7-29 (c) continued

without rearrangement
H
H HI r:-.
H2O: H
��?H :
..
�

H
H
�H�
C H H2O: H
1<H H
+ ..

H H
E+Z

H�
w ith hydride shift
H� H

~ 1<H
H
H +

- ./"'--r�
+(� ..
H20:
H HH -- .-.------- H
H �: H

El product from
unrearranged
carbocation

rearrangement by alkyl shift

El on rearranged c arboc ation

H
149
7-29 (d) continued
E1 on rearranged carbocation

� �H20 :.
<:;LJ 00 + H,o'
+

�
7-30 Please refer to solution 1 -20, page 1 2 of this Solutions Manual.

� 0 o
7 -3 1
Br
(a) (c) (d) (e)
Br

(f) (g) (h) r;

�
Br
1
(") �
Z E

(a) 2-ethylpent-l-ene (number the longest chain containing the double bond)
7 -32

(b) 3-ethylpent-2-en e
(c ) (3E,6E)-octa-l,3,6-triene
(d) (E)-4-ethylhept-3 -ene
(e) l-cyc lohexy lcyclohexa-l,3-diene
(f) (3Z, 5E)-6-ch loro-3-(chloromethyl)octa-l ,3,5 -triene

7 -33 (a) E (b) nei ther-two methyl groups on one carbon (c) Z (d) Z

� 0 [>-F
7-34

�F
A
F
(a)

F F
(Z)-l-fluoro­ (E)-l-fluoro- 2-fluoro- 3-fluoro- fluorocyclopropane
prop-l-ene prop-l-ene prop- l -ene prop-l-ene

(b) C4H 7 B r has one element of unsaturation, but no rings are permitted in the problem, so all the isomers
must have one double bond. Only four i somers are possible with four c arbons and one double bond, so

H
��
Br

H �
Br

Y
Br

y
Br

Br
B r - �/'o...'-
� .
�
�"
�
Br

�Br
�
� Br

� Br

C27H460,
Br

(b) Cholesterol, has fi ve elements of unsaturation . If only one of those is a pi bond, the other
four must be rings"
150
7-3 5

(a)
~ ~
trans, trans cis,trans
;=\'
trans,cis
�
cis,cis

(b) 2£,4£ 2Z,4£ 2£,4Z 2Z,4Z

This problem is i ntended to show the difficulty of using cis-trans nomenclature with any but the
simplest alkenes. Cis and trans are ambi guous: the first alkene in part ( a) is cis if the two similar
substituents are considered, but trans if the chain is considered. The £-Z nomenc l ature i s
unambiguous and i s preferred for a l l four o f these i somers.

7-36 (a) and (d) have no geometric i somers

(b) (c) �
trans-pent-2-ene cis-pent-2-ene trans-hex -3-ene cis-hcx-3-ene
(E)-pent-2-ene (Z)-pent-2-ene (E)-hex -3-ene (Z)-hex-3-ene

Br

�
y 1-
(e) trans- 1 ,2-dibromopropene B r cis- 1 ,2-dibromopropene
(E)- 1 ,2-di bromopropene (Z)- 1 ,2-dibromopropene
Br
Br

(f)

trans,trans-hexa-2 ,4-diene cis,trans-hexa-2,4-diene cis,cis-hexa-2,4-diene

(2£,4E)-hexa-2,4-diene (2Z,4E)-hexa-2,4-diene (2Z,4Z)-hexa-2 ,4-diene

7-37
F
1 F H F Br 1 Br Br CH3
(a)
>===< >===< (b)
>===< >===<
H H F H H H CH3 Br
di pole moment = 0
dipole moment = 0

Cl 1 Cl Cl 1 Cl
(c)
Br
A Br H
>===<
H
larger dipole moment
(no bromines opposing
the dipole of the chlorines)
7-3 8

( a)
o
( b)

maj or
+� minor
(c)

15 1 major mi nor
7 - 3 8 continued

(d)

mmor major
7-39 Only major alkene i somers are shown. Minor alkene i somers would also be produced in parts

H H
(a), (b) and (d).
H H
I I
(a) CH3-C-C-CH3 I I
CH3-C=C-CH3 + H20
H OH I I
E+Z

H
NaOC(CH3h HOC(CH3h
(b)
hindered base
-

en + NaBr +

II II
Br

H H H H
(c) CH3-C-C-CH3 + Zn
CH3COOH CH3-C=C-CH3
---....,..
�
I I
+ ZnBr2
E+Z

II II 3
Br Br

CH3 CH3
(d) CH3-C-C-CH NaOH, tl

H
�
Br
7 -40

(a)
Br

0
N aI, acetone

OR CH3COOH
..

'" Zn,

Q'0H H2S04,
Br

0
tl
(b) ..

Q' KOC(CH3h
0
Br
(c) ..

2 Q' KOC(CH3h
0 0
Br ' hv Br
(d) .. ..

7-41
(a) � (b) � + + 1\
\ J
only product �---�,,�---�
minor
major

152
7-4 1 continued

(c) � + � (d) � )l (e) � �

U + U
major rrunor
U +U
maj or rrunor

The E2 mechanis m requires anti-coplanar orientation of R and B r.

cSf
7-42 The bromides are shown here . Chlorides or iodides would also work.

Br
�
� Y
(a) (b) (c) (d)

Br
Br
Br
7-43
( a) There are two reasons w h y alcohols do not dehydrate with strong base. The potential leaving
group, hydroxide, i s i tself a strong base and therefore a terrible leaving group . Second, the strong base
deprotonates the -OR faster than any other reaction can occur, consuming the base and making the
leaving group anionic and therefore even worse.

(b) A halide i s already a decent leaving group. S i nce halides are extremely weak bases , the halogen
atom is not easily protonated, and even if it were , the leaving group abi l i ty is not significantly
enhanced. The hard step is to remove the adj acent R, something only a strong base can do-and
strong bases will not be present under strong acid condi tions.

)==I
7-44

(a) � (b) (c) (d) rearrangement

without rearrangement

�H maJor­
Zaitsev

153
 5 continued
7-4with rearrangement

hydride
shift

major­
Zaitsev

7- 4
61,
"y
only product from E2-

+
)
(a) /' ...... /' (b) + anti -coplanar is

��
possi ble only from
carbon wi thout CH3 by
maj or minor rem

N
major minor

� +� y
3

(c ) (d) (e)

maj or mInor D
major minor

C
ax
l

(CH3hC -.£:::::i CI eq

The conformation must be considered because the leaving +

4
group must be in an axi al position. The t-butyl group is so large
that it must be equatori al , locking the conformation into the
chair shown. As a result, only the Cl at position is axial, so
that is the one that must leave, not the one at position 3. Two
isomers are possible but it is difficult to say which would be

7- 4 7
etcH 0I ()+C
formed in greater amount.

H H

� .�H� .
H' H
�
H
...
V '\ H
,
- H20
'- /
' •
" H 20 .

�
_ _ _
H �

OSO 3H
El works well because only one carbocation and

HSO4- ..
only one alkene are possible. Substitution i s not a

ct
problem here. The only nuc leophiles are water,
H
which would s i mply form starting material by a
--�..-
reverse of the dehydration , and bisulfate anion.
Bisulfate anion is an extremely weak base and poor
nucleophile; if it did attack the carbocation , the
unstable product would quickly re-ionize, with no
154 net change, bac k to the carbocation.
7-48
I I I I I�I
CH3 CH3 CH3 CH3 CH3 CH3
-H20

�
I I I 1+ I +
CH 3-C-C-CH3 ---- CH 3-C-C-CH 3 --I"� CH3 -C-C-CH3
H+
:9 "'9oH2
l
HO HO HO
o
methyl shift

I
C H3
I
CH3
+

II I I
CH 3-C-C-CH 3
I
CH 3 -C-C-CH 3

: 0 : CH3 : OH CH3

The dri ving force for thi s rearrangement i s the great stabil ity of the resonance-stabi lized, protonated
c arbonyl group.
7 -49 NBS generates bromine w hich produces bromine radical. B romine radical abstracts an allylic
hydrogen, resulting i n a resonance-stabi l ized aUylic radical. The allylic radical can bond to bromine at either
of the two carbons with radical character. See the soluti on to problem 6-63.

NBS c::=>

1a
hv

CC
B r2 2 Br 0

H2 CH 2
Br
��
+ HBr
<;:, H
0 ____

� a
\.-I
H

reCYCI
CH 2
B ro + +

H
Br

7-50 Ph
H Ph

X JYJ
� CHCH3

�
CH3 Ph
�
� \ NaOEt
, H '-r----/ +
CH {" "
-----l.�
+
Ph CH2 CH3
Ph Br Ph Ph
A = E,Z mixture
25,3R B
H -CHCH 3
H ! Ph

X
Ph

CH {" "
,

Ph 25 5 Br
� Ph
+

Ph
,3
A = E,Z mi xture

E2 dehydrohalogenation requires anti-coplanar arrangement of H and Br, so specific ci s-trans I s ome rs (8 or

C) are generated depending on the stereochemistry of the starting material . Removing a h ydrogen from C-4
(achiral) will give about the s ame mixture of cis and trans (A) from either diastereomer.

155
 �
7 - 51
more stable than by 4 kJ/mote

~
more stable than by 16 kJ/mole

Steric crowdi ng by the (-butyl group is responsible for the energy difference. In cis-but-2-ene, the two

the t-butyl group crowds the methyl group in the cis isomer, increasing its strai n and therefore i ts energy.
methyl groups h ave only s l i ght i n teraction. However, in the 4,4-dimethylpent-2-enes , the l arger size of

() C1
7-52

V ()'
\. tri substituted \tri substituted
endocyclic exocyclic endocyclic exocyclic
disubstituted ) tri substituted)
V V
9 kJ/mole 5 kJ/mole

A standard pri nciple of science is to compare experiments which differ by only one vari able. Changing
more than one vari able c louds the interpretation, possibly to the poi nt of invalidating the experi ment.

The first set of structures compares endo and exocyclic double bonds, but the degree of substitution on the
alkene i s also di fferent, so this comparison is not valid-we are not isolating si mply the exo or endocyclic
effect.

The second pai r is a much better measure of endo versus exocyclic stability because both alkenes are
tri substituted, so the degree of substitution plays no part in the energy values. Thus , 5 kJ/mole is a better
value.

7-53
(a) CH3CH 2CH =CH 2
(b) No reaction-the two bromines are not trans and therefore cannot be trans-diaxial .

(e) 0 bromines are diequatorial­

cannot undergo E2

(d) (X) H H
No reaction-the bromines are trans , but they are diequatorial because of the
locked conformation of the trans-decalin s ystem. E2 can occur only when
the bromines are trans diaxial.

156
7-54 Inmolecules,
acyclic
E2, the two groups to be eliminated must be coplanar. In confonnationally mobile systems like
or in cyclohexanes, anti coplanar is the preferred orientation where the H and leaving
group are 1 80°apart. In rigid systems like-norbornanes, however, SYN-coplanar (angle 0°) is the only
possible orientation and E2 will occur, although at a slower rate than anti-coplanar.
The structure having the H and the Cl syn-coplanar is the trans, which undergoes the E2 elimination.
(It is possible that the other H and Cl eliminate from the trans isomer; the results from this reaction cannot
distinguish between these two possibilities.)

H Cl Cl
H
Cl Cly'/syn­ H
.

extremely slow to eliminate­ �oplanar

trans

H and C\ not coplanar

7-55 three
rings,
It is interesting to note that even though three-membered rings are more strained than four membered
-membered rings are far more common in nature than four-membered rings. Rearrangement
from a four-membered ring to something else, especially a larger ring, will happen quickly.

unstable 1 ° carbocation-­
short lifetime if it exists
at all
without rearrangement
H�
� CH + 2 H20:.. mmor
y--
with rearrangement-hydride shift
H
(P�H2 H20: minor
3° carbocation, but
•

still in a strained
4-membered ring

minor
157
7-55 continued
with rearrangement-alkyl shift-ring expansion
��H2 ("�-H�. O[ H MAJOR
H

H2C-C-H
-�.

H
C "......-A

2° carbocation on
. .
H2 H20:
I

5-membered ring­
H

HOORAY!
H
('xCH/'RiI
.�
� t -H 0
2

carbocation-terrible!-will rearrange; can't do

hydride shift, must do alkyl shift ring expansion
1°
=

this is an unstable carbocation even though it is 3°;

bridgehead carbons cannot be sp 2 (planar-try to make
a model), so this carbocation does a hydride shift to
2°, more stable carbocation
abstraction of adjacent
a

gives-bridgehead
Halkene violates t hydride shift
Bredfs Rule
this 2° carbocation loses an adjacent H to form an
alkene; can't form at bridgehead (Bredt's Rule)­
only one other choice

158
 8-1 Major products are produced in greatest amount; they are not necessarily the only products produced.
<r ¢Til
CHAPTER 8-REACTIONS OF ALKENES

(a) Br (b) Cl (c) H (d)

�H +H B'
O
Br

produced in about equal amounts

(mixture of cis and trans)
8- 2 H H H H allylic H H
H
H H
H
H+
--- H -t�
H H
H H-C+ H
.Q H H
· H \

:Br:
1 .. H H
H -O- H
Br H H H
+

3-bromobut-l-ene 1-bromobut-2-ene
Because the allylic carbocation has partial positive charge at two carbons, the bromide nuc\eophile can
bond at either electrophilic carbon, giving two products.
8-3
(a) initiation steps H3C-C-0-v' O-C-CH3 - 2 H3C-C-O·
� II
(this radical has

II
••
II
o ° °
another resonance
L1 fonn but it is not
gennane to this
mechanism)

H3C-C-O· H-Br H3C-C-OH • Br

°
II
••
II
°

"�JG
+ - +

propagation steps
• Br the 3° radical is more stable
�

~ +
than the 1° radical
-
C�

_) ��� k B' • Br
+

1-bromo-2-methylpropane
-

159
8-3 continued
(b) initiation steps

H2
H 3C-C -0·
• •

• •
+ H-Br
,,--JG
+ • Br
propagation steps
the 3° radical is more stable
than the 2° radical

+ • Br

I-bromo-2-methylcyclopentane (cis + trans)

2
(c) initiation steps �
-

+ • Br

H
propagation steps
y Br
I

- /C the benzylic radical is

Ph' · stabilized by resonance, and
more stable than the aliphatic
I radical

�
H

• Br
Br
+
I
Ph
H

2-bromo-l-phenylpropane
(recall that "Ph" is the abbreviation for "phenyl")

�
Br
8-4
� (b) �
HBr Br� HBr

(y
(a) • ..
ROOR

0 C)'
OH
(c) H2SO4 HBr
• .. Note: A good synthesis uses
�
major products as intermediates,
not minor products. Knowing

�
OH
orientation of addition and

� ~
H2SO4 HBr elimination is critical to using
(d) • •
� ROOR reactions correctly.
160 Br
 �
CH3 H CH3 H H
*
CH3
+ I CH3
/ C � CH3
8-5

H ----"" H-
CH3 CH3 �'--- �
O-H CH3 CH3 + H CH3
methyl

1
shift

H H 2°
..

HI
•

HI
"'" +
3°

CH3
nucleophilic attack by water

+ I CH3
't -H.. CH3 tf
CH3
CH3 jf
CH3
CH3
CH3/ \[)oo
C CH3
H
CH3
°
.. CHJ
-H
CH3 + H30+
k� H 2,3-dimethy-1 2-butanol
+ O
/ ')H /
:O O
0
0
HO
I I H
H
H

CH3 3
I CH3
;C \f CH3 1 ,CH3
proton removal

CH3 CH3/ "1' H30+

CH3
4 ....
.. +
'-.. :O- H
H� I
H 2, 3-dimethyl-2-butene

'6H �H
8-6

H'
H
(a) ( b) (c)

from 3° carbocation
U O
0d:J
from 3° benzylic carbocation

CH3
Af
8-7

CH >=<.H +
(a)

CH3
CH3
gOAC

(
Hg(OAc)

CH3 CH3
..

i
�

CH2CH3
H\ :
H

/ I ACO :

H3C-CII
°

CH3 CH3
1f
0 0

NaBH4
CH3tr
CH3 CH3
"Ac" = acetyl

CH3
gOAC

H3C-C'-O
(b)
II
o
..

H H
CH2CH3
"OAc" or "AcO" = acetate

CH2CH3
o
I I
16 1
8-8
CH 3

X : o.
(f'::
HO " H
(OAC) CI OCH3 l Hg(OAC)

U O
(a) (b) (c) "

II
I Hg(OAc) OCH3

O-
CI
(d)

OCH J

�
8-9
OCH 3
(a)
Hg(OAc}z NaBH4
�

H
.- .-
CH30H

(b)
&, KOH,�
.-

6 Hg(OAc}z
H2O
..
N aB H 4

OH
.-

O
Using an acid-catalyzed hydration In part

�
Hg(OAc}z (c) would initially form a 2° carbocation
(c) that would quickly rearrange to 3" on
carbon-3. The desired product would not
be synthesized.

�
8-10
H

� � OH
B H3 0THF H202
(a) , (b) .. B H2 .-

HO-

(c), (d ) � B H3 0T HF
..
�
H2 02
.-
�
HaO:
HO-

HaB:
B H2 OH

6
C C

(e) , (f)
BH3 0TH F , H20 2
.. .-

HO-

8-11
(a) � B H3 °

-----;.-�
THF H202
.-
HO�
HO-

�
OH
Hg(OAc}z NaBH 4
(b)
� H2 O
.. ..

(c)
� Br
KOH,�
..
� B H3 ° THF
.-
H2 0 2

H O-
.-
~ OH

162
8-12 Instead of borane attacking the bottom face of I-methylcycJopentene, it i s equally likely to attack the

s=<:.
top face, leading to the enantiomer.

BH3 · T HF
..

H H

6
8-13

(a) CH3
,'QH
(b)
V � +

OH
OH
major mi nor-steric
hindrance to
-

attack of B H 3 CH3

8-14 S S

Et � � Et

K
Et Et B H3 · THF
(a)
Me
>=< H '' "
H OH
Me H
Z )

enantiomers

R S

Et Et � � H

�K�
H B H3 • THF
( b)
>=< Et
Me Me' Et
�---------..
E H

V
enantiomers
The enantiomeric pair produced from the Z-a l kene i s diastereomeric with the other enantiomeric pair
produced from the E-al kene. Hydroboration-oxidation is stereospeci fic , that i s, eac h a l kene gives J specific
set of stereoi somers, not a random mi xture.

8- 15

CO CO
Hg (O Ach NaBH 4
(a) ... ...
H2 O
OH

CO cp
B H3 · THF H 202
(b) .. ..

HO -

OH

163
 continued
C
8 -15

(c) o
c5
8-16

CH3 CH3
empty p orbital in \bottom
"'-- :Br:
��
planar carbocation �
.

CH3 Br
The planar carbocation is responsible for non-stereoselectivity. The bromide nuc\eophile can attack from
the top or bottom, leading to a mixture of stereoisomers. The addition is therefore a mixture of syn and anti
addition.
8-17 During bromine addition to either the cis- or trans-alkene, two new chiral centers are being formed.
Neither alkene (nor bromine) is optically active, so the product cannot be optically active.
The cis-but-2-ene gives two chiral products, a racemic mixture. However, trans-but-2-ene, because of
its symmetry, gives only one meso product which can never be chiral. The "optical inactivity" is built into
this symmetric molecule.
This can be seen by following what happens to the configuration of the chiral centers from the
intermediates to products, below. (The key lies in the symmetry of the intermediate and inversion of
configuration when bromide attacks.) IDENTICAL-SYMMETRIC

�Br
��--------�

H",:\ H
( "\
�· ·
�------�
+

I
H"'�M " H
H3 GH3 �'
+

Br+
a Be nuc\eophile could : r OR :Br
, �:
attack at either carbon . :
l
J

H -+ Br CH3 H- Br Br f
H CH3 ':r-( Br-+ H
Br + H '---<' 'H H'" ", H + Br
Br CH3 CH3 Br
+

CH3 CH3
/ �
2S,3S ENANTIOMERS 2R,3R
continued on next page
--------------------------------------------------______________________________________ u __________ u __ •

164
8-17 continued ENANTIOMERIC
( B! CH � CH3
�
H"" ,U "
\
U
TRANS �------� �---------

1V\""11"'CH+
H'/CH3�( 3 \B/ bromide attack on this
r bsame
romonium ion gives the
a Be nucleophile could :Br: OR :Br: results
'

attack at either carbon

+

t
, •• J

Br + H CH3 � H Br Br )1-J, H CH H + Br
Br + H �" ' CH3 H\'\� H + Br
Br H CH3 Br CH3
+

CH3
/
ID ENTICAL-MESO 2R,3S
CONCLUSION: anti addition of a symmetric reagent to a symmetric cis-alkene gives racemic product,
2R,3S

while anti addition to a trans-alkene gives meso product. (We will see shortly that syn addition to a cis­
alkene gives meso product, and syn addition to a trans-alkene gives racemic product. Stay tuned.)

Enantiomers of chiral products are also produced but not shown.

+ Br .. 0 Br
8-18

(a) Br-Br � + :Br:

0�. "'Br
-

___

(b) (Hex) +
Br\ Br �e1-I
Br-Br --- , U ) '>---f/
:Br : '" Br
�

H" Et
"1 It"� .
�' Hex . EtH"'/
+

Bromide will attack

the other carbon of the
bromonium ion as well.
(c)

165
 continued
(d) Three new asymmetric carbons are produced in this reaction. All stereoisomers will be produced with
the restriction that the two adjacent chlorines on the ring must be trans.
8-18

Cl Cl
--G--I<
-

+
+ Cl-Cl ..

j
l
:Cl: :Cl:

h r�Cl I
C
CH �

Cl�
8-19 The trans product results from water attacking the bromonium ion from the face opposite the
CH3

bromine. Equal amounts of the two enantiomers result from the equal probability that water will attack
either C-l or C-2.
Q B, - �r <:v +

H H
Q�
water will do nucleophilic
..

attack at either carbon

H20:

equal amounts of enantiomers

enantiomer of product
from Solved Problem 8-5 a °\O+_ H �\ H in Solved Problem
8-20
H

the bromonium ion : -H �

8-5
H

shown here is the

�O
�+
�� :OH

enantiomer of the one

O-H O

Br U U
"",CH3
..
shown in Solved Br Br>
... CH
0
0 0
CH3 3

Problem 8-5
\ \
H
from Solved Problem 8-6: the bromonium ion shown is meso asHit has a plane of symmetry; attack
>
\
by the
nucleophile at the other carbon from what is shown in the text will create the enantiomer
H

a', H
,Br+ :Cl:
..
-

aH
"'Br
//� � �; these are the enantiomers of the
H

show products from HI;I � structures shown in the text

both nucleophiles ' Br
attacking at this carbon "
H
oR
a
I

OH
0
H
'"' H
-

166
8-21 The chiral products shown here will be racemic mixtures.
(b) 1 H
(d) ,----< '
H3C l-!
-;;61
(C)H3C C1 Cl

H
_

plus enantiomer
Br
� HO/ \"H"",'CH-�
plus enantiomer plus enantiomer
HO
C

(e) CH3 ,OH

(y Rr + (y Rr
CH3 ,Cl

plus enantiomers
8-22 l
(a) ..
C
(b)
CI
6CI
. .
6 0 .. ..
CI2
� ~
0H
KOH CI2
H2O
!t,. H2O

(c)
CH

O
H
H2SO4
.. 6 CI2 (y..
CH3 ,OH
Cl

8-23
!t,. H2O

(a) � (b) � (c) C):) (d) -0-<

8-24 Limonene, CIOH16, has three elements of unsaturation. Upon catalytic hydrogenation, the product,
CIOH20, has one element of unsaturation. Two elements of unsaturation have been removed by
hydrogenation-these must have been pi bonds, either two double bonds or one triple bond. The one
remaining unsaturation must be a ring. Thus, limonene must have one ring and either two double bonds
or one triple bond. (The structure of limonene is shown in the text in Problem 8-23(d), and the
hydrogenation product is shown above in the solution to 8-23(d).)
8-25 The BINAP ligand is an example of a conformationally hindered biphenyl as described in text
section 5 -9A and Figure 5 -1 7 . The groups are too large to permit rotation around the single bond
connecting the rings, so the molecules are locked into one chiral twist or its mirror image.
"rear"

"front" "front"
naphthalene naphthalene
nng ring
These simplified three-dimensional drawings of the enantiomers show that the two naphthalene rings arc
twisted almost perpendicular to each other, and the large -P(Phh substituents prevent interconversion of
these mirror images. 167
8- 26 Methylene inserts into the circled bonds.
(a)
S +
c5
(b) � + :CH2
�H
(c)
~ + d
BOTTOM VIEW
( b) (c)
8- 27

site of origi nal

(a)

double bond
__

the original 6-membered ring

SIDE VIEW
is shown in bold bonds

Br

CH21 2
8- 28

F Zn(Cu) R
(a)
•

CH2Br2
( b) 0 50% NaOH (aq)
�H
Br
cjCl Cl
•

OH
(c) H2SO4 CHCl3
6 L!
•

0 50% NaOH (aq)

•

(a)
8- 29
(b) (c)
CHo (d) CQ
H

H
"

0 0 ,

168 o
 Rc :O: � :O
(a) ' =o H+ ( � u-
8-30 +

fa . H )
H -
"C ( Ct" H
V ' 0l...''\
•

H""Et, A"Et" H '

---

H'�f\]\
t
"'
E;H
Et" - cis 'Et
, "

H-O: OR :O-H
" , "
'1 \"

H tI H
ENANTIOMERS
I I

r--------A.......
Et �" J-<Ofl fl0j---P -(Et ----� \

-H +
Etf!
,---<" H
Ofl fl0 '>-,!-I ---Y Et

EtH HEt HEt"7 "OH2

•

H O�Et
+

HO OH
+ •
'
I, ,\\
II/
\" +
2;.

