Patented Nov.

18, 1941

2,263,010

UNlTED STATES PATENT DFFICE

2,263,010
CHLORINATED KETONES Emil J. Rahrs, Rochester, N. Y., assignor to East
man Kodak Company, Rochester, N. Y., a cor

poration of New Jersey No Drawing. Application December 1, 1938, Serial No. 243,374
5 Claims.
This invention relates to treatment for improv
_ ing chlorinated ketones which normally tend to

(Cl. 23-250) However, by applying my novel puri?cation treat

ment in conjunction with the stabilization treat
ment to a well-prepared chlorinated ketone ap pears to produce the best product.

deteriorate upon standing or storage and more

particularly to the treatment of chloracetones,

such as monochloracetone to obtain a product

which does not materially deteriorate during

ketone would be in a more or less freshly pre Chlorinated acetones have been prepared in a pared condition. In this way, di?iculties due to number of ways. However, the di?iculty arises that when chloracetone is stored, in many in 10 contamination from polymerization products already formed and the like, would be minimized. stances it starts to turn dark in a few days time. Such freshly prepared chlorinated ketone, and At the end of a few weeks or a month the liquid in the particular instance under discussion, es becomes very dark. At still a greater length of sentially comprising monochloracetone, was neu time the product may change to a black, viscous, tarry mass. Hence, it has been necessary in 15 tralized with a saturated solution of a weak alkali, litmus being used as an indicator. many instances either to prepare the chlorinated Sodium bicarbonate is a satisfactory alkali, acetone immediately prior to its use, or redistill whereas ammonium hydroxide, for example, the product frequently. It has also been pro would not be employed. After this neutraliza posed to seal the liquid in dark colored con tainers and add various constituents thereto such 20 tion treatment the chloracetone is stirred with a hygroscopic salt such as calcium chloride. as hydroquinone, diphenylamine, isoamyl nitrate The chloracetone layer resulting may be poured or the like. off and further treated. To the chloracetone I have found that the aforementioned di?i from either of these steps is added a small culties may be overcome and that relatively large amount of calcium carbonate. quantities of chloracetone may be prepared and Or, in place of or supplemental to the pre stored. At the end of the storage period the ceding treatment, chloracetone may be mixed chloracetone treated in accordance with my in

storage.

However, as indicated, chlorinated acetone, which tends to deteriorate upon standing, may be obtained from any source. Preferably, the

vention described in detail herein, was in all

with calcium carbonate and distilled under re

instances in relatively satisfactory condition.

This invention has for one object to provide a

duced pressure. While I may treat chlorinated ketones from

various sources with calcium carbonate, barium carbonate or other carbonates, to obtain a prod

treatment which improves chlorinated ketones

such as, for example, chloracetones which nor mally tend to deteriorate upon standing. Still another object is to provide a preliminary treat ment which renders stabilization treatment more 2 e?ective. Another object is to provide novel pro cedure for storing my chlorinated acetones. A still further object is to provide a monochlor acetone which is capable of storage for extended

uct capable of storage for an inde?nite period, for a product particularly resistive to deteriora tion I prefer to prepare the chloracetone as follows: Vaporous acetone is fed into a reaction cham ber substantially simultaneously with the intro
duction of chlorine. By means of cooled or

periods without deterioration thereof.

I have found that chlorinated ketones and in

40

particular chloracetones which normally tend to darken and ?nally deteriorate to Viscous, tarry
masses, may if desired, be subjected to a pre

liminary treatment and ?nally treated with a carbonate such as calcium carbonate, thereby obtaining a product capable of storage for an inde?nite period without deterioration. For a more complete understanding of my invention,
reference is made to the following examples -

heated conduits, as conditions may require, posi tioned above and below the reaction chamber, the reaction is operated so that the chlorinated ketone formed immediately ?ows out of the reac tion chamber to a receiver. In ?owing from the reaction chamber, the chlorinated acetone is passed through a heated conduit which causes the stripping out of unreacted acetone, chlorine, etc., thereby delivering to the receiver chlorin
ated acetone more or less free of these con

stituents.
The cooled conduits tion chamber and in function to condense bon, acetone and the positioned above the reac communication therewith, out chlorinated hydrocar like which may be carried

