Synthesis of Chloroform

erowid.org/archive/rhodium/chemistry/chloroform.html

With Calcium Hypochlorite and Acetone

When chlorine is passed into boiling alcohol, both chlorination of the methyl group and
oxidation of the primary alcohol group to an aldehyde occur,
giving trichloro-
acetaldehyde or chloral: When chloral is treated with caustic alkali, fission of the C-C
linkage occurs, giving chloroform and a formate.
Acetaldehyde and also many ketones,
such as acetone, containing the CH3CO- group behave similarly when treated with
calcium or sodium hypochlorite,
chlorination of the CH3CO- group being immediately
followed by fission of the molecule by the alkali present in the hypochlorite solution.
The acetone
method clearly gives a much cheaper product than the alcohol method.

Required: Calcium Hypochlorite 100g (bleaching powder), acetone 44ml

Place 100g of calcium hypochlorite in a mortar and add 250 ml of water in small
quantities at a time: between each addition grind the mixture of
bleaching powder and
water well together and decant the cream-like suspension through a funnel into a 1-litre
flat-bottomed flask. Finally, when all the
water has thus been used, only a gritty residue
remains in the mortar. Fit the flask with an efficient reflux water-condenser, pour 44ml
(35g) of acetone
in small quantities, at a time, down the condenser and mix by
thorough shaking after each addition. The reaction usually starts spontaneously after a
few
minutes, and a bath of cold water should be available into which the flask may be
dipped if necessary to moderate the reaction. Should the reaction show
no signs of
starting within 5 minutes of the addition of the acetone, warm the flask cautiously on a
boiling water-bath until the reaction starts, and
then remove it immediately. When the
vigorous boiling has subsided, heat the flask on a boiling water-bath for a further 5-10
minutes (not more) to
complete the reaction. Cool the flask in cold water (to prevent
loss of chloroform vapour whilst the apparatus is being rearranged) and then fit the
flask with a fairly wide delivery-tube and reverse the water-condenser for distillation.
Heat the flask on a water-bath until distillation of the
chloroform is complete.

The chloroform thus obtained is usually acidic. Therefore shake it thoroughly with dilute
sodium hydroxide solution in a separating-funnel. (If the
chloroform tends to float on the
alkaline solution, it still contains appreciable quantities of acetone: in this case the soda
should be run out of the
funnel and the chloroform shaken with water to extract the
acetone. The extraction with the soda can then be performed after the water has been
removed.)
Carefully run off the heavy lower layer of chloroform into a small conical
flask, dry it over calcium chloride for 15-20 minutes, and then filter it
directly into a 75
ml. distilling-flask fitted with a clean dry water-condenser. Distill the chloroform,
collecting the fraction of bp. 60-63øC. Yield,
30g. (20ml).

Chloroform is a colourless liquid, of bp 61ø and d 1.50. It has a characteristic sweetish

smell, and is frequently used as a solvent in organic chemistry.

Reference: Mann & Saunders, Practical Organic Chemistry, 3rd Ed

Chloroform from Sodium Hypochlorite and Acetone

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by Cheapskate

Go get a five gallon bucket. The ones used for painting work well and are available
new, with a cover, in the paint department of most big homeowner
stores. The cover
can be used to keep bird droppings and bugs out of the reaction. Put the bucket
outside in a reasonably ventilated area with good
drainage away from any shrubbery
that can be killed by spills. Pour two gallons of 10% sodium hypochlorite solution into
the bucket. This material is
available in two one-gallon containers for around $4.00
from the local homeowner store in the swimming pool section labeled, "Liquid Pool
Chlorine."
Make sure you get the Sodium Hypochlorite, not the Hydrochloric Acid that's
in the same section, HCl is useful, but not for this reaction.

Add 5 pounds of ice to the Hypochlorite. Be careful pouring this stuff, it's bleach, but
twice as strong as the stuff Mom uses to do your laundry.
Each splash on your clothing
will eat a nice white hole. Stir with a plastic or wooden spoon, avoid metal. Metal
spoons won't spoil the reaction, but
it may spoil the spoon.

While the solution cools, measure out 340 grams of acetone into a container. Add
about half of the measured acetone into the ice solution and stir it up.
Wait about 10
minutes and feel the side of the bucket. It should feel warmer near the bottom and
colder as you raise your hand to the ice. Stir the ice mix
around and equalize the
temperature. Add the rest of the acetone and stir again. Let it set for about 10 minutes.

