Sciencemadness Discussion Board

1-chloro-2-propanone (chloroacetone)

Organikum - 21-10-2004 at 02:58

1-chloro-2-propanone, monochloroacetone, chloroacetone, acetonylchloride, chloropropanone, 1-chloro-2-ketopropane, 1-chloro-2-oxopropane.

Modified preparation after the french patent FR 2633614.

250 ml acetone are placed in a flask and cooled in a waterbath to about 5°C. 3 ml H2SO4 and 3 ml HCl (30% suffices) are added.
50 g TCCA (trichloroisocyanuric acid) are crushed and dissolved in 150 g hot acetone. After all TCCA is dissolved or at least broken down to a very fine powder the mixture is cooled to about 5°C.
Some crushed ice is prepared.
The TCCA in acetone is added in portions over two hours to the acetone/HCl/H2SO4. The mixture turns greenish after every addition - chlorine. The next addition has to wait until the greenish color has disappeared and the mixture has cooled down again. Patience! Crushed ice is added to the waterbath as needed, the temperature should always stay below 10°C. Stirring or swirling with every addition is advised.
Just waiting 15 minutes after each addition of TCCA works fine.

Let sit for 4 hours and the cyanuric acid will settle. Decant the liquid, filter and add 50 g chalk, preferable in chunks, or pieces of broken marble.
The cyanuric acid is extracted twice with 100 ml hot acetone. The filtered extracts are joined with the first decanted acetone/chloroacetone mixture with the chalk.
Let settle, decant and filter and distill using a column. To the distillation flask some 10 g marble or chalk are added.

Yield: ~40 ml chloroacetone. The acetone which distills over first can be reused in further runs. No water is involved, no drying is necessary at all. The chloroacetone comes over as brownish liquid, thats ok, use it at once or add 1% w/w chalk and store in a brown bottle at a cool place. Nevertheless it will get darker over the time and finally form a resin. As long its a liquid its usable as resin its dead.

ATTENTION!
Chloroacetone is a strong lachrymator, some tears will be unavoidable during preparation although this preparation keeps the crying low. Chloroacetone can be destroyed with strong lye, this gives a nice crimson color - do this before cleaning the glassware or you will cry a lot even if you believed the flask was empty.

More information on this compound and its properties can be found here


Edit: Title by C.

[Edited on 27-4-2005 by chemoleo]

The_Davster - 21-10-2004 at 05:08

Trichloroisocyanuric acid? That is 'stabilized' pool chlorinating agent, yes?

Trichloroisocyanuric Acid

Organikum - 21-10-2004 at 05:34

Symclosene, CAS 87-90-1, TTT, Chloreal, Bab-O, trichloroiminocyanuric acid, TCCA.


TCCA is sold as "7-day tablets" or "Minitabs" for pool chlorination.

Dont confuse with dichloroisocyanuric acid or the sodium salt of dichloroisocyanuric acid.


I dont have a clue what "stabilized pool chlorinating agent" is.

[Edited on 21-10-2004 by Organikum]

The_Davster - 21-10-2004 at 14:21

Sorry about the confusion, I had been using "'stabilized'pool chlorinating agent" as a general term for non-calcium hypochlorite chlorinator.
I checked out my box of mini tabs for the hot tub and it is 100%(90% available chlorine) trichloro-s-triazinetrione, another synonym for TCAA.:cool:

I just want to get a gas mask before I attempt this...

Organikum - 21-10-2004 at 14:44

Cleaning the glassware is the hard part, the reaction is no problem. Therefor my tip to destroy residues of chloroacetone with lye beforehand. :)

Chloroacetone is not so bad, in special not when cold and not a big surface area is subjected to the air. A simple plasticbag over the filter whilst filtering works wonders!

Swimming googles maybe helpful, I worked without any protection or fumehood. Not recommended but obviously not impossible.

Organikum - 22-10-2004 at 05:00

This picture shows the nice crimson-red color which results when chloroacetone is destroyed by conc. NaOH solution. In this case I treated a residue of chalk used for neutralizing the chloroacetone.



This illustrates the necessity and usefulness of treating residues and glassware with lye for not to cry (to much).

