ALCOHOLS & PHENOLS SOLUTIONS

Dont forget to study the generic functional groups and the common alkyl groups (isobutyl, etc).
1. IUPAC = I and common = c.
a) d)

4-isopropyl-2-methylphenol
6-methyl-4-propyl-3-heptanol
(this is the longest chain containing
the -C and with the most branch
points)
e)

b)
phenylmethanol (I)
4-cyclopentyl-2,2-butanediol benzyl alcohol (c)

f)

3-penten-2-ol

c)

(Z)-4-methyl-2-cyclohexen-1-ol g)
or 2-cyclopenten-1-ol
cis-4-methyl-2-cyclohexen-1-ol

2. Draw structures of the following compounds:

a) glycerol OH OH OH d) hydroquinone OH

CH2 CH CH2

(also glycerin or 1,2,3-propanetriol) OH

e) -naphthol
b) m-cresol
OH OH

CH3

c) resorcinol f) allyl alcohol

OH OH

CH2CH CH2
OH

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ALCOHOLS & PHENOLS SOLUTIONS

Give IUPAC names and, where possible, common names for the following compounds.

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ALCOHOLS & PHENOLS SOLUTIONS

g) CH3 j) OH

CH2
3 4
CH CH2 CH CH3 (c) sec-butyl alcohol
1 2 (I) 2-butanol
CH3
HO
3-(1-ethyl-3-methylbutyl)phenol CH3

H3C C OH
k)

CH3
h)
OH OH Br
(c) t-butyl alcohol
CH2CHCH2CH2CHCH3 (c) 2-methyl-2-propanol

5-bromo-1,2-hexanediol
l) OH

OH
i)
OH
catechol (c)
1,2-dihydroxybenzene (I)
isobutyl alcohol (c) 2-hydroxyphenol (I)
2-methyl-1-propanol (I)

3. Draw structures of the following compounds

a) isoamyl alcohol d) 2-ethyl-2-buten-1-ol

OH HO

e) trans-2-ethyl-3-methyl-2-penten-1-ol
b) 1-cyclopentyl-1-phenyl-2-propanol

OH
HO

c) cis-2-iodocyclohexanol f) (E)-1-chloro-1,2-cyclobutanediol
OH Cl

OH
I H

OH

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ALCOHOLS & PHENOLS SOLUTIONS

Note that this is a 3 alcohol.

g) Br
HBr, H2O SN1 OH
CH3 + H2O
CH3
1-bromo-1-methylcyclohexane

h)
Na O- Na+
Na metal is a very strong base.
CH3 + 1/2 H2
It deprotonates alcohols.

sodium 1-methylcyclohexoxide

i) H2SO4
CH3
3 alcohols are readily
+ H2O dehydrated by sulfuric
or phosphoric acids
and moderate heating
1-methylcyclopentene

j)
cold
Na2CrO4, H2SO4, H2O NO REACTION
3 are only oxidized under severe
(hot) conditions with strong oxidants

k)
Br
PBr 3
CH3 + PBr2OH
This is the same product as obtained with HBr
Again the mechanism is SN1 for 3 alcohols

4. What Grignard and what carbonyl will react to produce the following. Draw structures of all
possible combinations. O
O
C MgBr
CH3 + CH3MgBr C +
H3C CH3
OH

C(CH3)2 O

C
OR + 2 CH3MgBr

5. What hydride and what carbonyl will react to produce the following. Draw structures of all
possible combinations.

CH3 O O O
CH3 OH CH3 CH3

CH2 CH3 C C C CH3 C C

CH3 C CH3 C
H OR OH
CH3 CH3 CH3 CH3

+ NaBH4 + 2 LiAlH4 + 3 LiAlH4

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ALCOHOLS & PHENOLS SOLUTIONS

6. List the reagents needed for the following transformations

Any strong base will cause

CH3 CH2 CHBr CH3 CH3 CH CH CH3 KOH
a) this 2 alkyl halide to
dehydrohalogenate via E2

1 Hg(CH3COO-)2, THF, H2O

H3PO4 + H2O or 2 NaBH4
b)
or
CH3 CH CH CH3 CH3 CH2 CH(OH) CH3 H2SO4 + H2O Any of the standard reagents
used for hydration of alkenes

c) CH3 CH2 CH(OH) CH3 CH3 CH2 CHBr CH3

HBr or PBr3
Either reagent causes 2
alcohols to undergo SN2.

