3. Hydrogenation of alkynes (Section 7.

15):
General Reaction
R-C=C-R'
H
2
I Ni
2
B (P-2)
(syn addition)
R R'
" / C=C
. / "
H H
(Z)Aikene
R H
Li or Na "c=C/
NH
3
or RNH
2
/ "-
(anti addition) H R'
(E)-Alkene
Problems
subsequent chapters we shall see a number of other methods for alkene synthesis.
Key Terms and Concepts
he key terms and concepts that are highlighted in bold, blue text within the chapter are
efined in the glossary (at the back of the book) and have hyperlinked definitions in the
accompanying WileyPLUS course (www.wileyplus.com) .
. <Problems


"'] 323
Note to Instructors: Many of the homework problems are available for assignment via WileyPLUS, an online
teaching and learning solution.
1
STRUCTURE AND NOMENCLATURE
.25 Each of the following names is incorrect. Give the correct name and explain your reasoning.
(a) trans-3-Pentene (c) 2-Methylcyclohexene (e) (Z)-3-Chloro-2-butene
(b) 1,1-Dimethylethene (d) 4-Methylcyclobutene (f) 5,6-Dichlorocyclohexene
.26 Write a structural formula for each of the following:
(a) 3-Methylcyclobutene (e) (E)-2-Pentene
(b) 1-Methylcyclopentene (f) 3,3,3-Tribromopropene
(c) 2,3-Dimethyl-2-pentene (g) (Z,4R)-4-Methyl-2-hexene
(d) (Z)-3-Hexene (h) (E,4S)-4-Chloro-2-pentene
(i) (Z)-1-Cyclopropyl-1-pentene
(j) 5-Cyclobutyl-1-pentene
(k) (R)-4-Chloro-2-pentyne
(1) (E)-4-Methylhex-4-en-1-yne
,27 Write three-dimensional formulas for and give names using (R)-(S) and (E)-(Z) designations for the isomers of:
(a) 4-Bromo-2-hexene (c) 2,4-Dichloro-2-pentene
(b) 3-Chloro-1,4-hexadiene (d) 2-Bromo-4-chlorohex-2-en-5-yne
28 Give the IUPAC names for each of the following:



(b)q-
CI
(e) \
Cl

I
324
7.29
7.30
7.31
7.32
Chapter 7 Alkenes and Alkynes I
Without consulting tables, arrange the following compounds in order of decreasing acidity:
Pentane 1-Pentene 1-Pentyne 1-Pentanol
SYNTHESIS
Outline a synthesis of propene from each of the following:
(a) Propyl chloride (c) Propyl alcohol
(b) Isopropyl chloride (d) Isopropyl alcohol
Outline a synthesis of cyclopentene from each of the following:
(a) Bromocyclopentane (b) 1,2-Dichlorocyclopentane
(e) 1,2-Dibromopropane
(f) Propyne
(c) Cyclopentanol
Starting with ethyne, outline syntheses of each of the following. You may use any other ntieded reagents, and you
need not show the synthesis of compounds prepared in earlier parts of this problem. .
(a) Propyne (f) 1-Pentyne ( ~ ) CH3GH2C=CD
(b) 1-Butyne (g) 2-Hexyne (I) H. C CH
(c) 2-Butyne (h) (Z)-2-Hexene K
3
"c=C/
3
(d) cis-2-Butene (i) (E)-2-Hexene \ 0/ ';-D
1.
(e) trans-2-Butene U) 3-Hexyne
7.33 Starting with 1-methylcyclohexene and using any other needed reagents, outline a synthesis of the following
deuterium-labeled compound:
D
c::focH,
H
7.34 Outline a synthesis of phenylethyne from each of the following:
(a)
ox
( b ) ~ B <
(c)U
(d)
0
I # Br
I#
cY'
DEHYDROHALOGENATION AND DEHYDRATION
7.35 Write a three-dimensional representation for the transition state structure leading to formation of 2-methyl-2-butene
from reaction of 2-bromo-2-methylbutane with sodium ethoxide.
7.36 When trans-2-methylcyclohexanol (see the following reaction) is subjected to acid-catalyzed dehydration, the major
product is 1-methylcyclohexene:
CH
3
6,0H
HA
~
heat
0
"
However, when trans-1-bromo-2-methylcyclohexane is subjected to dehydrohalogenation, the major product is
3-methylcyclohexene:
x,.,B.
u ~ < c5
EtONa
EtOH, heat
H
Account for the different products of these two reactions.
7
7
7.
I 7.40
7.41
7.42
7.43
Problems