Chloroacetone is also destroyed by iron and probably by other metals.

atombum - 23-10-2004 at 19:49

Remember also: The addition of CaCO3 (the chalk mentioned), is not only for quality purposes in the preservation of chloroacetone, but also for safety. Chloroacetone often explodes on storage, even when stabilized...Not only an obvious hazard due to the inherent dangers of explosion and the toxicity mentioned by Organikum, but the material is so irritant you'd probably cause enough of disturbance to make the 5 o'clock news.

Organikum - 24-10-2004 at 01:53

I never heard of chloroacetone exploding on storage and believe this being a myth.
Chloroacetone resinifies quickly if not stabilized, thats the problem.

Store with some chalk added cold and in a brown bottle, keep away from light. No problems.

Some other info. about chloroacetone...

kazaa81 - 31-10-2004 at 11:33

I've found some info. about chloroacetone...for anyone who's interested, i post them follow....
It's seem to me an easily made compound :-) have fun, but watch for cry ;-)

Chloro-2-propanone
Formula Weight 92,5
Melting/Boiling Points MP -44,5°C / BP 119°C
Vapor Density 3,2 (air = 1,0)
Appearance: Clear liquid
Solubility: Sparimgly soluble in water, but easily in alcohol, ether, choloroform and other organic solvents.

80g. of acetone and 20g. of calcium carbonate (plain
white chalk, or maybe baking soda instead) in dumps are
placed in a wide necked flsk fitted with a 3 hole stopper.
Through 1 of the holes in the stopper a reflux condenser
passes, through the second a tap funnel (a large syringe is
easier) and throught the third a delivery tube for the
cholorine gas.
The calcium carbonate is added to neutralize the hydrochloric
acid created in the reaction.

Chlorine (made by adding hydrochloric acid to HTH pool
chlorinating powder) is passed throught the acetone, and
30-40 milliliters of water is gradually added from the tap
funnel (syringe).
The temperature is raised to 60°C on a water bath.
Chlorine is added until the calcium carbonate in the flask
is almost exhausted, then the gas current is stopped and the
mixture allowed to stand overnight.
The liquid then settles into two layers. The top layer is
separated and fractionally distilled.
The last step is unnecessary if your going to use it within
a few days, but essential for any long term storage.

I don't forsee any difficulty in scaling up the amounts to
multi-gallon quantities.
I think you could put 2 gallons of acetone in a metal 5
gallons can, add a quart of water and a couple of pounds of
chalks, and pass it chlorine till the reaction is done.

The minimum concentration producing tearing is 0,018 ounces
per 1'000 cubic feet.
It becomes intolerable at 0,1 ounces per 1'000 cubic feet.
Chloroacetone decomposes in contact with iron or steel,
so it can't be loaded directily into pipes or such.
A plastic or wax liner is needed.
It will eventually turn into a solid substance with no tear
gas ability, but that will take about a year.

Chloroacetone would be ideal, I think, for spraying large
areas since it is so cheap to make in mass quantities.
It's not as potent as CS or CN, but it ease of manufacture
coupled with the low cost and ready avaibility of the
materials would make it ideal for home manufacture.

Thanx to all.

Esplosivo - 31-10-2004 at 12:19

kazaa81's post smells somewhat of NBK's 'book' NBK2000, am I right? Especially the last paragraph.

[Edited on 31-10-2004 by Esplosivo]

The_Davster - 31-10-2004 at 13:14

*runs and gets disk*

Yes, everything there is directly out of NBK's book. Everything is taken from there, absolutly nothing is origional.

How about citing sources kazaa81?:mad:

Excuse to all...

kazaa81 - 31-10-2004 at 13:20

I'm sorry for having forget to cite the sources of my post...
Yes, it was from nbk2000's book.

Excuse me.

The_Davster - 31-10-2004 at 13:21

Sorry for the rather harsh reply then:)

Organikum - 1-11-2004 at 05:53

nbk2000 took the experimental part from the book "War Gases". Sadly he quoted it not absolutely correctly and I advise to read the original preparation before attempting to reproduce it.
The calcium carbonate has to be in fused chunks or in form of marble and sodium carbonate will NOT work.
With chalk in form of fine powder you need strong stirring or it will settle on the bottom, Cl2 will accumulate above, HCl will form and will NOT get destroyed immediately by the chalk at the bottom and you get a fucking runaway.
And thats about the worst you can imagine with chloroacetone.

Anyways, the method as presented by me is much easier, no Cl2 needed, no HCl evolved....

And I make this as chemical precursor and not as warfare agent.

