Experiment 23B

f-Pentyl Chloride

tD

II

13

13

209

11

IB

23

Infrared spectrum of n-buty! bromide, neat.

EXPERIMENT

23B

t-Pentyl Chloride
ez

Procedure

Preparation o f r-Pentyl Chloride. In a 125-mL separatory f u n n e l , place 10.0 mL

of r-pentyl alcohol (2-methyl-2-butanol, MW = 88.2, d = 0.805 g/mL) and 25 mL of
concentrated hydrochloric acid (d = 1.18 g/mL). Do n o t stopper t h e f u n n e l . Gently
swirl t h e m i x t u r e in the separatory f u n n e l f o r a b o u t 1 m i n u t e . A f t e r this period of
swirling, stopper t h e separatory f u n n e l and carefully invert it. W i t h o u t shaking t h e
separatory f u n n e l , immediately open t h e stopcock t o release t h e pressure. Close t h e
stopcock, shake t h e f u n n e l several times, and again release t h e pressure t h r o u g h
t h e stopcock (Technique 7, Section 7.4, p. 690). Shake t h e f u n n e l f o r 2 t o 3 minutes,
w i t h occasional venting. A l l o w t h e m i x t u r e t o stand in t h e separatory f u n n e l until t h e
t w o layers have completely separated. The r-pentyl chloride (d = 0.865 g/mL) should
be t h e t o p layer, b u t be sure t o verify this by a d d i n g a f e w drops o f water. The water should dissolve in the l o w e r (aqueous) layer. Drain and discard t h e l o w e r layer.
Extraction. The operations in this paragraph should be done as rapidly as posi.
_sible since t h e r-pentyl chloride is unstable in w a t e r and sodium bicarbonate solution. Itiw?asily hydr^
In each o f t h e f o l l o w i n g steps, t h e
organic layer should be o n t o p ; however, you should add a f e w drops o f w a t e r t o
make sure. Wash (swirl a n d shake) t h e organic layer w i t h 10 mL of water. Separate
t h e layers and discard t h e aqueous phase after m a k i n g certain t h a t t h e proper layer
has been saved. A d d a 10-mL p o r t i o n o f 5 % aqueous sodium bicarbonate t o t h e sep=

. ~

" 210

..000

Part One

3200

Preparations and Reactions of Organic Compounds

2800

2400

I
2000

FREQUENCY (CM*)
1800
1600

MOO

1200

1000

800

600

400

mm
CHa
CH3CCHj**CH3

CI

XS

II

t2

13

|J

-i

AB

Infrared spectrum of t-pentyl chloride, neat.

aratory f u n n e l . Gently swirl t h e f u n n e l (unstoppered) until t h e contents are thoro u g h l y mixed. Stopper t h e f u n n e l , a n d carefully invert it. Release t h e excess pressure
t h r o u g h t h e stopcock. Gently shake t h e separatory f u n n e l , w i t h f r e q u e n t release o f
pressure. Following this, vigorously shake the f u n n e l , again w i t h release o f pressure,
f o r a b o u t 1 minute. A l l o w t h e layers t o separate, and drain t h e lower aqueous layer.
Wash (swirl and shake) t h e organic layer w i t h one 10-mL p o r t i o n o f water, a n d again
_^
drain t h e lower aqueous layer.
S A ^ > S W K ^ r o o ^ i C HiD*~'H
Transfer t h e organic layer t o a small dry Erlenmgyer flask by p o u r i n g it f r o m t h e
t o p o f t h e separatory f u n n e l . Dry t h e crude t-pentyl chloride over 1.0 g o f anhydrous
calcium chloride u n t i l it is clear (Technique 7, Section 7.8, p. 696). Swirl t h e alkyl halide
w i t h t h e drying agent t o aid t h e drying.
> Distillation. Transfer t h e clear liquid t o a dry 25-mL r o u n d - b o t t o m flask using a
Pasteur pipet. A d d a boiling stone a n d distill t h e crude t-pentyl chloride i n a dry apparatus (Technique 8, Section 8.3, Figure 8.4, p. 711). Collect t h e pure t-pentyl chloride
in a receiver cooled in ice. Collect t h e material t h a t boils b e t w e e n 78 and 84C. W e i g h
t h e product, calculate t h e percentage yield, and determine t h e microscale b o i l i n g point.
Determine t h e infrared spectrum o f t h e product using salt plates (Technique 19, Section
19.2, p. 843). Submit t h e remainder o f your sample in a properly labeled vial, along
w i t h t h e infrared spectrum, w h e n y o u submit your report t o t h e instructor.
afcJ

Group

Range /

f. CNOj, Nitro compounds:

aromatic

Intensity Range cm-'

6.37-6.67
7.30-7.70
6.37-6.45
and 7.25-7.30
6.06-6.25
and 7.70-8.00
6.25-6.67
5.95-6.06
and 6.15-6.21

1570-1500
1370-1300
1570-1550
1380-1370
1650-1600
1300-1250
1600-1500
1680-1650
1625-1610

and

aliphatic
g. 0NOj, Nitrates
h. CNO, Nitroso compounds
i. 0NO, Nitrites
H A L O G E N COMPOUNDS, C - X
S T R E T C H I N G VIBRATIONS
a. C F

7
8
9
10
WAVELENGTH ( M O O N S )

11

Fig. 3-9 Di-n-butyl ether, liquid film.