If you didn't listen and used less than five pounds of ice in the solution, it will get hot
enough to boil off the Chloroform and leave you with nothing
but a bad smell, splatters
where it boiled over and probably holes in your shoes and clothes. As a matter of fact it
would be good to have an extra five
pounds of ice around in case you're doing this in
the middle of the day in Panama where the temperature is hovering around 104F. At
this temperature, or
if you're doing this in the Peruvian Mountains at 6500 feet it may
take more ice to keep it cool enough not to boil off the Chloroform as it forms. This
is a
very exothermic reaction, but it can be controlled easily by the addition of ice as
needed.

You should have a cool mixture of ice and something that is starting to look cloudy. It
will be colder on the top than the bottom and most of the ice
has melted. Let this
mixture set until the ice completely melts. Grab the bucket and carefully pour off the
water and fine white powder leaving behind the
Chloroform that has settled to the
bottom of the bucket. When you're pouring off the water, it may be hard to see the
Chloroform, but trust me, it's in
there. The Chloroform is heavier than water and falls to
the bottom in a bubble looking blob. The blob will have a white powder clinging to it.
Just pour
off the water until you can clearly see the blob and then pour blob, water and
powder into a smaller, easier to handle container. There may be some bubbles
forming
and rising to the top of the solution. Don't worry, this is normal and will not cause a
problem…unless you try to seal the reactants up.

Pour the Chloroform, powder and water through a coffee filter into a separatory funnel
and separate the crude Chloroform, which will sink to the bottom.
You will get around
200ml of crude Chloroform. Disappointed? This reaction uses very cheap materials and
is one of the simplest, cheapest methods known, so
just quit bitching and deal with it.
Since the procedure is so simple up to this point, make a few more batches before
moving to the next step.

The Chloroform has water and the white powder still in it and this needs to be removed.
The Chloroform can be vacuum filtered through a six inch sand
filter to remove the
powder and then passed through about 4 inches of anhydrous magnesium sulfate to

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remove most of the water, but the mechanical loss
would kill half of the product. The
best way to clean this up is to distill it. Use an appropriately sized flask, a one liter two-
necked flask will work
well, even for larger volumes. If you're doing more than half a
liter, pour it in as the distillation progresses. Use a fractionating column, I use a
400mm,
set up for normal distillation with an oil bath and magnetic stirring. If this last paragraph
doesn't mean a thing to you, go to the library and
get an organic lab survivor's guide.
These books have pictures and complete descriptions of all the pieces I'll talk about.

Remember, distilling Chloroform is not an incredibly safe procedure. Chloroform fumes

are toxic and narcotic, and may knock you out if aren't being
careful. On contact with
flames and hot surfaces it can decompose into the dangerous war gas phosgene. So
ventilate the area with fans to remove the
vapors and attach a vent tube to the vacuum
adapter that leads away from the area where you're working.

It is interesting watching Chloroform distill through a fractionating column. As the

solution comes to a boil a gray cloud rises up the column until
it reaches the distilling
head and spills into the condenser where it disappears into fluid. Below the rising cloud
the Chloroform condenses on the sides
of the column and drips back into the solution
to be converted into the rising cloud again. Keep the boil fairly slow, you don't want to
boil it dry while
you're off visiting the bathroom or kitchen. The first Chloroform that
comes over is tainted with water, don't worry about it, keep collecting. When the
Chloroform is almost gone from the source flask, add about 200 ml of water and bring
to a gentle boil to force the remaining Chloroform from the column
(there's a bunch of
stuff in there). You can tell when the Chloroform is done because the temperature starts
to rise pretty quickly from 60c to 80c.
Stop the distillation at this point.

As the Chloroform distilled it azeotropically carried over some water that can now be
seen as clear bubbles clinging to the sides of the receiving flask
or floating around on
the top of the clear Chloroform. It can also cloud up the Chloroform some. Pour the
Chloroform into a separatory funnel. Put a flask
fitted with a filtering funnel loaded with
a couple of inches of anhydrous Magnesium Sulfate under the separatory funnel, and
let the Chloroform slowly
drain through while separating the water. This will leave you
with clear anhydrous Chloroform in the flask.