Mendeleev - 21-11-2004 at 09:50

Rhodium's synthesis of chloroactone mentions that dichloroactone is formed, the asymmetric dichloroacetone cannot be separated by distillation because it boils at 120, only one degree higher than monochloroacetone. The only reaction which does not give poly chloroacetones used diazomethane. Here is the whole write-up straight from Rhodium:





Preparation of Chloroacetone and Bromoacetone
[ Back to the Chemistry Archive ]

Chloroacetone [1]

Good method of preperation 150 ml acetone 50 ml water 12 g Cupric chloride 6 g lithium chloride. Reflux till reaction completes. Literature states 24 hours but the reaction has a half-life of about 24 minutes at 20°C (same article half of marker in 24 minutes, the marker being oxygen consumption in a slightly different reaction), therefore 5 hours is probably sufficient at reflux.

After reacting, distill everything below 123°C. The still bottoms can be reprocessed to recover cuprous chloride and lithium chloride. Both can be recovered by disolving with minimum water. The mix is easily converted to cupric chloride-lithium chloride by boiling with 20-35% hydrochloric acid.

Redistill slowly through a packed column to remove acetone. This leaves two fractions one distilling at 89C which is water and chloroacetone and the second distilling at 121°C which is ?pure? chloroacetone. The second fraction may contain unsymetrical dichloroacetone I haven't had a sample analysed. Calcium Chloride will crash the water-chloroacetone mix which tends to form a colloidal solution.

Chloroacetone must be stabalized with 1% calcium carbonate or 0.1% water if it is stored or it forms an explosive sludge. Distillation of a water-chloroacetone mix at 89°C is the most efficient way of separating unsym-dichloroacetone from commercial products.

Chloroacetone [2]

This produces a product absolutely free from polychlorinated acetone, which usually is formed in the chlorination of acetone, and is almost impossible to completely remove by distillation.

A dried ether solution (approximately 500ml) containing 0.5 mole of diazomethane was placed in a 1000ml three-necked flask and practical grade acetyl chloride (0.25 mole) was added slowly from a dropping funnel with constant stirring of the solution which was maintained at a temperature not greater than 5°C. The reaction mixture was allowed to stand for two hours after the addition of the acetyl chloride and was then saturated with anhydrous HCl over a period of two hours. The bulk of the ether was removed by distillation, and the residual solution fractionated through a small column. The product boiling at 118-119°C at weighed 15.8g (68%), d 1.126.

Bromoacetone [3]

A 5-L, three-necked, round-bottomed flask is provided with an efficient mechanical stirrer, a 48-cm. Allihn reflux condenser, a thermometer, and a 500ml separatory funnel, the stem of which reaches nearly to the bottom of the flask.

Through the separatory funnel are introduced 1.6 1. of water, 500ml of pure acetone, and 372 ml of glacial acetic acid. The stirrer is started and the temperature of the water bath is raised to 70-80°C, so that the mixture in the flask is at about 65°C. Then 354 ml (7.3 moles) of bromine is carefully added through the separatory funnel. The addition, which requires one to two hours, is so regulated as to prevent the accumulation of unreacted bromine As a rule the solution is decolorized in about twenty minutes after the bromine has been added. When the solution is decolorized, it is diluted with 800 ml of cold water, cooled to 10°C, made neutral to Congo red with about 1 kg. of solid anhydrous sodium carbonate, and the oil which separates is collected in a separatory funnel and dried with 80g of anhydrous calcium chloride. After drying, the oil is fractionated and the fraction boiling at 38-48°C/13 mmHg is collected. The yield is 470-480 g. (50-51% yield). If a purer product is desired, the above product is refractionated and the fraction boiling at 40-42°C/13 mmHg is collected. The yield is 400-410 g. (43-44% yield).

The higher-boiling fraction contains a mixture of isomeric dibromoacetones.
References

[1] JACS 77, 5274-5278 (1955)
[2] JACS 76, 1186 (1954)
[3] Organic Synthesis Collective Volume II, p 88-89





It mentions that distilling a mixture of chloroacetone with water is the most efficient way to separate chloroactone from asymmetrical dichloroacetone. Would this be necessary following the reactions given here, with TCCA and Cl2?


[Edited on 21-11-2004 by Mendeleev]

Organikum - 21-11-2004 at 22:26

A certain amount of dichloroacetone is formed in the chlorination of acetone with TCCA, but its only small as acetone is used in big excess and temperatures are kept low.

