Synthesis of 1-bromobutane

Adapted from H.D. Durst and G.W. Gokel, Experimental Organic Chemistry, McGraw-Hill, N. Y., 1980.

Alcohols are easily converted into the corresponding alkyl halides by treating them with concentrated aqueous hydrogen
halides. Tertiary alcohols react almost instantly at cool temperatures via an SN1 mechanism since 3 carbocations are
relatively easy to form. Primary alcohols, on the other hand, react via the SN2 mechanism because 1 cations are difficult
to form. Addition of strong acid forms an oxonium ion from the 1 alcohol OH group, changing a poor leaving group into
a good one (HO is poor, but HOH is good because it is electrically neutral). In spite of this, because a 1 cation is too
hard to form, water does not actually leave until it is pushed out by an incoming nucleophile (the bromide ion). Note that
this is an equilibrium process, so it cannot be expected to go to completion. The reaction is shown below.

+
R-CH
2
-OH + H
+
R-CH
2
-OH
2
R-CH
2
-Br + HOH
+ Br
-


The purposes of this experiment are (a) to do an SN2 reaction and (b) to learn various techniques for synthesis, isolation,
purification, and characterization of a compound. Some techniques have multiple uses: in this experiment, distillation is
useful for both isolation/purification and characterization.

EXPERIMENTAL PROCEDURE

Caution: Sulfuric acid is extremely corrosive. Keep it away from your person and your clothing. Wash
copiously with water in case of contact.
Bromobutane is a lachrymator. Avoid breathing vapors and skin contact .

Note: several extractions are done using a separatory funnel. The position of the product layer may change
unpredictably. Do not discard anything until you know what it is!!! Recommended: use Erlenmeyer flasks to
hold layers you want to keep, and beakers to hold potential discards.

Synthesis: Put 25 mL of water in a 250 mL boiling flask and add 27 g of solid NaBr; partially dissolve the salt by
swirling for about a minute. Tare this flask in a beaker on a high-capacity balance and add 16 g of 1-butanol. The weight
does not have to be exact, but record the actual mass used. Get a 50 mL graduated beaker and pour approximately 25 mL
of concentrated H
2
SO
4
into a it. Take the beaker and flask to a sink, and as you swirl the flask under running water to
cool the contents, cautiously and in small amounts add the H
2
SO
4
until all is in. This will generate a lot of heat. Cool
enough to keep it from boiling. If you are careless some acid may run down the outside of the beaker or flask and get on
your hand. Be sure that no water enters the neck of the flask. After mixing is complete, clamp the flask near the front of
your hood, mount a heating mantle, add a boiling chip, and fit with a vertically-oriented condenser. Leave the upper end
of the condenser open. Begin heating the flask. While it is heating, lift the entire assembly off the desk top and agitate so
that the contents of the flask are thoroughly mixed (show the instructor). Also do this mixing at least once after boiling
starts. Boil the contents of this reflux apparatus slowly for 30 minutes.

[During the refluxing, obtain 10 mL of conc. H
2
SO
4
in your 50 mL beaker and put it inside your hood.]

Two layers gradually will become visible. When time is up, turn off the power and lower the heating mantle. Allow the
mixture to cool slightly until boiling ceases. Remove the condenser (leaving hoses connected) and lay it temporarily on
your desk. To the flask add two new boiling chips. Then mount a distilling head, attach your condenser, and complete
the set-up for simple distillation into a 100 mL round flask. Insulate the distilling head and flask, then raise and turn on
the heating mantle. Distill rapidly (as fast as condenser can handle it; Variac about 90) until the distillate no longer
contains two phases (check by capturing a few drops of distillate in a test tube). This process is called "steam distillation"
and serves to separate the desired product (along with some water) from most of the unwanted nonvolatile reactants.

Removal of contaminants: Pour the contents of the receiving flask into a separatory funnel. [You need to identify the
organic layer. To do this, carefully draw off about 0.25 mL of the lower layer into a test tube containing about 1 mL of
water and mix vigorously. If the liquid from the funnel dissolves in the water as you mix it, the lower layer is aqueous. If
two immiscible layers form in the test tube, the lower layer in the funnel is organic (in this case return the contents of the
test tube to the funnel).] Separate the layers, and save the organic layer (return it to the cleaned separatory funnel if
necessary). If there is any color in the organic layer (possibly due to elemental bromine), check with the instructor before
proceeding. Put the aqueous layer from the funnel into a 600 mL beaker kept in your hood.