Rc
• •

(b) , =o :O:�
H+
:O-H
+

fa l.... H
H ,v 'o'
('\t "Et
, "
H' A�" t H'�1\U(\�" Et )(
Et t
•
" ---

Et" trans
- 'H
" ,
" ,
" "
E

H-O: OR :O-H
"
'I

"c c" "

,
-

H + H
. . ..

IDENTICAL-MESO
I I

r�--------A------�\
Et �Ofl floyfl Et
- H + ,--<
f! Ofl flO � El
H

HO�H" Et HEt"'/ �OH +

H 0. / "HEt HEt"'/ "O H 2
+
+ •

stereochemistry shown in Newman projections:

"
-
2

Q)H
• • • •

OH OH
H Et Et H rotate
Et M ..
Et H £ : H � Et H Et
v
H --- ---

�
x:

OH
H� H- Et

trans MESO
Remember the lesson from Problem 8-17: anti addition of a symmetric reagent to a symmetric cis-alkene
gives racemic product, while anti addition to a trans-alkene gives meso product. This fits the definition of a
stereospecific reaction, where different stereoisomers of the starting material (cis and trans) are converted
into different stereoisomers of product (a dl-pair and meso form).

169
 R ,
� \-
8-31
R

<
R=

g
C-O

G0,
'
C=O
II \

o H
2

c t )�
t...H o C-O M +
0' • II
H "" ,
/ o

trans
"
"
"
C
----/'
�
==
H
I

All chiral products are racemic mixtures.

8-32

(a) � (b) CH 3 CH2 �

/
'-/
H

�
OH Ho

HO
t CH2CH 3

H
anti addition
trans-alkene gives
meso product
to a

o HO
��CH2CH3
CH2CH 3

(c) cj (d) � rotate. t�is is the (e) � trans

OH

product � OH
O
o

�
H
''''CH1
HO",
H
CIS

�
H
H " 'O H

� �
H OH
8-33 H+
�
+�
- H+

� �
\. or ) --- 1-Y
enantiomers
H H
--- --
H H
• •
CH3 0 H H OCH3
CH 3 -O:

8-34 All these reactions begin with achiral reagents; therefore, all the chiral products are racemic.
I
H

(a) (): (b) (c) H +�

o:�: �
Hl
CH 3 OH
OH HO
OH

HO
/ . � "'CH2CH 3 ==:>
H
HO + H

(d) (e)
CH3

(f)
H H H
CH 3 OH CH1 OH CH3 OH

H H X
�

same as (d)! same as (c)!

'" '"

=f�H
H H � CH2CH l

=f��
HO

=f��
HO CH2CH3 CH2CH 3 HO

H H H0

HO H HO H HO H

Refer to the observation in the solution to Problem 8-35 on the next page.
CH3 CH3 CH3

170
8-35

�
(a)
meso
HO OH

(b)�
�
HO OH
racemic (d,l)

�
�
(c) CH3C03H rotate
.. .. meso
H2 O
HO OH

� �
Os04 rotate
(d) .. .. racemic (d,l)
H20 2
HO OH

Have you noticed yet? For symmetric alkenes and symmetric reagents (addition of two identical X groups):
cis-alkene + syn addition ----7 meso Assume that cis/synlmeso +1 x +1 = +1
cis-alkene + anti addition ----7 racemic are "same", and trans/anti! +1 x - 1 = -1
racemic are "opposite".
trans-alkene + syn addition ----7 racemic Then any combination can -1 x +1 = -1
trans-alkene + anti addition ----7 meso be predicted, just like math! -1 x -1 = +1

8-36 Solve these ozonolysis problems by working backwards, that is, by "reattaching" the two carbons of
the new carbonyl groups into alkenes. Here's a hint. When you cut a circular piece of string, you still have
only one piece. When you cut a linear piece of string, you have two pieces. Same with molecules. If
ozonolysis forms only one product with two carbonyls, the alkene had to have been in a ring. If ozonolysis
gives two molecules, the alkene had to have been in a chain.

(a) two carbonyls from (b) two carbonyls from (c) two carbonyls from ozonolysis
ozonolysis are in a chain, so ozonolysis are in two different are in two different products, so
alkene had to have been in a products, so alkene had to have alkene had to have been in a chain,
nng been in a chain, not a ring not a ring

E or Z of alkene cannot be
determined from products

�o o�
8 - 37

�
H

(a)
03 Mc,� +
�

�
OH

(b) O

17 1
8-37 continued

(c )
0=0
03
•
Me2S

0
•
=0 0 + 0

�H
U
03 Me2S
(d) • •

0 0

KM n04 �OH
U
(e) •
t!.
0 0

(f)
U d
KMn04 ·aH
•

cold 1I110H

8-38 The representation for a generic acid w i l l be H-B, where B is the conj ugate base.

:x:r+} +/
J. C
H I
/ B:-

H
8-39 Catalytic B F3 reacts with trace amounts of water to form the probable catalyst:

F
+1 dimer

P Te\ � /, -
- I

_
_

catalyst

etc.
...

tetramer trimer

172
8-40 H-B is used here to symbolize a generic acid.

-
:B

�
alkenes

�
polymers
(colored)

Note : the dashed bond symbol is used here to i ndicate the continuation of a polymer chai n .

8-41

/ I I I
H H H H H H
I I \ I
H H
------ + ------ C-C-C-C ·
I
C-C · C=C
I I � n/)\...( \H I I I
H Ph � H Ph Ph H
10 radi cal , and not resonance-stabilized­
this orientation is not observed

Orientation of addition always generates the more stable intermediate; the energy difference between a 10
radical (shown above) and a benzylic radical is huge. The phenyl substituents must necessarily be on
alternating carbons because the orientation of attack is always the same-not a random process.

8-42 For clarity, the new bonds formed in this mechanism are shown in bold .
H
\ /
H
RO - OR 2 RO·
�'"o"+-",,
C C H
/ I
H H
I I
H
I
H , /V \
I I (
H
\
H H

)k)
+ H H
RO · ---t.� .. RO-C-C-C-C ·
I
C=C RO-C-C.
��
.!)\...( \H I I I I
H H H H H

l \ c / /
H
\H
H H
I I I I I I
H H H H

I I I I I I
etc. ---- RO-C-C-C-C-C-C·

H H H H H H

173
8-43 . .-
:0 : :0 :
II
o
II I
H C-OCH3
\ n/
H COCH3 H C-OCH3

\
I _I I II
HO : C=C --- HO-C-C : 11: . HO-C-C
.. �/ \ I I I I
H Me H Me H Me
o
II

\ n/
COCH3

C=C
/ \
H Me

. .
· 0· · ·
· · · 0·

I I
COOMe 11 COOMe I

I II
H H C-OCH3 H H C-OCH3
I I _I I

I I
OO - C - C-C - C
I I I
HO - C-C-C-C : • •

I I I

!
H Me H Me H Me H Me

ele.

COOMe COOMe COOMe COOMe COOMe

Plexiglas
"

Me Me Me Me Me

D ashed bonds mean that the chain continues.

"
8 -44
0
OH

a
O

<X ;Y
II

0
H3C-C-00H ' B r2
Na
�
.. -
B r�
�
-
H30+ OH hv
o

<X �
<X F
o
"'o

O
4 MCPBA
OH

OH

174
8-45 In the spirit of this problem, all starting materials will have six carbons or fewer and only one carbon-
carbon double bond. Reagents may have other atoms.
(a)
O:::J O::�-:y
H BC�
major product from resonance

Na .
stabilized radical on 10 and 30 C

:: �

anti-Markovnikov
syn stereochemistry

0: �
H CH,I, 0:
o � o

C CuCI CH3
�

(b)
Bhvr ey Br
3
Zn,

eyC::N
0
2
•

(c)
rB BC-p KOH Bhv·r 0- Br
(or NBS)

KOH o-
0
Br
2 2 0H

+ Na
:
•
- -
only substit on
NBS)

MCPS: � \{ 0-
(or is possible

-
0

OH ./

� ,A/ �

hi
H2 0

° � T
8-46 Please refer to solution 1-20, page 12 of this Solutions Manual.

�:3 _aCH3
8-47

( a) (c)
q H ,BH
intermediate
II
, " "

Br
2 OH

H Cl
(d) (el e/' (g) r--- L5F
Ao 1 V
0

peroxides do not
+

(f)
affect HCl addition
175
 continued
CH3 CH3
(i) ('f. IIOH
8-47

O'OH
""OH V ""OH
(h ) '"

QH CO
(I) (n)

OH
(0)

q; q;Cl
(p)

HgOAc
intennediate

(a)
8-48

initiation
RO-OR r-,ri.
2 RO·

RO.0 :JnBr
+ H .. ROH Br·
----

propagation
+

Br
-

H
Br·
r�
+� -..� + • Br

H
HH
+�L"
C
( b)

�H--C:S03; Q '--- :9-H

•

176
 'fH....,C... +
8-48 continued

H H
� H-nBr
1(..1- � (fit::
(c) H

�
n fH H hydride
shift
• OR •
I
.I

� :Br:
.. :B�:
.. I
t
Br Br
'Y' 'J'
(d)
,
+
-
HO- H-C-Br --- :C-Br --- Br-
----... Br Br
...... ,.--.10..1 I f"
+ :CBrz
BrI
Br
I

B'
�
00
V
JY
H
� Brz ..

aA
H--Q� HXH� :C1:
(e)
�
f/
H
C +
H I �CI
H��CH3
OR X+C �
CH3..O-H HOC;3 �OCH3
•

H I

�
• •

(f) �
� B_r_-B" ; r:J _ Br
� '--- .Br. •
• •
:
�Br
Br
& .
�� :Ci:
�CI
+

F�' �
CH30 -H H�CH3 Jy
.
• •
OCH
�
. .

177
 continued
(g) H � 0
8-48

H J...
- <T
. _H H-B •
H 3C �H H

Ph Ph Ph

Recall that "Ph" is the abbreviation for phenyl.

(a) (f Hg(OAc)z NaBH4

8-49

.. ..

(f HEr
ROOR
(b)

(0) (f
(d) (f
(c) (f Hg(OAc)z ..
NaBH4 .

OS04 � OH
H 20 2 OH
(f)
(f or cold, dilute KMn04
..

V
(g)
(f Zn(Cu)
� CI
OH
V
(h) ..

(i) � Br
50% NaOH (aq) V 'Br
178
 HQ

D--f0
8-50 0

-Q--("
"

~
OH
(a) CH3 (b) CH3 (c) H + CH2=O

� D-f
~
HO HO
H OH H 0H
(f)
, + CO2
(d) OH (e) OH
CH3
",

CH3

B D--f -b-\ Br
Br
(g)
-0-< (h) Br (i)

(j)
HO "8
Br
'
Br
OH (k)
C I� -b-f
Cl

"
Ci
Cl
CH,o
(I)
� OCH3
CH3 CH3

�
(m)
H
C 3

8-51 Each monomer h as two c arbons in the backbone, so the substi tuents on the monomer w i l l repeat
every two carbons in the polymer. Dashed bonds indicate continuation of the polymer chai n .
line formula representation

Cl Cl Cl Cl Cl
Cl Cl Cl Cl

�
I I I I

--- --- -CH2CHCH2 CHCH2CHCH2CH -- -- -

pol yvinyl chloride, PVC

F F F F F F
F F F F
F ..
F F
F F F

0
F

F F F
I I I I I I

F -;-- F F F F F
---- C - C - C - C - C -C---- -
-

I I I I I I F
F F F F F F
polytetrafluoroethylene, PTFE, Teflon

N N N N

..
N N N N N III III III III
III
C
III III III III
C C C C
C C C C

�
I I I I
--- ----CH2CHCH2CHCH2CHCH2CH - - - --
polyacry lonitrile , Orion

179
8-52 Without divinylbenzene, individual chains of polystyrene are able to sl ide past one another.
Addition of di vinylbenzene during polymerization forms bridges, or "crossl i nks", between chains, adding
strength and rigidity to the polymer. Divinylbenzene and similar molecu les are called crosslinkjng agents.

two polystyrene chains crossli nked

by a divinylbenzene monomer shown
in the dashed oval

H CH
/ 3
8-5 3 A peroxy radical i s shown as the initi ator. Newly formed bonds are shown in bold.

H CH �\.. ,C/ vC\

\

RO-CI -C.
I r H CH�
"-f--'

HI CH
I
3
_-I.�

etc. ---

'C-OCH2CH3
8-54 0,

H2C=CH
I ethyl acrylate

8 - 55 In each case, the compound (boxed) that produces the more stable c arbocation is more reactive.
3"

0 6
(a) (b) allylic
(c) � �

180
8-56 Once the bromonium ion i s formed, i t can be attacked by either nuc\eophile, bromide or chloride,

--
leadi ng to the mi xture of products.

~
Br Br

Q
�

H H H Br

��-�
� 'i---Y
H �.. :Cl :
H Cl

8-57 Two possible orientati ons of attack of bromi ne radical are possible:
(A) anti -Markovnikov
\ .
>= h
HBr
+ Br C, + Br
/
•
-- .- •

Br Br

'l-
3 ° radical
(B) Markovnikov

y;
r

>= � H2
HBr
+ • Br -- � + • Br
H
1° radical
The first step in the mechani s m i s endothermic and rate determi ning. The 3° radical produced in anti­
Markovnikov attac k (A) of bromine radical is several kl/mole more stable than the 1° radical generated
by Markovnikov attac k ( B ) . The Hammond Postulate tells us that it is reasonable to assume that the
activation energy for anti -Markovnikov addition is lower than for Markovnikov addition. This defines
the first half of the energy di agram.
The relative stabi l i ties of the final products are somewhat difficult to predict. (Remember that
stabi lity of final products does not necessari l y reflect rel ative stabi lities of intermedi ates; this is why a
thermodynamic product can be different from a ki netic product.) From bond dissoc i ation energies
(kJ/mole) in Table 4-2 :
anti -Markovnikov Markovnikov
H t0 3°C 3 81 H to 1 ° C 410

Br to 1° C 285 Br t0 3°C 272

666 kJ/mo\e 682 kl/mole

If it takes more energy to break bonds in the Markovnikov product, it must be lower in energy, therefore,
more stable-OPPOSITE OF STABILITY OF THE INTERMEDIATES!
Now we are ready to construct the energy di agram; see the next page .

18 1
8-57 continued
,
, - ..
, ,'/
, ,
,

t
Markovnikov

anti-Markovnikov

reaction --

It is the anti-Markovnikov product that is the kinetic product, not the thermodynamic product; the anti­
Markovnikov product is obtai ned since its rate-determining step has the lower activation energy.

GS
8 - 58 Recall these facts about ozonolysis: each alkene c leaved by ozone produces two carbony l
groups; a n alkene i n a chain produces t w o separate products; a n alkene i n a ring produces one product
in which the two c arbonyls are connected.
(a) O
+ CH2=O
(b) +
O �
H 0
H
o

CHO (d)

¢
0

H H

0
0 CHO

8-59 CH3

CY U
CH3C0 3H 'OH
(a) ..
H2 O
OH

(b)
0 (or cold, dilute KMn04)
O OH

OH

cis + syn trans + anti

(cis double bond plus (trans double bond plus
syn stereochemistry of addition) anti stereochemistry of addition)

182
8-59 continued

B r2 � Br anti addition of B r 2 requires t ra ns alkene to

(c )
� Br
..
gi ve meso product
1
This structure shows
a trans alkene in a
� tate around C-2

to-membered ring,

�'" :
just the rotated view
of the structure to Br2 H � 2
..
the right.
Br

(X
trans-cyclodecene

o
C l2 C!
(d)
""
OH

CO ~
B H3 - THF
(e) ..
�

OH

(f) �
V-/ or CO or �
�
Hg (OA c h� Na BH
_ _ _ _ _ -l..
CH30H
t,

8 -60
A ) Unknown X, CSH9Br, h as one element of unsaturation. X reacts with neither bromi ne nor KMn04,
so the unsaturation in X cannot be an alkene; it must be a ri ng.
B ) Upon treatment with strong base (t-butoxide), X loses H and Br to give Y, CSHg, which does react
with bromine and KMn0 4 ; it must have an alkene and a ring. Only one isomer is formed.
C) Catalytic hydrogenation of Y gives methylcyc lobutane. This is a B IG c l ue because it gi ves the
carbon skeleton of the unknown. Y must have a double bond in the methylcyclobutane skeleton, and X
must have a B r on the methylc yc lobutane skeleton .
D ) Ozonolysis of Y gi ves a dialdehyde Z, CSHg0 2' which contains all the original carbons, so the
alkene c leaved in the ozonolysis had to be in the ring.

Let's consider the possible answers for X and see if each fits the information.

.---:f'
d'
KO-t-B u °
ozonolysis
1)
I
> U > + O=CH2
if this is X this must be Y; DOES NOT FIT OZONOLYSIS RESULTS
only one product so this c annot be X and Y

more possi bilities on the next page

183
 d KO-t-Bu
8-60 continued

d 0(
Y would be a mi xture of alkenes , but the e l i mi nation
2)
Br 1 > + gives only one product. We already saw in ex ample 1
minor that the exocyclic double bond does not fi t the
if thi s i s X major
ozonolysis resul ts so this structure cannot be X.

c( Q 0(
KO-t- B u
Y would be a mixture of alkenes, but the e l i mination
3)
> + gi ves only one product, so this structure of X i s not
major minor consistent with the i n formation provided.
Br

�
+Q
i f this is X

K d
4) P Br
if thi s i s X
O t
- - u

SAME COMPOUND ;
this must be Y ;
l
ozOnOIYSiS
>
r<
o
Z, a dialdehyde
on ly one product

The correct structures for X, Y, and Z are gi ven in

the fourth possibi l i ty. The on ly structural feature of
X that remains undetermined is whether it is the cis
or trans i somer.
trans

'(S)(
8-6 1 The clue to the structure of a-pinene is the ozonolysis. Worki ng backwards shows the alkene position .
o � became carbony l carbons
bac kwards
o > a-pinene

'fit
After ozonolysis, the two carbonyls are sti l l connected; the al kene must have been in a ring, so

�� T
reconnect the two carbony l c arbons with a double bond.

BT

~
B r2 '
..
or

{iX
, I I CH3
CH3 Br

�
A A
Br
BT

~
B r2
H2SO4
..
.. Zaitsev product
H2O 'OH �
CH3

�o {L:(
B C

�
OH
PhC03H H 30+
.. ..

" OH
"

D E

184
8-62 The two products from pennanganate oxidation must have been connected by a double bond at the
carbonyl carbons. Whether the alkene was E or Z cannot be determi ned by this experiment.

CH3(CH2) 1 2 CH = CH(CH2hCH3
shown here as Z which is the naturally-occurri ng isomer

8-63
must have three alkenes
Unknown X
Pt in this skeleton

� A/ H
o 0 o 0

Unknown X CH2 = O + +
H
o

There are several ways to attac k a problem like this. One is the trial-and-error method, that is, put double
bonds in all possible positions unti l the ozonolysis products match. There are times when the trial-and-error
method is useful (as in s i mple problems where the number of possibilities is few), but thi s is not one of them.

Let's try logic. Analyze the ozonolysis products carefully-what do you see ? There are only two meth yl
groups , so one of the three termi nal carbons i n the skeleton (C-8, C-9, or C- l O) has to be a =CH2 . Do w e
know which terminal c arbon has the double bond? Yes, we can deduce that. If C- l O were double-bonded to
C-4, then after ozonolysis, C - 8 and C-9 must stil l be attached to C-7 . However, in the ozonolysis products ,
+ +
there is no branched chain, that i s , no combination of C-8 C-9 C-7 + C- l . What if C-7 had a double
H H
bond to C- l ? Then we would have acetone, C 3COC 3, as an ozonolysis product-we don 't. Thus, we
can't have a double bond from C-4 to C- l O. One of the other terminal carbons (C- 8 ) must have a double

8�
bond to C-7 .

� 10

9
6 5

The other two double bonds have to be in the ring, but where? The products do not have branched chains,

H)---
so double bonds must appear at both C- l and C-4. There are only two possibi l i ties for this requirement.

I or }{}- II

Ozonolysis of I would g i ve fragments contai ning one carbon, two carbons, and seven carbons. Ozonolysis
of II would gi ve fragments containing one carbon , four carbons, and five carbons. Aha! Our mystery
structure must be II.

(Editorial comment: Sc ience i s more than a collection of facts . The application of observation and logic to
solve problems by deduction and inference are critical scientific skills, ones that distinguish humans from
algae . )

185
8 -64 In this type of problem, begin by detennining which bonds are broken and which are fonned. These
w i l l always give c l ues as to w hat is happening.

H+
formed

1
goes to most
e lectronegati ve
atom
protonated epoxide opens to gIve
the most stable carbocation (3()

+ H

HOq� ..
\ 3 0 carbocation looks
for electrons, fi nds
them at nearby alkene,
formi ng a 6-membered
ring (yes ! )-leaves a
3 0 carbocation

+
8-65 See the solution to Problem 8 - 3 5 for simpl ified examples of these reactions .

eOOH HO OH
�
HOOC J H
(a) syn � racemic
HooeH1 ""eOOH
trans
,,

(b)

HOOe
fCOOH Hooe �
HO H
OH
7--<
�
" '" IleOOH
trans + anti � meso

(COOH Hooe� OH
(c)

eOOH
'---<
HO/ �/eOOH
IH cis + anti � racemic

(d)
(COOH
eOOH
OS04 HO
Hooe
�
"1
OH
�/HlleOOH
H
cis + syn � meso

186
8-66 CH3

a
B03 - THF 111 0

u -
H 20 2
.. ..
I I I OH
HO
H

� H �nB Cf.
8 -67 By now , these rearrangements should not be so " unexpected" .
H 20
I
�C H
"":
�
� +
U" CH3
H
H
alkyl mi gration with ring expansion
gives 3° carbocation in 6-membered
ring--carbocation nirvan a !