The cupric chloride/lithium chloride method does not work well in realworld.

Chloroacetone of trade contains 2% to 4% dichloroacetone anyways - this doesnt hurt in most reactions.

acx01b - 23-11-2004 at 04:05

what about the DCCA sodium salt?
(instead of 3 N-Cl we have 2 N-Cl and one N-Na)

and i guess DCCA sodium salt can be reacted with anhydrous ptsa to get DCCA acid ? (will ptsa react with the N-Cl forming HCl gaz ?)

[Edited on 23-11-2004 by acx01b]

frogfot - 23-11-2004 at 10:21

Quote:

With chalk in form of fine powder you need strong stirring or it will settle on the bottom, Cl2 will accumulate above, HCl will form and will NOT get destroyed immediately by the chalk at the bottom and you get a fucking runaway.


Wouldn't bubbling chlorine give sufficient stirring? I've never seen any good/pure source of prilled CaCO3 for this..
TCCA synth seems to be easier/cheaper. Org, did you use TCCA from pool store without further purification?

Organikum - 24-11-2004 at 03:08

Wouldn't bubbling chlorine give sufficient stirring? I've never seen any good/pure source of prilled CaCO3 for this..

- You use marble pebbles for this sold for garden-walkways for really cheap, purity doesnt matter here. I doubt you can bubble the chlorine so fast into the reaction without running into thermal problems. This is a reaction which tends to runaways.


TCCA synth seems to be easier/cheaper. Org, did you use TCCA from pool store without further purification?

- Pool store 100% TCCA was used and worked fine. Losses occur in the workup, the reaction probably has 100% yield, but nobody wants to cry for some ml chloroacetone, at least I dont want to.

Nosferatu - 25-11-2004 at 09:06

trichloroisocyanuric acid seems interesting for this preparation, good work.

I was thinking of the possibility to use this reagent in the preparation of benzylchlorides from toluenes via radical mechanism (as a substitute for NXS).

What do you think of using it in ring-chlorinations, for instance vanillin --> 5-chlorovanillin? I know, I know, sodium hypochlorite gives 90% yields, but I can't find stronger than 5% solution OTC where I live.

[Edited on 25-11-2004 by Nosferatu]

5-Chlorovanillin

Mephisto - 25-11-2004 at 15:47

I'm afraid TCCA will substitute OH on position 4 in vanillin through Cl. And I couldn't find any comparably reaction (e.g. with NCS), which could show, that your idea work.

Besides Chloro is a bad leaving group if you want to work further on a pathway to get TMBA or syringaldehyde. The Cu/NaOH method won't work with 5-chlorovanillin to get 5-hydroxyvanillin. In this case an iodination of vanillin would be preferable, IMHO.

Nosferatu - 26-11-2004 at 02:30

Quote:
Originally posted by Mephisto
I'm afraid TCCA will substitute OH on position 4 in vanillin through Cl. And I couldn't find any comparably reaction (e.g. with NCS), which could show, that your idea work.


Why do you think TCCA will substitue -OH? I can't see how that could happen... Generally, if you want to substitute the -OH on a ring, you will have to tosylate/mesylate it. The substitution itself gives higher yields with soft nucleophiles (i.e mercaptans), and preferably you should have an electron-withdrawing group on the ring in order to facilliate the attack on ipso carbon, otherwise the attack might as well go on your S=O of tosyl/mesyl...
Quote:
Besides Chloro is a bad leaving group if you want to work further on a pathway to get TMBA or syringaldehyde.The Cu/NaOH method won't work with 5-chlorovanillin to get 5-hydroxyvanillin. In this case an iodination of vanillin would be preferable, IMHO.


I have allready made syringaldehyde, so it is not the comound I'm after.


As for TCCA,

I was thinking that it could be a substitute for NXS, since the structures are such:


TCCA:



NBS:




As you can see both have a halogen attached to a nitrogen in simillar electron enviroment (carbonyls). The only problem as I can see is that the ratio carbonlyl/N-X in TCCA is 1:1 and in NBS is 2:1, but who knows, it might work.

I had some papers where they did ring-brominations in good yields with NBS on some non-phenolic (less activated) substrates.

But it would be great to try TCCA on toluene -> benzylchloride under UV as a start...

