1424 DURRANS: THB ACTION OB SULPHWRYL UELORIDE

CLXV1.-The Action of XuZphuryl Chloride on Organic Substances. Part II .

By THOMAS HAROLD DURRANS. THE action of sulphuryl chloride on more complex benzenoid substances than the simple mono-substituted derivatives of benz- ene previously investigated (T., 1922, 121, 44) has been examined under the conditions of experiment therein laid down, except where otherwise stated.

The table shows briefly the results obtained.

Organic substance. Benzyl benzoate. Benzyl acetate. Benzil. Anisole. Salicylaldeh yde. Anisaldehyde. Cinnamaldehyde. Cinnamic acid. Anthranilic acid. Anethole. Methylchavkol.

Products. Benzyl chloride. Benzoic acid. Traces of acetic anhydride and benzoic acid. No action. 2 : 4 : 6-Trichloroanisole. 6 -Chlorosalicylaldehyde. 3 : 5-Dichloroanisaldehyde. aS-Dichoro-B-phenylpropaldehyde. a@-Dichloro-8-phenylpropionic acid. 3 : 5-Dichloro-2-aminobenzoic acid. A tetrachloroanethole. A tetrachloromethylchavicol.

The positions of the chlorine atoms in the last two products have not yet been satisfactorily defined.

E X P E R I M E N T A L . Benzyl Benzoate.-Sulphuryl chloride (5 mols .) was distilled on

to benzyl benzoate (m. p. 19" ; 1 mol.) ; very little sensible reaction

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ON ORGANIC SUBSTANCES. PART If. 1425

took place. After three days, the excem of sulphuryl chloride having been removed by distillation, the remaining liquid gave two main fractions and a, black residue; the small, first fraction, distilling up to 80"/15 mm., was identified as benzyl chloride, the second fraction, b. p. 140-190"/15 mm., as benzoic acid.

It is probable that benzoic anhydride is one of the products of the reaction, but the low vapour pressure of this substance (b. p. 360") necessitates for its distillation a temperature which, in presence of traces of sulphur trioxide, is favourable to decomposition, water, and therefore benzoic acid also, being produced.

Benxyl Acetate.-A mixture of sulphuryl chloride (4 mols.) and benzyl acetate (1 mol.) was gently boiled under reflux for about eight hours and then fractionally distilled. After removal of the excess of sulphuryl chloride, two fractions were taken boiling approximately at 48"/12 mm. and 95"/10 mm., the second being comparatively large. The first fraction boiled under atmospheric pressure a t 118", the temperature rising rapidly to 135", and had all the characteristics of acetic anhydride. The aecond fraction, b. p. 212-216"/760 mm., was unchanged benzyl acetate. The residue remaining from the original distillation gave a sublimate of benzoic acid, m. p. 120".

Benzyl acetate is, in the main, unattacked by sulphuryl chloride under the conditions of the experiment, only small quantities of acetic anhydride and benzoic acid being produced.

BenxiL-Sulphuryl chloride (7 mols.) was distilled on to benzil (1 mol.), when solution took place with a slight absorption of heat. After three days, the excess of sulphuryl chloride was slowly distilled off, and the residue poured into water. The yellow solid obtained proved to be benzil in almost unchanged amount.

Anisole.-Peratoner (Gazxelta, 1898, 28, i, 197) found that p-chloroanisole is the prcduct of the reaction between sulphuryl chloride and anisole, while Boeseken (Rec. trav. chim., 1911, 30, 281), using aluminium chloride as a catalyst, obtained a chloro- anisole and dianisyl sulphoxide. Hugounenq (Ann. Chim. Phys., 1890, [vi], 20, 521) obtained a trichloroanisole, m. p. 60.5", by the action of chlorine on anisole. It has now been found that impure sulphuryl chloride can be made to yield the trichloroanisole of Hugounenq, probably by virtue of its partial dissociation into sulphur dioxide and chlorine (compare Trautz, 2. Elektrochem. , 1908, 14, 534).