H
(Y CH3
H

� 0
H

+
•

Br
: !lr: ' CH]
C H3

You must be asking yourself, "Why didn't the methyl group migrate?" To which you answered by drawmg
the carbocation that would have been formed:
I;I
O\} QC<1''-
2° 3°
C+ H
� C H3
CH3 I "
--

H CH3
H
The new carbocation is i ndeed 3 ° , but it is only in a 5-membered ri ng, not quite as stable as in a 6-
membered ring. In all probability, some of the product from methyl migration would be formed, but the 6-
membered ring would be the major product.

8-68 Each alkene w i l l produce two carbonyls upon ozonolysis or permanganate oxidation. Oxidation of
the unknown generated four c arbonyls, so the unknown must have had two alkenes . There is only one
possibi l i ty for their position s .

H
a�COOH H

CO
KMn04 C OOH
.. + I
/j. COOH
:: COOH
H H
the unknown

187
8-69
(a) Fumarase catalyzes the addition of H and OH, a hydration reaction .
(b) Fumaric aci d i s planar and cannot be chiral. Malic acid does have a chiral center and is chiral. The
enzyme-catalyzed reaction produces only the S enantiomer, so the product must be optically acti ve.
(c) One of the fundamental rules of stereochemistry i s that optical! y inacti ve starting materials produce
optically inactive products . Sulfuric-acid-catalyzed hydration would produce a racemic mixture of malic
acid, that is, equal amounts of R and S .
(d) If the product is opticall y active , then either the starting materi als or the catalyst were chiral . We
know that water and fumaric acid are not chiral, so we must infer that fumarase is chiral.
(e) The D and the OD are on the " s ame side" of the Fischer proj ection ( someti mes cal led the "erythro "
stereoi somer) . These are produced from either: (1) s y n addition t o cis alkenes, o r (2) anti addition to
tralls alkenes. We know that fumaric ac id is tralls , so the addition of D and OD must necessari l y be anti.
(f) Hydroboration i s a syn addition .

H ooe " " ,H

' == e '"
....... e '
1 . B D3 • THF

2. D 2 0 2 , DO-
..
D

DOOe H
,
"
""
H
OD
+
DOOe
,>-1(, R
H eO D
"

H eOOH D OD
H eOOD
eOOD eOOD

� +� � +�
(note that OH exchanges
with D in DO- )
D D

eOOD eOOD

As expected, tralls alkene plus syn addition puts the two groups on the "opposite" side of the Fi scher
proj ecti on (sometimes cal led " threo" ) .

�.
8-70 Hg(OAc) Hg(OAc )

(a)
+

0
H Hg(OAc)
--

. .
AcO :
mercunntum ion

Br Br

Br - Br
..

bromonium ion

188
8-7 1 The addition of BH3 to an alkene is reversible. Given heat and time, the borane will eventually
" walk" its way to the end of the chain through a series of addition-elimination cycles. The most stable
alkylborane has the boron on the end c arbon; eventually, the series of equilibria lead to that product
which is oxidized to the primary alcohol.

..

..

...

�
----
H2
most stable H

189
8-72 First, we explain how the mixture of stereoisomers results, then why.
We have seen many times that the bridged halonium ion permits attack of the nucIeophile only from the
opposi te side.

Ci-CI
CI�
Q W �:S:1: ~
expected: ---
�
H Ph H Ph H Cl
trans only

A mixture of cis and trans could result only if attack of chloride were possible from both top and hottom,
somethi ng possible only if a carbocation existed at this carbon.
actual:
'"

0� H
H Ph
--�CI
+� H H Ph
trans cis

This picture of the p orbitals of benzene show

resonance overlap with the p orbital of the
carbocation. The chloride nucIeophile can form
a bond to the positive carbon from either the top
or the bottom.

Why does a carbocation exist here? Not only is it 3°, it is also next to a benzene ring (benzylic) and
therefore resonance-stabilized. This resonance stabilization would be forfeited in a halonium ion
intermediate.

0"::::
+

r'�/ //

�CI
� �

CI
'Ci
:Ci : C
aCI CC"'H 0:CI
Ph
' Ph
+
. .
-

CI
�
IIi
H

190
 CHAPTER 9-ALKYNES

9-1 Other structures are possible i n each c ase.

CH3CH2C:::CCH2CH3 CH3CH2CH2CH2C:::CH

0- C:::CH HC:::C - CH2CH = CHCH2CH2CH3

9-2 New IUPAC names are gi ven. The asterisk ( * ) denotes acetylenic hydrogens of terminal alkynes.
*
(a) CH3CH2 -C:::C - H CH3 - C:::C-CH3
but- l -yne but-2-yne CH3
* I *
(b) CH3CH2CH2 - C:::C - H CH3CH2 - C::: C - CH3 CH3CH - C:::C - H
pent- l -yne pent-2-yne 3-methylbut-l-yne

9-3 The decomposition reaction below is exothermic (/)J{0 - 234 kJ/mole) as well as having an increase
=

in entropy. Thermodynamical l y, at 1 500°C, an increase in entropy will have a large effect on AG

(remember AG /)J{ - TAS). Kinetically, almost any activation energy barrier will be overcome at
=

1 500°C. Acetylene would likely decompose i nto its elements:

HC::CH
1 500°
� 2 C + H2

9-4 Adding sodi um amide to the mixture will produce the sodium salt of hex- l -yne, leaving hex- l -ene

}
untouched. Distillation wi ll remove the hex- l -ene, leaving the non-volatile salt behind.

CH � CHCH2CH2CH2CH3 NaNH2.. J �H� CHCH2CH2CH2CH3

H -C C-CH2CH2CH2CH3
= 1 Na+ _ C C - CH2CH2CH2CH3 • = non-volatile salt
9-5 The key to this problem is to understand that a proton donor will react only with the conjugate base of
a weaker acid. See Appendix 2 at the end of this Solutions Manual for an in-depth discussion of acidity.
-
(a) H -C:::C-H + NaNH2 -- H -C:::C : Na+ + NH3
-
(b) H-C:::C -H + CH3Li -- H-C:::C : Li + + CH4
(c) no reaction: NaOCH3 i s not a strong enough base
(d) no reaction: NaOH is not a strong enough base
-
(e) H-C:::C : Na+ + CH30H -- H-C:::C - H + NaOCH3 (opposite of (c))
-
(0 H -C:::C : Na+ + H20 -- H-C:::C-H + NaOH (opposite of (d))
-
(g) no reaction: H - C :::C : Na+ is not a strong enough base
(h) no reaction: NaNH2 is not a strong enough base

191
9-6
H-C:::C-H NaNH2 H-C:::C : Na+ CH3CH2Br H-C:::C-CH2CH3
-

� NaNH2
.. •

CH3(CH2)S-C:::C-CH2CH3 CH3(CH2)SBr Na+ :C:::C-CH2CH3

..

9-7
(a) H-C:::C-H NaNH2 1)
2) CH3CH2CH2CH2Br H-C:::C-CH2CH2CH2CH3
..

(b) H-C:::C-H NaNH2 1)

• H-C::: C -CH 2 CH 1)
2 CH 3 NaNH2.. CH3-C:::C-CH2 2CH3
CH
2) CH3CH2CH2Br 2) CH3I
(c) H-C:::C-H 2) NaNH21)
.. H-C::: C -CH2CH3 1) NaNH2 CH3CH2-C:::C-CH2CH3
•
CH3CH2Br 2) CH3CH2Br
(d) cannot be synthesized by an reacti S N2 o n-woul d requi r e at t
20a ck on a al k yl hali d e
r/ 2°
CH3-C::: C : Nale;+ CHCH2CH3 fr CH3-C:::C-CHCH2CH3
_ �� +

second order CH3

stmustrongbenucleophi I
CH3
low yields; not practical
(e) H-C:::C-H NaNH2 1)
2)
..
CH3I CH3-C::: C -H1)
2)
NaNH2
BrCH2CHCH3 CH3-C::: C-CH2CHCH3
..
I
I
CH3 CH3
(f) H-C:::C-H NaNH2 1)
2)
..
Br(CH2)8Br H-C:::: C-?H2
Br�
� NaNH2
H2C-C:::C-CH2 ..
....!----
.
�. Na+ -,C-=C-CH2
� r'.
Br�
Intwilramol
be intramolecular and not [Link] carried out in dilute solution so the last displacement
e cul a r cycl i z ati o n of large ri n gs must S N2

9-8

(a) H-C:::C-H NaNH2

H2C=O
H20 H-C:::C-CH20H
1)
2)
.. ----l.�

192
9-8 contin ued
NaNH2 H 2 0 1)
9H
(b) H-C:::C-H Ph yCH3 H3C-C-C::C-H
2)
.. ----l.-�
I

Ph
o

NaNH 2 1) NaNH 2 OH 1) I

(c) H-C:::C-H CH3I CH3-C:::C-H 2) HCCH2CH2CH3.- CH3-C:::C-CHCH2CH2CH3

2)
�

II
o
H20 3)

NaNH2 1) NaNH2 OH 1) I

(d) H-C:::C-H 2) CH3I CH3-C:::C-H 2) CH3CCH2CH3 CH3-C:::C -CCH2CH3

� �
I
.

CH3 II
o
H20 3)

9-9
(Br H H H � -oo:�H H
H -C �C-CH2CH2CH3 :OH C=C
1 1 \
H-C=C-C-C�C� ,1
I)
_ 1

o
.. �

Br H�oo Br{) \CH2CH2CH3

1 1

1
Ii

t: H
}
/

=(=
-
0 0

�
HI ) H HI 1
H-C C-CH2CH3 HO-H H-C=C=C-CH2CH3 H-C=C-C-CH2CH3 _
_
_

U�
--- �

1
0 0 0 0

H 1-
}
t :OH
0 0

�
0 0

i
H-OH H U I -
H-C=C=C-CH2CH3 H-C-C=- C-CH2CH3
1
-

0 0
�
-0 0

H-C-C=C-CH2CH3
1
�

I
H H H
9-1 0 To determine the equilibrium constant in the reaction:
!J.G = Keg

( !1G) )
RT In
(
tenninal alkyne � internal alkyne -

!J.G - 1 7.0 kJ/mole

= -(-17,000)
Keg = RT (8.314)(473)
e e e4.32
(- 4.0 kcallmole) = = = 75
R = 8.3 1 4 JIK-mole [internal] 75 98.7% i nternal
[terminal] 1 .3 % tenninal

193
 i -
9-11 (a) This isomerization is the reverse of the mechanism in the solution to 9-9.

H �- H2 - .
}
• •

I)
•

. N
H-C-C C-CH2CH3 .. H-C-C C-CH2CH3
1
.

1
---- H-C==C==C-CH2CHJ
1
• •

}
H H H
I( H 2
. HJH
i
H H
1-
H-C C-C-CH2CH3 H-C==C==C-CH2CH3 _ 1
� H-( C==C==C-CH2CH31

�H
� �
• •

I
• • • •

H -U2 � l
\""' NH
:�

H 1
H-C C-C-CH2CH3 I
H
KOH,
(b) All steps in part (a) are reversible. Wi th a weaker base like an equilibrium mixture of pent-I­
yne and pent-2-yne would result. With the strong base NaNH2, however, the final tenninal alkyne is
deprotonated to give the acetylide ion:

H-C C -CH2CH2CH3 + NaNH2 - Na+ :C C-CH2CH2CH3 NH3

== +
Because pent-l -yne is about l O pK units more acidic than ammonia, this deprotonation is not reversible.
The acetylide ion is produced and can't go back. Le Chatelier's Principle tells us that the reaction will try to
replace the pent- l -yne that is being removed from the reaction mixture, so eventually all of the pent-2-yne
will be drawn i nto the pent- l -yne anion "sink".
(c) Using the weaker base
pent-2-yne predominating.
KOH 200°Cat will restore the equili brium between the two alkyne isomers wi th

9- 12
(a) Br Br
( 1) H3C-T-T -CH3 KOH H3C-C C-CH3
1 1
---

L1
H H Br Br

(2) CH3CH==CHCH3 CCl4.. CH3CH-CHCH3

Br2' I 1

(b) Br Br
I I NaNH2
(1) H-C-C-(CH2hCH3 1500 H-C C-(CH2hCH3
1 1
•

H H Br Br

(2) CH2 CH(CH2)sCH3 Br2' CCl4 H2C-CH(CH2hCH3

== •
1 1

194
9- 12 continued
(c) KOH
(1)

Br Br
Br2' CCl4 CH3CH "
(2) --- -CH(CH2)4CH3
�
-I..

(d) Br
(1) KOH at insteadcoulofdNaNH
200°C
been used have 2
H Br
(2)

H
9- 1 3

Lindlar catalyst
Na

(c) Br
Wcis
NaNH2
H
Oneo convert
treacti of the oneusefulstereoi
"tricsks"omerof iorgani
n t o c chemiHavi
another. stry nisg tahepaiabilr ofity
that ons opposi
give like thetetwsteoreochemist
reductionsryshown i s inuseful
very parts (a), because
and (b)a
eicommon intermediateThi(thes princi
ther stereoisomer. alkyne)ple canis usedbe transformed
again in partin(d).to
195
9- 13 continued Br
(d)
~
KOH
� -C C�

I
,
trans Br H2
Licatalndlaryst
H H
\ I
C == C cis
/ L
9- 14
molTheeculne,goaletsheofisfibromine
twothe bromi to add onlcouly oned addequitovthealenttriofplebromine,
r st drops of al k yne wi l encount bond
e r a l i
a f always avoiwasdiinngexcess.
bromine
rge excess of
an excessIf theof bromi
bromine. I nst e ad,alkyne
addi
ne,is because
n g added toto
bromine
the alkyne will always ensure an excess of alkyne and should give a good yield of dibromo product.
H

-H
I

� :B�:
+
CH3CH2CH2 - C == C �

2°
1°
betcarbocat
ter thanion 0 0

2° carbocation and
resonance-stabilized

9- 16 CI H H CI
I I I I
H3C - C - C - (CH2)4CH3 + H3 C - C - C- (CH2)4CH3
I I I I

i }
Cl H H Cl
(b)of The second addition occurs to make the carbocation intermediate at the carbon with the halogen because
resonance

:ci: �
stabilization.
:C 1: H H : I: H

y+ - - ---- -�-k- -- k
I I H+ I I II I resonance
C==C ....
..
t-----��
-t C- - stabilization
0 0

:C1: H
I I no stab·lIlzat
· l. On
-C-C -
I +

196
9-17
initi ation: RO - OR
hv 2 RO·
RO • H-Br
+ --- RO- H Br + •

Br.� H-C C -CH2CH2CH3

propagation:
j -CH2CH2CH3
J
==

I
•

Br

The 2° radi c al i s more stabl

1°.e than The anti - Markovni k ov orientati o n occurs because t h e bromi n e radi c al
fiatrtstacks(seefirtsthetosolmake
utiontheto most stable radical, which is contrary to electrophilic addition where the attacks
9-15).
H+

9- 18
H -C==C-(CH2hCH3
I I
E + Z
CI Cl
(b) C C-(CH2hCH3 HBr
H-
ROOR
H-C==C-(CH2hCH3
I I
E + Z
Br H
H C C -(CH2hCH3
HBr - ==

I I
BrH
Br BrI I
H-C-C-(CH2)3CH3
I I
Br Br
Licatnadlarlyst
(or Na, NH3) H Br
2HBr H-C-C-(CH2)3CH3 I I

I I
H Br

197
9- 19

r +
) ;)(�( both 2° vinyl CH3-
+
= -CH2CH3

A
CH3- =c CH2CII3
carbocations

! H2 :O H2 :0 !
CH3-C ==C - CH2CH3 CH3-C == C-CH2CH3
1 1+ +1 1
H HO: H

�H
:OH

)
I) I)

! !
H

H2 :O 0
H2 :

CH3- 'f 'f ( -CH2CH3 CH3- 'f 'f) -CH2CH3

H R
: H �
H : H

t H+ H+ t
H H
1 +
resonance- + 1

r' 1
CH3-C-C-CH2CH3 stabilized CH3 - C - C-CH2CH3
(resonance forms
not shown)
, '",\ carbocations
H :O-H H-O : H

..; � �. 0 t
t
H
Hi : H2 :

H
I I
CH3-C-C-CH2CH3 CH3-C-C-CH2 CH 3
I II II 1
H 0 0 H
3-pentanone 2-pentanone

The role of the mercury catalyst is not shown in thi s mechanism. As a Lewis acid, it may act like the
proton in the first step, helping to form vinyl cations; the mercury is replaced when acid is added.
-H +
---I.... CH3-C ==C - CH2CH3
I I
+Hg OH

198
9-20
(a) But-2-yne is symmetric. Either orientation produces the same product.
CH3 CH3 CH3 CH3 °
Sia2BH / H202 / HO- II
C
\ \
CH3-C C-CH3 .. C=C .. C=C ---I"� CH3CHz - - CH3
/ \ HO- / \
H BSia2 H OH

(b) Pent-2-yne is not symmetric. Different orientations of attack will lead to different products on any
unsymmetrical internal alkyne.
CH3-C C-CH2CH3

CH3
�H �
CH2CH3
S

CH3 CH2CH3
\ / \ /
C=C C=C
/ \ / \
H B Siaz Sia2B H

� H202 , HO- � H202 , HO-

CH3 CH2CH3 CH3 CH2CH3

\ / \ /
C=C C=C
/ \ / \
H OH HO H

� HO-

° °
II II
CH3CH2-C -CH2CH3 CH3 -C -CH2CH2CH3

II
9-2 1 ° °
II
(a) (1) CH3CCH2CH2CH2CH3 (2) HCCH2CH2CH2CH2CH3
° °
II II
(b) ( 1 ) CH3CCH2CH2CH2CH3 + CH3CH2CCH2CH2CH3

(2) same mixture as in (b) ( 1)

° °
II II
(c) ( 1) CH3CH2CCH2CH2CH3 (2) CH3CH2CCH2CH2CH3

�O �O
VV
VV
(d) ( 1) (2)

199
9-22

\
(a) CH3 H H CH3
I I \ /
-
----1
.. 1 H -C-C-BH)- + C==C
I I /
CH3 CH3 H3C CH3

CH3 H H H CH3
I I I I I
H-C-C-B-C-C- H
I I I I
CH3 CH3 CH3 CH3
disiamylborane, Sia2BH
(b) There is too much steric hindrance in Sia2BH for the third B-H to add across another alkene. The
reagent can add to alkynes because alkynes are linear and attack is not hindered by bulky substituents.
9-23 o 0 o
II II II

(a) (1) HO-C-C-(CH2hCH3 (2) CO 2 + HO-C -(CH2hCH3

oxidation of a tenninal alkyne with oxidation of a tenninal alkyne with
neutral KMn04 produces the ketone wann, basic KMn04 cleaves the
and carboxylic acid without carbon-carbon bond, producing the
cleaving the carbon-carbon bond carboxylic acid and carbon dioxide
o 0 o 0
II II II II
-
(b) (1) CH3 C-C - CH2CH2CH3 (2) CH3 - C-O H + HO -C-CH2CH2CH3

o 0 o
II II II

(c) (1) CH3CH2-C-C-CH2CH3 (2) CH3CH2-C-O H

o 0 o 0
11 II II II

(d) (1) CH3CH-C-C-CH2CH3 (2 ) CH3CH-C-O H + HO -C -CH2CH3

1 1
CH3 CH3
o
(e) ( 1) (2) OH
HO
o

9-24
(a) CH3 -C:::C- (CH2)4 -C:::C-CH3

200
9-25 When proposing syntheses, begin by analyzing the target molecule, looking for smaller pieces that
can be combined to make the desired compound. This i s especially true for targets that have more carbons

People who succeed at synthesis know the re a ctions-there i s no shortcut. Practice the reactions for
than the starting materials ; immediately, you will know that a c arbon-carbon bond forming reaction will be
necessary.
each functional group until they become automatic.
(a) analysis of target from
,,- -, -. acetylene

3° acetyl enic alcoho ls made

from acetylide plus ketones \/
... I\:'��\�i;��>,:':
( ./'""'-.r.f : ...
from alkylation
of acetyhde

.
�'--'
-

, OH ' •• _---'

" •
' - , : put on less reactive
forward direction: 8r group first
�
+ NaNH2 H-C=:C: Na+ H-C=C�

t
H-C=:C-H ---- ..

NaNH2

......f------ Na+ -:C=:C�

� o

anal ysis of target: cyclopropanes are made by carbene insertion into alkencs;
to get cis substitution around cyclopropane, stereochemistry of alkene must be
cis; cis alkene comes from catalytic hydrogenation of an alkyne

NaNH2 CH31 NaNH2 CH3CH2Br

I
H-C=:C-H ..
------I� ---- H3C-C =: C-H .. .. H3C-C=:C-CH2CH}

,
H2
Lindlar
catalyst
H H

>=<
CH212
..
Z n(C u) H3C CH2CH3

analysis of target: epoxides are made by direct epoxidation of

)" 0 /(
(c) H CH2CH2CH3
alkenes; to get trans substitution around epoxide,
stereochemistry of alkene must be trans; trans alkene comes
CH3CH2 H from sodium/ammonia reduction of an alkyne

9-26 Please refer to solution 1-20, page 12 of this Solutions Manual.

20 1
9-27
(a) CH3CH2-C::C -(CH2)4CH3 (b) H3C-C::C-(CH2)4CH3 (c) ( )- C::C-H

(d) o- C::C-H (e) CH3CH2-C:: C - CHCH2CH2CH3

I

CH3

(f)
�' Br
(g)
OH
I
CH3CH-C::C - (CH2hCH3 (h) H3C

H
\

I
C=C
C::C-CHCH2CH3
I

H
I
CH2CH3

CH3

(i) H - C:: C - CH2 - C::C - CH2CH3 (j) H-C::C-CH=CH2 (k) H-C::C -( "
H

C=CH2
,
9-28 H
(a) ethylmethylacetylene (c) sec-butyl-n-propylacetylene
(b) phenyl acetylene (d) sec-butyl-t-butylacetylene

9-29
(a) 4-phenylpent-2-yne (c) 2,6,6-trimethylhept-3-yne (e) 3-methylhex-4-yn-3-ol
(b) 4,4-dibromopent-2-yne (d) (E)-3-methylhept-2-en-4-yne (f) cycloheptylprop-I-yne

9-30
(a) internal alkynes terminal alkynes acetylide ions

CH3 - C::C-CH2CH2CH3 H - C::C - (CH2hCH3 C:: C - (CH2hCH3

hex-2-yne hex- l -yne
CH3CH2 - C:: C - CH2CH3 H - C::C - CHCH2CH3 - C:: C-CHCH2CH3.
I I

hex-3-yne CH3 CH3

3-methylpent- l -yne
NaNH2
CH3-C::C-CHCH3 H - C :: C-CH2CHCH3 C::C-CH2CHCH3
I I I
CH3 CH3 CH3
4-methylpent-2-yne 4-methylpent- l -yne
CH3 CH3
I I

H -C::C - C - CH3 C::C-C-CH3.