[Edited on 26-11-2004 by Nosferatu]

[Edited on 26-11-2004 by Nosferatu]

fritz - 26-11-2004 at 04:36

Beilstein suggests an electrolysis of a mixture of acetone and hydrochloric acid. Unfortunatelly without amounts of educts/yields/purity of product.
A method for separating (mono-)chloroacetone from 1,1-dichloroacetone can be found in „Purification of Laboratory chemicals“:
Chloroacetone is dissolved in water. The sol. Is shaken repeatedly with small (!) amounts of Et2O which extracts the dichloroacetone. The mono-compound is the extractet from aq. Phase by a larger amount of ethe and, distilled at low pressure. Further purification can be drying with CaCl2 and storing at dry-ice temp. Or dried with CaSO4, distilled and stored over CaCO3.

Mephisto - 26-11-2004 at 07:21

In many cases TCCA doesn't behave like predicted. The oxidation of benzyl alcohol to benzaldehyde - not to benzoic acid - was a good example on this board for this strange behaviour. Depending on the conditions TCCA can oxide alcohols or chlorine substitute them. Maybe your idea will work (under aqueous conditions in acetic acid?), too. At least, I was unable to find comparably reactions with NCS, as NCS could be substituted in most cases by TCCA as chlorination agent.

Related on MSDB:
- "Efficient method going from OH to Cl.pdf" in the thread Methods of Chlorination of Primary non Benzylic Alcohols
- Good Read: Trichloroisocyanuric Acid - A Safe and Efficient Oxidant

refs

Nosferatu - 26-11-2004 at 08:10

Quote:
Originally posted by Mephisto
At least, I was unable to find comparably reactions with NCS, as NCS could be substituted in most cases by TCCA as chlorination agent.


Reaction
Reaction ID 77045
Reactant BRN 635760 methylbenzene
113915 N-chloro-succinimide
Product BRN 471308 chloromethyl-benzene
No. of Reaction Details 3
Reaction Entry Date 1988/06/27
Reaction Update Date 1988/06/27
Field Availability List
RX Reaction Details 3
Reaction Details 1 of 3
Reaction Classification Preparation
Other Conditions Irradiation.UV-Licht
Entry Date 1988/06/27
Note 1 Handbook
Ref. 1 1738584; 1988/06/27; Journal; Hebbelynck; Martin; BSCBAG; Bull. Soc. Chim. Belg.; 59; 1950; 193, 196, 197, 202, 203.
Reaction Details 2 of 3
Reaction Classification Chemical behaviour
Entry Date 1988/06/27
Note 1 Handbook
Ref. 1 1738584; 1988/06/27; Journal; Hebbelynck; Martin; BSCBAG; Bull. Soc. Chim. Belg.; 59; 1950; 193, 196, 197, 202, 203.
Reaction Details 3 of 3
Reaction Classification Chemical behaviour
Temperature 95 - 140 C
Entry Date 1988/06/27
Note 1 Handbook
Ref. 1 1045061; 1988/06/27; Journal; Adam et al.; BSCBAG; Bull. Soc. Chim. Belg.; 65; 1956; 523,526.

unfortunately i can't acses those papers...

chloroacetone

chemchem - 26-4-2005 at 19:40

hello all !! Been searcking for a simple method one could produce chloroacetone with chlorine gas. Ive seen a method in a post once that simply bubbled chlorine gas into chilled acetone untill fully saturated. Then distiliation could seperate the un reacted acetone from the much higher boiling chloroacetone. My feelings are this method could produce more unsymdichloroacetone than desired product? I know the two are easily seperated < Hopefully anhydrous and low temp conditions will be enough to banish this dreaded bi product ?? What do we think ??

hodges - 4-8-2006 at 15:59

Quote:
Originally posted by Mendeleev
Chloroacetone [1]

Good method of preperation 150 ml acetone 50 ml water 12 g Cupric chloride 6 g lithium chloride. Reflux till reaction completes. Literature states 24 hours but the reaction has a half-life of about 24 minutes at 20°C (same article half of marker in 24 minutes, the marker being oxygen consumption in a slightly different reaction), therefore 5 hours is probably sufficient at reflux.

After reacting, distill everything below 123°C. The still bottoms can be reprocessed to recover cuprous chloride and lithium chloride. Both can be recovered by disolving with minimum water. The mix is easily converted to cupric chloride-lithium chloride by boiling with 20-35% hydrochloric acid.