which are set forth primarily for the purpose of illustrating my preferred embodiment and not to be construed as limiting my invention. Chlorinated ketones from various methods of manufacture may be treated by my process. 55

out with the escaping hydrogen chloride. By

2,263,010
to the storage thereof. Also, as indicated, the further preliminary steps of neutralization and
drying with a salt such as calcium chloride, as

employing a chlorine feed which merely gives a

slight greenish tinge to the reaction chamber,

namely, a quantity of chlorine not greatly in excess of the acetone, relatively large yields of

described, assist in rendering the carbonate step

preliminary puri?cation comprising neutraliza

monochloracetone may be obtained. As indi 5 more effective. I have found, however, that the cated, the chlorinated acetone is collected in a utilization of the Various carbonates such as bar receiver. ium, strontium, calcium and the like, at one or This crude chloracetone was subjected to the more points in the preparation of chloracetone,
produces a chloracetone more resistant to deteri

tion with sodium bicarbonate, litmus being used 10 oration upon storage. I prefer to employ calcium
as the indicator. Thereafter the chloracetone was agitated with calcium chloride and the

chloracetone layer poured off and subjected to further treatment with calcium chloride. The chloracetone from this latter treatment was mixed with approximately 1% by weight of
calcium carbonate. This mixture was distilled

carbonate inasmuch as this is relatively economi cal and readily obtainable, and store the chlorace tone in contact therewith. Relatively small amounts of the calcium car bonate, as for example 1 to 6 grams of calcium carbonate added to 100 grams of chloracetone

no injury and may be added if desired. a water-cooled still head and the product col Chloracetone treated in accordance with my lected in a water-cooled receiver. The chlorace 20 invention, even after several months storage was tone collected as the head product was further satisfactory for use without redistillation. If de distilled and a cut boiling between 117-1200 C. sired, the chloracetone in accordance with my collected. This cut essentially comprised mono invention, may be stored in colored containers chloracetone. as, for example, amber colored glassware, but This chloracetone fraction from the aforemen this is not necessary. tioned preliminary treatment was then further Therefore, it is apparent from the foregoing treated with a small amount of calcium carbon that my invention is susceptible of some modifi ate. It was found that this chloracetone did not cation. Hence, I do not wish to be restricted, materially change even after long periods of excepting insofar as is necessitated by the prior storage. art and the spirit of the appended claims. In accordance with the following example, a What I claim and desire to be secured by Let crude dichloracetone was obtained, Dichlorace ters Patent of the United States is: tone may be prepared in accordance with the pro 1. The method of treating a freshly prepared

under slightly reduced'pressure in a still having

would be su??cient.

However, a surplus causes

crude chloracetone was fractionated as described

cedure already described. Supplying larger chloracetone fraction boiling within the tempera quantities of chlorine to the reaction tends to 35 ture range of 117 C.120 C., which comprises cause the production of the dichloracetone. The treating said chloracetone with a small amount
This dichloracetone
of an alkaline earth metal carbonate. 2. A composition of matter essentially com

and the residue of the fractionation essentially

and distilled chloracetone stored in the presence

prising chloracetone having a small content of earth metal carbonate incorporated therewith. of a small amount of calcium carbonate. It was 3. A composition of matter essentially com likewise found that this dichloracetone which prising monochloracetone having a small content had been treated with the calcium carbonate did of calcium carbonate. not materially change, even after an extended 45 4. A composition of matter essentially com period of storage. prising at least one chlorinated ketone having a It is therefore apparent from the preceding small content of alkaline earth metal carbonate examples, that chloracetones which normally incorporated therewith. tend to deteriorate upon storage, may be treated 5. The method of treating a freshly prepared with carbonates to obtain a product resistant to 50 chlorinated ketone which comprises treating said such deterioration. In most instances I would ketone with at least a su?icient amount of an prefer to subject the crude chloracetone to a dis tillation treatment in the presence of calcium alkaline earth metal carbonate to prevent de carbonate and thereafter adding a small amount terioration during storage. of calcium carbonate to the distilled product prior 55 EMIL J. RAHRS.
was distilled in the presence of calcium carbonate 40 alkaline

comprised dichloracetone.