I I
CH3 CH3
3,3-dimethylbut- l -yn
(b) All four terminal alkynes will be deprotonated with sodium amide.
9-3 1
�
(R�-: -
OH
H20
I
.C==CH •

�a
CH3CH2-C ---
CH3CH2 - C-C-CH ethchlorvynol

Hb "
NH2
HC
I
"�
CHCl HC CH 202 CHCI
9-32
NaNH2 CH3(CH2hBr NaNH2

"1
H-C:::C-H .. .. CHiCH2h-C::: C -H
CH3(CH2)12Br
CH3(CH2h (CH2)12CH3
\ I H2
C=C CH3(CH2h -C::: C - (CH2) 12CH3
/ \
....
..
1-------
Lindlar
H H catalyst
muscalure

9-33 Cl Cl
I I

(a) CH2 = CCH2CH2CH3 (b) H3C-C-CH2CH2CH3 (c) CH3CH2CH2CH2CH3

I

Cl

H - <? - <? - CH2CH2CH3

H Br B r Br
\ I I I

(d) CH2 = CHCH2CH2CH3 (e)

I
C=C
\
(f)
Br CH2CH2CH3 B r Br

o 0 0
II II II

(g) HO - C-C-CH2CH2CH3 (h) CO2 + HO - C - CH2CH2CH3 (i) H2C = CHCH2CH2CH1

0 0
- II II

G) Na+ : C ::: C-CH2CH2CH3 (k) H3C - C - CH2CH2CH3 (I) H - C - CH2CH2CH2CH3

9-34
Br
I NaNH2 H2O
(a) H3C - C -CH2CH3 .. ..
H-C:::C -CH2CH3
I
1500
Br
Br
I
KOH
(b) H3C - C -CH2CH3 .. H3C-C::: C-CH3
I
2000
Br

_
NaNH2 _

(c) CH3CH2-C=C-H .. CH3CH2-C=C: Na+

� CH3CH2CH2CH2Br

CH3CH2 -C:: C -CH2CH2CH2CH3

H3C H Br B r
\ I B r2 I I KOH
(d) C=C CH3C -CCH2CH2CH3
\
I
--- .. H3C -C::: C -CH2CH2CH3
CCl4 • I
2000
H CH2CH2CH3 H H this product could contain minor
amounts of 3-hexyne from
rearrangement

H H Br Br 1 ) NaNH2
\ I B r2 I I
1 500 ..
(e) C=C CH3C -CCH2CH2CH3 H - C == C - CH2CH2CH2CH3
\
---
I
CCl4 • I
2) H2O
H3C CH2CH2CH3 H H
203
9-34 continued
Hz

W
(f) ..

Lindlar cis
catalyst

Na

W
(g) ..

NH3 trans

H z0
(h) HC:: C - CHzCHzCHzCH3 ___---i"�
HZ S04
[ CH2 = �� H2CH2cH2cH3
unstable enol .
1 - �
H3C - CH2CH2CH2C H]

HgS04

this product could contain minor amounts of

3-hexyne from rearrangement
Br B r
I I KOH
CH3C-CCH2CH2CH3 ---J"� H3C - C:: C -CHzCH2CH3
I
•
200° major
H H

•I catalyst
Hz Lindlar

H3C CHzCH2CH3
\ I
C=C
I \

H H

� �
9-35

Br �
Br
KOH
..
200°
HC

\
+

from rearrangement-
t
J
MixtureA

j
could contain 3-hexyne

Y
'--------.. /

�
o
only the terminal alkyne reacts
with NaNH2 and acetone 2

t
OH

+ � Mhture B

J� �
OH
CompoundD
b.p. 1 40- 1 50°C
under vacuum
CompoundC
b.p. 80-84°C
204
9-36
elimination
on 3° halide

(c) CH3CH2-C:::C - CH20H

(after H20 workup)

(e)
OH
I

CH3CH2 -C::: C - CHCH2CH2CH3

(after H20 workup)
Na+ -0-0
OH
I

(g) CH3CH2 - C::: C - C -CH2CH3

I

CH3
(after H20 workup)

9-37
NaNH2
(a) HC::C-H • HC::C:

NaNH2 CH3CH2CH2B r

�
(b) HC::C-H • HC::C: --=----"'--..::.-
.. ..
. HC::C -CH2CH2CH3
NaNH2
...
..f-----.
CH3I

H3 C CH2CH2CH3
H2 \ I
(c) H3C-C:: C - CH2CH2CH3 •
C=C
Lindlar
synthesized in part (b) catalys t H H

H3C H
Na \ I
(d) H3C -C:: C - CH2CH2CH3 C=C
I \
synthesized in part (b) H CH2CH2CH3

2 equiv.
H2
(e) H3C-C:: C - CH2CH2CH3
Pt
synthesized in part (b)
Br
2HBr I
(f) HC = C- CH2CH2CH2CH3 H3C -C -CH2CH2CH2CH3
I
synthesized in part (a) Bf

205
9-37 continued Sia2BH H-CCH2CH2CH2CH3
1)
o
I I

(g) H-C::fromC-CH2CH2CH3
(b)
°
(h) from (b)
H-C::C-CH2CH2CH3
H 0 H3C-CCH2CH2CH3 2
•
II

H2S04
HgS04
(i) HC::C-H NaNH2 HC:: C:
..
---t�

catLindlal yastr
alproduce
kene mustthe be ciproduct
(±)
s to Review the stereochemistry in the
solution to Problem 8-35, p. 171 of
from anti addition this Solutions Manual.

U) HC::C-H NaNH2�
..
-t HC::C: Na+ 1) NaNH2 H3C-C::C-CH3
---l"�
--

2) CH31
1
H2 catLindlalyastr
Alternatively,attedrans-but-2-ene
anti-hydroxyl with aqueouscoulperaceti
d be c acid. H3C
OS04 C=C CH3 \ I

I \
Review the stereochemistry in the
solution to Problem 8-35, p. 171 of
H H
this Solutions Manual.
meso almesokeneproduct
must befromcis tosynproduce
additiothen
9-38
dX PtH2 o-CH2CH2CH2CH3
5

T�:�
o
II
2
O O I'�II
� the fact that five equi v alents of hydrogen are consumed

'I? 'I?
I I
says thatskelemust
carbon
\11O O
ton have fi ve pi bonds in the above
X

0
I I II
H-C-CH2CH2 -C-C-H H-C-C-H H-C-C-OH H-C-OH
'-. + � +
'"'-
-__----.
+
)
� y�-----
from C::C
carbonyls
6 alkenes
� 3 carboxylic acids 2 alkyne� 1

o-CH=CH-C::CH beWhetdetheerrmithneedalkfrom ene ithese

s cis orresultransts. cannot
Compound X 206
9-39 Compound Z
o o o o
I I II II II

�
ozonolysis CH3(CH2)4-C-H CH3-C-CH2-C-OH HO-C-H
\ J \.'-__...... ,-__ -.;)
y y
from alkene from alkyne
Compound CH3(CH2)4CH C -CH2 -C C-H Whether
Z:
=
I
==
Z cannot thedetalkeenerminised
be E or

CH3 from this information.

9-40 All four syntheses in this problem begin with the same reaction of benzyl bromide with acetylide ion:
HC::CH .. HC::C: � CH2Br .. PhCH2-C::CH .. PhCH2-C::C:
N�� _
N��

6
use this
helow

I bromide
?' benzyl
�

+ Br � PhCH2-C::C � 6-phenylhex-l-en-4-yne
allyl bromide
(b) PhCH2-C::C: Br....../ .. PhCH2-C::C� P aS04.. Ph '>={
+
\ dlB
ethyl bromide quinoline cis-l-phenyl H pentH - 2-ene
Lindlar catalyst
Na
X
(c) PhCH2-C::C: Br....../ +
Ph
ethyl bromide
trans-l- phenylpent-2-ene
(d) Thestructure,
meso diol witalh tthough he twothisOHonegroupsis notonmeso
the same
because sidethine tthoep Fischer
and bot projom egroup
t ction isarethdifferent
e equival. eStntilof, iat
gives aorclueby anas tanto itsi addit
bond, syntihonesitso. aThetrans"meso"
[Link] Webe formed
saw thebysameeitherthinga synin taddit
he solution itono atocis double
9-37 (j).
Ph '>={ OS04 Ph ..

Hcis H syn addition H30+

product anti addition product trans

from part (b) CH2Ph from part (c)

H + OH
H + OH
CH2CH3
racemic
207
9-4 1

(a) CH��-C�C-H SiH202, a2BH

HO-
1)
•

(b) �.. reaction �H-O-Et

2)
f\ '"
R�C= \{ -==:-l 1

{
-.. /
R-C C-H :O-Et + •

H :O Et � O�Et
\ y\ \H
H +O�E'
R �-� R-�-t react � 'c=/
�

/
- ... •

H H 1
H H ion2 R/
! H20 :
H :o�H+
H 1
H O-Et 1 1 1 1
H : O�Et 1 I)
R-C-C-H .. R-C-C-H
1 1 • •

1 1
R-C-C-H •

1 1
H :O�H H20: H OH H OH
ilJ ! - HOEt
H 1
H
1
H
R-?-? -H 1
}
II
+

R-C-C-H -----<
R -C-C"+-H ....
..f----;.�
1 1
H ° H :OVH H : O-H ..

(c) alkyne RO-

R-C CH R-C=CH The •

An sclorbiosertalthiats cleloeserctronsto aarenucltoeusthethannuclaeus,p orbithetalmoreis, asstapble.

1

2sp carbaniORon carbani

orbitalsoaren iselmore
2sp carbanion has es than
ongatstedablaway from an the
sp 3 nucl
carbani e us.
o n An sp2
because t h e
alkene RO- e nuclcharact
iwhis clcohseris tonlo thye positsivcharact 33%
tehranandspin2andancarbani
eeusr. The spthe3 carbanion
electron pair
R-C=CH2 1
R-C-CH2 to form because of its relative stabil i ty. on easier
•

1 I
25% is

H 3sp HcarbaniORon

208
9-42 Diols orareantmadei-dihydroxyl
witusehinorgani
Os04' by two react
a t i ionsviafrom
on an Chapteusing
8
epoxide r anda peroxyacid
revisited in and water.
9-4 1 (d): either
As t hsyn-dihydroxyl
is probl e m attioon
says
c reagents, the solution shown here wil l use OS04.
Recall the stereochemical requirements of syn addition as outlined in this Solutions Manual, p. Problem
8-35:
17 1,

cis-alkene addition meso

+ syn �

+ anti �
citrsans--alkaenelkene additadditionion racemic (±)
+ syn � racemic
(±)
trans-alkene addition meso
+ anti �

Part
(b) wil(a)l asksrequiforre synthe addit
synthesis
ion toofthethetrameso
ns-alisomer,
kene to sogivsyne thaddit
(±) e iproduct
on will .have to occur on the cis-alkene. Part

(a)
Bf
NaNH2
"!
HC::C-H HC::C : Na+
i
OS04
..

f \
..

Lindlalyastr -Zc::cJ-
cat
alproduce
kene mustthe meso be cisproduct
to H H
from
reduct synion addit
is ion,withso
done
theLindlciasralcatkenealyst to produce
(b)
HC::C-H NaNH2 HC::C : Na+ Bf
NaNH2
"! i
..

OS04 Na
.. ..

NH3 -Zc::cJ-
alkene mustthe be tproduct
produce (±)
rans to from
syn addit
done withion,Na!NH3so reduction is

209
9-43 This synthesis begins the same as the solution to problem
9-40:

HC::CH NaNH2.. HC::C:

01
NaNH2
_�
+ CH2Br .. PhCH2-C:::CH .. PhCH2-C:::C :
�
benzylde
bromi
The anion will add across the carbonyl group of the aldehyde:
°

lf
1
H +
PhCH2-C::: C : --- H30+
acid-catalyzed dehydration
H2S04,
Ll

•
MCPBA

210
 CHAPTER 10-STRUCTURE AND SYNTHESIS OF A LCOHOLS
10-1 Please seepropan-2-ol
(a)(b) 2-phenyl the note on p. 136 of this Solutions Manual (d) t regardi
ra ns-2-met nghplylcycl
acementohexan-l-olof positio("n 1"numbers.
is optional)
5-bromohept a n-2-ol
(c) 4-methylcyclohex-3-en-l-ol (" 1" is optional) (2R,3S)-2-bromohexan-3-ol (e)
(f)
(E) - 2-chl o ro-3-met h yl p ent-2-en-l-01
10-2 IUPAC name first, then common name.
(a)(b) cyclopropanol
2-methylpropan-2-01; ; cyclopropyl
t-butylalalcohol
cohol (c)(d) l-cycl
3-met hoylbutbutylapn-l-01;
ropan-2-01; i s noycommon
opent l al c ohol name
(also isoamyl alcohol)
10-3 Only constitutional isomers are requested, not stereoiOHsomers, and only structures with an alcohol group.
g
(a) C3H O �OH propan-l-ol A propan-2-01
(b) C4HlOO � � �OH �
OH OH OH
butan-I-ol butan-2-01 2-methylpropan-I-ol 2-methylpropan-2-01
g
(c) C4H O has one element of unsaturati on, either a double bond or ring.
HO i>-
a

�opropanol 2-methylcyclopropanol
OH OH
d
cyclobutanol cyclopropyl [>-Jmethanol l-methylcycl
cis or t ra ns
� OH
OH * HO�
� OH �
J:H
but-3-en-I-ol but-3-en-2-01 but-I-en-2-01 but-I-en-I-ol (E or Z)
�OH � �OH *
but(E-2-en-l-ol OH
but-2-en-2-01 2-methyl- 2-methylprop-2-en-l-01
or Z) (E or Z) prop-l-en-I-ol
(d) C3H40
doubl e hasortwaothree-membered
bonds, elements of unsatrinugratandi on,asodoubleache bond.
structureAllmuststructureshave eimust ther contai
a triplen bond,
an [Link] (Intwothe
name, the "e" is dropped from "yne" because it follow by a vowel in "01".)
HO-C::C-CH3
* HC::C-CHOH2 H2C=C=C!I * y. 0H
propa-l,2-dien-I-ol cycloprop-l-en-I-ol cycl'\Zoprop-2-en-l-ol
prop-l-yn-l-ol prop-2-yn-I-ol OH OH
*Thesealcompounds
"vinyl c ohol s . " wistthructure
The the OHwibonded
t h OH direct
on a ly to the carbon-carbon
carbon-carbon tripl e bond doublis cale lbond
e d an areynolcal. lThese
ed "enols"
are or
unstable, although the structures are legitimate.
211
1 0-4 (a) 8, 8-dimethy lnonane-2,7 -diol
(b) octane-l,8-diol
(c) cis-cyclohex-2-ene-l,4-diol
(d) 3-cyclopentylheptane-2,4-diol
(e) trans-cyclobutane-l,3 -diol

1 0-5 There are four structural features to consider when determining solubility in water: 1) molecules with
fewer carbons will be more soluble in water (assuming other things being equal); 2) branched or otherwise
compact structures are more soluble than linear structures; 3 ) more hydrogen-bonding groups will increase
solubility; 4) an ionic form of a compound will be more soluble in water than the nonionic form.
(a) Cyclohexanol is more soluble because its alkyl group is more compact than in I-hexanol.
(b) 4-Methylphenol is more soluble because its hydrocarbon portion is more compact than in I-heptanol ,
and phenols form particul arly strong hydrogen bonds with water.
(c) 3-Ethylhexan-3-ol is more soluble because its alkyl portion is more spherical than in octan-2-01.
(d) Cyclooctane-l,4-diol is more soluble because it has two OH groups which can h ydrogen bond with
water, whereas hexan-2-ol has only one OH group. (The ratio of carbons to OH is 4 to 1 in the former
compound and 6 to 1 in the latter; the smaller thi s ratio, the more soluble. )
(e) These are enantiomers and wil l have identical solubility.

10-6 Dimethylamine molecules can hydrogen bond among themselves so it takes more energy (higher
temperature) to separate them from each other. Tri methylamine has no N-H and cannot hydrogen bond,
so it takes less energy to separate these molecules from each other, despite its higher molecular weight.

1 0-7 See Appendix 2 at the back of thi s Solutions Manual for a review of acidity and basicity.
(a) Methanol is more acidic than t-butyl alcohol. The greater the substituti on, the lower the acidity.
(b) 2-Chloropropan-l-ol is more aci dic because the electron-withdrawing chlorine atom is closer to the
OH group than in 3-chloropropan-l-ol.
(c) 2,2-Dichloroethanol i s more acidic because two electron-withdrawing chlorine atoms increase acidity
more than just the one chlorine in 2-chloroethanol.
(d) 2,2-Difluoropropan-l-ol is more acidic because fluorine is more electronegati ve than chlorine; the
stronger the electron-withdrawing group, the more acidic the alcohol.
10-8
most least
acidic acidic
sulfuric acid » 2-chloroethanol > water > ethanol > t-butyl alcohol > ammonia > hexane
(CH3hCOH

Sulfuric acid is one of the strongest acids known. On the other extreme, alkanes like hexane are the least
acidic compounds. The N-H bond in ammonia is less acidic than any O-H bond. Among the four
compounds with O-H bonds, the tertiary alcohols are the least acidic. Water i s more acidic than most
alcohols inc luding ethanol. However, if a strong electron-withdrawing substituent l i ke chlorine is near
the alcohol group, the acidity increases enough so that it is more acidic than water. (Determining exactly
where water appears in this list i s the most difficult part.)
10-9 Resonance forms of phenoxide anion show the negati ve charge delocalized onto the ring only at

HQ
carbons 2, 4, and 6:

66' O 6
: 0: : 0: : 0: : 0: : 0:

5::::-'"
4
3
.. ..
.

::::-...
.. ..
6 C-
H
.. ..
h-
.
H
... ..

2 12
10-9 continued
Nitro group at position 2
. .

:0: :0: :0: :0: Nitro at position 2

delocalizes
negative charge.

Nitro group at position 3

:0 :

Nitro at position 3 cannot delocalize negati ve charge at position 2 or 4-

no resonance stabilization.

:0 :

Nitro group at position 4

:0 : :0:
.. ..
Nitro at position 4 delocalizes negative charge.

-
.."N , -

+
• • . •

:0'" 0:
Only when the nitro group i s at one of the negative carbons will the nitro have a stabilizing effect (via
resonance). Thus, 2-nitrophenol and 4-nitrophenol are substantially more acidic than phenol itself, but 3-
nitrophenol is only slightl y more acidic than phenol (due to the inducti ve effect).

10- 10 OR

A �
�
(a) Structure A is a phenol because the OH i s bonded to a benzene ring. As a phenol, it will be acidic
enough to react with sodium hydroxide to generate a phenoxide ion that w ill be fairly soluble in water.
Structure B is a 2° benzylic alcohol, not a phenol, not acidic enough to react w ith NaOH.
(b) Both of these organic compounds will be soluble in an organic solvent like dichloromethane.
Shaking this organic solution with aqueous sodium hydroxide will ionize the phenol A, making it more
polar and water soluble; i t w i l l be extracted from the organic layer i nto the water l ayer, while the alcohol
will remain in the organic solvent. Separating these i mmiscible solvents w i l l separate the original
compounds. The alcohol c an be retrieved by evaporating the organic solvent. The phenol can be
i solated by acidifying the basic aqueous solution and filtering if the phenol i s a solid, or separating the
layers if the phenol is a liquid.
2 13
1 0- 1 1 The Grignard reaction needs a solvent containing an ether functional group: (b), (t), (g), and (h) are
possible solvents. Dimethyl ether, (b), i s a gas at room temperature, however, so it would have to be
liquefied at low temperature for it to be a useful solvent.

�Li -D- �+
10- 1 2 Li
(a) CH3CH2MgBr (b) + LiI (c) F MgBr (d) LiCI

1 0- 1 3 Any of three halides-chloride, bromide, iodide, but not fluoride-can be used. Ether is the typical
solvent for Grignard reactions.

(a) o MgCl +
H

H
\

I
C=O
ether H30+
-- .. O CH2OH

�
H ether H30+
+
�
\
(b) MgBr I
C=O -- ..

OH
H

(c)
o- MgI
+
H
\

I
C=O
ether H30+
-- ...
o- CH2OH

H
Note: the alternative arrow symbolism NO! Me BAD!
could also be used, where the two steps This means that water is present with
are numbered around one arrow: ether during the Grignard reaction.
,

1 ) ether 'ether "

,
'

... 'ce ' •

2) H30+ OK 3 +'
,}'fo "
,

1 0- 1 4 Any of three halides-chloride, bromide, iodide, but not fluoride-can be used. Grignard reactions
are always performed in ether solvent; ether is not shown here.

y
(a) two methods
H

I
H30+
Ib:
MgCl Where two methods can be
+ -- ...
used to form the target

H
0 compound, the newly
formed bond is shown in

In
H30+
Ib:
+ CH3MgI -- ...
bold.
0

�
(b) two methods OH

o
1.&
MgB, 0
H30+
+
� -- ..

�
H
0 OH

~
H H30+
+ IMg -......./ -- ..

214
 �
1 0- 1 4 continued OH
o

o dD
(c) MgCI
+ H

10- 1 5 Grignard reactions are always performed in ether. Here, the ether i s not shown.
(a) Any of the three bonds shown in bold can be formed by adding a Grignard reagent across a ketone.
(i)
:
CH3C 2MgBr
(ii) 0 � (iii)
CH3C 2CH2MgBr : (i )
,\ ?:;-
O� �O
Ph
+ PhMgBr 01
( Ph
'-("') 111

Ph
(ii )

Ph MgBr + "-- 'c = 0

� Ph H30+
Ph
I
(b) :- -- � Ph -C-OH
I I
Ph Ph

(d) two methods

\ Cy
�MgCI

� >= O
H30+
+ -- �

Cy
+ Cy-MgCl
Cy = cyclohexyl

:C!0 :0
?) �
10- 16

CH3 -C� MgBr

II : II ketone

�
- CI-
CH3-C-CI -Ph intermediate

l
--- �

I
Ph
(This is just a nucleophilic substitution where Ph-MgBr
CI is the leaving group. The unusual feature
is that it occurs at a carbonyl carbon.)

OH
I
�:o:I
TPh
CH3- -Ph
work-up
step
CH -C-Ph
3 I
Ph

215
1 0- 17 Acid chlorides or esters will work as starting materials in these reactions. The typical solvent for
Grignard reactions i s ether; i t i s not shown here.
0 Ph
II H30+ I

(a) Ph-C-Cl + 2 PhMgBr � • Ph-C-OH

Jy
I
Ph
H30+
(b)

0
OCH] + 2 CH3CH2MgI � •

~ OH

o
o
II
(c) Ph-C-Cl + 2 MgCI

:qD
II
. .

:?j
10- 18

(a) H-C � ./'0... . MgB r

--- H-C-OEt
aldehyde
intermediate

��
OH

�C�
I
I
H
o
II
(b) (i) HC-OEt + 2 CH3CH2MgBr �
H30+
• �
OH
0
II
(ii) HC-OEt + 2 <} MgB r �
H30+
•

� MgBr
II H30+
(iii) HC-OEt + 2 � •
�
OR

� OR
10- 19 Ether i s the typical solvent in Grignard reactions.

(a) <} MgBr +

U
o

216
10- 19 continued

� �OH
0 H30+
(b) MgCl +
U ---- �

gl 0 H30+ � OH
(c)
� +
U ---- �

10-20

�D
_ ?'"O
(a) HC C:

(b)

10-2 1 There are more than one synthetic route to each structure; the ones shown here are representative.
The new bonds formed are shown here in bold. Your answers may be different and still be correct.

(a) � Br
Li
- ----
CuI (�C UL i
�
Br
� �
2

� Br ( �C (
()l U
Li CuI (
(b) -----
U Li �

I (�C
CJ"
� Li Cu
(c) Br -----
ULi �

Alternatively, coupli ng lithium dicyclohexy!cuprate with I-bromobutane would also work. As

this mechanism i s not a typical S N 2, it i s not as susceptible to steric hindrance like acetylide ion
substitution or a similar S N 2 reaction.

(d)
�
Br
Li
-----
CuI
(�C 2
ULi

10-22 These reactions are acid-base reactions in which an acidic proton (or deuteron) is transferred to a
basic c arbon in either a Grignard reagent or an alkyllithium.
(a) +
CH3D Mg(OD)I (b) CH3CH2CH2CH3 LiOCH2CH3 +

0 CH3C-OLi
(d) II
+

217
10-23 Grignard reagents are incompatible with acidic hydrogens and with electrophi lic, polarized multiple
bonds like C=O, N02, etc.
(a) As Grignard reagent is formed, it would instantaneously be protonated by the N-H present in other
molecules of the same substance.
(b) As Grignard reagent is formed, it would i mmediately attack the ester functional group present in other
molecules of the same substance.
(c) Care must be taken in how reagents are written above and below arrows. If reagents are numbered
" 1. . .. 2. ... etc.", it means they are added in separate steps, the same as writing reagents over separate
arrows. If reagents written around an arrow are not numbered, it means they are added all at once in the
same mixture. In thi s problem, the ketone is added in the presence of aqueous acid. The acid will
immediately proton ate and destroy the Grignard reagent before reaction with the ketone can occur.
(d) The ethy l Grignard reagent will be immediately protonated and consumed by the OH. Thi s reaction
could be made to work, however, by adding two equivalents of ethyl Grignard reagent-the first to consume
the OH proton, the second to add across the ketone. Aqueous acid will then protonate both oxygens.

