1344 ROWE AND DAVIES: CXLV.-Studies in the Acenaph thene Se'vies. Part I. me Conversion of o- A'itroamines into isoOxadiuxole Oxides. By FREDERICK MAURICE ROWE and JOHN STANLEY HERBERT DAVIES. IN four previous communications (T. 1912 101 2452; 1913 103, 897 2023; 1917 111 612) one of us has shown that many o-nitro-amines in the benzene and naphthalene series are converted into f uroxans (furazan oxides or isooxadiazole oxides) when oxidised in alkaline solution with sodium hypochlorite. I n order further to test the generality of this reaction we have now carried out similar experiments in the acenaphthene series. Sachs and Mosebach (Ber. 1911 44 2852) have shown that whilst the direct nitration of acenaphthene yields a dinitro-derivative which contains the nitro-groups in the 3 4- or peri-position the reduction of 3-nitro-acenaphthene followed by acetylation nitration and hydrolysis of the resulting nitroacetylaminoacenaph thene gives rise to 2-nitro-3-aminoacenaphthene.The latter compound which contains the nitro- and amino-groups in the ortho-position with respect to one another has now been submitted to the hypochlorite oxidation. It is interesting to note that although the yield of the oxidation product was low the methylene groups of the acenaphthene ring remained unaffected and acenaphthene-2 3-isooxadiazole oxide was obtained. The corresponding compounds in the benzene and naphthalene series possess a charact'eristic almond odour and are readily volatile with steam but this compound is odourless and non-volatile.It is reduced by hydroxylamine to acenaphthene-2 3-quino?zediozime which may be converted into acenaphthene-2:S-isoozadiazole in the usual manner although the yield is not good. An attempt to reduce 2-nitro-3-acetylaniinoacenaphthene to the corresponding nitroso-compound in a similar manner to that used by one of us for the preparation of o-nitrosoacetanilide (Zoc. c i t . ) , in order to prepare acenaphthene-2 3-isooxadiazole from it by the alkaline hypochlorite oxidation proved unsuccessful. o-Quinoneclioximes are readily converted into isooxadiazole oxides by oxidation in alkaline solution with sodium hypochlorite, and consequently it was t o be expected that the oxidation of acenaphthene-7 I 8-quinonedioxime in this manner would yield an isooxadiazole oxide derivative of acenaphthene of a different typ STUDIES IN THE ACENAPHTHENE SERIES PARTI.1345 from that already described. This in fact proved to be the case, and acenaph thene-7 8-isooxadiazole oxide was obtained. On the other hand acenaphthene-7 8-quinonedioxime resisted all attempts to convert i t into acenaplithene-7 8-isooxadiazole by the removal of water. It remained unaffected by prolonged boiling with aqueous sodium hydroxide and when heated with aqueous sodium hydroxide in a sealed tube decomposition occurred with the form-ation of acenaphthenequinone and ammonia whilst no better result was obtained by heating with water in a sealed tube. Moreover, treatment of the diacetyl derivative of acenaphthene-7 S-quinone-dioxime with sodium hydroxide merely resulted in hydrolysis with no dehydration.This failure to dehydrate acenaphthene-7 8-quinonedioxime suggests that this coinpound most probably has the structure of a P(anti)-dioxime (I). The failure of this compound 0-0 HO*N:C-C:N*OH N 5 .. .. C-C! to give a nickel salt when treated with ammoniacal nickel solutions, as described by Atack (T. 1913 103 1317) in an investigation of the three stereoisomeric henzildioximes further supports this view. The preparation of acenaphthene-7 8-isooxadiazole oxide was of interest in view of the fact that Francesconi and Pirazzoli (Gazzetta 1903 33 i 36) prepared a compound by boiling acenaphthene-7 8-quinonedioxiine with aniyl nitrite to which the peroxide formula (TI) was provisionally assigned.This compound is described as forming reddish-brown crystals decomposing a t 90° and melting a t 1 4 0 O . It