I realize this is an old thread but I just ran across it while looking for information on reactions with acetone. I would be curious as to what the reaction is. Presumably the copper (II) chloride is reduced to copper (I) chloride by one of the hydrogens in the acetone, as the acetone is converted to chloroacetone. But what purpose would the lithium chloride serve? Why not just use copper (II) chloride by itself?

Hodges

Nicodem - 5-8-2006 at 00:30

Quote:
But what purpose would the lithium chloride serve? Why not just use copper (II) chloride by itself?


I would guess the purpose of LiCl is to catalyse the limiting step of the reaction, the enolisation of acetone (since LiCl is a relatively strong Lewis acid). It might also help by increasing chloride concentration thus stabilizing the Cu2Cl2 by complexing it to [CuCl2](-) (this should lower the transition state vs. product energy difference).
When CuBr2 is used there is no need for any such catalyst, but then again CuBr2 is in the 2CuBr2 <-> 2CuBr + Br2 equilibrium already at room temperature so obviously there is no need to increase its reactivity or catalyse the enolisation step.

Organikum - 5-8-2006 at 03:05

Quote:

Why not just use copper (II) chloride by itself?
Works, but is terrible slow.
/ORG

nb198 - 14-3-2014 at 20:50

When I tried to distill off my chloroacetone, I was left with a black sludge in the boiling flask. Any idea what it is? The solution going into the distillation was clear and yellow (from cl2 i assumed). No idea where the blackness came from. The sludge is also heavier than water and sinks right to the bottom if some is added to a beaker of water.

Chloroacetone - Distillation lead to black death

nb198 - 16-3-2014 at 11:53

I carried out the procedure as per Organikum and everything went well. I just needed to do the workup. I unfortunately had to do it over 3 days and I forgot to cover the flask with tinfoil, so it kind of yellowed by the time i was able to do the distillation.

The distillation seemed to be going well. I did a simple distillation. The acetone came off with only a minor amount of chloroacetone present. I tested this using concentrated NaOH. The acetone/chloroacetone prior to distillation resulted in a dark crimson color immediately upon addition. The acetone distillate require a few minutes to produce a faint red color, indicating to me that the concentration of chloroacetone was much lower.

The chloroacetone seemed to come off okay and I got a yield of about 20 mL which was very low, but acceptable. However, I was left near the end of the distillation with a dark black death that was insoluble in water and appeared to be miscible in acetone. I didn't distill until it was dry and left about 20ml of the chloroacetone in the death liquid.

Here is what it looked like near the end of the distillation

http://i.imgur.com/XDQWGNU.jpg

What was it? Is it the polymerized chloroacetone that was concentrated from my yellowed chloroacetone mixture? I was afraid to distill it to dryness so I just stopped the distillation and killed the black death with a load of 25M NaOH.

Metacelsus - 16-3-2014 at 14:20

Ah yes, the famous aldol tar . . .
The tar is formed by polymerization of acetone / chloroacetone.
I ran into much the same problem while trying to produce chloroacetone by electrolysis of a mixture of acetone and hydrochloric acid (forming chlorine in situ). I made the mistake of distilling nearly to dryness. The stuff is horrible to clean off glassware, and still possesses considerable lachrymatory power.

nb198 - 16-3-2014 at 14:47

Quote: Originally posted by Cheddite Cheese  
Ah yes, the famous aldol tar . . .
The tar is formed by polymerization of acetone / chloroacetone.
I ran into much the same problem while trying to produce chloroacetone by electrolysis of a mixture of acetone and hydrochloric acid (forming chlorine in situ). I made the mistake of distilling nearly to dryness. The stuff is horrible to clean off glassware, and still possesses considerable lachrymatory power.


How do you prevent it from happening? I had to leave the acetone/chloroacetone for 2 days in the fumehood before distillation and in the sunlight(absentmindedly). Do you think it yellowed because of this and formed tar? Would distilling it immediately after filtering/synthesis reduce the formation of the tar? Is the tar dangerous or relatively inert after killing with naoh?

I'm thinking of doing it again, except only make like 2ml. I could probably do it in like 4-5 hours max. I would like to avoid the tar though.