'G!..P

325
7.37 Write stfuctutai formulas for alL the products that would be obtained when each of the following alkyl halides is
heated with sodium ethoxi.de in ethanol. When more than one product results, you should indicate which would be
the major product and which wduld be the minor product(s). You may neglect cis-trans isomerism of the products
when answering this question.
(a) )y
Br
(d) (fsr


/""-Br
(e)C(_
<ocx.s_r
7.38 Write structural formulas for all the products that would be obtained when each of the following alkyl halides is
heated with potassium tert-butoxide in tert-butyi alcohol. When more than one product results, you should indi-
cate which would be the major product and which would be the minor product(s). You may neglect cis-trans iso-
merism of the products when question.

Br
JX

/""-Br

(e) (fsr
7.39 Starting with ai1.fippropriate alkyl halide and base, outline syntheses that would yield each ofthe following alkenes
as the major (or only) product:


(c) )y (d) D
(e)o-
7.40 Arrange the following alcohols in order of their reactivity toward acid-catalyzed dehydration (with the most reac-
tive first):
1-Pentanol 2-Methyl-2-butanol 3-Methyl-2-butanol
7.41 Give the products that would be formed when each of the following alcohols is subjected to acid-catalyzed dehy-
dration. If more than one product would be formed, designate the alkene that would be the major product. (Neglect
cis-trans isomerism.)
(a) XH
(b)
)y
OH

/""-oH
(d)
(e) ('r(

7.42 l -Bromobicyclo[2.2.1]heptane does not undergo elimination (below) when heated with a base. Explain this fail-
ure to react. (Construction of molecular models may help.)
7.43

When the deuterium-labeled compound shown at right is subjected to dehydrohalo-
genation using sodium ethoxide in ethanol, the only alkene product is 3-methylcy-
clohexene. (The product contains no deuterium.) Provide an explanation for this
result.
:X

\
326 Chapter 7 Alkenes and Alkynes I
7.44 Provide a mechanistic explanation for each of the following reactions:
7.45

acid (cat.)
(b) CrOH
acid (cat.)
t.
t.
(major product)
(y
(major product)
(c) 'l
(d) PhXH;-Ph
.-- f''H
Br
INDEX OF HYDROGEN DEFICIENCY
AgN0
3
EtOH
>=<
(major product).
EtONa
EtOH, t.

/ -\Ph
(E only)
Caryophyllene, a compound found in oil of cloves, has the molecular formula C
15
H
24
and has no triple bonds.
Reaction of caryophyllene with an excess of hydrogen in the presence of a platinum catalyst produces a
compound with the formula C
15
H
28
. How many (a) double bonds and (b) rings does a molecule of caryophyl-
lene have?
7.46 Squalene, an important intermediate in the biosynthesis of steroids, has the molecular formula C
30
H
50
and has no
triple bonds.
(a) What is the index of hydrogen deficiency of squalene?
(b) Squalene undergoes catalytic hydrogenation to yield a compound with the molecular formula C
30
H
62
. How many
double bonds does a molecule of squalene have?
(c) How many rings?
STRUCTURE ELUCIDATION
7.47 Compounds I and J both have the molecular formula C
7
H
14
. Compounds I and J are both optically active and both
rotate plane-polarized light in the same direction. On catalytic hydrogenation I and J yield the same compound K
(C
7
H
16
) . Compound K is optically active. Propose possible structures for I, J, and K.
7.48
(+)-I (CyH14) H2, Pt

K (CyH1
6
)
(+)-J (C7H14) (Optically active)
Compounds Land M have the molecular formula C
7
H
14
. Compounds Land Mare optically inactive, are non-
resolvable, and are diastereomers of each other. Catalytic hydrogenation of either Lor M yields N. Compound
N is optically inactive but can be resolved into separate enantiomers. Propose possible structures for L, M,
and N.
l (CyH14) H2, Pt
(Optically inactive)
N
M (CyH14)
(Optically inactive)
;'((Optically inactive,
resolvable)
(L and M are diastereomers)
7
7
7.521
7.53
7.54
1.