is soluble in organic solvents with decom-position forming a black substance which does not melt a t 260O. We therefore prepared a quantity of this compound in order to determine whether it was identical or not with acenaphthene-7 8-isooxadiazole oxide. After repeated crystallisation it was obtained finally in small brown needles decomposing at 190° and melting a t 206*5O and when pure it was not decomposed by organic solvents. This substance possesses quite different properties from those of acenaphthene-7 8-isooxadiazole oxide ; for example the former dissolves in cold aqueous sodium hydroxide with a pale yellow colour whilst the latter is quite insoluble in alkali hydr-oxides and moreover is readily reduced to acenaphthene-7 8-quinonedioxinie by hydroxylamine.J t is evident that the tw 1346 ROWE AND DAVIES: compounds are not identical and Francesconi and Pirazzoli’s com-pound was not examined more closely but in view of its properties, it seemed doubtful whether it possesses the peroxide formula assigned to it by these authors. When the present investigation was commenced the literature contained no reference to nitro-derivatives of acenaphthenequinone, and it was decided to fill in this blank. After the necessary experi-ments had been carried out however these compounds were described by Mayer and Rauffmann (Ber. 1920 53 [B] 296). The product of moiionitration is 3-nitroacenaphthenequinone melting a t 218O (M.and K. give 1 9 9 O ) which forms a monophenyl-hydrazone melting a t 234-235O (M. and K. give 186O) and the product of dinitration is 3 4-dinitroacenaphthenequinone melting and decomposing above 300° which forms a monophenylhydrazone darkening a t 260° and melting at 287O. I n conclusion ii appeared of interest t o ascertain whether the nitro-derivatives of acenaphthenequinone could be prepared by the oxidation of the nitro-derivatives of acenaphthene as the pre-paration of a substituted acenaphthenequinone by the oxidation of the corresponding derivative of acensphthene has been effected only in one instance namely by Graebc ( i l 9 ? n d e n 1903 327 7 7 ) , who found that 5-bromoacenaphthene was oxidised either to bromo-acenaphthenequinone or bromonaphthalic acid according to the conditions used.Experiments were made with S-nitroace-naphthene using a series of oxidising agents under a variety of conditions but i t was found that this compound either remained unaffected or was oxidised t o 4-2iitronaphthalene-1 8-dicarboxylic acid melting as anhydride at 229-230° (Graebe gives 220°) and in no case could we isolate any 3-nitroacenaphthenequinone . E X P E R I M E N T A L . The 2-nitro-3-aminoacenaphthene required was obtained by Sachs and Mosebach’s method (Zoc. cit.). Acenaphthene (m. p. 96O) was nitrated in glacial acetic acid suspension and the product extracted with light petroleum (b. p. goo) in which any dinitro-derivative formed simult.aneously is insoluble. The yield of 3-nitroacenaphthene7 yellow needles melting a t 101-102° was 89 per celntl.(S. aad M. give 84 per oemt.). The r d u d i m od th STUDIES IN THE ACENAPHTHENE SERIES. PARTI. 1347 nitro-compound is best effected in aqueous-alcoholic solution with sodium hyposulphite. The yield of 3-aminoacenaphthene almost colourless silky needles melting a t 104-1Oti0 was 71 per cent. (S. and M. give about 77 per cent. of an almost pure product). The monoacetyl derivative is best prepared with acetyl chloride. After repeated crystallisation from methyl alcohol 3-acetylamino-acenaphthene glistening needles melting a t 238O was obtained in a yield of 92 per cent. The melting point of this compound is greatly affected by traces of impurities; thus Quincke (Ber. 1885, 21 1457) gives 176O Graebe (Aniznlen 1903 327 77) gives 1 8 6 O , and Sachs and Mosebach (Zoc.cit.) give 1 9 2 O . A number of nitra-tions were carried out but the yield was always low owing to oxidation ; 2 - nitro - 3 - acetylaminoacenaphthene