6
10-24 Sodium borohydride does not reduce esters. OH
(a) CH3(CH2) gCH20H (b) no reaction (c) no reaction (PhCOO- before (d)
acid work-up)

1 lf
o

�OCH3 °
(e) HO· Y Y (I) c,tcc OH

OH

6
10-25 Lithium aluminum hydride reduces esters as well as other carbonyl groups. OH
(a) CH3(CH2) 8CH20H (b) CH3CH2CH20H + HOCH3 (c) PhCH20H (d)

� OH HO
� OH
HO �
(e) HO (f)
y + HOCH3
OH
10-26
(a) �H NaBH4
• �OH OR
1) LiAlH4
•
CH30H 2) H30+
o
OR
� OH 1) LiAIH4
•

2) H30+
o

OR
OR 1) LiAIH4

�
•

2) H30+

o OH
� �
(b) NaBH4 1) LiAIH4
•
OR •
CH30H 2) H30+
218
1 0-26 continued

~ ~
NaBH4 1) LiAIH4
(c) ..
OR ..
CH30H 2) H30+
0 OH

W C�X:f
(d) O NaBH4 LiAlH4 will NOT give the desired
..
CH30H product. LiAIH4 will also reduce the
ester in addition to the ketone.
0 OH
1 0-27 Approximate pKa values are shown below each compound. Refer to text Tables 1-5, 9-2, and
1 0-3, and Appendix 5 at the back of the text.
CH3S03H > CH3COOH > CH3SH > CH30H > CH3C:: CH > CH3NH2 > C H3CH3
< 0 4.74 "" 1 0.5 15.5 25 "" 35 50
most acidic least acidic

1 0-28
(a) 4-methylpentane-2-thiol
(b) (Z)-2,3-dimethylpent-2-ene- l -thiol (" 1" is optional)
(c) cyclohex-2-ene- l -thiol (" 1" is optional)

�
� �
10-29
HBr NaSH
..
Br SH 3-methylbutane-I-thiol
ROOR

� Br � SH
�o
NBS
�
----l..
NaSH
..
2-butene-l-thiol

c
(but-2-ene-l-thiol)

�
OR
(see Problem 8-2)

1 0-30 Please refer to solution 1-20, page 12 of this Sol utions Manual.
1 0-3 1
(a) 5-methyl-4-n-propylheptan-2-01; 2°
(b) 4-(I-bromoethyl)heptan-3-01; 2°
(c) (E)-4,5-dimethylhex-3 -en-l-01; 1°
(d) 3-bromocyclohex-3-en- l -01; 2° (" 1" is optional)
(e) cis-4-chlorocyclohex-2-en-l-ol; 2° (" 1" is optional)
(f) 6-chloro-3-phenyloctan-3-01; 3°
(g) (l-cyclopentenyl)methanol; 1°

1 0-32
(a) 4-chloro- l -phenylhexane- l ,5-diol
(b) trans-cyclohexane-l,2-diol
(c) 3-nitrophenol
(d) 4-bromo-2-chlorophenol

219
1 0-33
(a)

OQ
I 0

C-OH
(b)
OH
(c)

6
OH
(d) � (e) �H
OH OH

-6
� 6 U)
OH

&
¢
OH HO H SH CH3S-SCH3
(f) OH (g) (h) H (i )
OH

~
(k)
I

10-34
(a) Hexan- l -01 will boil at a higher temperature as it is less branched than 3,3-dimethylbutan - l -01.
(b) Hexan-2-01 will boil at a higher temperature because its molecules hydrogen bond with each other,
whereas molecules of hexan-2-one have no intermolecular hydrogen bonding.
(c) Hexane- l ,5-diol will boil at a higher temperature as it has two OH groups for hydrogen bonding.
Hexan-2-ol has only one group for hydrogen bonding.
(d) Hexan-2-ol will boil at a higher temperature because it has a higher molecular weight than pentan-2-01.
All other structural features of the two molecules are the same, so they should have the same
intermolecular forces.
1 0-35
(a) 3-Chlorophenol is more acidic than cyclopentanol. In general, phenols are many orders of magnitude
more acidic than alcohols.
(b) 2-Chlorocyclohexanol is slightly more acidic than cyclohexanol; the proximity of the electronegati ve
chlorine to the OH increases its acidity.
(c) CyciohexanecarboxyJic acid is more acidic than cyclohexanol. In general , carboxylic acids are many
orders of magnitude more acidic than alcohols.
(d) 2,2-Dichlorobutan- l -ol is more acidic than butan-I-ol because of the two electron-withdrawing
substituents near the acidic functional group.

1 0-36
(a) Propan-2-ol is the most soluble in water as it has the fewest carbons and the most branching.
(b) Cyclohexane- l ,2-diol is the most soluble as it has two OH groups for hydrogen bonding. Cyclohexanol
has only one OH group; chlorocyc lohexane cannot hydrogen bond and is the least soluble.
(c) Cyclohexanol is the most soluble as it can hydrogen bond. Chlorocyclohexane cannot hydrogen bond,
and 4-methylcyclohexanol has the added hydrophobic methyl group, decreasing its water solubil ity.

OH

�
1 0-37
Hg(OAch NaBH4
�
l
(a) • .-

N
H2O

U ({
(b) BH3' THF H202
• •

HO- "
"
OH

220
 continued BH3 H202 OH
(c)�
1 0-37
- THF
�

HO- ~ �

OH
(d)� H2O Hg( O Ach NaBH4 �
OH
� ..

(a) OH (b)� JyPh

10-38

OH
V
(e)

(OHd) Thigroup,s prothbleefmirsconft thinugsetshata lhappens

ot of peoplis eth. atWhenthe GraiGrgnarigdnarredactresagentby reimovis addedng tthoeaH+compound
from [Link] has an
o

+ CH3 M g1 et h er 0 o

CH4
00H (Gngnar 1
o�ly oned requieagentvaleaddednt of! �0- +MgI If a second equivalent (or excess)
� +

no morbefe Groriegnaracidd reagent H30+ CH3etherMg1 atbefofwitlGrhoergieigketvhydrnare [Link]

Iisf added sAciis, dthhydriens addeditolysisadd
o l .
mathydreorilaylsiiss,rtehcoveren [Link]
will

Mg 3 H H H
00H ( ' 0 p'. X 3
a

Ph Ph 0- +MgI Ph UOH
(e) Q--'OH Ph+OH (f)
Ph ( g)Ph 6 0H (h)
crtu
HO�OCH3 HO�OH OH
(i) V 0 U) V (k)� �

d:) HO OH (n) HOOH

�
(l) (m) (0)

221
 ndicating that the Grignard
ws are sacihownd isiadded.
reactionAlislalGrloiwedgnardtorepractoceed,ions arande runtheninietn [Link],Twodiluarrte oaqueous
H3 0 + H
10-39

(a) � H BrMg -..../ o

?
Mgether CH20..
.. �

�Br --
+ ---

OH
0 Hp+ OH
(b) �

(c) )lH BrMg-Q

0 ~
+ ..

'
---

(d) O -- B Mgether U (YbH H3 0 +

'
.. ..

(e) O etMgher CH20 H30+ VOH

' h
R -- .. ..

(f)
O
i l CH3
COCH2 o

(g ) � H
o OH
~
(h ) �0 XMgC C-CH3
Techni c al l y , XMgC=CCH3 i s a Gr ig nar d r e agent
+

RMgX
Gr ignar d H-C=C-CH3
��------�
becaus
magnes e i i
utm.i s an or g
Howeveranomet
, it ia
s l i
notc compound
made i n t h of
e usual
alrekagentyl or wheralkenyle R is f a s h i o n; i t is made by depr o t o nat ing t h e te rm inal
�------�
( - '\

alkyne as shown.
+

any

(a)
1 0-40
BH3 -THF
H
..

(b ) Ph _

........", 'CI ether

/'....
Mg
--
CH2 ..
0 H3 0
..
+ Ph �OH
222
1 0-40 continued OH o
(c) 6 d) eq. H2
° °

6 OH
( 6 Pt .. 6 1

(e) �OEt �OEt

o

( f) � OEt
o o
H30+.. � OH OH o
o
(a) V MgBr CH,O _e_th_e--;r.. �
10-4 1
+
OH
V
OH
�

(b) V HO� � V
NaOH..
( d) Mgether �
o
� OH
(e ) '-- Br NaSH
�

r-==\.
---f
+
�SH
� Br� ( 1 \CULi � Br
(f)

I
� '

:"�
+

j .�
sequattrongerionTheaciwidtposihandthetiosweaker
tnroofngertheacibasequideandlwiiblrbasiualmwe canayswil berbeeactdetfatvoreormined
gievdeatthequibye weaker
the streacingtdhandof tbashe acie, sods torhethsiedebasofetsh. eThe
librium. See Appendix in this Solutions
Manual for a review of acidity.
1 0-42

(a) CH3stroCngerH20� <stronger'}- OH CH3weaker CH20H <weaker'}-o-

2

base acid acid base

+ +

products favored
223
 KOH Cl-Q- OH
1 0-42 continued
H20 Cl-Q- 0-K'
Cl Cl
(b) + +

stronger stronger weaker weaker

acid acid base

OH
base
p roducts favored

(c)
c6 h
CH3 O - h
+

stronger stronger weaker weaker

a OH
acid base base acid

KOH H20
products favored

+ +
(d)
weaker stronger
weaker base acid stronger
acid base

(CH3hCO- CH3CH2OH (CH3hCOH CH3CH20-

reactants favored

(e) + +
stronger stronger weaker weaker
base acid acid base

(CH3hCOH HO-
products favored

stronger stronger weaker weaker

base acid acid base

KOH CH3CH20H
products favored

(g) +
weaker weaker stronger stronger
base acid acid base

�OH OR LiAIH4
reactants favored

(a) � H
1 0-43
I)

OR
•

� OH LiAJH4
°

OR
1)

� OR 1 ) LiAJH4
•

H30+ o
2)
•

224
 continued0 OH
(b) � CH3NaBH40H LiH3A0lH+ 4...
1 0-43

�
1)
OR
0 NaBH, . OH
..

2)

(C) � CH30H ~ OR LiH3A0lH+ 4 I

1)
...

0 OH
2)
,&

(d) NaBH4
CH3 0 H OR Li
H3 A0l H+ 4...
OO 00
1)
...

2)

NaBH4 OH
OEt CH30H � OEt
r---<
(e) (' '\
...

0 0
LiH3A0IH+',. OH
HOCH2CH3
OEt Q OH
(f) / " 1)
+
2)

0
ThefragmentproTheducts whigoalhaschiscoultocarsyntdbbeonshjesio,isonzedetthhienelatoagiGrirgcetalgnarcompound (biooxed)n" in fworromkisntgarbackwar
ting matedrsiaislstwofosisixxcarcarbbonson or fewer.
II

"didscronnect
bond, and Brdouble bonds aro e madeMgBr from [Link] thebesprot ductwaystoofmakeGrignarepoxid redactes iiosnsfro. m the double
10-44
12

Methger ... OH y
O I I
H30+ H 4 VD
t MCPBA
cro
,&

-- I
h
2 S0
+
o ,&
�

H�

225
v<b
target
 steps are reversible.
10-45 All

HO><�
H �
H � I+ i
HO H - H20.. ./CHO··I · .. .. H-O H20 :.. :0:
A
�} • •

X A
The symbol H-B represents a generic acid, where B-is the conjugate bas0
.

e.
/ + .......

OH H- { H :OH f v }
H lI
1 0-46

�
(a) H H � H -t- C�
H� n
/ B :- -H
H 0:

T\.
� H ---

H H H H

� o:
+

(b )
H-B

..B � cr
+

r
OH H
crH � + H-B
? , OH H
• •

r
��
"
-

H
ao :
H
Q( :
�

(C ) �
Q(
0:
:
H J H�' H a
>-

I I
H
\.
6MgBr
. .
•
-
H : O -H
_ �

C -......

�
• •
H • •

H
1 0-47

Mg -...: :: 2 °-...::: + :O-H

6' .. 6
. .

et h er ° ° ..
A

I)� 1 2) H,o'
B c
isobutylcyclohexane
exH2cesst
OH �P
H2S04 ..
/).
2 Br2..
D E F

226
 10-v4i8ngThiforscemechani
driunder f o r t h e srmeactisiosinmiislarreltioefclofeavagering softraitnheinepoxithe 4-demiember n ethyleednecycloxiicdeetbyherGr, whiignarchdisrewhyagentitswi. Thel
go a Grignard reaction whereas most other ethers wil not.
R "MgX .D . --- +
+

MgX
�U
10-49 When mixtures of isomers can resCH3ult, only the major product is shown.
(y O 1) CH3Mg1 OOH HZS04 o- CH3 HPtz .. CH3
2) H3O+ ...
A '" U
t KM�04 t Hz�04
A B

� CH3
(J=O
OH
tOH Hz�04
"

t 1 )H3CH3OM+ g1
"

G D

Q1 "1 "1" 0
2)

(J-O
F
t 2) Mg,cycloetpentheranone C

t PhC03H
3) H3BrO+ HEr
I)

U 0
tThe1o0-s5trs0uoctdiTheuurmesmosbihavicart nibmgonatporone,etainttswbasro,eactoricaenough
tnthreine toxygens
he deskunkion tnhge smiulxfuturr; ealilsofhydrthesogene [Link] are [Link]
..

can wash them away. sulfenic acitodisonize these acids, smakiulfinnicg acithemds water soluble whersulfeotnihec acisoapds
E

H z O z H zO z P H H z O z �O
3-� methylbutane-l- SH thiol �OHS � S
.. ... ...
II
S-OH
HzOz �S HzOz � S'OH HzOz
I II II
° °

�SH OH
�°

S-OH
(2-butbut-2e-ne-lene-l--thtihoilol)
II
.. ... ... �
I I I I I
° °

227
1 0- 5 1
1 ) �0
Br Mgether �MgBr H30+ H �
t KOH, H20
� ----..

H2
2)

S 04
..

, OH
�OH
D E

+
+ Na 21 )
) 03
fj,

�
A

�O- Na+ B

H G�
� F

Br
Br2 �
�O
+
�O � C O� Br
/' Br

H KOH, �
+

H �C::C�
fj,

plus other alkynes

1
O� I)Sia2BH H -C::C ---"" .......,) NaNH 2 , 150° C + H20
7- HBrnon-l-+yne
2)

H .......
/"'.. /"'.. /"...
.. .......,
1
I

Na+-C =C� Br 2

Br
J

CH2CH31
L
o

�
HO- CH3C -C=C�
I

228
((ab)) botoxihdatreiacton,iooxinsdarateiooxin, dreatductionsion, oxidation
C H A PTER l l-REA CTIONS OF ALCOHOLS

((cd)) onereductcariobn:on C-O is oxidiiszedreplandacedone carC-Hbon is reduced-no net change

1 1-1

(e) oxineitdhateriooxin (adddiatiotnionnorofrXeduct2) ion-the C stil has two bonds to 0

((hg)) neineitthherer oxioxiddatatiioonn nornor rreeductductiioonn ((aelddiimtiinoatniofon of H20)
by

(i) oxithedfatirsiot n:reactaddiionngisanoxi0dattoioeachn as cara newbonC-Oof thebonddoublise fbondormed to each carbon of the alkene; the
(f)
HX)

shasecondonerbondeactiotno ioxygen s neither oxidation nor reduction, as H20 is added to the epoxide, and each carbon
st(hkeatcond) neiin ftruhencteractoxiiioonaln;datovergrioonupsanorl , onlirnevolducty Hand
ion: OHH-Bareisadded,
addedsiontthhere efirisstnoreactnetiooxin, dandatioBn inors replreaductcediobyn.0(Ninottehe
(j )
sti l l

oxidized or reduced before thevingchange two cartboonsthelfikuenctalikoenesnal groroupalkiynes,s clasbotifiehdcarasboxionsdathaveion toro bereduction.)
0 OH 0
net

(a) H2Cr04
6 6H 6
1 1-2

pcc
.. �

(b) no reaction H2Cr04 PCC no reaction

0
..

o OH
�

0
(c) cY H2Cr04 PCC
..

cY 0
�

cY
(d) no reaction H2Cr04 6 pcc
no reaction
(e) no reaction H2Cr04 0 PCC no reaction
.. �

H2 C r04 0
H3C -C-OH PCC no reaction
.. �

no reaction
0 H2Cr04 CH3CH2OH PCC H3C -C-H 0
(f) II

(g) H3C -C-OH

.. �

II

0
II

H2 C r 0 4 0
H3C -C-H PCC no reaction
.. �

(h) H3C -C-OH II

..
II

229
�
(hydra) Aogen alincfoholonnilnogseaskettwoone;hydreachogensalcwhen ohol i [Link]
s to the allodsehyde,
e s an and a fralomcoholthe sluolsfeusr;oneit is clearly
oxygen
diefrefduced.
sepctroporon tt(hiIoefnatyoueleiomentngotretactshiosnioeoxaln:twoneyo,l youchlCoidirsidoxidethidseiz"prednootblchange".
oeCO2m corandrectthlye.)otToherbeC irisgroreduced ous, oxalto CO;yl chlhowever oride under, thegnetoes
1 1 -3
10 20

(oxib)diTextzed toseDMSO. ction shows that dimethyl sulfide reduces an ozonide. In the process, dimethyl sulfide
8- 1 5B is

(enera) Dehydr
g y ) f o r othgenatis reaciontiodoesn, ornotioccur t i s t h atmodynami
er C-eictaherl y: unfthaervoreaibls ae,hiwighthki[)'nGet>ic barriTheer (alathiergposh actsiibviatlitiyonis
supporC (tseedebytextthseefctaicotnthat theCre)verandsethrereaceftoioren has(cat[)'alGytic [Link] makesion tofheaquescarbtonylion of) kisnpetonticsaneous at c-a
1 1 -4

academi
250 1)

(rhydrebact)andoiogenatn(cth)atioKinetcnaandnnoticsdehydr
prwiolceiedmprmusovet [Link] for virtually all reactions, so both the
2) O.
is
<

orgenat ion.n rTheeactansionswerwilisgothatfatshteerrm. Iodynamics n this case,wihowever , tthhies quesreacttiioonn asis howthe to
250 1 0- 1 1

fteampervor thaetudehydr o genat i o n e act i o l favor

es[)'5ti>matesitnhrceeationesMi>[Link] tikeyhseconver prisotducthetefduketndament
oto tnewo:platuhlserthydrheerfomroeodynami
gen, [)'is5lecs equatstAtablieloontwhan[)'teGmperthe sMiataturtri-engTflSalcoholC. )We, Mi. Alcanso.
overdomiwnathelesmbecaus Mi, ande T[)'iGs swio slmbecome all, so [)'negat G > [Link] hitghhe enough reactionteinmperquesattuioren,, tthheis-T[)'mus5t tbeermthewicasl begie at n to C.
=

0
0 - T < O. (250

3000

(a)
1 1 -5
AND HO-
PCC
(b) all three reagents give the same ketoneCH3pro(ducCHt2wi)4 Y"­ th a secondary alcohol
(c) - H Na2H2CS04r207 AND PCC
--.....,.�

OOH • •

(d) all three reagent><s givHe no reaction with a tertiary alcohol

V
NR ( n o react
�
-ion) -.-

230
 Note-PCCto the st(puyrdentidin: iuForm chlsimoplroichrcityo,matthise)bookto oxiwidlizeuse talhescohole stasndarto alddlehydes; aboratory methods of oxidation:
-H2
-cr 0C3,r0H2S04, 4 (chromiacetc acioned)(Jtoonesoxidreizagente )altcooholoxidsitzoecarbaloxylcoholicsacitodkets; ones.
1°

Under
PCCas [Link]
are legi, andtimatCole; floinrsexampl e,orSwemPCC oxiwildatoxiiodnizwore aks about welo a lketasone
1°

reagent al c ohol t
2°

consult the table in the text befohavere Proablquesem tion about the appropriateness of a reagent you choose,
as
2°

1 1 -2.

(a) �OH PCC � H

1 1 -6
0
(b )
•

H2 C r0 4 0
� OH
cr03 �
� OH •

(c) �OH H2SO4 acetone 0

•

(d ) PCC 0
� OH �H
H2 C r 0 4 0
•

(e) OH � � OH
(y oH cr03 &0
..

H2SO4 BH3•
(f)
oH - H2O 6 H202, HO- Ll
•
1) THF
•

H2SO4
acetone
•

hanolA, chrmolso roeeniquiculc [Link] ethashanolinduced"antidmorotee" ADH moleculenzesymeto actto asbe aprcompet
esent toitihandl
ve inhie blairtgoer tamount
o "tie up"s thiemextbibreda
2)

etenzyme
1 1 -7 of

OH OH CH3-C-CH o0 o 0
pyruvaldehyde pyruvicCH3-C-COH
1 1 -8

pyru vi c aci d
[0] [0]

in the bracieakdown
d is a norof mglalucosmeteabol("biloteod sugar")
I I II II I I
..

231
 "Ts"
1 1 -9 From this problem on, will refer to the "tosyl" or "p-toluenesulfonyl" group:

Ts � -�� �� CH3
o

CH3 I
CH3 I
(a) CH3CH2 - OTs KO - C-CH3+
I
� CH3CH20 - CH3 C
I
- + K OTs
CH3 CH3
(E2 is also possible with this hindered base; the product would be ethylene, CH2=CH2)
(b) �OTS NaI + � I NaOTs � +

TsO H H
� � NaOTs
c5
(c)
R
NaCN + � "
+ inversion--SN2
S

6
T, + H3 -0TS NH2
cS
excess
(d)
3 NH
..
NH3 + , OTs .. + NH

(e) � OT s + Na+ :C=CH ---l.� �C=CH NaOTs +

1 1 - 10
(a) � OH OT NaBr
TsCI
pyridine
.. � s • � Br

excess
(b) � OH TsCI � OTs NH3
pyridine
• •
�
NH2

(c) � OH TsCi �OTs NaOCH2CH3 � O -...../

pyridine
.. •

(d) � OH TsCI � OTs KCN � CN

pyridine
• •

1 1-1 1
(a)Q- CH20H TsCl - d- " Q-CH20TS OR Q-CH20-�-o-CH1 o

pyn me
o
232
1 1 - 1 1 continued

( b) 0- CH20Ts

( c) ( d)

Pt
maj or minor

O O �
6� B
Br
H

o
o ro
0 0
+
----

o
: Br :
0

t
� o� nBr
oo H- � �H2
+

--=-
�
V Sr
+ H20
V V "-- :B�:
o
·

n
1 1-13
CH3 � CH
�+ +
CH3
: CH 3
t - OH I I I
H - C� H20 :Cl
H3C -
_

H 3 C - C - OH2 H3 C - C +-- H3C - C - Cl

I I I �
----'l.�
I
_
0 0 0 0

CH3 CH3 CH3 CH3

carbocation
intermediate

1 1 - 1 4 The two standard qualitati ve tests are:

1 ) chromic acid-distinguishes 3 ° alcohol from either 1 ° or 2°

R H2Cr04 R ( or H) H2Cr04 R(or H)

R + OH (orange)
• n o reaction
(stays orange)
R + OH (orange)
• R-C=O
I
+ erJ+
R H blue-green

233
1 1 - 1 4 continued

2) Lucas test-<listinguishes 1 ° from 2° from 3° alcohol by the rate of reaction

R R
ZnCl2
R
+ OH + HCl .. R
+ Cl + H20 insoluble-" c loudy in < I minute
II

R R
soluble
R
+ OH + CI
R
ZnCl2
2° R + HCl .. R + H2O insoluble-"cloudy" in 1 -5 minutes
H H
soluble
H H
1° R + OH + HCl
ZnCl2
.. R + CI + H2O insoluble-"cloudy" in > 6 mi nutes
( no observable reaction at room temp. )
H H
soluble
- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - . - - - - - - - - - - - - - - _ . .

