BUQHES AND TITEERLEY: THE ACTION OF AMHONIA, ETC. 2'19

X X V L - T h e Action of Ammonia .on 6-Chloro-Z-pl~enyl- 1 : 3 -benxoxazine-4- one.

By ERNEST CHISLETT HUGHES and ARTHUR WALSH TITHERLEY.

IT ha.s already been noted by the authors (Trans., 1910, 97, 1377) that ammonia reacts with 6-chloro-2-phenyl-1 : 3-benzoxazine-4-one (I), producing a yellow, crystalline compound. This action, which hss since been studied closely, is similar to that of ammonia on 2-phenyl-l : 3-benzoxazine-4-one (Titherley and Hughes, Trans., 1911, 99, 1493), the yellow compound, 5-chlorosalicylbenzamidine (TIT.), being formed from the hypothetical additive compound (11). By long-continued action of ammonia, however, in hot alcoholic solution, a pale yellow, very insoluble substance is formed, which on investigation proved to be the chlom-derivative + of o-hydroxy- triphenyltriazine (IV). This compound is also produced .by the

* This particular relationship between the gas volumes, ehich is strikingly comtant, may be explained by the following equation, assuming that the highly deliquescent salt during its introduction into the decomposing tube absorbs two molecules of water for every seventeen molecules of the salt :

17NEt3,HN0,+ 2H20 = 12NO + 3N20 -I- 3N2+ 10Et3 + 21EtOH.

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220 HIJGHES AND TITHERLEY: THE ACTION OF AMMONIA ON

condensation between phenyl 5-chlorosalicylate (V) and benzami- dine, evidently through 5-chlorosalicylbenzarrlidine (III), which, from analogy to the condensation previously described (Trans., 1911, 99, 1499) between phenyl salicy1at.e and benzamidine, must be first formed. This assumption is confirmed by the fact that it is also obtained readily by the direct condensation of benzamidine and 5-chlorosalicylbenzamidine.

The same triazine derivative may, however, be obtained still more readily by the 'condensation of benzamidine and 6-chlorc~2-phenyl- 1 : 3-benzoxazine-4-one. It is therefore evident that, in the long- continued action of ammonia on the latter, a portion of the result- ing 5-chlorosalicylbenzamidi11e must undergo ammoniolysis, yielding benzamidine, which then condenses with the remainder, producing, by addition, rearrangement, and loss of water, the triazine deriv- ative (IV). These relations are expressed in the scheme:

co

(111.) p 3 I

+ CPh(:NH)*NH,

Cl/ \CO*N: CPh*N:CPh*NH, ()OH

p z o

N CPh

Cl/\CO,Ph ()OE

(111.)

The properties of 5-chlorosalicylbenzamidine and the triazine derivative are similar in all respects t o the corresponding parent compounds free from chlorine, previously described (Zoc. cit.).

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6-CHLORO-2-PHEN17L-1 : 3-BENZOXAZINE-4-ONE. 221

EXPERIMENTAL. 5-ChZorosa.ZicyZbenzam~dine, OH*C,H,Cl*CO*N:CPh*NH,.

Two grams of 6-chloro-2-phenyl-l : 3-benzoxazine-4-one were heated with 10 C.C. of concentrated ammonia and sufficient alcohol to dissolve the solid. The resulting bright yellow solution was rapidly concentrated on the water-bath to half its bulk, when on cooling bright orange-yellow needles (2 grams) separated, consisting of 5-chlorosaZicylbenzamidi7t.e, which after recrystallisation from light petroleum melted a t 156O: 0.1304, by Kjeldahl’s method, required 9.5 C.C. N/lO-HCI. N= 10.20.

C,,H,,O,N,Cl requires N = 10.22 per cent. The compound is sparingly soluble in ether or light petroleum,

moderately so in cold alcohol or chloroform, and readily so in acetone or hot alcohol. The acetone solution gives a strong reddish- violet; coloration with ferric chloride.

5r-Chloro-2f-hydroxy-2 : 4 : 6-triphen,yZ-1: 3 : 5-trkzine, OH*C,H,Cl*C,N,Ph,.

(1) This compound is formed by the continued action of ammonia on 6-chloro-2-phenyl-l : 3-benzoxazine-4-one. Five grams were dis- solved in the least possible quantity of hot alcohol, and 10 c . ~ . of strong ammonia added. The resulting bright yellow solution was heated on the water-bath for several hours, during which 5 / -ch lor~ 2’-hydroxy-2 : 4 : 6-triphenyl-1 : 3 : 5-triazine separated continually as a pale yellow solid. On cooling, a further quantity separated, and the whole after recrystallisation from alcohol was obtained in fine, flocculent needles, melting at 224.5O.

0.3748, by Kjeldahl’s method, required 30.9 C.C. N / 10-HC1.

0-3902 gave 0.1532 AgCl. Cl-9-71. C,,I~,,ON,Cl requires N = 11.61 ; Cl= 9-82 per cent.

The compound is very sparingly soluble in the usual solvents in the cold except acetone, in which it is moderately soluble. It is somewhat soluble in hot iight petroleum, benzene, or alcohol, from which it crystallises in characteristic matted needles on cooling. It dissolves in concentrated sulphuric acid with a bright red colour, which disappears on warming. The compound does not show phenolic properties, and it is not affected by sodium in boiling benzene solution or phosphorus pentachloride in boiling chloroform solution.

(2) Preparation from 6-Chloro-2-phe~yl-1: 3-b enzoxazine-4-one.- One gram of the chloro-derivative dissolved in hot alcohol was

The yield was 3 grams:

N = 11.54.

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222 HIGQINS : AN EXPERIMENTAL ENVESTJQATION

treated in alcoholic solution with 0.35 gram of benzamidine freshly prepared from 0.5 gram of its hydrochloride. A bright orange solution immediately resulted, which in a few seconds e v e place to a thick mass of pale yellow needles, which after washing with boiling alcohol melted at 223O. The yield was 1 gram, and a further 0.3 gram was recovered from the mother liquor. The substance was identical with 5/-chloro-2/-hydroxy-2 : 4 : 6-triphenyl- 1:3:5-triazine obtained by method (I), and a mixture of the t w o melted at 223O.

( 3 ) Preparation. from 5-Clhlorosalicylbensa~~cFine.-One gram of 5-chlorosalicylbenzamidine in alcoholic solution was heated to boiling with 0.35 gram of benzamidine for several hours. Slow action took place, and 5’-chloro~2/-hydroxy-2 : 4 : 6-triphenyl-l : 3 : 5- triazine was continually deposited in a pure form as pale yellow needles melting at 222O (yield, 0.3 gram).

(4) Preparatiorn from Ph,enyt ti-Chlorosalic;yZnte.-One gram of phenyl 5-chlorosalicylate in alcoholic solution was heated to boiling with 0.5 gram of freshly prepared benzamidine. A yellow solution was obtained, and after several hours a voluminous, pale yellow precipitate of pure 5/-chloro-2’-hydroxy-2 : 4 : 6-triphenyl-l : 3 : 5-tri- azine wm obtained (m. p. 220°), phenol being eliminated. The yield was 0.3 gram. .

ORGANIC LABOR.ATORY, UNIVERSITY OF LIVERPOOL.

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