golden-yellow needles melting a t 255O was obtained in a yield of 35 per cent. (S. and M. give 253'; yield about 54 per cent.). When hydro-lysed with alcoholic' hydrochloric acid 2-nitro-3-aminoacenaphthene, blunt red prisms with a green lustre melting at 222O was obtained in an almost t,heoretical yield (S. and M. give 85 per cent.). The oxidation of 2-nitro-3-aminoacenaphthene was best effected by the addition of an excess of alkaline sodium hypochlorite to a hot alcoholic solution of the nitroamine. The mixture was boiled for a short time cooled diluted with water and the precipitate collected.When crystallised from alcohol or acetic acid, acenaphthene-2 3-isoozadiazole oxide forms pale brown needles melting a t 177-178O. The compound is odourless non-volatile with steam and when heated with zinc dust ammonia is evolved and naphthalene formed (Found N = 13.32. A yield of 50 per cent. was obtained. C12FI,02N2 requires N = 13.2 per cent.). This cornpound was formed by the reduction of acenaphtheae-2 3-isooxadiazole oxide with an excess of hydroxylamine (at least four molecular proportions). It was difficult t o isolate owing t o the ease with which it was converted into acenaphthene-2 3-iso-oxadiazole. The best results were obtained by dissolving the isooxadiazole oxide in alcohol and adding an aqueous solution of hydroxylamine hydrochloride after which the mixture was rendered alkaline with sodium hydroxide a t 50° and heated for twenty minutes on the water-bath at 60°.The brown solution was cooled acidified with acetic acid and diluted with water. Th 1348 ROWE AND DAVIES: precipitate was extracted with dilute sodium hydroxide filtered, and the filtrate precipitated with acetic acid. The quinone-dioxime separates as a colloidal precipitate which it was not found possible to crystallise. When dry it forms a brown amorphous powder which decomposes when heated and does not melt below 280° sparingly soluble in organic solvents but dissolving readily in alkali hydroxides with a brawn colour. On oxidation with sodium hypochlorite i t is reconverted into acenaphthene-2 3-iso-oxadiazole oxide and on heating with sodium hydroxide it is converted into acenaphthene-2 3-isooxadiazole (Found N = 13.34.CI2H,,O,N2 requires N = 13.08 per cent .) . CH,*CH . . A cenaphthene-2 3-isooxaditsxole, Acenaphthene-2 3-quinonedioxime was dissolved in dilute sodium hydroxide and distilled in a current of steam. The product after recrystallisation from acetic acid forms yellow needles melting a t 143-144O. It is only slightly volatile with steam and the yield is low owing to the formation of a large proportion of a black, non-volatile decomposition product (Found N = 14.45. C,,H,ON, requires N = 14.28 per cent.). 0 . . A cennphthene-7 8-isoozadiazole Oxide C = W /\I \/\/ The acenaphthene-7 8-quinonedioxime required was obtained by Francesconi and Pirazzoli's method (Zoc.cit.). Five grams of powdered acenaphthenequinone (m. p. 259O) were suspended in 450 C.C. of boiling alcohol and 3.8 grams of hydroxylamine hydro-chloride dissolved in the minimum quantity of water added. The mixture was boiled for one hour under reflux and the major por-tion of the alcohol removed by distillation. The product colour-less needles melting and decomposing a t 220° was obtained in almost theoretical yield. An excess of alkaline sodium hypochlorite was added to a solu-tion of acenaphthene-7 8-quinonedioxime in dilute sodium hydr STUDlES IN THE ACENAPHTHENE SERIES. PARTT. 