322  Chapter 7: Alkynes

11.  Reduction Using Na or Li Metal in NH3(l ) (Section 7.8C) Alkali metal reduction is stereoselective:
anti addition of hydrogens to an internal alkyne gives a trans-alkene. The mechanism involves a radical
mechanism with two sequential single-electron transfers from the Na or Li metal, each followed by
deprotonation of the amine solvent.

7.9 Organic Synthesis

●●
When planning an organic synthesis involving several reactions, it is best to use the following
systematic approach:
1. Count the carbons in the products versus the starting material so that you know what fragments
must be added or subtracted.
2. Analyze the functional groups.
3. Work backward (retrosynthesis).
●●
A functional group often reacts in the same fashion whether it is in a relatively simple molecule or
a more complex molecule that contains numerous other functional groups.
– Although they do not react directly, other functional groups often have an influence over the
regiochemistry or stereochemistry of a reaction.

P 7.6, 7.14, 7.20, 7.21–7.34; 7.35

Organic synthesis of 2-Heptanone

Problems
Red numbers indicate applied problems.
7.7 Enanthotoxin is an extremely poisonous organic compound found in hemlock water drop-
wart, which is reputed to be the most poisonous plant in England. It is believed that no
British plant has been responsible for more fatal accidents. The most poisonous part of
the plant is the roots, which resemble small white carrots, giving the plant the name “five
finger death.”Also poisonous are its leaves, which look like parsley. Enanthotoxin is thought
to interfere with the Na1 current in nerve cells, which leads to convulsions and death.

How many stereoisomers are possible for enanthotoxin?

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 Problems   323

Preparation of Alkynes
7.8 Show how to prepare each alkyne from the given starting material. In part (c), D indicates
deuterium. Deuterium-containing reagents such as BD3, D2O, and CH3COOD are avail-
able commercially.

(a) (b)

(c)

7.9 If a catalyst could be found that would establish an equilibrium between 1,2-butadiene
and 2-butyne, what would be the ratio of the more stable isomer to the less stable isomer
at 25°C?

CH2"C"CHCH3 m CH3C#CCH3  DG0 5 216.7 kJ (24.0 kcal)/mol

Reactions of Alkynes
7.10 Complete each acid-base reaction and predict whether the position of equilibrium lies
toward the left or toward the right.

(a) # 1 2 1

(b) # 1 1 2
l

(c) # 2 1 1

7.11 Draw structural formulas for the major product(s) formed by reaction of 3-hexyne with
each of these reagents. (Where you predict no reaction, write NR.)
(a) H2 (excess)/Pt (b) H2/Lindlar catalyst
(c) Na in NH3(l ) (d) BH3 followed by H2O2/NaOH
(e) BH3 followed by CH3COOH (f) BH3 followed by CH3COOD
(g) Cl2 (1 mol) (h) NaNH2 in NH3(l )
(i) HBr (1 mol) (j) HBr (2 mol)
(k) H2O in H2SO4/HgSO4
7.12 Draw the structural formula of the enol formed in each alkyne hydration reaction;
then draw the structural formula of the carbonyl compound with which each enol is in
equilibrium.

(a) # 1 9999: 9:

(b) # 999999999: 9:

7.13 Propose a mechanism for this reaction.

# 1 "
Acetylene Acetic acid Vinyl acetate

Vinyl acetate is the monomer for the production of poly(vinyl acetate), the major use of
which is as an adhesive in the construction and packaging industry, but it is also used in
the paint and coatings industry.

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324  Chapter 7: Alkynes

Syntheses
7.14 Show how to convert 9-octadecynoic acid to the following.

9-Octadecynoic acid

(a) (E)-9-Octadecenoic acid (eliadic acid)   (b) (Z)-9-Octadecenoic acid (oleic acid)
(c) 9,10-Dihydroxyoctadecanoic acid    (d) Octadecanoic acid (stearic acid)
7.15 For small-scale and consumer welding applications, many hardware stores sell cylin-
ders of MAAP gas, which is a mixture of propyne (methylacetylene) and 1,2-propadiene
(allene), with other hydrocarbons. How would you prepare the methylacetylene/allene
mixture from propene in the laboratory?
7.16 Show reagents and experimental conditions you might use to convert propyne into
each product. (Some of these syntheses can be done in one step; others require two or
more steps.)

(a) 9 (b) (c) (d)

7.17 Show reagents and experimental conditions you might use to convert each starting mate-
rial into the desired product. (Some of these syntheses can be done in one step; others
require two or more steps.)

(a) (b)

(c) (d)

7.18 Show how to convert 1-butyne to each of these compounds.

(a) CH3CH2C#C2Na1  (b) CH3CH2C#CD

(c) (d)

7.19 Rimantadine was among the first antiviral drugs to be licensed in the United States to
use against the influenza A virus and to treat established illnesses. It is synthesized from
adamantane by the following sequence (we discuss the chemistry of Step 1 in Chapter 8
and the chemistry of Step 5 in Section 16.8A).

"

Adamantane 1-Bromoadamantane

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 Problems   325

Rimantadine

Rimantadine is thought to exert its antiviral effect by blocking a late stage in the assembly
of the virus.
(a) Propose a mechanism for Step 2. Hint: As we shall see in Section 22.1C, reaction
of a bromoalkane such as 1-bromoadamantane with aluminum bromide (a Lewis
acid, Section 4.7) results in the formation of a carbocation and AlBr42. Assume
that adamantyl cation is formed in Step 2 and proceed from there to describe a
mechanism.
(b) Account for the regioselectivity of carbon-carbon bond formation in Step 2.
(c) Describe experimental conditions to bring about Step 3.
(d) Describe experimental conditions to bring about Step 4.
7.20 Show reagents and experimental conditions to bring about the following transformations.

