyne from acetylene and any necessary alkyl halides.
Another name for 3-decyne is ethyl n-hexylacetylene. It can be made by adding an ethyl group and a
hexyl group to acetylene. This can be done in either order; we begin by adding the hexyl group.
Solved Problem 1
Solution
Chapter 9
90
Chapter 9
91
Recall the methods for increasing the saturation of
alkenes and alkynes.






But, what if you want to reverse the process
or decrease saturation?
10.12 Synthetic Strategies
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -92
Halogenation of an alkene followed by two
dehydrohalogenation reactions can decrease
saturation.


We will have to wait until Chapter 11 to see how to
convert an alkane into an alkene, but here is a preview.



What conditions would you use in step B?


10.12 Synthetic Strategies
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -93





In the alkene to alkyne conversion above, why is water
needed in step 3) of that reaction?

Practice with SKILLBUILDER 10.6.
10.12 Synthetic Strategies
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -94
Give necessary reaction conditions for the multi-step
conversions below.
10.12 Synthetic Strategies
Copyright 2012 John Wiley & Sons, Inc.
Klein, Organic Chemistry 1e
10 -95
Chapter 9
96
Chapter 9
97