[As you wait for layers to separate in the following steps, disassemble your distillation apparatus as convenient. Pour
the pot residue carefully with stirring into the 600 mL waste beaker -- it will get hot. Keep this beaker inside in your
hood. Rinse all the glassware, making sure all the rinse water goes directly down the drain opening. Thoroughly dry
the distilling head, thermometer adapter, vac. adapter and condenser. Ask instructor about proper glassware drying
procedures.]

The product (in the separatory funnel) may be contaminated with unreacted alcohol. After getting rid of as much water
layer as possible, cautiously add about half of the concentrated H
2
SO
4
from the 50 mL beaker in your hood (the acid will
react with and dissolve any residual alcohol and water). Swirl without inverting, venting if necessary and noting whether
heat is generated or any other changes occur. Finally, shake vigorously, venting occasionally, for at least 30 sec., allow
the layers to separate, and identify the organic layer. (The H
2
SO
4
layer is probably the lower one. If so, when a few
drops of it are mixed with water in a test tube, you will see Schlieren lines and the test tube will get warm. Minor
cloudiness in the test tube is due to 1-butanol coming out of H
2
SO
4
solution. Check with the instructor if in doubt.)
Stirring as you do so, carefully discard the sulfuric acid layer into the 600 mL beaker. Save the organic layer and shake
it vigorously with the remaining unused H
2
SO
4
to assure complete removal of unreacted 1-butanol. Discard acid as above
.

Purification: Weigh a 50 mL boiling flask, eventually to use as your receiving flask. Put the acid-washed organic layer
into a DRY 25 mL boiling flask, add a boiling chip, and distill through DRY glassware. Be sure that your thermometer is
properly positioned!! Insulate the apparatus (see instructor). Collect any forerun (b.p. lower than 95) in an
Erlenmeyer flask and discard down the sink. If the temperature is rapidly rising as it passes 95, do not discard
anything. Change to the weighed receiving flask and collect only that material which boils 95 - 104 C. Record the
temperature at which you started collecting your product, the temperature at which most of it boiled, and the temperature
at which you stopped collecting (three entries). After weighing, pour the product into the flask marked 1-bromobutane -
student prep. Discard any pot residue into the container marked halogenated organic waste.

Clean-up: Take the 600 mL beaker containing acid wastes to a hood. Get a plastic dish basin and put a layer of sodium
bicarbonate all over the bottom. Pour your waste acid over the bicarbonate in small portions with good stirring.
Beware of strong foaming. Continue adding small portions of waste while stirring. You are finished when all waste has
been added and no foaming occurs if you add new solid bicarbonate. Solid Na
2
SO
4
will form; this is expected. Discard
everything down the drain with lots of water.

Rinse glassware cautiously, pouring all rinse water directly down the drain (dont let it splash in the sink). Then wash
with Alconox, and again pour the wash water directly down the drain. Instructors will show you how to clean "tarry"
glassware.

Report: follow the usual guidelines. Don't forget these items in their proper places:
- Show the complete equation for this reaction, including a curved arrow mechanism.
- Report your yield in both grams and as % of theory. Show calculations in an Appendix- you will need to use
information from the Table in your lab notebook.
- Compare the boiling point of your product (the temperature at which the bulk of it boiled) with the published value
(source?).
- Yields are always less than 100% due to conditions that did not favor complete reaction or to losses during work-up.
Recalling theory as well as observations you made during the experiment, discuss specific causes of low yield. (Do
not use the words "Human error". Instead, consider the concept of equilibrium, possible competing reactions, and
identify any specific mistakes you know of.) Can you think of any improvements to this procedure?

Questions (answer in an appendix):

1. a. Liquid reagents are often measured by volume rather than mass. Show how to compute the volume of 1-butanol that
would provide 16 g.
b. Why is it more accurate to weigh liquids than to use a graduated cylinder to measure them?

2. 1-butanol is a likely contaminant of your product. Its boiling point is higher than that of 1-bromobutane. Compare
their molecular structures to explain this fact.