FREE-RADICAL CHLORINATION WITH SULFURYL CHLORIDE (11/04/2008)

Alkanes are typically very unreactive saturated hydrocarbons. One of the few reactions that
alkanes do undergo is free-radical halogenation to produce alkyl halides. This free-radical
process may be initiated when a mixture of an alkane and a halogen (chlorine or bromine) is
heated at 300-500oC or is irradiated by ultraviolet light. The high temperature is necessary to
generate the halogen radicals needed to initiate the free-radical chain reaction.

R H + ∆ or hν R X + H X (1)
X2

Although alkanes have very few synthetically useful reactions, the introduction of a single
halogen functional group opens the door to a number of synthetically useful functional group
transformations via nucleophilic substitution, elimimation, and organometallic reactions.

Nu
R Nu + X (2)

strong base
R X alkenes (3)

OH O O O
Mg various
R MgX RCHR , RCH , RCR , RCOH (4)
ether reagents

A major drawback to free-radical halogenations, especially with chlorinations, is that mixtures of

monosubstituted and polysubstituted products that are usually difficult to separate are often
obtained.

Let us turn our attention to free-radical chlorination. Although thermolytic and photolytic
generation of chlorine radicals from molecular chlorine may be easily implemented in industrial
processes, this method is not very practical for laboratory applications. The generation of
chlorine radicals from molecular chlorine may be initiated under much milder conditions if an
initiator is used. An initiator (In-In) is a compound that undergoes homolytic cleavage to
generate radicals upon mild heating or UV irradiation. Two common initiators are benzoyl
peroxide (1) and azobisisobutyronitrile [2,2'-azobis(2-methylpropanenitrile)] (2), often
abbreviated as AIBN.

O O O
C O O C ~80 oC C O
2 In (5)

1
 CH3 CH3 CH3
~80 oC
CH3 C N N C CH3 2 CH3 C In (6)
CN CN CN
2

+ (7)
In Cl Cl In Cl + Cl

But even with these milder conditions, chlorination with molecular chlorine is still not well
suited to laboratory applications because of the highly toxic properties of and the difficulties
involved in handling of chlorine gas. Fortunately, there are safer and more convenient sources
of chlorine radicals such as liquid sulfuryl chloride, SO2Cl2.

There are three distinct stages involved in a free-radical chain reaction. The first stage involves
initiation steps that generate small concentrations of chlorine radicals from neutral molecules.
When AIBN is the initiator, initial heating results in homolytic cleavage of AIBN to form the
isobutyronitrile radical which in turn attacks sulfuryl chloride to generate a chlorine radical and
sulfur dioxide.

Initiation Steps

∆ (8)
AIBN 2 (CH 3) 2CCN

O Cl O
(CH 3) 2CCN + Cl S Cl (CH 3) 2CCN + S Cl (9)
O O

O
S Cl SO2 + Cl (10)
O

The next stage involves propagation steps in which the initial chlorine radical abstracts a
hydrogen atom from an alkane to generate hydrogen chloride and an alkyl radical. The Alkyl
radical then abstracts a chlorine atom from a molecule of sulfuryl chloride to generate an alkyl
chloride molecule and a new sulfuryl radical which subsequently fragments to form sulfur
dioxide and a new chlorine radical.

Propagation Steps

R H + Cl R + H Cl (11)
 O O
R + Cl S Cl R Cl + S Cl (12)
O O

O
S Cl SO2 + Cl (13)
O

The propagation reactions of equations 11-13 repeat over and over producing a free-radical chain
reaction. Thus, many molecules of alkyl chloride are produced from the initial chlorine radical
produced by the decomposition of one molecule of sulfuryl chloride.

Once initiated, the chlorination reaction might continue until the limiting reagent is used up, but
in practice, the third and final stage involving termination steps kills the chain reaction.
Termination steps are reactions in which two radicals combine to form molecules without the
generation of any new radicals to continue the chain reaction. Thus, new initiation steps must
occur to keep the reaction proceeding to completion.

Termination Steps

Cl + Cl Cl Cl (14)

R + R R R (15)

R + Cl R Cl (16)

As stated earlier, free-radical chlorination of alkanes generally produces mixtures of various

monochlorinated and poly chlorinated products. The ratio of the amounts of the different
monochlorinated products can be readily predicted by multiplying the number of each different
type of hydrogen by its relative reactivity. The reactivity ratio for primary, secondary, and
tertiary hydrogens toward chlorine radicals is 1 : 3.9 : 5.1, respectively. For example, the ratio of
1-chloropentane : 2-chloropentane : 3-chloropentane formed in the chlorination of pentane is
predicted to be (6 x 1) : (4 x 3.9) : (2 x 5.1) = 6 : 15.6 : 10.2.