(h)
(i)
(a)
(g)
" (j)
#
(b)

(f)

(c) (d) (e)

# "

7.21 Show reagents to bring about each conversion.

(c)

(d)

(b)
(a)
(e)

(f)

7.22 Propose a synthesis for (Z)-9-tricosene (muscalure), the sex pheromone for the common
housefly (Musca domestica), starting with acetylene and haloalkanes as sources of carbon atoms.

7.23 Propose a synthesis of each compound starting from acetylene and any necessary organic
and inorganic reagents.
(a) 4-Octyne    (b) 4-Octanone   (c) cis-4-Octene
(d) trans-4-Octene    (e) 4-Octanol   (f) meso-4,5-Octanediol

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326  Chapter 7: Alkynes

7.24 Show how to prepare each compound from 1-heptene.

(a) 1,2-Dichloroheptane   (b) 1-Heptyne (c) 1-Heptanol
(d) 2-Octyne       (e) cis-2-Octene  (f) trans-2-Octene
7.25 Show how to bring about this conversion.

Looking Ahead
7.26 Alkyne anions react with the carbonyl groups of aldehydes and ketones to form alkynyl
alcohols, as illustrated by the following sequence.

2 1 2 1
# 1 9 9 # 9 # 9

Propose a mechanism for the formation of the bracketed compound, using curved arrows
to show the flow of electron pairs in the course of the reaction.
7.27 Following is the structural formula of the tranquilizer meparfynol (Oblivon).

Oblivon

Propose a synthesis for this compound starting with acetylene and a ketone. (Notice
the -yn- and -ol in the chemical name of this compound, indicating that it contains al-
kyne and hydroxyl functional groups.)
7.28 The standard procedure for synthesizing a compound is the stepwise progress toward
a target molecule by forming individual bonds through single reactions. Typically, the
product of each reaction is isolated and purified before the next reaction in the sequence
is carried out. One of the ways nature avoids this tedious practice of isolation and pu-
rification is by the use of a domino sequence in which each new product is built on a
preexisting one in stepwise fashion. A great example of a laboratory domino reaction is
William S. ­Johnson’s elegant synthesis of the female hormone progesterone. Johnson first
constructed the polyunsaturated monocyclic 3° alcohol (A) and then, in an acid-induced
domino reaction, formed compound B, which he then converted to progesterone.

Progesterone

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 Problems   327

A remarkable feature of this synthesis is that compound A, which has only one stereo-
center, gives compound B, which has five stereocenters, each with the same configuration
as those in progesterone. We will return to the chemistry of Step 2 in Section 16.7 and to
the chemistry of Steps 3 and 4 in Chapter 19. In this problem, we focus on Step 1.
(a) Assume that the domino reaction in Step 1 is initiated by protonation of the 3° alcohol
in compound A followed by loss of H2O to give a 3° carbocation. Show how the series
of reactions initiated by the formation of this cation gives compound B.
(b) I f you have access to a large enough set of molecular models or to a computer
modeling program, build a model of progesterone and describe the conformation
of each ring. There are two methyl groups and three hydrogen atoms at the set of
ring junctions in progesterone. Which of these five groups occupies an equatorial
position? Which occupies an axial position?

Progesterone

Organic Chemistry Reaction Roadmap Reaction

Roadmap
7.29 Use the reaction roadmap you made for Problem 6.54 and update it to contain the reac-
tions in the Study Guide section of this chapter. Because of their highly specific nature, do
not use reactions 1 and 6 from this chapter on your roadmap.
7.30 Write the products of the following sequences of reactions. Refer to your reaction road-
map to see how the combined reactions allow you to “navigate” between the different
functional groups. For example, in part (a) below, notice how the reaction sequence re-
sults in the conversion of an alkyne into a haloalkane in two steps.

(a)

An alkyne

(b) 8

An alkyne

(c)

An alkyne

(d)

An alkyne

(e)
An alkene

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328  Chapter 7: Alkynes

Multistep Synthesis
7.31 Using your reaction roadmap as a guide, show how to convert acetylene and bromoeth-
Reaction
Roadmap ane into 1-butene. All of the carbon atoms of the target molecule must be derived from
the given starting materials. Show all intermediate molecules synthesized along the way.

Acetylene Bromoethane 1-Butene

7.32 Using your reaction roadmap as a guide, show how to convert ethylene into 1-butene.
Reaction
Roadmap All of the carbon atoms of the target molecule must be derived from ethylene. Show all
intermediate molecules synthesized along the way.

Ethylene 1-Butene

7.33 Using your reaction roadmap as a guide, show how to convert 3-hexyne into propanal.
Reaction
Roadmap All of the carbon atoms of the target molecule must be derived from the starting material
as efficiently as possible. Show all intermediate molecules synthesized along the way.

3-Hexyne Propanal

7.34 Using your reaction roadmap as a guide, show how to convert the starting trans-alkene to
Reaction
Roadmap the cis-alkene in high yield. Show all intermediate molecules synthesized along the way.

trans cis

Reactions in Context
7.35 Functional groups such as alkynes react the same in complex molecules as they do in
simpler structures. The following examples of alkyne reactions were taken from syntheses
carried out in the research group of E. J. Corey at Harvard University. You can assume that
the reactions listed involve only the alkyne, not any of the functional groups present in
the molecules. Draw the expected products for the following reactions.
(a)

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 Problems   329

(b)
8

(c)

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