Grignard en El Ultrasonido
Grignard en El Ultrasonido
Grignard en El Ultrasonido
Students can run Grignard reactions in regular laboratory- boil spontaneously. If it doesn’t, put the tube back into
grade ether and in equipment that has not been specially the ultrasonic bath.
dried. The reaction begins within one minute and the product 3. When the reaction starts boiling spontaneously, remove
alcohol is ready for assay in one hour. This technique, which the tube from the ultrasonic bath. Add about 0.5 mL
requires only the simplest of glassware and a low-power ultra- of pure ether. When the initial boiling has slowed, add
sonic laboratory cleaner, is so robust that it deserves wider more 1-bromobutane–ether solution at a rate to keep
use. Because no particular care is needed to dry either the the reaction going moderately well. If the reaction
solvent or the equipment, large savings in time result for slows, add another 0.5 mL of pure ether to make up
for evaporation loss. If it goes too vigorously, place the
instructors and students. tube in cool water.
Using this technique, the magnesium can be handled
with the fingers during weighing. The diethyl ether can come 4. After adding all of the bromide–ether solution, add
from a half-full can of “anhydrous reagent ether” open for enough ether to keep the liquid level to the mark on
the test tube. When the reaction slows and almost all
two months and in use in an undergraduate laboratory (even of the magnesium is gone, sonicate the mixture for a
the can containing the Pasteur pipet and bulb lost by a student). few minutes more.
The bromide and the ketone are from bottles suffering from
5. Remove the tube from the ultrasonic bath. Pipet the
numerous years of student use. The glassware is right off the
solution into a dry 50-mL Erlenmeyer flask. Rinse the
shelf. The yield of product is typical of student reactions. This test tube once with 0.5 mL of ether and add the
“non-dry” procedure has worked as described on the second washings to the 50-mL flask. Cool the flask and its
day of a rain storm, with open laboratory windows, hoods contents in an ice bath. Any magnesium remaining in
pulling in the very humid air, and using glassware directly the tube can be air-dried and weighed.
out of student desks. 6. Any properly scaled standard procedure for adding the
The ultrasonic initiation of Grignard reactions (1) does ketone to a Grignard reagent may be used at this point.
not appear to have made the “mainstream” of use in current CAUTION : It is important that the ether solution of
lab manuals. However, its theory and applications have been the ketone be added dropwise into the 50-mL Erlen-
discussed in this Journal (2) and elsewhere (3), and, indeed, meyer flask using cold reagents! The reaction with the
the use of ultrasonic initiation of the Grignard reaction has ketone is very vigorous and material explodes from the
been reported in this Journal (4 ). The use of allyl bromide open end of a test tube with a range of about two labo-
and acetophenone, mediated by zinc in water and THF, has ratory benches!
recently been proposed (5) to circumvent the perceived
problems with the need for anhydrous solvents, ultradry Results and Discussion
glassware, and slow initiation for Grignard reactions. A standard laboratory ultrasonic parts cleaner of 125 W,
60 kHz has been used. A single unit of 3-L size is adequate
Experimental Procedure for a lab section of 20 or more, with only slight crowding or
CAUTION: All steps need to be conducted in a fume hood, waiting. Such a cleaner lists in laboratory supply catalogs for
as considerable amounts of ether will evaporate. The instructor about $470. The water bath will heat up to about 35 °C in
should put water in an ultrasonic bath to a depth of about about an hour of continuous sonicating. Students should go
three inches. Several beakers filled with water to the same to another hood after their reaction starts. A sizable amount
depth are placed in the bath to support students’ test tubes. of ether evaporates during sonication and reaction.
A beaker filled with cold tap water should be handy in case My students follow the general procedure above for
rapid cooling of the reaction is needed. Then: forming Grignard reagents, and the scaled version of the
ketone addition step from their regular laboratory manual.
1. Add 0.010 mol (0.25 g) of clean magnesium turnings
They are assigned alkyl or aryl bromides and ketones almost
to a 6′′ test tube (tube A). Add 0.100 mol (1.41 g) of
pure 1-bromobutane and 3.1 mL of anhydrous ether
at random, but some care being taken by the instructor that
to a similar tube (tube B). Mix well. Note the level of the product will give a pattern in the NMR that a beginner
liquid in tube B and place a line on tube A at this height. can interpret (see list below). Students are responsible for ad-
justing the mass of reagents to the formula weights of their
2. Use a Pasteur pipet to add enough of the bromide–
ether solution to tube A to partially cover the magne- compounds and for predicting the IR and NMR of their
sium. Place this tube into a water-filled beaker in the product.
ultrasonic bath and begin sonicating. CAUTION: Make
sure the tube points away from other people! Watch
the contents of the tube. When the liquid turns gray
or white, remove the tube. The ether should begin to