(a) OH

A
Lucas: c loudy i n 1 -5 min . cloudy in < 1 min .
H2Cr04: i mmediate blue-green n o reaction-stays orange
(b) OH o

A �
Lucas: cloudy in 1 - 5 min . no reaction
H2Cr04: i mmediate blue-green no reaction-stays orange
(c) �
OH

Lucas: no reaction cloudy in 1 -5 min .

H2Cr04: D OES NOT DISTINGUISH-i mmediate blue-green for both
(d) � OH � OH ( * *Remember that allylic catioIlS are reson �nce­
stabilized and are about as stable as 1° cations.
Lucas: cloudy in < 1 min. * * no reaction Thus, they will react as fast as 3 u i n the Lucas test,
H2Cr04: D OES NOT D ISTINGUISH- even though they may be 1 °. Be careful to notice

+OH
i mmediate blue-green for both

�
subtle but important structural features !)
(e )

Lucas: no reaction cloudy in < 1 min.

H2Cr04: D OES NOT D ISTINGUISH-stays orange for both

methyl 3° � • • -

+jI' ,CH3 : Br : Br
shift
---1 -
.. C I
/ 1 .... C H2
�
�
1°
Even though 1 ° , the neopentyl carbon is hindered to backside attack, so SN2 cannot occur easi ly.
Instead, an SN 1 mechanism occurs, with rearrangement.
234
 a=
H This 3 ° c arbocation is planar at the
CH3 C+ so that the C l - can approach
C - CH3 from the top or bottom gi ving both
+ the cis and trans isomers.

- approach
: Cl : from
approach
: C l : from below
above

0=
H
CH3

;: Cl
CH 3

o� �
1 1-17

CH 3 H3 CH (from Hel)

'
0 G
H 3° .� - CH CI
+C '

"
I •

" ·H : Cl :

O O
•

ZnCl2 "
" H + C 2°
• •
,

• --- - •

hydride
shift

� �
1 1-18

3 OH + PBrJ -� 3 Br + P(OHh

1 1 - 19 OH Cl

( a)
6 -
CH3
SOCl2

6 retention

OH OT s Cl

6 6 o
Another possible answer
( b) TsC I NaCI
would be to use PCl 3 .
pyridine
-
SN2-inversion
CH3

23 5
(a) OH1 : �\S =O0 +0H1 -1S ,- O· D +O-S=O
I) �I .
·· · .
1 1 -20

Cl X I (C .. . +
Cl H

..
Cl • • • • -

0
D D

O I
O I
• •
I .
-
--
:Cl :

� - HCI
al �0 } r.
- � - S = R:
Cl

{ A· + D "

� tH
allylic! O
- . . I
:o - s = o :

I
·0 .. +

j
�
-

S02
e l
:Cl :

b
+

0 0+
D

tcar(hber)beTheonforwiekeyesthcposiapeis thttatihveethicharoeninpaitgee,rmedi
r andnot jabecome
te carbocata "firoene icars alblocatylic,iovern".y Thestablnucle andeophirelaltiicvelchly oloring-de [Link]
ust the one closest. Since two carbons have partial positive charge, two
products result.
(a) OH ZnCIHCl 2 no reaction unles heated, then �CI
1 1 -2 1

HEr �Br
� ...

PBr3 �Br
�

P12
SOCI2
�I
-

�
�CI

236
 IOH ZnCIHCl 2 IClr (C) �OH ZnClHCl 2 �C
1 1 -2 1 continued

(b) l
..

�
�

B
HE r
-
I HBr
�
Br

�
PBr3

II
Br
-

1SOCl2 2
PBr3 Br
..

I
P

C
-

12 �I
(poor reaction on 3°)

I
l P
- ..

SOCI2 �C
(poor reaction on 3°)

l
-

CI
(poor reaction on }O)

(d)
�OH ZHCl 2 nCI
• no reaction unless heated, then
S N I -rearrangement �
�Br
1 °, neopentyl
HB r Br

�
•
+

SN2-minor S N l -rearrangemen t
(hindered)

PBr3
� - Br

12 �I
P
-

SOCIl. �Cl

237
11-21 continued CI carbocat ionfromi ntermedi
SN 1 ; ate
(e) HCI
ZnClz 'eY
..
+

can be att a cked ei t h er

side by chloride
HEr � U
" ,Br SN2 with inversion of configuration
� ,Br SN2 with inversion of configuration
U "

� " I SN2 with in version of configuration

U
p
Iz "

SOClz �CI retention of confi guration

U

11-22 OH
�
(a) +

major rrunor
(b) � OH +

major (cis + trans) minor

OH
(c) � HzS04 , �
+

major (cis + trans) mmor

Jx OH
(d)
U major minor
(e) HZS04 , �

major minor trace

238
 �N
11-2 3 goo d leavi ng gro up
° .. �

0
� II� ° ° H
(y O: -CI+ II
lo �
H H
I+
�- f - �-.�
I

..
P, '

O
Cl'l Cl l C - -CI N

V
Cl I
""i
V o
• •

•
Cl .. Cl +

E2
!O
0
H
1+
°
II
N
cy clohex ene was fonn ed
o
• •

withouta car boca tion + : O-P-CI +

I
• •

in ter media te
Cl
this produc tca n reac t with two
morea lcohols ot b eco me leavi ng
groups in the elimi na tion
11 2- 4 E2

B oth mecha nis ms b egin with protona tion of the oxy gen.

�H H H H H
. H+
1 1 1 1 1+
H-C-C-O-H
•
.. H-C-C-O-H
• .
1 1 1 1 • •

H H H H

O ne mecha nis m inv olv es a nother molecule of etha nola ctingas a bas e, giv ing elimi na tion.
H H H
H H
1 1 1+ \

T�
T� i{q
/
H- .-A -H
/ \
•
C=C + H20
· CH2CH3
H H H

The other mecha nis m inv olv es a nother molec ule of etha nola ctingas a nuc leophi le, givi ngs ubs it tution.

H H H H
�
+ I)
• •

1 1 1+ ItqCH2CH3
O-CH2 CH3
H-C-C-O-H

H
1 �
U· H
··
.. CH3CH2-O-CH2CH3
HOCH2CH3
··
• •
.. CH3CH2 -

11-2 5 A n equi mola r mi xtur e of metha nola nd etha nol would produc ea ll ht ree possib le ethers . T he
diffi culty ins epa ra ting thes e compounds would pr eclude this method fromb ein ga prac tica l route toa ny
one of them. T his method si prac tica lo nly fors ymmetri c ethers , tha tis , wherebo tha kl y l groups ar e

..
identica l.
H+
CH3CH20H + HOCH3
tl.
H20 + CH3CH20CH3 + CH30CH3 + CH3CHzOCH2CH3

239
11-2 6
H H �
H20 CH3-O-CH3 .H CH3-O-CH3
,"",1+ CH39' �I+
3CH -O-H H+ CH3 -O-H CH-3-O-H
• •
�
• •

�
• •
• • • • • • •

• •

11-27 H
(a) X�H ' H+ X� H �

&H
HC H I+

a
• •

�
1 y---..
#"--. . H 20 : �
+
• •

VH VH - H 2 0 •

H
a :CHl H20:
0.
•

(b) OCH3 H-OH +

9.CH3

H H+ --­

H
H H
O
/·· -H : H d
-CH30H HH H+ H
: O� OCH3 (cjOCH3
+ • • : OH
aH
CH
aH
1+
• •

.. -

H H

l H20:
a -

er
CH2 '-"h!'
(C� CH2-�H 1°
+
HC
H,I/.H
�H
)b
O O - H2 0 H(5
� H+
H �
hydride
shift_
+ H

� H 20 )
----;.� ..

H � H
�+6
+1

(1: � L) 240
�
H
 (!j
11 2- 7 conti nued

(d) a�H,- Ol+-

H3C CH
�
CH3

)
H3c
CH3

;"C o
1
CH3

"
il
- ''""' '--C+
w H
_

___ Hz O

7 rmg
H20: .
contraction

H2C

11 -2 8

(a) n n n
++0
-H20

CH, w· H3C -T-rf- CH3 · H3C -t- 1 -CH3

�
H3C

HO :"OH
" HO OH HO
+
1
H
M ethy ls hift

H'C � � Q-� : Q-
HO
CH

H�: CH3
H

H
'"
R+ CH3
CH3 - QCHl
0 CH3

"- ""
H20:

� -0
A lky ls hif-
t ri ng contraction

-W---- Q ·
H'C

""
H3C H,C,+ H3C
C-CH3 4

+ C CH3 CH3 H20: CH3

1
o
HO '"
H-O: H-O+

241
(b) oH.f + oH
1 1-2 8 co ntinued

.. H H2 0H °�
30 and doubly

CX;; OH cYf G:O-H O<�C

�
H benzylic carbocation
1+
-

�
• •
\ +

/\ ���;
�
Ph Ph Ph Ph Ph Ph nS oi n

o H2··0 : +OH / �-H U

a a a Ph � Ph
.----- -
+

Ph
Ph Ph Ph

11 2- 9
OH0 H+ OH H [c
O-H /
C +O-H
ij�
H V- C f'-.-- /
rIng + • •

�
�
C==C / ,
�C-C-H •
+
1
expa ns oi •n
� CH
�

[�-CH3
H H /
H H " / 1 1
- 3
1

� HS�4-
H H
S imila r ot the pina co l rea rra ngement, this mecha nis m
invo lves a ca rbo ca tio n next ot a na lco ho l, with
rea rra ngement ot a p ro ot na ted ca rbo ny l . Reliefof
so meri ngs tra in in the cyclo propa ne si a na dded
a dva nta geof ht e rea rran gement. c:fCH]
°

H3C",C'H 0
11 -30

(Y"' CH2=0
II

(a ) 2 (b) +

° °

+H�
if �:
(c) (d)

° °
11 -3 1
a( ) Cl-C-CH2CH2CH3 + HOCH2CHzCH3 (b) CH3(CH2hOH Cl-CCH2CH3
II II

0
+

(c) H3C-<, }-OH + CI-CCH(CH3h [>-OH Cl-C-0

II
(d) +
II
� !J

242
 : ..
11-32 -
• II .
: 0: 0: · 0·
II I
: O-S- O CH3 0==S- O CH3 0==S- O CH3
.. II •• II •• I
...
..
__--i..
� ....
..f--
. -l..
�

:0 :
..
:0 : :0 :

11-33 Proton transfer ( acid- base) reactions are much faster than almost any other reaction. M et ho xide wi ll
act as ab ase and remove a proton fromt he oxyg en much fast er than methoxide will act as a nuci eophile and
displace water.
CH 3CH2 -O H + H+ ---

11-34

( a)

o-
o-
-- O CH2CH3
OH

(b) T here are two problems with this att emptedb imolecular dehydr at ion. F irst, all three possible ether
combinations of cyci ohexanol and ethanol would be produced. S econd, hot sulfuric acid aret he co nditions
for dehydrating secondary al cohols like cyci ohexanol, so elimination would comp ete with substituti on.

11-35
(a) W hat the student did:
-

X X
N a+ 0, H CH3 CH2- O "" H
+ TsO- CH2CH3
,
---� �
..

H3 C CH2CH3 H3 C C H2 CH3
sodium (S) -2- butoxide (S)-2- ethoxybutane
T he product also has the S config uration , not the R. W hy? T he sub stitution is indeed anSN2 rea ct ion,
b ut the substitution did not take place at the chiral center, sot he config uration of the starting material si
retained, not inverted.
( b) T here are two ways to make (R) 2- - ethoxybutane. S tart with (R)-2-b utanol, mak e ht e anion, and
substitute on ethyl tosylate simi lar to part ( a), or do anSN2 inversion at the chiral center of (S)-2- butanol .
SN2 works better at 1° carb ons s o the for mer method would b e preferred t o the latter.
( c) T his is nott he optimum methodb ecause it req uiresSN2 at a2° carbon, as discussedi n part b( ).

X X X
HO H • T S- O H H O CH2 CH3
TsCI
H3 C CH2 CH3 pyri dine H 3C CH2CH3 low temperature H3 C CH2CH3
(S)-2-b utanol ( high temp. (R)-2- ethox yb utan e
(S)-2- butyl tosylate favors el mi
i natio n)
no inversion yet INVERSI O N!

243
11-36

o-
-
� OH o-� + CH/�"'0-S03CH3 ---o-� OCH3 :0-S03CH3
�
-
0: N a +
.. � -
+
"

1 1-37

(a)
o
SOCI2
CH3CH2-C-OH • CH3CH2-C-CI H30+
II CH3 C
°
IIH2MgBr CH2 C H3
CH3CH2-COH-CH2CH3
1) 2
•
I

2) I

BH3 • � H2S04
CH2CH3 H202, HO- CH2CH3 1) TIIP

CH3CHCHCH2CH3 I
CH3CH C-CH2CH3 .
2)
......I--
I

OH
--- =

OH cr03
b( ) CH3CH2CH20H PCC CH3CH2-C-H CH3H30C+ H2MgBr.. � H2S04• �
----
°
II 1)

2) acetone
°

(alo- 0H H+ HC03H OH
11-38

any peroxy acid canb e usedt o fOlm the

---
f!. o H30+ U •
epox ide whi ch is c l eaved to the trans­

(blo- 0H cr03 O �
'OH H3 0+ Q--\OH HCI CI
" dia l in aqueous acid

H2PBr3SO: Mg,CH3CH2MgBr'"
U Q--\ ---

CH3CH20H CH3CH2Br
___
/'
�
ether

(c)

���
OH Br M g MgBr
�
---
U
O 3
Ho+ � �
H H+
T
� .. ---

OR:o-cr030H � �! ���A
ether from Dart (b )
H2S04o- Br Mg H,
o + ) �
-- .. Q-f; 0H
rn
--­ ----'�
�
-
ether

0 ) - �gBr O-(;;C
(d)
o- 0H � O- Br ��. 0 CH3Br �
HJ _

Q-f;
ether

CH30H �r3
from (c)
see the nex t pag efor an al tern ati ve endi ng

244
1 1- 38
rom the previous page � H30+ 0--* CH30H
(d) contcontinOHuedinuedf� ° SN I
/"'y
U U
/"'yBr � ether fmm _ ____ OH H2S04 �OCH3.
_

e) There.e Your
(exampl are severexamplal possie mayblebecomdibf ienratentionsandofsGrtil igbnare cord rreeactct. ions on aldehydes or ketones. This is
eel
one

CH3CH2CH20H �C O
o- 0H PB,) ____ /"'y
U
___ Br etMgher h H)O' �OH cr03
_ ____

H2 S
/'..

04 - �o
'>

�OH H+ Br2 �Br etMgher �MgBr

L\
___ �
hv
____ ___

� CH3SNCIH20H �';­ H 3 0+

OCH2CH3" H2S04 �OH

1 1- 39 Please refer to solution page of this Solutions Manual.
1-2 0, 12

(a) �OH SOCl2 - �CI (b) Q- 0H SOCl2 o- CI

1 1- 40 2°

PBr3 -�Br PBr3 - o-Br

..

1°

---�I
P12 ..
P12 0-1
(c) oH HCl - 01 Cd) (jOH SOCl2 &CI
3°

PBr3 &Rr
..

HBr - 0'
P12 &1
..

-0 III
-

245
(a) �
11-41

" (b) � (e) cJ (d) lfH

°

COOH
R
(f ro min version )

Cl CH20MgBr
(e)
Q (f)
Q (g) �Br (h)

bCH3CH3
(i) + OCH] � CH30H 0 H +

U) + (I) C;-H (k)

(m) �O� � major � (n)

mInor EtOH + +

(y 0H (y 0- Na+ CH)CII,Br (y 0CH2CH3

11-42

(a) V V � V
ether synthesis
•

W li li amso n

Br OH
d NaOH. d� V
( b)
�H Mg M gB r Sr

, (( d y
+
�

ether

t
t H30+
H2S04 ..
t:,.

0 MgBr H� � cr03 OH ° °

H , SO
O H ; �
(C ) II
B rM
-E..
ether p' 1)
2)
•
a ceton e

H OH
(d) VOH �o 2) CH3H30C+ H2MgBr .. U
� � 1)

246
 Major product for each reaction is shown.
(a)� (c)� (dl O (el O 0
11-43

(b)� (t)
cis + trans-rearranged cis + trans cis + trans

Note that (d), (e), and produce the alkene.

( f) ,
rearranged

same

(a) CH3CH2CH2COOCH3
11-44

(c) V COOCH2CH3 I h-

(d) CH3CH20-OCH2
P-OHCH3o
II

(y 0-�-CH3 +HN CI-

Cl-�-CH3 pyridine V 0 + a
11-45 o
II I

o
II
..

chlmetohrianesul
de fonyl
o

(a) HO", �H SOCl2 C�

11-46

/�
S-retention
_
.
..

(b)
HO', -.;H pyriTsCdiIne TSO� KEr
/"-..../ "-..../
Alt�rnatlvely,

R-inversion PBr3 c()uld be

_
.

S S
used,

(c) HO", �H pyrTsCidiIne TSO�

/"-.�
S
.../
_
.
..

S R-inversion
could use NaOH
if kept cold to
avoid elimination

247
 PBr
1 1- 47 inued ts alcohols to bromides without rearrangement because no carbocation intermediate is
cont3 conver
produced. OH Br
qU H q
(b)

� PBr3 �
U
OH �o
11-48
·

U
(a) pec.

OH PBf3• Bf
V V'
(b)

(e) 0 0H 0°- Na CH3.I

�

d) H OH SOCI2 l l
QCH3H �CH3H SN2 CH3H
TspyriCdiIn..e
(

OR ct- •
qCH3' H •

HCH3
OH retention

(e) ct H2S04 CK. 2) Me203 S HI04 q. oH

inversion

Y
1)
�
•
I .. ...

OH
( f)
a CH2 0 H H2 C r0 4
..
a COOH
(g -t-o- 0H HCr2S0O43 • +0 0
)

acetone
(h) -t-o- 0H H2SO4 -to
�I TsCI
�
..

OH P,I2 aI
(i)

CH3 cis OH pyridine � ..

CH3 cis OTs (j)

a ..
248
(a)
1 1 -49
yaH PBr3 )J""Br .. inversion

(b ) yaH SOCl2 yCi • retention

( c) yaH ZnClHCl2 QCI • SNi

and
yaH HBr QBr
cis trans

(d) • SNi

and
yaH TsCl, pyridine )J""Br
cis trans

(e ) 1)
• inversion, SN2

H
2) NaBr

O
(a) �OH
1 1- 50

no reaction �
cloudy in min.
Lucas:

(b) cloudy�
O H OH
1- 5

�
immediiante [Link] [Link] orange
1 -5 < 1

(c) Q-OH o
climomediudy iante blumie [Link] nono rreeactactiioonn-stays orange
Q- OH
1 -5

(d) 0 0
iclmmoudyediiante blumie [Link] nono rreeactactiioon-sn tays orange
1-5

(e )
Lucas: no reaction clooc
udy in min. < 1

249
 }
1
1 1-5 1
\-
H H H
\
H
...
/
:c-c
/

p =c\

(b){ / \\
(a) •

H : 0: H 0:
-

' �
. . . .

o:s
: 0: : 0:

... ..

cO
:::::-.... �
.. •

cO . .

t
: 0: : 0: : 0:

cO . .
-
... •

:00 .. •

00
t : 0:

c6 ' � : 0: : 0:

c6 .
.
.. •

� �
... •

cO � �

The las t three res onance for ms ar es imi lar to the firs t three; the change si that the electr ons ar e shown in
al tern ate pos itions in the benzeneri ng. To ber igorous ly cor rect, thes e threer es onance for ms sho uld be
included, but mos t chemis st would not wr ite thems ince they do notr eveal extr a char ge del ocalization;
unders tand that they woulds till bes ignificant, even if not wri tten with the others.

(c) : 0: : 0: : 0:
II I II

:0 :
: O-S- CH3 0 ==S- CH 3 0==S- CH3
• II
....

• II
...
f---l.� ....
..
f---l.�

. . • . I
: 0: : 0:

� � �
1 1-5 2
Mg
•
ether
OH Br

I
A C M gBr
+ ---

�
B0 E O M gBr

250
 �Br M g 0' HO

O-D
M gBr _----;.�

U
era
__ --i.�
ether
w X

[��+ f)]J,
v

1 1- 54 +
CH
00 �
00 _-_H_2-i�� �5
10
alkyl shift-. ri ng exp ansion fr om 1 °
.
n ng expansIO n car bocation to 2°, resonance­
recall that c arbocations stabilized c ar bocation
probably do not exist; this could
N OTE : be considered a transition state

T he mi gration directly above does N OT occur

as the cationpr oduced is notr esonance- stabilized.

An alternative mechanism could be proposed: protonate the ring oxygen, open the ring to a 2°
carbocation followed by a hydride shift to a resonance-stabilized cation, ring closure, and dehydration.

r?\ t OH j
hydride sh i ft to resonance
stabilized cation

( OH

:96 � II:� b
H: 9 -
-

2° car bocation

. .

o �90. H
H+ off o ne 0, H+
on the other °
H-O+
..

251
1 1 -5 5

( a) ("f OH
. � o -z nCI 2
r ,., - oc/ :ci: 0 ��
H Cl

}\
'----A Z
• -

V V H
. nCl2

I n ht i s presentati on of the mec hanis m, ht e + HO - Z- n Cl 2

rearrangementi s sh ownc onc urr ently with Cl- + H20 t- ZnCI2
' .
c leavage of ht e C- O bond wi th no 1 0 H -Cl
c arbocati oni nter medi ate.

r'0 r'0 � � �+ -
9+
( b)
V A.. H V ; C ' H
.

V � OH H i" QS 0 3H

Cf(+
_

• •
� '---'tf

�
H + H20
H • •

Onc e ht i sc arboc ati on si formed, �H2

removal of adjac ent protons C __ ----;.�
produces thec ompounds sh own.

.
H OH2
,-- .

.. \
c( ) A ll thr ee of ht e produc ts go thr ough a c omm on carboc ati oni ntermediate.
� H�
� � �c� \ . �
H ... ... H
H dS 03H
• •

'"
� � + H20: �
�
• - -

OH OH OH
..
�: O ... H
H dS 03H +
f

i OU+r:(ll-_H
) �J
� CO C

! Y ' 0)
� +
'
H ·· H

+ 00
H20: H20 :

00
ci? T h;s;s the pc oduc t fc om a p; nacol re arr ange ment.

252
(a) 00Hcr03 a CH3MgBr o-CH3
11-56
a
- 0-°1
CH3
H2Saceto0ne4 ..

t
..
MgBr a

CH30H CH3Br PBr 3 Mg, ether

+

---

CH3OH HOI p�HO �

I
OR: alternati"ve end" ("{- 109
V H2 S 04 d � 1
Griaftegrnarhydrd prolyosductis of SN1
...

OH
(b) 0oH PBr3 0 Br e� Mg o MgBr .. HO+3 if ..

PCC a
r 0 3
acetone�
..

CH3CH20H H � �
H 2 SO 4 a

o MgBr 0- MgBr' if
(c) OH H2CrS003 4
I
I
�

acetone
•

�
a
II
f r o m (b ) . �
V
I
CH3 I . oE °

orshouswne theparS t (meta) hod

1
10
N

�OH PBr3.. Br etMgher ! MgBr EtOH, H+

"

(d) 2 2 � - 2 �
a a

� H2S
cr03 0 4 �
H3
.. 0 H
+
.. . C ..
II

.. OEt ..