1400-1000

1380 c m ) . Weak absorption near 13.85

(722 c m ) is cause
bending vibrations of the group ( C H . 2 ) , where n > 4.
Simple replacement of a methylene group of a saturated hydroca
by an oxygen atom causes the aj.riarance of absorption caused by s
C O stretching vibrations near 9 ji ( 1110 c m ) . This is shown b
spectrum of di-rt-butyl ether (Fig. 3-9). When a hydrogen atom
hydrocarbbn is exchanged for a hydroxyl group, the spectrum chanj
a very predictable way; it now shows absorptions owing to O H
C O stretching vibrations in addition to the hydrocarbon chromop
groups present. The spectrum of lauryl alcohol, C H ( C H 2 ) C H
Fig. 3-10, is an example; absorption owing to O H stretching vibr
is present at 2.9 p. (3448 c m ) as a strong absorption typical c
polymeric association of hydroxyl groups. Absorption centered at
( 1053 c m ) is typical of the C O stretching vibration o f a pri
alcohol. The spectrum of isoborneol (Fig. 3-11), determined in cs
- 1

CBr'

21
5. SULFUR COMPOUNDS
a. S H Stretching vibrations
b. C = S Stretching vibrations
c. S = 0 Stretching vibrations:
sulfoxides

3.85-3.92
8.33-9.52
9.35-9.71
8.62-8.77
and 7.41-7.69
8.13-8.70
and 7.00-7.41
8.44-8.59
and 7.30-7.46
8.48-8.77
and 7.41-7.69
8.27-8.70
9.43-9.71
and
-15.4

sulfones
sulfites
sulfonyl chlorides
sulfonamides
sulfonic acids

t Abbreviations: s = strong, m i
= approximately

- 1

2600-2550
1200-1050

()
(!)

(*)
(s)

()
(s)
()

()

- 1

1070-1030
1160-1140
1350-1300
1230-1150
1430-1350
1185-1165
1370-1340
1180-1140
1350-1300
1210-1150
1060-1030
-650

1 0

- 1

- 1

4000 3000

medium, w = weak, v = variable, b = broad, sh = sharp,

2000

1500

CM'

1000

900

--"*":!i5t.<S!

absorptions in terms of wavelengths or wave numbers. The remainder of

this section is devoted to an examination of a number of infrared spectra.
Significant structural features and absorptions are indicated.
The infrared spectrum of nujol (Fig. 3-3), a mixture of saturated
hydrocarbons, contains absorptions resulting from vibrations typical of
groups that are present in such molecules, i.e., C H stretching (3.39
and 3.54 ji, 2950 and 2820 cm" ), C H bending ( - 6 . 8 6 /i,
1458 c r n - i ) , and C C H bending (6.86 and 7.28 /i, 1458 and
1

7
8
9
10
WAVELENGTH IMICCONS)

- f fzbtorph*"

it

i :...E:L''!tE?.'.t^H

.:r!;i?

'->t-'..pcfe,i;:?!:i

AppliedW

BG0

ioo|

Fig. 3-10 Lauryl alcohol, liquid film.

Sp .cAw$Cofy &hOr**4AJc
e

Qw&**t*P.3$'

Preparation of tert-Amyl
\j-

Chloride

p^Tr-yl -a if ok i
CH3

CHH

9H3
OH

HCl

*~

CHdCHg

-C

CI

HO
2

room temp
CH3
tert-amyl alcohol
2-methyl-2-butanol

CH3
tert-amyl chloride
2-chloro-2-methylbutane

The conversion of tert-amyl alcohol to tert-amyl chloride goes by a SN-1

mechanism (Substitution Nucleophilic Unimolecular). The OH, the hydroxyl
group, is substituted by CI. The tert-amyl alcohol readily forms a tertiary (3)
carbocation at room temperature.
This reaction is reversible (an equilibrium process) - LeChateiier's Principle is
operating.
The preparation of the tert-amyl chloride is driven to the right because of
the concentrated hydrochloric acid and the fact that the tert-amyl chloride
separates from the hydrochloric acid.
The tert-amyl chloride can be coverted to tert-amyl alcohol, reaction driven to
the left, by exposure to water. This is a hydrolysis reaction.

Mechanism - Nucleophilic Substitution Unimolecular (SN-1)

1) Protonation of the Hydroxyl - Conversion into a Good Leaving Group
Acid-base chemistry fast

<?H

-H

CH3CH2-

CH3

CH3CH2',

CHa

4>

good leaving group

poor leaving group

2) Formation of the Carbocation - The Slow or Rate Determing Step

CH
CH3CH2-

QH

TPs.
CH

CH3CH2c
1H

3 carbocation (sp hybridization)

good leaving group

3) Nucleophilic Addition of Chloride - fast

CH3

Cr^CH^

CH CHg'
3

CH3CH2

Cl

ca

top/bottom attack on carbocation