1349 oxide and the mixture boiled. A yellow precipitate separated, which changed in colour through red to pale pink and boiling was coiitinued until no further colour change occurred.After crystal-lising twice from alcohol the compound forms pale pink needles melting a t 199'. Acenaphthene-7 8-isooxaddazole oxide is reduced by liydroxyl-amine to acenaphthene-1 2-quinonedioxime (Found N = 12.96. C,,H,O,N requires N = 13.30 per cent.). co-co 3-hTitroacenaphthenequinone, Ten grams of acenaphthenequinone dissolved in 50 C.C. of con-centrated sulphuric acid were nitrated in the cold with one mole-cular proportion of nitric acid (D 1-51) mixed with twice its volume of concentrated sulphuric acid. A t the end of the addition, the mixture was warmed for one hour a t 30° and poured on ice. The yield was 92 per cent. Purification by immediate crystallisa-tion proved unsatisfactory and the best results were obt'ained by a mild oxidation which removed the impurities without affecting the nitroquinone.The product (11.5 grams) was dissolved in glacial acetic acid the solution filtered and 5 grams of powdered sodium dichromate were slowly added to the filtrate. The mixture was heated on a boiling-water bath for a quarter of an hour and poured into water. After repeated crystallisation from acetic acid, 3-nitroacenaphthenequinone forms yellow needles melting a t 218O. It dissolves in sodium hydrogen sulphite with a red colour and dissolves in dilute alkali hydroxides with a brown colour whilst it is converted by hot concentrated aqueous sodium hydroxide into 2(or 3)-nitronaphthaldehydic acid as described by Mayer and Kauffmann (Zoc.cit.). 3-Nitroacenaphthenequinone is oxidised by sodium dichromate and acetic acid to 4-nitronaphthalene-1 8-dicarboxylic anhydride, almost colourless needles melting a t 229-230° identical with the product obtained by a similar oxidation of 3-nitroacenaphthene. When distilled with lime a-nitronaphthalene is obtained (Found : N=5*93. Calc. N=6*17 per cent.) i\? \/\ NO, A cold glacial acetic acid solution of 5 grams of 3-nitx-m acenaphthenequinone was mixed with a cold glacial acid! solution of 2.4 grams of phenylhydrazine and the dark red mixture was left a t the ordinary temperature for half an hour with frequent shaking. The monophenylhydrazone separates as a maroon-coloured precipitate. After several crystallisations from pyridine, the product forms reddish-brown needles melting a t 234-235O (Found N= 13-22.Calc. N = 13.25 per cent.). co-co Q' \/ 3 4-DinifroacenaphtrfLen.eyui7Lone, 0% KO, Ten grams of acenaphthenequinone dissolved in 150-206 C.C. of conoentrated sulphuric aoid were nitrated by the addition of a mixture of 7 C.C. of nitric acid (D 1-51> and 20 C.C. of concen-trated sulphuric acid. The mixture was cooled a t first then warmed to 80° and poured on ice. The product after extraction with very dilute sodium carbonate crystallised from nitric acid in orange-yellow needles melting and decomposing above 300O. It. dissolves with a red colour and is soluble in alkali hydroxides with a reddish-brown colour. 3 4-Dinitroacenaphthenequinone is oxidised by sodium di-chromate and acetic acid to 4 5-dinitronaphthalene-l 8-dicarb-oxylic anhydride almost colourless needles melting and decom-posing above 310° identical with the product obtained by the oxidation of 3 4-dinitroacenaphthene.No dinitronaphthalene is obtained when distilled with lime as 1 €Ldinitronaphthalene decomposes below its boiling point (Found N = 10.17. Calc. : N = 10.29 per cent.) DIETHYLENETRIAMINE AND TRIETHYLENETETRAMINE. 1351 3 4-DinitroacenaphtherLeyuinone-7-.znonophen~lh~dra~one, i /\ r\l I \/\/ 0,s NO, An acetic acid solution of 2 grams of phenylhydrazine was added to an acetic acid solution of 5 grams of 3 4-dinitroacenaphthene-quinone a t 50° and the mixture allowed to remain for one hour a t the ordinary temperature. On dilution with water the product separated as a reddish-yellow precipitate. It crystallises from acetic acid in brown glistening plates darkening above 260° and melting a t 287O (Found N = 15.57. C,,H,,O,N requires N=15.47 per cent.). I n conclusion we desire to express our thanks to Messrs. Hardman and Holden Ltd. who have kindly supplied us with the acenaph thene required in this investigation. DYESTUFFS RESEARCH LABORATORY, MUNICIPAL COLLEGE OF TECHNOLOGY, MANCHERTER. [Received October 8th 1920.