[Edited on 16-3-2014 by nb198]

Metacelsus - 16-3-2014 at 16:49

You can prevent it by removing residual acid (with sodium bicarbonate) and keeping it cold. Distilling it immediately would help. I don't know how dangerous the tar is after treatment with hydroxide.

nb198 - 16-3-2014 at 17:07

Quote: Originally posted by Cheddite Cheese  
You can prevent it by removing residual acid (with sodium bicarbonate) and keeping it cold. Distilling it immediately would help. I don't know how dangerous the tar is after treatment with hydroxide.


I removed residual acids using the chalk like Organikum said to. I think ultimately I left it out for what amounts to like 2 days in the sunlight...I really feel like that is what ruined it.

macckone - 16-3-2014 at 19:26

Don't use sodium bicarbonate. It can form side products.
Don't ask me why sodium bicarbonate forms side products and
calcium carbonate (chalk) does not. I suspect it is because of the
much higher pH.

The usual methods of stabilization are neutralizing with calcium
carbonate. And then if storing, add calcium carbonate or water to the
mixture. I believe the recommended amount is 1% by weight.

Generally in chlorination reactions there are polychlorinated products
and they can be more reactive than the monochlorinated products.
For distilling chloroacetone, one trick is to distill the acetone off,
then add water which forms a constant boiling mixture (89C).
This reduces the likelihood of polychlorinated products coming over.
Based on the procedure that started the thread there is
polychlorinated acetone in there.

After distilling over the water-chloroacetone mix, you can separate
it my using salt and a seperatory funnel.

Also be careful with this stuff. It is a war gas for a reason.

*edited based on polychlorination from procedure.*

[Edited on 17-3-2014 by macckone]

nb198 - 17-3-2014 at 04:35

Quote: Originally posted by macckone  
Don't use sodium bicarbonate. It can form side products.
Don't ask me why sodium bicarbonate forms side products and
calcium carbonate (chalk) does not. I suspect it is because of the
much higher pH.

The usual methods of stabilization are neutralizing with calcium
carbonate. And then if storing, add calcium carbonate or water to the
mixture. I believe the recommended amount is 1% by weight.

Generally in chlorination reactions there are polychlorinated products
and they can be more reactive than the monochlorinated products.
For distilling chloroacetone, one trick is to distill the acetone off,
then add water which forms a constant boiling mixture (89C).
This reduces the likelihood of polychlorinated products coming over.
Based on the procedure that started the thread there is
polychlorinated acetone in there.

After distilling over the water-chloroacetone mix, you can separate
it my using salt and a seperatory funnel.

Also be careful with this stuff. It is a war gas for a reason.

*edited based on polychlorination from procedure.*

[Edited on 17-3-2014 by macckone]


Thanks! Ill try that out the next time I do it

Mush - 13-12-2015 at 09:45

Raman spectra of aliphatic chlorine compounds: IV. Chloroketones and chloroacid chlorides (pages 1409–1428)

Recueil des Travaux Chimiques des Pays-Bas
1955 Volume 74, Issue 11

H. Gerding and H. G. Haring
10.1002/recl.19550741109

"Monochloroacetone
Following Fritsch (9), it was tried to prepare pure monochloroacetone by chlorination of acetone in the presence of marble and water. Initially, only mixtures of mono- and dichloroacetone were obtained, which could not be separated by fractional
distlllatlon owing to their small difference in boiling point. It was found that by changing the reaction conditions in various ways, viz. by maintaining a large
excess of acetone - e.g. 5 parts of acetone and 1 part of marble and carrying out the chlorination slowly, at 5-10 C. until about one-third of the marble has been consumed, spectroscopically pure samples of CH2Cl.CO.CH3, are obtained (i.e. no Raman lines of CHCl2.Co.CH3, could be detected) (19)."

(9) P. Pritsch, Ber. 26, 597 (1893) Ueber die Chlorirung des Acetons
DOI: 10.1002/cber.189302601125

English translation can be found here:
http://chemistry.mdma.ch/hiveboard/chemistrydiscourse/000505318.html
Original source:
The war gases, chemistry and analysis, 1939

Attachment: 10.1002_cber.189302601125 P. Pritsch, Ber. 26, 597 (1893).pdf (109kB)
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Attachment: Recueil des Travaux Chimiques des Pays-Bas; vol. 74 (1955) p. 1409,1416.pdf (981kB)
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Quick question

Assured Fish - 14-8-2016 at 00:48

I realize this is an old thread but i could not find the answer to this question anywhere, why is it that chloroacetone undergoes an aldol condensation when treated with NaOH however bromo and iodoacetone undergo substitution?

