Sartori The War Gases Chemistry and analysis

154 HALOGENATED KETONES

bromoacetone. That is, by brominating methyl ethyl ketone with sodium bromide in presence of sodium chlorate. In this preparation bromomethyl ethyl ketone is not the only product, a mixture with the isomeric methyl-a-bromoethyl ketone always being obtained.1

PHYSICAL AND CHEMICAL PROPERTIES

Bromomethyl ethyl ketone is a colourless or pale yellowish liquid which boils at ordinary pressure at 145° to 146° C. with decomposition. Its specific gravity is 1-43. It is insoluble in water; alteration on exposure to light is rapid. It is not decomposed by the action of water, and in general its chemical behaviour is very similar to that of bromoacetone. It is easily absorbed by active carbon. Places contaminated with bromomethyl ethyl ketone can be decontaminated by spraying with a soapy solution of " liver of sulphur."

Bromomethyl ethyl ketone is an irritant especially to the eyes. The minimum concentration capable of causing irritation of the eyes is 1-6 mgm. per cu. m., according to Muller. The limit of insupportability is n mgm. per cu. m. of air (Fries), and the mortality-product is 6,000.

(B) AROMATIC

The halogenated ketones of the aromatic series may be prepared, like those of the aliphatic series, by the action of the halogens on the corresponding ketones. Some may be obtained by the Friedel and Craft synthesis, that is, by condensing an aromatic hydrocarbon with an aliphatic halogen acid in presence of anhydrous aluminium chloride.

In the preparation of these war gases by direct halogenation it is necessary to follow the exact procedure given so as to introduce the halogen only into the side-chain, as compounds with a nuclear halogen atom have no lachrymatory properties.

In order to ensure this, according to Graebe 2 and Staedel,3 the halogenation should be carried out at the boiling point of the ketone, or, according to Gautier * and Hunnius,5 by operating in presence of special solvents such as carbon disulphide, acetic acid or carbon tetrachloride,6 which seem to have the function of directing the halogen atom into the side-chain.

1L. v. REYMENANT, Butt. acad. roy. Belg., 1900, 724.

2GRAEBE, Ber., 1871, 4, 35.

3STAEDEL, Ber., 1877, 10, 1830.

4GAUTIER, Ann. chim. phys., 1888, 14, 377.

5HUNNIUS, Ber., 1877, 10, 2006.

• WARD, /. Chem. Soc., 1923, 123, 2207.

The aromatic halogenated ketones, unlike those of the aliphatic series, are quite stable compounds. Another difference is that the aromatic derivatives, although they contain a carbonyl group, form no additive compounds with bisulphite.1

Recently, some fluorinated members of this group have been prepared, such as fluoroacetophenone? a brown liquid with a pungent odour, which boils at 98° C. at 8 mm. pressure. It is described as having lachrymatory properties, but the magnitude of these is not reported.

An interesting fact concerning these compounds from the aggressive point of view is that the halogenated aromatic ketones have superior lachrymatory properties to the corresponding aliphatic compounds. Thus chloroacetophenone has a much more powerful lachrymatory action than the chloroand even the bromoderivative of acetone. This fact, besides having great advantages on the economic side—and being by no means negligible from the purely offensive point of view—indicates that it is not only the halogen to which the lachrymatory properties of these compounds is due, but also to the rest of the molecule to which the halogen is united.

With regard to the biological properties, it has been found that several substances of this group, like a-chloroacetophenone and a-3-4 trichloroacetophenone, cause,3 besides lachrymation, a painful sensation of itching when they penetrate the pores of

a-Chloroacetophenone—also termed to-chloroacetophenone, phenacyl chloride or phenyl chloromethyl ketone—was prepared in 1871 by ^Graebe4 by absorbing chlorine in acetophenone. Later, in 1884, Friedel and Craft 5 succeeded in obtaining it by the action of chloroacetyl chloride on benzene in presence of aluminium chloride:

C6H6 + C1CO—CH2C1 = C6H5—CO—CH2C1 + HC1.

It may also be prepared by the action of diazomethane on benzoyl chloride in ethereal solution 6 :

CHLOROACETOPHENONE : PROPERTIES 157

lined vessel fitted with a thermometer and a fractionating column connected with an absorption tower, which is filled with coke and serves to absorb the hydrochloric acid. The vessel is heated to about 98° C., while the calculated quantity of dry chlorine gas is slowly passed in.

Monochloroacetic acid is thus obtained and this is transferred without further purification to another similar vessel. Sulphur monochloride is added, and chlorine is introduced, while heating to 45°C., to complete the chlorination. The chlorinated product is then transferred to a third vessel in which fractional distillation separates the chloroacetyl chloride from the other products (sulphur chloride, excess monochloroacetic acid, etc.).

The calculated quantities of benzene and aluminium chloride

mass is warmed to 60° to 70° C. for 2 hours and then poured into cold water. The layer containing the chloroacetophenone is freed from benzene by distillation and the chloroacetophenone finally purified by steam distillation.

PHYSICAL AND CHEMICAL PROPERTIES

Chloroacetophenone forms colourless or slightly yellowish crystals which melt at 58° to 59° C. (Staedel).