H ..[Link]

.. .. OH
a acet
•

o ne OH twoerRMgX
est , maki ncang a addaltcooholan H2Cr04 t
1t1) H3Br0M+g Mg PBr3 HO grwiothupstw;oseeequisovlualtieontn Rto CH.,OH 3°
-..../ --..../
problem
___ �

2)
10-18

OH
(e) MgBr VOH a

fO
l)�

rom H30+ (b)

2)
..

253
1 1 -56 conti nued
P B r3 Mg
(f) HO� B rM g�

�o
.. ..
ether
H

V OH P CC..

(g)
�
HO"
H
TsCI
..
pyri di ne TS O"
H
� K CN
..
H'
NC
�
Br

o -
B r2
hv 6 Mg
ether
-
PCC

OS 04
..
CH 3CH2B r
P B r3 t
CH 3CH20H

I I -57 F or a compli cated synthesi s il ke this, begi n by work ing backwar ds. Tr y to fi gur e out where the
carbon framework came from; in thi s problem we are restricted to alcohols containing five or fewer
carbons. The dashed boxes show the fragments that must be assembled. The most practical way of
formi ng car bon- carbon bondsi s by G ri gnard reacti ons. The epoxide must be f ormed from an alkene, and
the alkene must have come fromd ehydration of an alcohol produced in a Gri gnard reaction.

�o�<>,,l, ,H °
BfM g�.

)
Mg
ether

t H30:

\ cr 03 , H2S 04, aceto ne

0:
�
MgB r

!W
1. TsCl, p
maj or 2. KO H,1\

L� o-
i somer
avoid c arbocation conditions 2. Mg
to prevent rearrangement 0H
254
can(sao)[Link]- synthesese, thsufe fNer fcondi rom tthioensmiofsconcept iioonntcannothat incompat ibtlhe rtheagent scondi
or conditionstioofns
1 1 -5 8

e fTheirst exampl i o ni z at exi s t wi e

tert,iawoulryincartdhbegiocatsveecondithoen [Link](fTiprrhestosductitreopnywoulwiisththoutdatnottthheewaifsodiirtstarustomeundpmetbylohitngoxiselenough f or t h e
sodit-butnuymtlhbemetrosemicondhoxide dinreemetactto beihoanoln,added f , th e so lv ol y sis of
S 1 SN2

Ilfuric aciibdleswioluthtiothn,e tbhasie itcnhscondi e acidtiiconscondiof [Link] sItfebpasinicwhisodichumthemetalchoholoxidies werproteoadded d e. )

nated artoethe
isnucompat
the starting alcohol. No reacttiaontnaonneousthe alacicohold-baswoule neutdroccur [Link] would give methanol, sodium sulfate, and
(b)

war m SN1 solvolysis conditions

Several synthetic sequences are possible for the second synthesis.
�OH Na �O-Na+ CH31 �O/
OR �OH pyrTsCIidine �OTs NaOCH3 �O/
.. .-

.- .-

OR�OH PBr3 �Br NaOCH3 �O/ .- ..

�
Compound OH al-muscoholt;becan'a t be° oral2°lylaliccasoholthiswiwoulth andalgikvene;e a posnoirteivacte Lucas
11-59
X: 1 ion witthestLucas leads to a 10

Compound possi Y: -musbltebe a cyclic ether, not an alcohol and not an alkene; other isomers of cyclic ethers
6
J5 TS
"-J5 pyridinetworhiskresactfinie,on NOcannotREACTIdo anOSN!N2 reaction
Ts C I NaOCH3
___

.. ---l'-�

but wai t
Theare twWiolreiaasmsonsonwhyetherthsyntis tohsylesiasteiscannot . . . . an SN2unerdisplgoacement ofreacta leioavin. nFig rgrsto, upbacksiby andealatktaoxickdcannot e ion. Theroccure
bbriecausdgeheade thecarbackbonsicannot de of thunder e bridggehead an S N 2
o invercarsionbonbecausis bleockedof thebyconsthetotrahinertsbriofdtthhgehead. eisbricardbgedonSecond, ing sytsihnteeverm.t
rcannot
atbblackstoackedckidise H -§r OTs H� \:::J::t'
� OTS whimechanich issrmequired in the SN2

side view 255

side view
11-61 LetThe'saxibegialnalbycoholconsisidoxieridnigzedthetefnacttism. es as fast the equatorial alcohol. (In the olden days, this
observation was used as evidence suggesting the stereochemistry of a ring alcohol.) as

2) loss of H and chromate to form the C=O. Let's look at each mechanism.
Second, i t i s known t h at t h e oxi d at i o n occur s in two s t e ps : 1) f o r m at i o n of t h e chr o mat e est e r ; and
�
I

; ::7
'.( H ( � Ste p2 . 0� FA STER
0,\.Cr03H
A A
X
OH H ��� H

EQU TORI L

HO � A A

So whatoriadol posweitknow
equat i o n t h aboutin ththeeseaxiasyl spostemsiti?onWebecausknowe anythatgrsuobsuptiattuentthesaxiarealmorposeitisotanblhase the
an in

diequataxiaolriinaltechrractoimatonse. estSoewhatr woulifdStfoerpm fwerasteer tthheanratthee-laxiimiatlinchrg sotematp? eWeestewoulr; sindceexpectthis isthcontat thraery to
1
1 ,3-

whatis ratethliemdatitinag,shweow,woulStepd expect is not tlhikeelappry toobeachraofte-tlhime basitineg.(pHowrobablabouty watStere)pt2?o the equatthe eloimriainl ation If

hydrhydrstericoogengenconges((eaquatxitiaolnochrassoci
riaolmatchraeotematestd wieert)esthwoulsucher).daMorbelarfgaestovere egrrot,[Link] taxiThiheaapprsl iests consioeachr issmoroftenttheewimotbasthietvhatteoertdehleatotaxiivleeavearlatedues ofto
1

rmechani
eaction sfrmomis exper r a t e - l [Link], it is reasonable to conclude that the second step of the
i
11-(<0
a) 62 oH01 ° �' p oo (y' C I
-p/ Cl
,O Oo
O O <00-P=CI O QVO-P=O - H 1O
o Cl - 'Cl O
Cl 0 H Cl : C I:- H Cl
�
\ / " 00
0
__

00 � 00
(Cl I
0 0 �
+ I")
00
1 00
00
00
�
00
00 C l
Ell H H
o-p=o
Cl 1 (';( H �H :o-f=o
Cl
CI CI
__
+

LiZ \.finH
1

continued on next page �>

H H
256
�:N
I 1-62 (a) co ntinued CI O( H C I
G5H J� N)
H
+1
E2
O-P=O
H • •
'- • •

0
0 N 1

C
•

H + +
1
l

H3� POC�I3 H3CK:;> NOTH3C �H

H
(b)

h�h H H •
.....-

OH pyrid ine

Therem ust be a stereo chemi cal requirem ent in this elimi nation. I f theS ay z
t eff alkene is not p roduced
Z aitsev

because them ethy l gro up is trans ot thel eaving group, then the H and the leaving gro upm ust be trans and
the el m
i i nationm ust be anti- the characteri stic stereochem istryo f E2 elimi natio n. This evidence
differentiates between the two po ssibilities inp ar t (a).

-CH3 0H
..
uRCH3�H · U�HQCH3 1 Qtc5� }
11-63
(a)

°
+ °
1+
H

H2� �
f) O9.) :OH
+ -H
H+
--
O:OH --0
H2 0 r; O
H H
---
�
H
\
• •

+
H H
• • • • • •

HO
H
.. °
.. : 01 + '--- • •

'
'---"" H
• • • • • •

t
H..V O
·9t
H H2 � H 0 0 ---.-
..
°
H

H
OCH3
It is equally likely for pro ot nation to occur first on the ringo xy gen, fol ol wed by ri ng opening, ht en
replacemento f by water.

� ('l
D r. K anto rowski suggests this altern ative. H e and I will arm wrestle ot determi ne whi ch mec hanism

H .. �-� H H+kO � 0
is co rrec _

� ��+ O
H

�
2 ' H H0 °

257
 8SZ

H�
\ O�
I)
H

(Il
�qtJ
..

(q)
p;}nUllUO::l £9-11
 CHAPTER 12-INFRARED SPECTROSCOPY AND MASS SPECTROMETRY
See p. 270 for some useful web sites with infrared and mass spectra.
12- 1 The tabl e is com pleted by r eco gniz ing that: (V) (A) = 1 0,000

v (cm·l) 4000 3300 3003 2198 1700 1640 1600 400

A Jl
( m) 2 .50 3.03 3. 3 3 4.55 5.88 6.10 6.25 2 5 .0

12-2 I n general,o nly bo nds with di pol e mom ents will have an I R abso rptio n .
H-C C-H H-C C-C� �C-C C-C�

t t t t t
no y es yes no y es
/
y es
H
I
C H3
\
H
\
H 3C CH 3
I I

k ytes t t
H3C-C-H C=C C=C
I \ I \
H H H H
no y es y es
12- 3 (weak)
(a) al kene: C=C at1 640 cm-I , =C-H at 3080 cm-l
(b) al kane: no peaks indicating spo r sp2 car bo ns pr esent
( c) This IR sho wsmo re thano ne gro up. There is atermi nal alky ne sho wn by: C=C at 2 100 cmI - , =C-H
at 3300 cm! - . These signals i ndicate an aro matic hy dro carbo n as well: =C- H at 3050 cm!
- , C=C at16 00
cm-! .
12-4
(a) 2° ami ne, R- N H-R : o ne peak at 3300 cm-! indicates an N-H bo nd; this spectr um also sho ws a
C=C at1 640 cm-!
(b) carbo xy lic acid: the extremely bro ad abso rptio n in the 25 00-35 00 cml
- range, w ith a "sho ul der"
aro und 2 500-2 700 cm-! , and a C=O at1 7 10 cm! - , ar e com pel ling evidence for a carbo xy lic acid
(c) al co hol: stro ng, bro ad O- H at 3330 cm-!
12 -5
( a) co nj ugatedk eto ne: the small p eak at 3030 cm! - suggests =C-H, and the stro ng peak at 1 685 cm-! IS
co nsistent with a keto ne co nj ugated wi th the alkene. The C=C is indicated by a very sm all peak aro und
1 600 cm! - .
(b) ester: the C=O absor ptio n at 1 73 8 cm! - (higher than the keto ne's 1 7 1 0 cm-! ),i n co nj unctio n with the
stro ng C-O at 12 00 cm-! , poi nts ot an ester
(c) ami de: the two peaks at 3 160- 3360 cm-! ar el ikely ot be an NH2 gro up; the stro ngp eak at 1 640 cm-! is
ot o stro ng fo r an al kene, so itm ust be a differ ent yt peo f C=X, in this case a C=O , so ol w because it is part
o f an a mi de
12 -6
(a) The sm al l peak at1 642 cm-! indicates a C=C, co nsistent with the=C- H at 3080 cm-! . This appears
ot be a simpl e al kene.
(b) The stro ng absorp tio n at 1 69 1 cm-! i s unmi stakably a c=o. The smaller p eak at 1 62 6 cm-! indicates a
C=C, pro bably co nj ugated with the C= O . The two peaks at 2 7 12 cm-! and at 2 8 14 cm-! r epresent H-C= O
co nfirm ing that this is an al dehy de. 259
1 2- 6 conti nued
(c) The str ong peak at 1 650 cm-' is C=C, probably conjugated as it is unusually str ong. The 1 703 em'
peak appear s to be a conj ugated C=O, undeni ably a car boxy lic acid because of the str ong , br oad O-H
absor pti on from2 400-3 400 cm-' .
(d) The C=O absor ption at 1 742 cm' - coupled with C-O at 122 0 cm-' suggest an ester. The smallp eak at
1 604 cm-' , p eaks above3 000 cm-', and peaks in the 600- 800 cm-' regioni ndicate a benz ener ing.
12 -7
(a) TheM an dM +2 p eaks of equal inten sity i dentify the presen ce of bromi ne. The mass ofM ( 1 56 ) mi nus
the weight of the lighter isotope of br omi ne (79) gi ves the mass of the rest of the molecule: 1 56 79 = 77.
-

The C6HS (p hen yl) group weighs 77; this compound isb romob enz ene, C6HSBr .
(b) The mJz 12 7 peak shows that iodine is presen t. The mol ecular ion mi nus iodine gives ther emainde r of
ht e molec ul e: 15 6 -12 7 = 2 9 . The C2HS (ethyl) group weighs 2 9; this compound is iodoethane, C2HSI.
c( ) The M an d M +2 peaks have relative intensities of about3 : 1 , a sure sign of chlor ine. T he mass of M
mi nus the mass of the lighter i sotope of chl orin e gi ves the mass of ther emainder of the molecul e: 90 35 =
-

55. A fragmen t of mass 55 is not on e of the com mon al ky l groups (IS, 2 9, 43 , 57, etc.,i ncreasi ng in
ni cremen ts of 1 4 mass units (CH2)), so the presence of an atoml ike oxy gen must be consider ed. I n addit oi n
to the chlorin e atom, mass 5 5 coul d be C4H7 or C3H30 . P ossible molecular formulas ar e C4H7CI or
C3H3ClO.
(d) The odd-mass molec ul ar ion in dicates the p resenc e of an oddn umber of nitrogen atoms (alway s beg ni
by assumi ng onen itrogen). The rest of the mol ecule must be: 1 1 5 - 1 4 = 1 0 1; this is most likely C7H 17
The formula C7H17N is the correct formula of a molecul e withn o elements of un saturation. The seven
carbon s probably incl ude alky l gr oups like ethyl or p ropy l or isopr opy .l
12- 8 Recall that radical s are not detected ni mass spectr ometry; only positively - char ged ions ar e detected.

CH3
I +
CH3-CH-CH2 + CH2-CH3

mJz 57 mass 2 9
r adicals

[ J. j r
not detected

12 -9
CH 57 CH3 CH3 CH3
CH3- H � � CH2 - H CH3 -
I
CH3-CH
+
+
I
CH2-CH-CH3
43 85
mJz 43 mass 57
mJz 1 00
CH3 CH3
I + I
- CH3- <;H + CH2-CH-CH3
mass43 mJz 57
CH3 CH3
I I
- CH3-CH-CH2-CH + CH3
+
mJz 85 mass 15

260
 1 2- 1 0 The molecular weig ht of each isomer is 1 16g/ mole, so the molecular ion app ear s at rnJz 1 1 6. The left

iH2C:O� .. H2C";�t iH2C: �'" H2C,,+�}

h al f of each str ucture is the same; loss of a three car bon radicalg ives a stabiliz ed cation , each with rnJz 73:

• .. ·
.. .. .° °.
rnlz73 rnlz73
. .

W here the two stru ctures differ is ni the alpha-cleavage on ht e right side of the oxy gen . A lpha-cleavage on

[ �I o0-/-r CH2CH3
the left structure loses two carbon s, whereas alpha- cleavage on the right structure loses on yl on e carbon.

[ �o*- r
t
alpha- loss of I alpha-
t cleavag e loss of CH3
{�..O.. �H2 ... �O�.. CH2}
cleavage
J �..,�,
1 R +
... . �+��,}_ R
C9H200, rnJz 87
1 2- 1 1 2,6-D imethy lheptan -4-01 ,
rnJz 1 0 1
has molecular weight 144. The hig hest mass peak at 1 26
the molecular ion , but rather is the loss of water ( 1 8) from the molecular ion .
is not

[�r - H,o+ [�r

rnlz 1 44
Th e peak at rnJz III is loss of an other 1 5 (CH3) rnlz 1 26
from thef ragmen t of rnJz 1 26 . This is called ally lic
cleavage; i t gen erates a 2°, ally lic, reson an ce-stabiliz ed carbocation.

[ � r-i�+- �}+ CH)

rnJz 1 26 rnJz III
The peak at rnlz 87 results fromfrag men tation on on e side of the alcohol :

�:����!C H}
[�r {JJH )ji + �
rnlz 1 44
_

mlz 87
reson an ce-stabiliz ed
.
mass 57

1 2- 1 2 P lease ref er to solution 1 -20,p age 1 2 of thisS olution s M an ual .

1 2- 1 3 D ivide then umbers ni to 1 0,000 to arrive at the an swer.
(a) 1 603 cm-1 (b) 2959 cm1
- (c) 1 709 cm1
- (d) 1 739 cm-1 (e) 22 1 2 cm-1 (f) 3 300 cm-1
1 2- 1 4
H C==C CH2CH3
, /
CH2
O==C H CH3
/
(a)
H t 'H
/
1 660 cm-1
or
t '
1 7 10 cm1
-
stronger absorption-larger dipole
261
1 2- 14 continued
H CH2CH3 H OCH2CH3
I \ I

\H
\

\H
C=C C=C

t
or
t
(b)
I I
H H
1660 cm-1 1 640 cm1
-
stronger absorption-larger d ipole
CH2CH3 H CH2CH3
I \ I

\H \H
"N=C or C=C

t t
(c)
/ I
H H
1 660 cm1
- 1 660 cm-1
stronger absorption-
larg er dipole

H CH3 H CH2CH3
I \ /

\H
\

\H
C=C or C=C

t t
(d)
I I
H 3C H
1 660 cm1
- 1 660 cm1
-
(no dipole moment) stronger absorption - larg er dipole

1 2- 1 5

<'c=cl
H3C CH3 H CH3
\ I
3000-
C=C
\
(a) and
t -
\
t CH(CH3h
I -
3 100 cm1 I
H3C CH3 H
1 660 cm1 1 660 cm-1
weak or non- existent moder ate i ntensity

(b) O� � .
1 620 cm-l and
�
0
1 645 cm�1

conj ug ated not conj ug ated

(c) both car bony ls show str ong absor ptions ar ound 1 7 10 cm-1

+
o o
II II
CH3(CH2)3 - C H and CH3(CH2h - C - CH3

2700-2800 c m-1
two small peaks

(d) 0\ o y-
. H
3300 cm1 -
br oad, str ong
and
a�
1200
1 7 1O cm�1
c m-1 str ong
262
12 - 1 5c ontinu ed
C 3 300 cm1
-
CH3(CH2h - C:: C - H and CH3(CH2)6 -C:: N

t t
(e )

2 100-22 00c m-1 22 00-2 300c m1 -

weak to moder at e intens ti y moder ate tostr ong int ens ti y

( f) bot hc ar bonyls s hows rt ong abs or pt ions ar ou nd 1 7 1 0c m-1 � 3300c m-1

fH br oad,str ong
0
I
o ' 0
CH3 - CH - CH2 - C - H
1\ 1\

CH3CH2CH2 - C - OH and
2 � 00 cm1 - t
ver y br oad 2 700-2 800 cmi
-
t wos mall peaks

0/ 1 650 cm-1 1 7 1O cm-i � 0

�-�
II II

(g) CH3CH2CH2 -C - and CH3CH2 - C -CH2CH3

o/ 3300 cm1
-
two peaks
12 - 1 6 o� 1 700 cm1
- o� 1 7 1 5c m-I
(a) II (b) II
H C-OH CH3-CH-C-CH3

t
/ .......-
\ I
C=C 2 400-3400c m-1
\
/
CH3
H CH3
1 640c m-1

(c ) tV 3000- 3 1 00 cm-I (d) H

./ 3000-3 1 00 cmi
-

� 3400 cmi
-

a/"
H
N ..... V

V,
CH2 -C
\
N

I
"'=::

"-
t
22 o cm1
�,
,
CH2CH3
T ,
2 900 -3000 cmI
-
1 600 cmI
-

�71
1 600c m-I

12 - 1 7

[ 1
+
CH3 CH3

j
(a) •

� I
CH3 H CH2CH2CH3 • + CH - CH2CH2CH3
mlz 71
43

mlz 86 CH3
I
• CH3-CH mlz 43
+

263
 [ b�� � r �i b b }
1 2- 1 7c ontinued
H3 H3

(b) CH3 -CH= CH2CH3 ----l.. CH3_CH= <iH, - CH3_ H_ � CH,

9
rnJz 69

] 1 t
rnJz 98- allylic c leavage

(c )
[ Jb��j-
cH H CH,- H-CH1
CH3

b
t alpha-
c leavage
----I� ..
:OH
I
CH3
I
+ CH - CH2 - CH -CH3
+ OH
II
CH3
I
___ CH - CH2 - CH - CH3

45 rnJz 87
rnJz 1 02

··
alpha­
c leavage

+ i�
:OH

[ j
.
CH3

CH3 -CH==CH - H -CH3 � CH3- H

rnJz 45
rnJz 84

(d) [&f-. () �
H
H' C

o
rearr ange T he tropylium ion si a
.. ch ar ac teris tic fragment
fr om phen ylalkanes.

��
benzylc ation
rnJz 1 3 4 m1z 9 1

C
y
/CH3 H' r earr an ge H3C, + "CH3
HC+

�H3
.. C
rnJz 77 I
rnJz 43 CH3
rnJz 57

G CH
rnJz 85

•
rnJz 1 44

O- }
alpha-c leavage

1O- F c�
H3
• •

rnJz 1 29
� =c �
H3

264
 �CH2+ + H2C' CH3
[�r �CH2+ H2C......./
1 2- 1 8
•

(a ) -----
mJz 85 mass 29

rnJz114 +

�CH2+ Hi �
mJz 7 1 mass 43

+
:
H +

(5 cJ +
.
mJz 5 7 mass 57

(b) o CH3 -----

mass1 5
mJz 98 rnIz 83

c( ) CH3
CH3-C==CH-CH2+ I

+ oCH3
--

+j i :OH +OH }
m1z 69

mass 15
OH
[ �Hj CH, -CH,CH,CH, �H' gH, +. CH,CH,CH,CH,
.
(d) •
. . .

- -

! H20
31 rnIz 88 mJz 31 mass 57

CH2=CH -CH2-CH2 + CH3

-

[ CH,=CH- c::t C� CH,

mJz 70 55 mJz 5 5
+
0

mass 1 5

�
{ CH2=CH- �H2 ---- � H2-CH = CH2 } CH2CH3 + 0

mJz 4 1 mass 29

-----
Oc+
1.0 rnJz 77 + 0 NHCH2CH3
mass 44
mJz 1 2 1
c ontinued o n nex t page
265
12- 1 8 (e) c ontinu ed

[a�::rr mlz 121

12- 1 9
(a) Thec har act er si t ci fr equ enc ies of t he OH abs or pt ion andt he C=C abs or ption will indic ate the pr es enc e
or abs enc e of t he gr ou ps. A s pectru m with an abs or pt ion ar ou nd 3300c m-i will haves omec yc lohexanpl i n
it; i ft hat s ames pec tru m als o has a peak at 1 645c m-i ,t hent hes ample will als oc ont ains omec yc ol he xene.
Pur es amples will have peaks r epr es ent at ive of only one of thec ompou nds and not the other . N ote that
quantitation of thet woc ompou nds wou ld be ver y diff ci u lt by I R bec aus e thes rt ength of abs orpt ions ar e

0\
ver y diff er ent . Us ually, ot her met hods ar eus ed in pr ef er enc et o I Rf or qu antitat ive measur ements .

O
o y- 3 300c m- i
'H hr oad,str ong
-- 1 645c m-1
moder ate
12 00c m-1
(b) M ass s pec trometr yc an be mis leading wit h alc ohols . Usu ally, alc ohols dehydr ate in the inlet s ystem of
a mass s pec rt omet er , andt hec har ac ter si t ci peaks obs er ved in the mass s pec tru m ar e thos e of t he alken e,
not of t he par ent alc ohol. F or t his par ticu lar analys si , mass s pectr ometr y wou ld beu nr eliable and per haps
mis leading.

12-2 0
(a) The "stu dent pr ep"c ompou nd mus t be I- br omobu tane. The mos t obvious featur e of the mass spec rt um
si t he pair of peaks atM andM +2 of appr oximat ely equ al heights ,c har act er si tic of a br omine atom. L oss of
br omi ne (79)fr om the molecu lar ion at 1 36 gi ves a mass of 57, C4H9, a butyl gr oup. W hic h of t hef our
possi ble bu tyl gr ou ps? The peaks at 1 07 (loss of 29, C2Hs) and 93 (loss of 43 , C3H7) ar ec ons si tent w ti h a
linear c hai n, not a br anc hedc hain.
(b) The bas e peak at 57 si s os rt ong bec aus e thec ar bon-halogen bond si the weakes t in the molecu le.
Typic ally, loss of halogen si the dominant fr agmentat ion in alkyl halides .