Metacelsus - 14-8-2016 at 05:36

Substitution and aldol condensation are probably competing reactions. Bromide and iodide are better leaving groups than chloride, so the substitution will be faster for bromo- and iodoacetone. Therefore, a much smaller amount of those compounds will undergo aldol condensation.

Doped-Al2O3-fusion - 8-2-2019 at 15:16

Sorry to resurrect an old thread, but I'm really glad I found it. I was trying to find out what substance I accidentally made yesterday during electrolytic recovery of copper and finally came to the conclusion it must be chloroacetone. It began with a drying step since I was trying to avoid yield loss of elemental copper to copper oxide(s). I used acetone to rinse the copper and at some point grabbed the beaker with the rinse by mistake and added it back into the copper chloride solution. On my next run of electrolysis, I developed these small crystals in solution which I assumed to be a chloride salt because I had added sodium chloride into the solution earlier on.

I vacuum filtered the solution to remove the salt using a fritted glass Buckner funnel. As I scraped the salt out, it appeared to look like small crystals of elemental silver, which I knew couldn't be the case, but it looked just like it. Confused, I examined a sample under my microscope and it was composed of trigonal clear crystals and what appeared to be a lot of dark colored contaminates, which presumably was copper. I went back down to my work area and noticed the rest of the sample began to turn a yellowish color. It was sitting under my overhead full spectrum florescent light.--I mention this because this is what prompted me to believe I was on the right track as the wiki article stated this compound to be light sensitive and turns yellow-amber. I don't have a sense of smell, so I couldn't detect any pungent odors. I'm guessing the copper chloride could have catalyzed the reaction during electrolysis.

The copper powder itself shortly turns a purplish color hue upon exposure to the air. If placed quickly into a beaker of full strength acetone, the solution turns murky blue and the copper settles to the bottom looking like copper powder, but I'm positive it's not pure copper powder. I performed a number of small tests and using stannous chloride on a small amount turns the copper into a bright copper color, but after rinsing it off and exposing it to air to dry, it eventually does the same thing. Adding this solid into a beaker of distilled water is where things became really weird to me. The solution quickly turned cloudy blue, then yellow and finally a yellow-orange color. My eyes did get a bit irritated despite having such a small quantity of sample test solution and mild air flow through the room.

I still don't know what the crystals were, as I only find mention that this compound is a liquid, but I assume it can form crystals. Mine were fairly water insoluble and they eventually turn into a yellow-amber color as they oxidize (the sample on the microscope slide eventually changed color as well). I'm also not sure what to do with the remainder of the copper chloride solution, but I'm most likely to add sodium hydroxide to it. The percentage of acetone is about 10% of the solution at this point. It's definitely an annoying mistake as I'm really not wanting more waste solution to have to store for the immediate future.

RedDwarf - 25-11-2019 at 11:03

I found this thread when searching for some info after viewing nile red's (nb198 I assume?) video on chloroacetone synthesis. I've got two questions if anyone can help:

1) What's the beautiful red compound formed when chloroacetone is added to NaOH?

2) I thought most blackboard chalk was Calcium Sulfate, not Calcium Carbonate, so which is being added to the product (I'm assuming you want the carbonate to neutralise the HCl as the sulfate wouldn't have any effect or have I missed something?)

Metacelsus - 25-11-2019 at 17:11

1) What's the beautiful red compound formed when chloroacetone is added to NaOH?

From experience: a mess of aldol condensation products.

2) I thought most blackboard chalk was Calcium Sulfate, not Calcium Carbonate, so which is being added to the product (I'm assuming you want the carbonate to neutralise the HCl as the sulfate wouldn't have any effect or have I missed something?)

You are correct. Most blackboard "chalk" is gypsum (calcium sulfate dihydrate). But real chalk (the mineral) is calcium carbonate.

[Edited on 2019-11-26 by Metacelsus]

S.C. Wack - 25-11-2019 at 18:57

It appears that the making of chalk for chalkboards as it was in my youth is a lost art unknown to the Chinese, and it's very popular to write internet articles saying that chalk isn't chalk, even though much of the chalk sold on amazon clearly says is made of CaCO3. And stuff.

If crushed marble is recommended by real chemists of yesteryear, it would probably not be unwise to use crushed marble, yes? Likewise the directions specifically insist on no yellowness.