It boils at ordinary pressure at 244° to 245° C. and may be distilled without any decomposition. At 14 mm. mercury pressure it boils at 139° to 141° C. Its specific gravity at various temperatures is as follows :

The vapour tension of chloroacetophenone at ordinary temperatures is very low. It is given as a function of temperature in the following table :

158 HALOGENATED KETONES

The volatility is 30 mgm. per cu. m. of air at o° C., and 105 mgm. per cu. m. at 20°C.

The specific heat of chloroacetophenone is 0-264 calorie and the latent heat of evaporation 89 calories.

Chloroacetophenone is soluble in alcohol, benzene (40% by weight), ether and carbon disulphide,1 as well as in many of the other war gases. For instance, phosgene dissolves 9-5% by weight, and cyanogen chloride 63% by weight. It is, however, very slightly soluble in titanium tetrachloride, silicon tetrachloride or water (i gm. in 1,000 ml.).

The solubility of chloroacetophenone in the readily volatile solvents is utilised in diffusing it in air. For this purpose benzene is the best solvent, carbon tetrachloride also being occasionally employed. When a solution in one of these solvents is sprayed into the air the solvent evaporates rapidly, leaving the chloroacetophenone dispersed in a state of fine subdivision.

Chloroacetophenone is quite stable. It is not hydrolysed by water even on boiling and it is unaffected by humidity. It is completely decomposed by 60% oleum. Hot aqueous solutionsof sodium carbonate convert it into hydroxymethyl phenyl ketone of the formula (Graebe), C6H5—CO—CH2OH, which forms crystals melting at 86° C. and boiling at 118° C. at n mm. mercury pressure. It is soluble in alcohol, ether and chloroform.

Chloroacetophenone is oxidised in benzene solution by such oxidising agents as chromic acid or potassium permanganate to benzoic acid.

By adding it in small quantities to a mixture of fuming nitric acid and sulphuric acid, shaking after each addition, it is converted into benzoic acid and w-nitro-a-chloroacetophenone z :

This forms crystals melting at 100-5° to 102° C.

C6H6COCH2C1 + C12 = C6H5COCHC12 + HC1.

This is obtained as crystals melting at 20° to 21-5° C. Its density

1STAEDEL, Ber., 1877, 10, 1830.

2BARKENBUS and CLEMENTS, /. Am. Chem. Soc., 1934, 56, 1369.

3H. GAUTIER, Ann. chim. phys., 1888, [6] 14, 345-385.

is 1-34 at 15° C., and it boils at ordinary pressure at 247° C. with decomposition. At 25 mm. pressure it distils unaltered at 143° C. It has inferior lachrymatory properties to chloroacetophenone.

With more vigorous chlorination, at a temperature of 200°C. aided by sunlight, ocaa-trichloroacetophenone 1 is formed :

C6H6COCH2C1 + 2C12 = C6H5COCC13 + 2HC1.

This is a liquid boiling at 145° C. at 25 mm. pressure and having a density of 1-425 at 16° C.

Chloroacetophenone reacts with sodium iodide in solution in aqueous alcohol, forming «-iodoacetophenone 2 :

C6H5COCH2C1 + Nal = C6H5COCH2I + NaCl.

This is a crystalline substance melting at 29-5° to 30° C., which boils at 170° C. at 30 mm. pressure and is insoluble in water, but soluble in alcohol, ether and benzene.

With hydriodic acid or, better, by boiling with an acetic acid solution of potassium iodide, chloroacetophenone separates iodine and forms acetophenone 3 :

C6H5COCH2C1 + 2HI = C6H6COCH3 + HC1 + I2.

Alcoholic ammonia converts chloroacetophenone in the cold to a-aminoacetophenone *:

C6H5COCH2C1 + HNH2 = C6H5COCH2NH2 + HC1,

which is partly converted into iso-indole. With aniline, phenacyl aniline is formed 5 :

C6H5COCH2C1 + NH2C6H5 = C6HBCOCH2.NHC6H6 + HC1. Urotropine forms an additive product of the formula8

C6HBCOCH2[N4(CH2)6]C1.

which forms crystals melting at 145° C.

Chloroacetophenone dissolved in alcohol reacts at 60° C. with an alcoholic solution of sodium sulphide to form phenacyl sulphide, as follows 7 :

Chem., 1927, 7, 67.

160 HALOGENATED KETONES

ether and acetic acid. On heating to 100° C. it decomposes, forming hydrogen sulphide, acetophenone and products whose nature has not yet been denned.

By boiling an alcoholic solution of chloroacetophenone with an aqueous solution of sodium thiosulphate, the sodium salt of phenacyl thiosulphuric acid is formed :

C6H5COCH2C1 + Na2S2O3 = NaCl + C6H5COCH2.S2O3Na.