Commercial sulphuryl chloride was mixed in large excess with anisole ; a solid substance formed which subsequently dissolved in the excess of sulphuryl chloride. The solution was heated under reflux for several hours, and the excess of sulphuryl chloride

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1426 D U ~ A N S : THE ACTION OF SULPHURYL CHLORIDE

then slowly distilled off. The residue was poured into water and after purification melted a t 60" (Found : C1= 50.12. Calc, for C,H50C1,, C1 = 50.36 per cent.). The substance is identical with that obtained by Hugounenq (Zoc. cit.) and is 2 : 4 : 6-trichloro- anisole. SccZicyZuldehy&e.--Sulphuryl chloride (5 mols,) was distilled on

to salicylaldehyde (1 mol.). Vigorous reaction ensued, much heat being evolved, and the mixture passed through a series of colour changes, from purple to red, orange, and finally to yellow (compare Silberrad, T., 1921, 119, 2030). After about half an hour, the mixture solidified. The excess of sulphuryl chloride was distilled off; the residue boiled a t about 105"/12 mm. The distillate, crystallised from benzene, gave long, flat needles, m. p. loo", of 5-chlorosalicylaldehyde, identical with the compound obtained in a similar way by Peratoner (Zoc. cit., p. 235) (Found : C = 52.53; H = 3.37. Calc., C = 53.67; H = 3.19 per cent.). The crystals, oxidised with chromic acid mixture, gave a small yield of 5-chloro- salicylic acid, m. p. 172".

Anisaldehyde.-Vigorous action occurred when sulphuryl chloride (9 mols.) was distilled on to anisaldehyde (1 mol.), and the mixture rapidly darkened. After remaining for three days a t room temperature, the sulphuryl chloride was slowly distilled off. From the residue was obtained a large fraction, boiling a t about 149"/11 mm., which solidified on cooling. The bright red solid, after crystallisation from alcohol, melted a t 61-5", was odourless and colourless, and had the properties of an aldehyde (Found: C = 46.95; H = 2.96; C1 = 34.77. C8H,02C12 requires C = 46.82 ; H = 2.93 ; C1 = 34.63 per cent.). Oxidised with chromic acid mixture, it gave an 80 per cent. yield of an acid, m. p. 202- 202*5", which, by the melting point of the mixture, was identified as 3 : 5-dichloroanisic acid (compare Reinecke, 2. Chem., 1866,366). On boiling this acid with concentrated hydriodic acid, 3 : 5-dichloro- 4-hydroxybenzoic acid, m. p. 265" (corr.), was obtained (compare Mazzara, Guzxetta, 1899, 29, i, 388; Tarugi, ibid., 30, ii, 490; Bertozzi, ibid., 29, ii, 39).

The 3 : 5-dichbroanisaZdehyde, similarly treated with hydriodic acid, yielded 3 : 5-dichloro-4-hydroxybenzaldehyde, ,m. p. 156", an odourless, white solid (compare Auwers and Reis, Ber., 1896, 29, 2356).

It is evident that the product of the reaction between anis- aldehyde and sulphuryl chloride is 3 : 5-dichloroanisaldehyde. No dichloro-derivative of anisaldehyde appears to have been previously known.

Cinnama;ldehyde.-The reaction between cinnamaldehyde and

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ON ORGANIC SUBSTANCES. PART 11. 1427

sulphuryl chloride was very vigorous, free chlorine being liberated along with sulphur dioxide. The product, obtained in good yield, was a liquid, b. p. 151-153"/20 mm., which would not solidify when cooled to - 12" and had a sharp, weak odour reminiscent of ozone. It would not readily yield chlorine to alcoholic silver nitrate solution (Found : C = 52-76 ; H = 3.79 ; C1= 34.88. C,H80C1, requires C = 53-20; H = 3.94 ; C1= 34.97 per cent.). The substance can be readily oxidised with nitric acid, and difficultly with chromic acid mixture, to yield an acid which on hydrolysis with sodium hydroxide solution gives w-chlorostyrene.

It seems evident that the compound formed by the action of sulphuryl chloride on cinnamaldehyde is orp-dichloro-p-phenylprop- aldehyde, although the properties of the product obtained as above are not in agreement with those recorded by Naar (Ber., 1891,24, 246) for this aldehyde. Naar states that it is a crystalline solid which has lachrymatory properties, and gives off hydrogen chloride very readily, thus making accurate analysis difficult.

Cinnumic Acid.-Sulphuryl chloride (46 mols.) was run on to cinnamic acid (1 mol.) ; the acid dissolved, but no reaction was observed. After six weeks, the excess of sulphuryl chloride was removed and the residue poured into water. The solid thus obtained, after purification, melted a t 167-168" and was sparingly soluble in carbon tetrachloride or carbon disulphide (Found : C1= 32.17. Calc. for C,H80,C1,, C1= 32.42 per cent.).

The product, hydrolysed with sodium hydroxide solution, yielded an oil, b. p. 83"/18 mm., having the characteristic hyacinth odour of o-chlorostyrene (Found : C = 68.65; H = 6.12. Calc., C = 69.31 ; H = 5-06 per cent.).