In this experiment, 1-chlorobutane will be chlorinated using sulfuryl chloride as the chlorine
radical source and AIBN as the initiator. The resulting product mixture will be fractionally
distilled, the fractions will be analyzed by gas chromatography, and the gas chromatographic
data will be used to determine the reactivity ratio for the different types of hydrogens.
 Experimental Procedures

Chlorination

Assemble the glassware as shown in Fig. 1 using a dry, 50-mL round-bottomed flask and equip it
with a thermowell. Be sure the apparatus has been assembled such that the thermowell may be
readily lowered to allow easy removal of the reaction flask. Remove the flask and add a stir bar.
Dispense 3.6 mL (6.0 g, 4.4 x 10-2 mol) of sulfuryl chloride directly into a pre-weighed,
stoppered flask. Confirm the mass of the addition, then add 9.3 mL (8.2 g, 8.9 x 10-2 mol) of
1-chlorobutane into the flask and stopper. Finally, add 0.04 g (2.4 x 10-4 mol) of AIBN, stopper,
and weigh the flask and its contents.

Reattach the flask to the condenser, place 100 mL of 2 M sodium hydroxide solution in a beaker,
and adjust the funnel until it just touches the surface of the sodium hydroxide solution. This
arrangement will ensure that the noxious sulfur dioxide and hydrogen chloride gases produced
during the reaction will not escape into the laboratory. Turn on the water to the condenser and
heat the reaction mixture to a gentle reflux for 20 min. Lower the thermowell, cool the reaction
mixture, remove and stopper the reaction flask, and weigh the stoppered flask and its contents.
If the loss in weight is less than the theoretical, add another 0.04 g of AIBN and heat the reaction
mixture under reflux for another 10 min. The theoretical weight loss may be calculated from the
fact that each mole of SO2Cl2 that reacts produces 1 mole each of SO2 and HCl gas.

Once the expected loss in weight has been realized, raise the funnel (to prevent a vacuum from
pulling the sodium hydroxide into the reaction flask) and cool. Cautiously pour the reaction
mixture into 20mL of ice water with stirring. Transfer this mixture to a separatory funnel and
separate the layers. If the mixture does not readily separate into two layers, add a few milliliters
of saturated sodium chloride solution and swirl gently. Wash the organic layer with 10 mL of
0.5M sodium carbonate solution. Check the aqueous wash with pH paper; if it is not basic,
repeat the washing of the organic layer until the aqueous layer is basic. Then wash the organic
layer with 10 mL of saturated sodium chloride solution, and dry it over a few grams of
anhydrous sodium sulfate. Decant as much of the dried organic layer as possible into a 25-mL
round-bottomed flask and then transfer the remainder (of the organic layer) using a Pasteur pipet.

Fractional Distillation and GC Analysis (Week II)

Outfit the 25-mL flask with the necessary glassware for a fractional distillation using an
unpacked fractionating column. Carefully fractionally distill the mixture to separate the excess
starting material from the dichlorobutane products. Collect material with a boiling point range
of ambient-82 oC as your first fraction in a tared collection vessel. After this fraction has been
collected (and the apparatus is cool enough to handle), remove the fractionating column and
continue with a simple distillation. Collect material with a boiling point range of 82-165 oC as
your second fraction in a tared collection vessel.

Determine the weights of both distillation fractions and analyze the second fraction by gas
chromatography. Assuming that the first fraction is almost entirely 1-chlorobutane, determine
the percent yield of the dichlorobutanes based on the weight of the second fraction and the
percent composition obtained from the gas chromatogram. Correct these percentages for the
statistical factors (divide by the number of H’s) and determine the reactivity ratio for the four
different types of hydrogens. These percent yield and composition calculations should be
attached to your summary.
Name:__________________________________ Section:_______Date:________

POSTLAB EXERCISE
FREE RADICAL CHLORINATION WITH SULFURYL CHLORIDE

¾ Due 1 week after completion of the experimental portion of the notebook (30pts
TOTAL). Please answer questions on this form. Attach supporting GC’s and
calculations as necessary.

A. PRODUCT INFORMATION (10pts)

BOILING POINT (oC) FRACTION I FRACTION II

(2pts) (2pts)

%YIELD (All C4H8Cl2 Products) (3pts)

(Fraction II only)

REACTIVITY RATIO (for all 4 types (3pts)

of hydrogens)

B. SUMMARY QUESTIONS (20pts)

1. (5pts) Why was sulfuryl chloride used in much less than the stoichiometric amount necessary
to convert all of the 1-chlorobutane into dichlorobutanes?
2. (5pts) Why is the potential contamination of the dichlorobutanes with (CH3)2C(Cl)CN
derived from AIBN of little concern in this experiment?

3. (5pts) Why does your experimental percent composition of the dichlorobutanes in fraction 2
differ from that predicted by multiplying the usual primary : secondary : tertiary reactivity
ratio of 1 : 3.9: 5.1 by the appropriate statistical factors? Keep in mind that the hydrogens on
the 1-carbon are considered to be primary hydrogens.

4. (5pts) From which of the three compounds: cyclohexane, heptane, or 1-bromobutane; should
it be easiest to prepare a single pure monochlorinated product by free-radical chlorination?
Why?