On refluxing equimolecular amounts of chloroacetophenone and potassium thiocyanate together, needle-shaped crystals are formed of the following formula :

C6H5COCH2SCN,

which melt at 72° to 73° C. and are soluble in alcohol, ether and chloroform.1

i mol. chloroacetophenone reacts with 3 mols. hydroxylamine hydrochloride in dilute methanol solution at ordinary temperatures, with formation of a-chloroacetophenone oxime, of the formula 2 :

C6H5-C-CH2C1

HO-N

This forms crystals melting at 88-5° to 89° C. whose vapours have a powerful lachrymatory action. This substance causes persistent and strong irritation when applied to the skin in the solid state or in solution.

Chloroacetophenone, on treatment in the cold with sodium phenate in aqueous or alcoholic solutions, reacts as follows 3 :

C6H6COCH2C1 + NaOC6H6 = C6H6COCH2.OC6H5 + NaCl.

Chloroacetophenone does not attack iron containers. It is resistant to heat and insensitive to detonation, so that it can be loaded into projectiles without fear of its suffering change.

It was used, melted with magnesium oxide and mixed with nitrocellulose, for the preparation of irritant candles.4

Graebe noted that the vapours of chloroacetophenone irritated the eyes, and the Americans (Fries) have found that a concentration of 0-3 mgm. per cu. m. of air is sufficient to provoke lachrymation. According to Muller,5 the lachrymatory action commences at a concentration of 0-5 mgm. per cu. m., while it

1DYCKERHOF, Ber., 1877, 10, 119.

2KORTEN and SCHOLL, Ber., 1901, 34, 1901.

3LELLMANN, Ber., 1890, 23, 172.

4Federal Laboratory, U.S. Pat. 1,864,754.

6 MULLER, Militar-Wochenblatt., 1931, 116, 754.

mortality-product is 4,000 according to Miiller and 8,500 according to American experiments (Prentiss).

Bromoacetophenone was obtained by Emmerling and Engler1 by the reaction of bromine on acetophenone.

C6H5CO-CH3 + Br2 = C6H5-CO-CH2Br + HBr.

PREPARATION

In the laboratory it is usually prepared by Mohlau's 2 modification of Emmerling's original method, that is, by the action of bromine on acetophenone.

25 gm. acetophenone and 125 gm. acetic acid are placed in a flask through whose stopper passes a reflux condenser, a tap-funnel and a delivery-tube for carbon dioxide. While agitating the contents of the flask, 30 gm. bromine3 are added little by little from the tap-funnel, meanwhile passing a current of carbon dioxide through the liquid to remove the hydrobromic acid formed in the reaction. When all the bromine has been added, the current of carbon dioxide is continued for 5-10 minutes and then the whole allowed to stand for about i hour before heating on the water-bath to remove the carbon dioxide completely. When the liquid in the flask is colourless it is poured into much water. The bromoacetophenone separates for the most part as a yellow oil which forms a crystalline mass on cooling. The crystals are collected and purified by alcohol.

PHYSICAL AND CHEMICAL PROPERTIES

Bromoacetophenone forms white rhombic prisms whichbecome greenish on exposure to light, owing to incipient decomposition. It melts at 50° C. and boils at ordinary pressure at 260° C. with decomposition, and at 12 mm. mercury pressure at 133° to 135° C. with partial decomposition. It is insoluble in water, but soluble in the common organic solvents (alcohol, ether, benzene, etc.).

Bromoacetophenone is not decomposed by water even on

1EMMERLING and ENGLER, Ber., 1871, 4, 147.

2M&HLAU, Ber., 1882, 15, 2465.

»WARD, /. Chem. Soc., 1923, 123, 2207.

162 HALOGENATED KETONES

boiling. With potassium permanganate it reacts to form benzoic acid.1 With cold fuming nitric acid it gives bromotrinitroacetophenone.

Treated in the cold with alcoholic ammonia, it forms iso-indole. The reaction with aniline is more vigorous than in the case of chloroacetophenone.2

Bromoacetophenone 3 in alcoholic solution when treated with an alcoholic solution of sodium -sulphide reacts vigorously, evolving hydrogen sulphide and forming a crystalline mass of phenacyl sulphide (see p. 159).

S(C6H5COCH2)2.

On treatment in the cold with sodium phenate in aqueous or alcoholic solution, bromoacetophenone reacts according to the equation 4 :

C6H5COCH2Br + C6H5ONa = NaBr + C6H5COCH2.OC6H5.

It combines with hexamethylene tetramine to form an additive product of the formula :

C6H8—CO—CH2[N4(CH2)6]Br,

which forms crystals melting at 165° C.5

The lachrymatory power of bromoacetophenone is less than that of chloroacetophenone.

CHAPTER XII

HALOGENATED NITROCOMPOUNDS

THE presence in a molecule of a nitrogen atom united by a double link to an oxygen almost always involves a certain degree of toxicity. Moreover, this toxicity is increased and lachrymatory action is added if halogen atoms are also present.

During the last war much interest was taken in the trihalogen derivatives of nitromethane as war gases :

Since the war, research on the halogenated nitrocompounds has been continued, especially on the corresponding compounds of the higher homologues of methane. The following results have been obtained :

(1) Symmetrical dichlorotetranitro ethane,1 obtained by the action of chlorine on the potassium salt of symmetrical tetranitro ethane :

CHBr CHBrN02 forms colourless crystals melting at 133° to 134° C.