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Author: Subject: 1-chloro-2-propanone (chloroacetone)

1-chloro-2-propanone (chloroacetone)





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]







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









Trichloroisocyanuric Acid





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]







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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.



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













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.







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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.







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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.





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.







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Some other info. about chloroacetone...





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.





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



[Edited on 31-10-2004 by Esplosivo]







Theory guides, experiment decides.





*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?









Excuse to all...





I'm sorry for having forget to cite the sources of my post...

Yes, it was from nbk2000's book.



Excuse me.





Sorry for the rather harsh reply then













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.







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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]





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.







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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]





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?





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.







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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





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.







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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]







Grof Orlock





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.





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







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refs





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...







Grof Orlock