[4
�{�
:r r
�
/' Br
+

rnJz 1 07
+
mass 29
rnJz 1 36 H2C. + H2C-..../
+ Br
rnJz 93 mass 43
/'-../
+
+ Br
•

rnJz 57 mass 79

266
12 -2 1
(a) D euter ui mh as twic e ht e mas s ofh ydr ogen,bu ts imilar s pr ingc ons tant,k . Compar e th e fr equenc y of
C-D vibr ation to C-H vibr ationb ys ettingu p ar atio,ch an ging only ht e mass (su bs titu te 2 m for m).

= = �lt2 = 0.707

0.7 07 vH = 0.7 07 (3000 em-I) 2100 cm-1

Vo = '"

( r-
(b) The func tional gr oup mos t lik ely to bec onfus ed with a C- D str etc h si the alk yne c( ar bon- c ar bon tn ple
bond), whic h appears in ht es amer egion and si of ten ver y weak.
�
+
12-22
� a 1°c ar boc at ion- not favor able
m/z 57
m/z 1 14

[+r m/z 1 14
�

1+m/z 57
a 2°c ar boc at ion-r eas onable

r*r m/z 114

�

�.
m/z 57
a 3°c ar boc ation-t he best

The most likely rf agment ation of 2 ,2, 3,3- tetr amet hylbut ane will give a 3°c ar boc at ion,th e mos tst able of the
c ommon alkylc at ions. The molecu l ar ion s hould bes mall or non- exis tent whi le m/z 57 si lik elyt o be the
bas e peak , wher eas t he molecu lar ion peaks will be mor e pr omi nent for n -oc tane and for 3 ,4- di methylh exane .
12 -2 3
(a) Th e infor mat iont hat this mys teryc ompound si ah ydr oc ar bon mak es inter pr et ni g the mass s pectru m much
eas ier . ( It si r elat ivelys i mple to tel l i f ac ompound has c hlori ne, br omine, or nitr ogen by a mass s pec rt u m, but
oxygen si di ffic ult to determ ine by mass s pec rt ometr y alone. ) A h ydr oc ar bon with molec ular ion of 1 1 0c an
have only 8c ar bons ( 8 x 12 = 96) and 1 4 hydr ogens . The for mula CgHl4 has t wo elements of uns atur at ion.

(b) The IR will be us eful in detenni ning whatt he elements ofu ns atur ation ar e. Cyc loalk an es ar e gener ally
not dist inguish able inth e IR. An alk en esh ouldh ave an abs or ption ar ound 1 600- 1 650 em-I; none si pr es ent in
ht si I R. A n alkynes houldh ave as mall,shar p peak ar ound 22 00 em-I-PRESENT A T 2 12 0 em-I! A s l o, a
sh ar p peak ar ound 3 300c m-1 indic ates ah ydr ogen on an alk yn e,s o ht e alk yne si at on e end oft he molec ul e.
B ot h elements of uns at ur at ion ar e acc ounted for byt he alk yne.

267
 12-2 3
(c ) T he onl y question is how ar e theo ther carb ons arr anged. T hem ass spec rt um sho ws a pr ogr ess oi n of
peak s fr om themo lec ular ion at 1 10 to 95 (lo ss of CH3), to 8 1 l(os so f C2Hs), ot 67 (loss o f C3H7). The
mass spec rt um suggestsi ti s a il near chain. T he extr a ev idence that hydro genation of the mystery com po und
giv es n-o ctanev eri fies that the chain is linear . T he origi nal c ompoundm ustb eo ct- 1- yne.
( d) T he base peak is so str ongb ecause the ion pr oduc ed iss tabil z i edb yr esonanc e.

�
+

m/z 95

� m/z 8 1
m/z l lO +

�_
+

m/z 67
+

m/z 39 '-.....
c:::=:::>

12 -2 4
(a) and (b) T hem as s spec is consistent with the for mul a of the alkyne, CSHJ4' mass 1 1 0. T he IR isno t
c onsistent with the al kyne, howev er . O ften, symmetric all y substituted alk ynes hav e a mi nisc ule C=C peak,
so the fac t that the I R does not sho w this peak does not prov e that the alkyne si ab sent. T he m i pOlt ant
I
ev idenc e in the I R si the signific ant peak at 1 62 0c m- ; this abs orp tion isc har ac teri stic of a conjugat ed
diene. I nstead of the al kyneb eing form ed, the reac tion must hav eb een a doubl e el m i ination to the dic nc .

�*+ Br

12 -2 5
o-
II \\
H
I
O , ...,... 1 72 0 cm-1
11--
(a) b( ) '/ '\

- k t
C-C-H

"

0
27 1 0,
1 600c mI
- 2 82 0c m-1
�

Q g
17 60cm-I
c( ) II � O- -CH3
- \
T
I

12 00 cm-J
,
1 5 80cm-J

268
 o
12 2- 6
(a)
Mg /""-.... /""-....
A H30+.. �OH
� Br ether
.. ,,/ ........",
- M gB r

2m
- eth yl hexan-2-01
C7HI60 m ol. wt. 116

b( ) T he mol ec ul ar i oni s not vi sib le in the spec rt um. Alc ohols typic ally dehydr atei n the hot inlet system of
the mass spec rt om eter , especi all y true for 30 alc ohol s that ar e the easi est type to dehydr ate. T he two
fragmentati ons that produc e a resonanc e-stabiliz edc arb oc ation give the m ajor peak s in the spec rt um at mlz

[ � OH l t {
59 and 1 0 1 .

___
;<�-H ..
_
_� /<O+-H }
� H3C CH3 rnIz 59
H3C CH3
mass 1 1 6

O-H
. }
c(+CH3
..

�
rnIz 1 01

12 -2 7 T he unk nownc om pound has peak s in the mass spec at rnIz 1 98, 1 55 , 127 ,7 1 , and 43. I ti s helpf ul
that them asses of two of the fr agm ents, 1 5 5 and 43, sum to 198, as do the other two fragm ent masses,
127 and 7 1 . W ec an say wi thc ertai nty that the mol ec ul ari oni s at rnIz 1 98, and that the unk nowni s a
rel ativel y sim pl em ol ec ul e wit h twom ai n fragm entati ons.
T hi si s a fairl y hi ghm ass for a sim pl ec ompound; som e heavy group mustb e pr esent. W hat is N O T
CI
pr esenti s N b ecause of the even mol ec ul ar ionm ass, nor nor B rb ec ause of thel ack ofi sotope peak s,
nor a phenyl groupb ec ause of no peak at77 . T he progression of alk yl gr oupm asses: 1 5 ,2 9,43 , 57 ,71 ,
85, 99- incl udes two of the peak s, soi t appear s that the unk nownc ontai ns a pr opyl gr oup and a pentyl
group (the pr opyl c oul db e part of the pentyl gr oup). T he 12 7 fragm enti sk ey; the fragm ent C9HI9
has
thi s m ass,b ut we would expec tm uc hm or e fr agm entati on fr om a ninec arb on pi ec e. T here mustb e som e
o ther expl anati on for thi s 127 pe ak.
A nd ther e is! T her ei s one pi ec e-m ore speci ifc al ly, one atom- that hasm ass 127: i odine! I n all
prob abil ity, the iodi ne atom i s attac hed to a fr agment of mass7 1 whic hi s CsHl1
' a pentyl group. W e
c annot tell withc ertai nty whati som er i t is, so unl ess ther ei s som e other evidenc e,l et' s pr opose a str ai ght
c hai ni somer, 1 i- odopentane.
155 127
T he 155 rf agment probabl y
I has thisb ir dged struc ture
b ec ause iodi nei s sobi g:

269
12-2 8
CH3 CH3 CH3
I I I
(a) HC-C-C-CH3
3 HC-C-C-CH3
3
/ 0 CH3
I I II I
OH OH s rt ong peak around
T
broad,s rt ong OH peak 17 1 5 cm 1
-

around 3300 cm-I

o OH br oad, strong 011 pe ak

str ong peak ar ound ar ound 3 300 em-'
(b) 1 690 cm-I

two peak s at
27 00 and 2 800 cm-I

o o

(c) H
0/
t
ver y br oad br oad COOH band
2 500- 3 500 cm-1 mi ss ing
with a "shoulder "
ar ound 27 00 cm-I still has a str ong
O H at 3300 cm-I
butd iffer ent fr om
COOH

I f you wish to find IR spectr a and mass spectr a of comm on compounds, ther e ar e two w eb sites
that ar e ver y helpfuL E nter ing a name or molecular form ula will giv e isom er s fr om which t o
choose the desir eds rt uctur e and the IR or MS if av ai lable in their d atabase.
http:// webbook .nisLg ov/
"NIS T " is the U.S . N ational I ns titute ofS tandards and T echnology.
[Link]
T his si fr om the N ational I nstitute of A dvanced I ndustr ialS cience and T echnology of J apan.

270
 CHAPTER 13-NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY

A b enzener ing canb e wri tten with thr ee altern ating doub leb ond s or with a cir cle in ther ing. A l l of the
carb ons and hydr ogens in an un sub stitutedb enzener ing ar e equivalent,r egar dless of which sy mb olis m is
used.
equi val entto
o
The Japanese web site listed at the bottom of p. 270 also gives proton and carbon NMR spectra.
Reminder: The word "spectrum" is singular; the word "spectra" is plural.

1 3- 1
650 Hz
( a) = 2. 17 x 1 0-6 = 2. 17 ppm dow nfield rf om TMS
300 x 1 06 Hz
(b) D iffer ence in magnetic field = 7 0,459 gauss x (2 . 17 x 1 0-6) = 0. 1 5 3 gauss
( c) T he chemical shift does not change w ith field str ength: «52 . 17 atb oth 60 MHz and 300 MHz.
( d) 2( . 17 ppm) x ( 60 MHz) = 2( . 17 x lO-6 ) x ( 60 x 1 06 Hz) = 130Hz

*
1 3-2 N umb er s are chemi cal shi ft values, in ppm, derived fr om Table 1 3 -3 and the A ppendix in the text.
Your predictions should be in the given range, or within 0.5 ppm o/the given value.
( a) b ( b) a
H
.... CH3 �
CH3 b b b
......
' CH3 � CH3
c
I
CH3 \ / a = «5 5-6 a = «57 2.
b C= C b b «5 0.9 b «52 .3
/ \
= =
h-

......
CH3 CH3 CH3
H C.... b b
a CH3 \ H
b C� a
b

� �

*
( c) ( d)
� H3
c

� �
b a = «52- 5
a = /)7 2. b =
/)2 . 5
b /) 3 .6 CH3-C-C::C-H
c p OC J c /) 1-2
em
=
c =

a
H H
a a
c c

�
( e) H H ( f) b
� �H3
--u-
b a =
«5 3- 4
c b a b «5 1- 2
CH3 -C-CH2 Br =
H CH2-C-O-H I a
Br
H H
c c
a = /) 10- 12
b "" «5 3 ( between tw o deshielding gr oups)
c =
/)7 2
. ( Th eh ydr ogens l ab el ed "c" ar e not equival ent.
Th ey appear atr oughly the sam e chemi cal shift
b ecause the sub stituent is neither stro ngly electr on-
d onating nor withdr awing.) 271
1 3 -3

(a)
c
CH3CH2CH2Cl
b

three types of H
a
(b )
b
CH3CHCH3
I
Cl
a b
(c) a
CH3-C-CH2CH3
�H3 b
a
c (d)
b
H * H

�
a
C 3 �

*:
I h
two types of H CH3 H Br
a a c
d
H
1 3 -4 3 three types of H
(a) � t fiv e types of H

H h H
c c (b) T he three types of aromatic hydrogens appear in a relativ elys mall
s pace around () 7.2 . The signal si complexb ecause all the peaks from
H
d
the three types of hydrogens ov erlap.
four types of H

N ote: N MR spectra drawn in thisS olutions M anual w ill repres ent peaks as single lines. T hese lines
may not look like "real" peaks,b ut this av oids the problem ofv ar iation am ong spectrometers and
printers. I ndiv idual spectra may look different from the ones presented here,b ut all of the i mpor tant
information willb e contained in thes e representational spectra.

1 3 -5
c �
CH3 a a 9H

/
c I II a II b
H3C - C - O - C - CH 2 - C - CH3
I
CH3 12
c 3H

�
2H � TMS

-.J
I
I I I I I I I I I I I
10 9 8 7 6 5 4 3 2 o
8 (ppm)
1 3 - 6 The three spectra are identified with their str uctures. D ata are giv en as chem ical shiftv alues, with the
integration ratios of each peak giv en in parentheses.
S pectrum (a) S pectrum (b )
b

*
a a
OH a = cS 2. 4 ( 1 ) ( 1 H) H H
a
� �
C I
CH3 - C - C::C - H b = cS 2. 6 ( 1 ) ( 1 H) a = cS 6.8 (2 ) (4H)
I c = I) 1 . 5 (6) (6H) c ,o OC J b = cS 3.7 (3 ) (6H)
CH3
c
H H
a a
S pectru m (c)
b
b CH3 a = I) 3 . 9
( 1 ) (2 H ) (Thisi s the compound in Problem 1 3-2 ( f). You
a
CH3-� - CH2Br
I
b = cS 1. (3) (6H) may wish to check your answer to that questio n
9
agains t the spectrum. )
Br 272
1 3- 7 Chem ical shift values ar e appro ximate and mayv ar y sli ghtly fro m yo ur s . T he splitti ng and
integr atio n values sho uldm atch exactly, ho w ever.
(a) b b Q
H3C , /CH3 12 H
a HC - O - CH a
/ ,
H3C CH3
b b
.1!
2H
(To show the pattern
TMS
of peaks, this multiplet

" III, I
is larger th an it would
appear on a real spectrum . )

I I I I I I I T T I T
10 9 8 7 6 5 4 3 2 1 o
(5 (ppm)

Q
(b)
a c 0 II b 3H
ClCH2CH2 - C - O CH3

.1! �
2H 2H

TMS

III LI I
I I I I I I I I I I I
10 9 8 7 6 5 4 3 2 1 o
(5 (ppm)

(c)

Note : the three types of

5H
.1!

a
H
*� a
H

� /;
-
a
H

C
/
c
CH]
b Q
�
6H

aromatic protons above IH

are accidentally
CH3
H H c
equivalent because the a a

,
isopropyl group has little
(To show the pattern
effect on their chemical o f peaks, this m ultiplet TMS

III, 1
shifts. is larger than it would
appear on a real spectrum . )
"

I I I I I I I 1 I I I
10 9 8 7 6 5 4 3 2 o
(5 (ppm)

273
 *
1 3-7 co ntinued
aH H a
(d)
c b b e �
l! CH3CH20 � Ii OCH2CH3 6H
4H
All four aromatic aH H a
protons are
equivalent .
12
4H TMS

I II I I I
1I
I T I I I I I
10 9 8 7 6 5 4 3 2 o
8 ( ppm)

( e) 12
4H �
c a 0 b b 0 a c
II II 6H
CH3CH20 - C - CH2CH2 - C - OCH2CH3
l!
N o splitting is ob serv ed when chemically 4H
equivalent hydr ogens ar e adjacent to each
other , as with hydr ogens "b " ab ov e.
TMS

I II I I I
I
T
I I I I T T I
10 9 8 7 6 5 4 3 2 o

):
8 ( ppm)
1 3-8 0
( aJ b( )
5 2.4 H2 ? H 8 5.8
o
8 1 . 8 H2C
H 8 6 .7
H3C CH3 J 8 1 . 5 H2C
I
\

'(
8 1 .2 8 1 .65 H2C H 8 6. 2
,
T he signals at 1 . 8 and 2.4 ar e C CH3
H2
rt ipletsb ecause each seto f 8 1 .7
pro tons has two neighbo ring 8 2. 1 allylic
hydro gens. T he N + 1 r ule allylic
corr ectly pr edicts each ot b e a T he thr ee CH2 gro ups canb e distinguishedb y chemical shift
triplet. andb y splitting. T he a l l y l i c CH2 w il l be thefarthest downfield
o f the thr ee, at 2. 1 . T he signal at 1 . 5 is a rt iplet, so that mustb e
the one witho nly two neighbor ing pr oto ns. T he CH2 sho w ing
the multiplet at 1 .65 mustb e theo neb etween theo ther two
CH2 gr oups.

274
1 3 -9
(a) aH Ha Q

�*� }
9H
i!
5H
T he thr ee typeso f
aro matic pro ot ns 12 � H C=C
IH IH / \
ar e accidentally a
equivalent. J ", 15 Hz 1 = 1 5 Hz H C(CH3h
,......I-.. ,......I-.. b d TMS

I
10 9 8 7 6 5 4 3 2 0
8 (ppm)

(b) 12
b c 3H �

CH30 CH3
3H
\ /
C=C
/ \
Cl H i!
a IH
TMS

I II I
I I I I T I I I I I I
10 9 8 7 6 5 4 3 2 o
8 (ppm)

c( ) �
9H
e o
c d
(CH3hC - OCH2CH 3
II

\ F
C =C
/ \ Q
H H 3H
a b �
2H

IH IH TMS

10 9 8 7 6 5 4 3 2 1 o
8 (ppm )

275
 (x x>=
1 3-9 continued
Q
d
3H
c c
H H
'-'::
I b I .& b
11 The electron-withdrawing H H
The chemical shift
Q � c arbonyl group deshields the
�C
of -COOH is
2H 2H protons adjacent to it, moving O "' OH
variable. It is TMS
usually a broad them downfieid from their
a

1
peak. usual position at 8 7 .2.

I I I I I
o
I I I I I I

10 9 8 7 6 5 4 3 2
8 (ppm)

The formula C3H2NCI has three elements of unsaturation. The IR peak at 1 650 cm- I indicates an
1 3- 1 0
alkene, while the absorption at 2200 cm- I must be from a ni tri le (not enough carbons left for an alkyne).
These two groups account for the three elements of unsaturation. So far, we have:
\ I
C N

C=C + 2H + Cl
/ \
\ 1 -
H C=N
The NMR gi ves the coupling constant for the two protons as 1 4 Hz.
I \
C=C
This large J value shows the two protons as trans (cis, J = 10 Hz;
geminal , J = 2 Hz). The structure must be the one in the box . Cl H

1 3- 1 1
(a) C3H7CI-no elements of unsaturation; 3 types of protons in the ratio of 2 : 2 : 3 .
a b c a = <5 3 . 8 (triplet, 2H) ; b =
<5 2. 1 (multiplet, 2H);
Cl - CH2CH2CH3
c = <5 1 .3 (triplet, 3H)

(b) C9H 1 002-5 elements of unsaturation; four The other NMR signals are two 3H singlets,
protons in the aromatic region of the NMR two CH3 groups . One at <5 3.9 must be a CH30
i ndicate a disubstituted benzene ; the pair of c=:====�> group. The other at <5 2.4 is most likely a CH3
doublets with J = 8 Hz indicate the group on the benzene ring.

(para) < 1>

substituents are on opposite sides of the ring

+ 3C + 6H + 20 +
CH3
+ OCH3 + C + 0 +
-Q-
1 element of unsaturation
� 1 e lement of un saturation

One way to assemble these pieces consistent with the NMR i s : /

*g
b a
(Another plausible structure is to have the
H H

�
0 a = <5 7.9 (doublet, 2H) methoxy group directly on the ring and to put

�
b = <5 7.2 (doublet, 2H) the carbonyl between the ring and the methyl.
C 3 - OC 3 c = <5 3 .9 (singlet, 3H) Thi s does not fi t the chemical shi ft " a l ues
d = <5 2.4 (singlet, 3H) quite as well as the above structure, a s the
H H methyl would appear around <5 2. 1 or 2 . 2
b a 276 instead o f 2.4.)
 � 5. 1

. . '
.. .. ..
1 ... .. ..

1
I
, .
, . , .

� I � J bc
,

J bc =
. , .

l .4 Hz = 1 .4 Hz

13-13
JJ----_
--JU
(a)
= 8 1 2. 1 (broad singlet, I H)
o
c II a a
H C - OH = 8 5 . 8 (doublet, I H)

c=c
b
\ / c = 8 7 . 1 (multiplet, I H)
= 8 2 .2 (quartet, 2H)
/
d
= 8 1 . 5 (sextet, 2H)
f e d \
CH3CH2CH2 H e
b f = 8 0.9 (triplet, 3H)

(b) The vinyl proton at 8 7 . 1 is He ; it is coupled with Hb and Hd, with two different coupling constants,
J beand Jed ' respectively. The value of Jbe can be measured most precisely from the signal for Hb a t 8 5 . 8 ;
the two peaks are separated by about 1 5 Hz, corresponding to 0.05 ppm in a 300 MHz spectrum. The
value of Jed appears to be about the standard value 8 Hz, judging from the signal at 8 7 . 1 . The splitting
tree would thus appear:
8 7. 1

1
J be = I 5 Hz

. ... ,
" .. . .. ...

,
,

J ed = 8 Hz J ed = 8 Hz II Jed = 8 Hz Jed = 8 Hz 'I

,
' ,, '

� �
over� n NMR

� U L

277
 *
13-14 o
c II a a =
8 9.7 (doublet, I H)
H

-
(a) C- H b =
8 6.7 (doublet of doublets, I H)
d \ I 8 7.5 (doublet, I H)
H C C
c
8 7.4 (multiple peaks, 5H)
=

, d =

d H
H � Ii � b The doublet for He at 8 7.4 OVERLA PS the 5 H peaks of Hd.

H H
d d
(b) J ab can be determined most accurately from Ha at 8 9.7: Jab "" 8 Hz, about the same as "normal " alkyl
coupling.
be measured from Hb at 8 6.7, as the distance between either the first and third peaks or the
J be can
second and fourth peaks (see diagram below): J bc "" 18 Hz, about double the "normal" alkyl coupling.

0 6.7

... ..
.. . . . . . . . . . . 1 . . . . .. . . . . . . .
(c )

1 J bc 1 8 Hz
1
=

r;.:� �'� '1 f"��:� �'� '1

J � � L
1 3- 1 5 0
II
(a) a =
0 1 .7 (b) a doublet
mu l t ip l e t (two overlapping quartets-see part (c»
=
b d
H
b 0 6.8
C - CH3
"" b =

\ I c =
0 5 -6 c =
doublet
c=c d 0 2. 1 d singlet
I ,
= =

a
H3C H
c
(c) using J bc =
1 5 Hz and J ab = 7 Hz: o 6.8

· · · . . .; : J .1:· ;: · · .
r 1
-;.
. .
. · ·

.
. . . . 'I;� ·;: :::·1- · · · · · · · · · · · '1';:'-;'
=

.
.
�.
1-· · · · · ·
�.. '�� : :

(j:�'= 7 Hz ( �• • • • • , ••••
• •,
•
• •

� � L J � 278
L
13-16

replace He
�

cis diastereomer

replace Hd
�

trans diastereomer

13-17
(a) replace Ha
..
non-superimposable mirror i mages =
nantiomers; therefore, Ha and Hb arc
replace Hb enantiotopic and are not distingui shable by
NMR
�

(b)

replace He on the left

�

enantiomers
replace He on the right
..

(c) The Hd protons are also enantiotopic.

1 3- 1 8
(a)

a
Xy
Br
"
�
H
b

e
CH3
(b)
e
H H
e

CH3
-::.,
H H
c d
This compound has fi ve types of protons. H
� and Hd are diastereotopi c . a = � 1 . 5; b
b = � 3.6; c,d = � 1 . 7; e 8 1.0 This compound has six types of protons He and
Bct are diastereotopi c , as are � and Hr. a =
=

8 2-5 ; b = 8 3 . 9 ; c , d = 8 1 .6 ; e,f = 8 1 .3

279