O
d)
CH3 CH2 CH(OH) CH3 PCC or Collins
CH3 CH2 C CH3
or KMnO4 or HNO3
Any mild or moderate oxidant
will oxidize a 2 alcohol to a ketone

e)
CH3 CH2 CH(OH) CH3 CH3 CH2 CHCl CH3
HCl or SOCl2
will convert alcohols
to alkyl chlorides

f) COOH Only a rhodium catalyst

COOH
allows hydrogenation of
H2/Rh an aromatic ring at standard
pressure and temperature.
Carboxylic acids are not reduced
by hydrogen.

g)
COOH CH2OH
1 LiAlH4 Only this reagent will reduce
carboxylic acids but it does not
2 H2O reduce alkene/alkyne unsaturation

7. Number the following compounds in order of acidity, i.e., 1 = most acidic, 4 = least acidic
OH OH
COOH

NO2
2
3 4 1
Carboxylic acids are more acidic than phenols. The nitro group is electron
withdrawing so it will help stabilize the negative phenoxide ion after
deprotonation, making it more acidic than phenol. Benzene has only non
polar C-H bonds, they are not acidic.
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ALCOHOLS & PHENOLS SOLUTIONS

8. The shortest routes are shown below. In some cases, other, longer synthetic routes are
possible.

a)
OH
CH2 CH2 OH CH CH3

H2O Markovnikov
H2SO4 product
POCl3,
H2O
N CH CH2
E2

b) CH2 CH2 OH CH2OH

POCl3,
H2O KMnO4 1 LiAlH4
N 2 H2O
or O

CH CH2 C OH

hot KMnO4

OH
OH
c)
C CH3
CH CH3
CH3

1 CH3MgBr
Cr+6, H+ ether
O
+
any oxidant 2 H3O
C
CH3

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ALCOHOLS & PHENOLS SOLUTIONS

9. This one is tougher. Note the addition of the ethyl group. The only methods weve learned for adding
Carbon groups are 1) chain lengthening terminal alkynes, 2) FC alkylations/acylations to aromatics,
3) Grignards, organosodium and Gilman reactions. Obviously the first two dont apply here, so look
for an opportunity to perform a Grignard rxn, i.e., synthesize a carbonyl to add the Grignard to:

OH
OH

antiMarkovnikov
addition
oxidize CH2CH3
Cr+6, H+ 1 BH3, THF
2 NaOH, H2O2, pH8

1 CH3CH2MgBr, ether conc. H2SO4

+
2 H3O CH2CH3
O

3
Grignard reaction CH2CH3 dehydration

OH

10. For the following reaction:

a) Write products for the reaction
Show the mechanism of the reaction
.. ..
b)

Calculate pKeq H O: Na+

c)
..
O
Na+OH-
.. + H2O

pKb = -1.74
phenol sodium phenoxide
pKa = 9.9

pKeq = pKa + pKb - 14 = (9.9 -1.74 - 14) = -5.8 (100% extent of reaction)

11. This 3 alcohol is undergoing an SN1 reaction. OH is a poor leaving group, but once protonated by a
strong acid, a better leaving group is formed (H 2O).
CH3
.. ..
H3C C
..
O H H Cl :
..
3 CH3

SN1 H3C C Cl

CH3 H CH3
+
H3C C
..
O H H3C C+
H2O ..
: ..
Cl :

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ALCOHOLS & PHENOLS SOLUTIONS

12. Remember to consider whether the substrate is 1, 2, or 3

CH3 CH3
a) KOH This 3 halide undergoes E2
Br KBr H2O
+ + rxn. with strong bases

b) O
H3C
H3C PCC in CH2Cl2
CH C PCC is a mild oxidant, oxidizing
CH CH2 OH H 1 alcohols to aldehydes
H3C
H3C

O
c) OH
Jones Reagent
C CH3 2 alcohols are oxidized
CH CH3 to ketones by mild or
moderately strong oxidants

1. Cl S CH3 CH3 O
d) CH3
O
H3C C CH2 OH
H3C C CH3 + HO S CH3

H O
H LiAlH4
2. Tosyl chloride converts the OH group to a good
then
H3O+ leaving group, which is then displaced by Hydride
in an SN2 reaction.

e)

Na Very strong bases like Na metal

OH O- Na+ + 1/2 H2 deprotonate weakly acidic protons
in water and alchols

2 PBr3
f) Like HBr, this reagent converts alcohols
OH Br + PBr2OH to alkyl bromides. The mechanism is SN2

POCl3
CH3CH2CH2CH2OH CH3CH2CH CH2 POCl3 converts to OH group to a better leaving group
+ H2O
g)
and pyridine acts as a strong bulky base forcing
N: an E2 dehydration reaction even in 1 alcohols.