To make anhydrous Magnesium Sulfate, get some Epsom Salts at the drug store and
pour about a pound into a casserole dish. Heat the casserole dish in
the oven at 450F
for about 4 hours. After cooling and chipping and crushing the fused material you have
anhydrous Magnesium Sulfate. Putting it in a thick
plastic bag and tapping gently with a
hammer can crush this stuff. Use a butter knife to get it out of the pan, not an ice pick!
You can also line the pan
with aluminum foil to make removal easier, but sometimes it's
hard to get the aluminum loose from the Magnesium Sulfate. Don't grease the pan
stupid!

Now look back at what's left in the distilling flask. It's got water and some nasty green
stuff clinging to the sides and a white powder setting on the
bottom. See why you
distilled it? This crud would have been left in the chloroform and screwed up everything
you used it for.

Put your crystal clear, anhydrous Chloroform in a brown bottle, cap tightly and store
away from light. If you're going to store it for a long time put a
couple of drops of 95%
alcohol in to stabilize it. Warning, Chloroform will eat rubber, so don't use a rubber
stopper. Glass or teflon seals are the best.

Chromic: Corrections to Cheapskates chloroform writeup (update 9/9/02)

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Cheapskate messed up in his calculations in
http://rhodium.ws/chemistry/chloroform.html.
This is certainly not an uncommon
mistake, as I too messed up the corrections
before this update!

6 mol OCl- is required for 1 mol acetone. Depending on the source of

hypochlorite, the
overall reaction is:

CH3COCH3 + 6 NaOCl -> CHCl3 + NaCH3COO + 2 NaOH + 3 NaCl

2 CH3COCH3 + 6 Ca(OCl)2 -> 2 CHCl3 + (CH3COO)2Ca + 2 Ca(OH)2 + 3
CaCl2

To repeat the calculations with Cheapskate's original scale of 340g of acetone,

that is
431.5mL or 5.85mol of acetone. 5.85mol of acetone requires 6x the
equiv of NaOCl, or
35.12mol of NaOCl. That is 2.613kg of pure crystalline NaOCl,
or 24.197kg of 10.8%
NaOCl (52.264kg of 5% NaOCl).

10% NaOCl has a density of 1.16g/mL. So that is a volume of 20.9L of NaOCl.

Or 5.52
U.S. gallons (1gal = 3.78L). Cheapskate is using 2 gallons, ie he is
only using 36% of
the amount he should be using (it's a surprise he made any
chloroform!).

However, where I live, bleach is sold in 4L containers... so all this makes

no sense to
me anyways! So I'll redo the calculations.

The final word is: For every 1g of acetone (1.27mL) you want to oxidize,
use 71.2g
(61.4mL) of 10.8% NaOCl (142.3g of 5% NaOCl).

Also, if you're having trouble oxidizing anything with NaOCl, use 1-2 mol
of HCl to 1
mol of acetone required, and drip it in with what you're
oxidizing. Ie, if you want to make
sure the NaOCl oxidizes the acetone
easily, add 1-2 mol eq's of 31% HCl relative to the
acetone, and drip
the acetone/HCl into the mixture slowly. If you're not using acid, the
reaction hardly comes to reflux (a condenser or some cooling is needed
though).

Beware, if you use too little bleach, this is a fast exothermic reaction as
Cheapskate
wrote about. Distillation of chloroform is not anything to be
worried about, no more so
than methylene chloride or any other chlorinated
solvent. There is no need for a
fractionating column when distilling all
of the acetone is gone, but do add some ethanol
as Cheapskate indicates!
Good luck with the Reimer-Tiemann formylation!

Data I used for the calculations:

10.8% NaOCl (w/w)

31.25% HCl(aq) (w/w)
0.03646 g/mmol HCl
0.0744 g/mmol NaOCl
0.05808 g/mmol acetone
0.788 g/mL acetone
1.16 g/mL 10.8% bleach
1.08 g/mL 5% bleach

Chloroform, if stored for more than a few months, decomposes to Phosgene; which as
you know was a WW1 era chemical weapon. To prevent this, small
amounts of
methanol should be added to the Chloroform to prevent it from decomposing to
Phosgene. Also, I think it is worth warning the reader
that if the reaction between
Calcium Hypochlorite and Acetone is not cooled properly, it may produce Phosgene.
Have a good day.

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 -Tariq

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