From the aqueous alkaline solution remaining after hydrolysis, or-chlorocinnamic acid, m. p. 139", characterised by its extraordin- arily high solubility in many organic solvents, was isolated. This acid is evidently a-chlorocinnamic acid (compare Sudborough and James, T., 1906, 89, 105) (Found : C = 69-16; H = 3.94. Calc., C = 59.17; H = 3-83 per cent.).

The product of the reaction between sulphuryl chloride and cinnamic acid is therefore ap-dichloro- p-phenylpropicnic acid.

Anthrunilic Acid.--Saturated acids are, in general, not acted on by sulphuryl chloride, but the highly basic nature of anthranilic acid causes i t to react readily.

Sulphuryl chloride (4 mols.) was distilled on to anthranilic acid (1 mol.). Action commenced immediately and a white solid sublimed. After a short period, the excess of sulphuryl chloride was distilled off, a light bluish-green, insoluble solid remaining. This solid, which was almost completely soluble in sodium hydroxide

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1428 ACTION OF SULPHURYL CHLORIDE ON ORQANIC SUBSTANCES.

solution and was reprecipitated therefrom by acids, crystallised from benzene in needles, m. p. 223" (Found : C = 41.23 ; H = 2.54 ; C1= 33.78. NH,*C,H,Cl,~CO,H requires C = 40.77; H = 2.42; C1= 34.46 per cent.). The substance was converted by recrystallis- ation from glacial acetic acid into a solid, m. p. 278", which was probably the acetylamino-derivative.

The dichloroamino-acid boiled a t about 260", prolonged boiling causing the boiling point to decline to about 247", with evolution of carbon dioxide and formation of 2 : 4-dichloroaniline (compare Dorsch, J. pr. Chem., 1886, [ii], 33, 52; E'ranke, &bid., 1891, [ii], 44, 432). A substance obtained in small quantity from the original reaction mixture had an olive-green colour, melted a t 277", was insoluble in acids and alkalis and in most organic solvents, and left no ash on ignition. The amount of the substance was too small to allow it to be identified,

The main product of the reaction between sulphuryl chloride and amthranilic acid is therefore 3 : 5-dichloro-2-aminobenzoic acid.

Since this work was completed, Eller and Klemm (Ber., 1923, 55, [B] , 2177) have obtained f is t 5-chloro-2-aminobenzoic acid and finally 3 : 5-dichloro-2-aminobenzoic acid by acting on anthranilic acid with sulphuryl chloride in ethereal solution.

Andhole.-Sulphuryl chloride (6 mols.) was distilled very slowly on to anethole (1 mol.), a very vigorous reaction taking place. After forty-eight hours, the excess of sulphuryl chloride was removed and the residue distilled under diminished pressure. By repeated fractional distillation, a large yield of colourless, nearly odourless, crystalline solid was obtained, m. p. 70*5", b. p. 191"/17 mm. (Found : C = 41.97, 41-50 ; H = 3.65, 3.38 ; C1 = 50.1. CloHl0OCl4 requires C = 41.66 ; H = 3.47 ; C1 = 49.3 per cent.).

The substance on boiling with alcoholic silver nitrate solution loses one atom of chlorine (Found : loss = 12.45. Calc., loss = 12.32 per cent.).

Boiling with N-alcoholic sodium hydroxide yields a substance, b. p. 164"/20 mm., m. p. 36", having a very faint odour resembling that of amyl salicylate (Found : C = 47.62 ; H = 3.58. C,oH,OC1, requires C = 47.72 ; H = 3.57 per cent.).

It does not seem possible that this substance can be the trichloro- derivative described by Darzens (Compt. rend., 1897, 124, 564), although the melting points are similar.

The constitutions of these two substances have not yet been satisfactorily established.

Met~~ZchavicoZe.--Sulphuryl chloride (4 mols.) was distilled on to methylchavicole (1 mol.), reaction immediately ensuing. After fractional distillation, a liquid was obtained which boiled a t 199'/13

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INVESTIGATIONS OF THE CHROMATICS OF THORIUM, ETC. 1429

mm., but would not solidify even at - 15" (Found : C = 41.66; H = 3.47 ; C1= 49.57. C,@,,Cl, requires C = 41-53 ; H = 3.56 ; C1= 49.30 per cent.). This tetrachloro-derivative is different from that obtained in a similar manner from anethole and has not yet been identified.

THE DYSON PERRINS LABORATORY, OXFORD. [Received, A p d 28th, 1923.1

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