H3C H3C
h) SOCl2 Thionyl chloride coverts all alcohols to
CH CH2 OH CH CH2Cl alky halides. The OH group is converted
to a good leaving group. This 1 alcohol
H3C HCl SO2 H3C reacts via an SN2 reaction

i) O OH
LiAlH4 reduces carboxylic acids and
1 LiAlH4
CH2 CH C O CH3 CH2 CH CH2 esters to 1 alcohols but it does not
2 H2O reduce C to C unsaturation.

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ALCOHOLS & PHENOLS SOLUTIONS

13. Draw the structures of a Grignard and a carbonyl compound that can be used to synthesize
the following alcohols. Show all possible combinations.
Also draw the structures of any carbonyl compounds that can be reduced by a LiAlH4 to
prepare these compounds O
O
a) C MgBr
OH OR + 2 CH3CH2MgBr CH3CH2 C CH2CH3 +
C CH2CH3
O
CH2CH3
C
CH2CH3 + CH3CH2MgBr

O O
b)
OH
C OR + 2 LiAlH4 C OH + 3 LiAlH4
C H

H O O

C H + NaBH4 C + MgBr
H H

14. Write equations to show how the following transformations can be carried out. More than
one step may be required. Show all reagents and the products of each step, but do not
show any transition states. Mechanisms are not required
a)
OH OH
CH3

Cr+6, H+
1 CH3MgBr
+
O 2 H3O

b)
OH O CH2CH3
CH3 CH3
Na or
Na+NH2- CH3CH2Cl
SN2
O- Na+
CH3

O CH2CH2CH3

c) CH3CH2CH2I
H2SO4
SO3 SN2
300 C
1 NaOH O- Na+
SO3H OH NaOH
+
2 H3O
acid/base

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ALCOHOLS & PHENOLS SOLUTIONS

15. . :O.. H H+HSO4- Zaitsev product

(CH3)2C C(CH3)2
C(CH3)3 CH CH3
E1

CH3
H +
H3C C C CH3
:O H
C(CH3)3 CH CH3 CH3 H
CH3 HSO4-
3
+
H3C C C CH3
rearrangement via
CH3 H methide shift
2

16. Draw the structure(s) of all reagents which would give the following alcohol when reduced
with LiAlH4
O O O
(CH3)2CHCH2OH (CH3)2CHC OR or (CH3)2CHC OH
(CH3)2CHC H or

17. Draw the structures of all sets of reagents that would give the following alcohol when
reduced with a Grignard reagent. Show Grignards as well as other reagents.
O O O
OH
CH3CH2CCH2CH3
CH3CH2CCH2CH3 CH3CH2CCH3 or CH3COR +
or
+ CH3MgBr + CH3CH2MgBr 2 CH3CH2MgBr
CH3

18. Draw the formulas or structures of the products of the following reactions ...
a) H3C 2 H3C H3C
POCl3 converts the OH group to
POCl3
+ a good leaving group. Pyridine acts
OH as a strong bulky base causing E2
N dehydration to the alkene.
Two products form.
b) H3C H3C
2 PBr3 works like HBr to convert
PBr3
Br PBr2OH alcohols to halides.
OH +
SN2
H3C
H3C cold KMnO4 2 alcohols are normally oxidized to
2
aqueous O ketone except under severe conditions
c)
OH in which case they are oxized to
carboxylic acids and cleaved.

O
H3C H3C H3C
d) hot concentrated
O C OH
HNO3
OH C OH + C OH
C O
OH
Cleavage occurs on either side of the -carbon O

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ALCOHOLS & PHENOLS SOLUTIONS

3-methylcyclohexanol potassium 3-methylcyclohexoxide

H3C H3C
19.
K
OH O - K+ + 1/2 H2

K (like Na and Li) is a very strong base and deprotonates

the weakly acidic alcohol in an acid/base reaction.
This is a rapid lab test for identifying alcohols; H2 gas is evolved.

20. Remember to think backwards from the product as well as forwards from the reagent.
a)

CH2CH2OH CH2OH

KMnO4
H3O+ 1 LiAlH4
O 2 H2O

COH

b) Br 1
OH
CH2 Markovnikov
CH3 product

KOH H2SO4
SN2 H2O
OH
POCl3,
CH2 CH2
E2
1 N

OH
c)
SO3
CH2Br
H2SO4 (PhCO2)2
NBS
OH
SO3H 1 NaOH, 300C
+
2 H3O OH AlCl3 CH3
CH3Cl

H3C O H3C
d)

CH C OCH3 C C

H3C H3C

POCl3, N
H3C OH
2 equiv. or
1 C6H5MgBr CH C H2SO4
+
2 H3O
H3C

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