Dec., 1940,
NEw COMPOUNDS
added. The mixture was heated for fifteen minutes on a steam-bath and then diluted with 300 ml. of water. The precipitation and purification of the base was as described in method A. SAINTAUGUSTIXE'S COLLEGE AUGUST20, 1946 RALEIGH,NORTH CAROLINA RECEIVED
NEW COMPOUNDS 3,4-Dimetho.xy-lO-rnethyl-2,4,7-naphthitatrien-l -one*
2745
S o success attended efforts to synthesize o-nitroacetophenone oxime by direct reaction of the ketone with hydroxylamine, although apparently such a compound can be made2by reaction of a nitrite on o-nitroethylbenzene. (2) Hochster Farbw., German Patent 109,663; Chcm. Za?rlr.. 71, 11,458 (1900).
CHEMICAL LABORATORY CHARLES D. HURD KORTHWESTERN UNIVERSITY OTISE. FAKCHER EVANSTON, ILLIXOIS WILLIAM A. BONNER RECEIVED hfAY 16, 1946
A New Acetylene Silver Nitrate Complex Methylation of the sodium derivative from 1 g. of The customary precipitate formed by interaction of 2-methoxy-5-methyl-2,7-naphthitadiene-l,4-dione2(0.13 acetylene with aqueous silver nitrate solutions has been g. of sodium i n liquid ammonia) in benzene using 2 g. of considered to have the formula Ag2Cz.AgXOat having a methyl iodide, which was added in three portions during crystal form of fine needles and crosses. We find this twenty-six hours, gave 657 mg. of crude crystals. One re- conclusion t o be true for only dilute solutions. As the crystallization from benzene followed by two from hexane silver nitrate concentration of the solution is raised above gave nearly colorless needles, m. p. 136-137" (cor.). about lo%, there is a tendency for rhombohedral crystals Calcd. for C13HIGO3: C, 70.9; H, 7.3. Found: to form and above about 25% silver nitrate concentration the rhombs form to the exclusion of the needles. We C,7C.5; H , 7.1. In a second experiment 5 g. of the monomethoxydione have found these rhombs to have the formula of AgzC2. gave 4.3 g. of crude dimethyl ether; once crystallized from 6AgNOs. When 80 ml. of acetylene is bubbled through 25 ml. of hexane, i t melted a t 129-132". A few mg. on a steam-bath with three drops of concentrated hydrochloric acid for 30% aqueous silver nitrate a t 25" and atmospheric prestwenty minute.5 gave 5-methyl-7-naphthitene-l,2,4-trione sure, the acetylene is a t first completely absorbed to form a enol, m. p. 165 169"; mixed with authentic material4 m. p. clear solution, followed toward the end of the absorption by the appearance of the white rhombohedral crystals. 166-170'. The mixture is then filtered by suction through a fritted glass filter, washed with acetone and dried a t first by suc(1) This work was supported by an allotment from the Special tion and then in a vacuum desiccator over sulfuric acid. Research Fund (Bankhead-Jones Act of June 29, 1935). h-ot subThese rhombs were analyzed by us for silver carbide ject to copyright. and total silver gravimetrically and for water-soluble sil(2) Orchin and Butz. J. Org. Chem., 8,509 (1943). ver volumetrically. We previously found that an acidiMa, 1:niversity of Chicago. (3) B y Ur. T . :i. metric titration of the filtrate from the rhombs showed (4) Butz and Butz, J . Ore. Chem., 8,497 (1943). free acid equivalent to that customarily released by the BUREAU OF ANIMALINDUSTRY acetylene present. AGRICULTURAL RESEARCH ADMINISTRATIOX Anal. Calcd. for Ag~C2.6AgN03: A g G , 19.19; AgVSITED STATE:, DEPARTMEST OF AGRICULTURE BESJAMINL. DAVIS KO3, 80.81. Found: A g G , 19.13; AgN03,81.30 (molar BELTSVILLE, h'f ARYLAND LEWISW.BUTZ ratio 1 to 5.97). This substance crystallizes in the rhombohedral system; RECEIVED SEPTEMBER 13, 1946 it has a characteristic X-ray diffraction pattern, differing from t h a t of AgN03 or AgzCz.AgNO3. It has a great tendency to form supersaturated solution$. Upon heatSalicylobutylamide and o-Nitroacetophenone 2,4-Dinitro- ing, it first melts and then suddenly but feebly decomposec phenylhydrazone with the evolution of red vapors of nitrogen oxides above Salicylobutylarnide .-Methyl salicylate (108 g.) and 308" and below 327", the respective melting points of n-butylamine 160 g.) were refluxed together for seven sodium nitrate and metallic lead. This datum is to be hours. I'olatile material was then expelled up to 160" contrasted with a detonating point of about 212" which we (30 mm.) and the 125 g. of sirupy residue was distilled a t have found for Ag2C2.AgN03. Water decomposes the rhombs to Ag&n.AgSOs and sil15:3-156* a t 3 inin. The salicylobutylamide was a colorver nitrate. Likewise, any reagent that acts t o reduce less. viscou5 sir I ~ D . Anal. (by R. Pivan) Calcd. for CIlHISNOz: N,7.35. the silver nitrate concentration of the solution in which the rhombs may be existing tends to destroy them in favor Found : X, 7.43. of the precipitation of AgzCz.AgN03. An excess of acetya-Nitroacetophenone 2,4-Dinitrophenylhydrazone.-A lene added to the solution will act in this manner, as acetymixture of 2 g. of 2,4-dinitrophenylhydrazine, 1.5 g. of lene removes about fifty times its own weight of silver a-nitroacetophenone and 100 ml. of alcohol was heated to nitrate from solution under these conditions. Conversely, hoiling, 2 nil. of concd. hydrochloric acid was added, and if rhombs and needles exist in the same solution the needles the mixture was boiled under a reflux condenser €or five can be completely by increasing the silver nitrate minutes. Copious separation of crystals occurred on cool- concentration, the removed normal silver carbide being~. very soluble ing. Recrystallization from alcohol gave a pure product, in strong silver nitrate. in. p. 153-15.1" cor. Contribution from the Multiple Fellowship on Gas Anal. (by i v . Brandt) Calcd. for CI4Hl1O6S5:S, Purification sustained by Koppers Company, Inc., Pitts20.29. Found: S,20.18. burgh, Penna. _____ h f E L L O N INSTITUTE O F INDUSTRIAL RESEARCH (1) This work mas done under contracts, recommended by the UNIVERSITY O F PITTSBURGH JOSEPH A. SHAW National Defense Research Committee and the Committee on MediPITTSBURGH, PA. ELTONFISHER cal Research, between the Office of Scientific Research and Development and Northwestern University. RECEIVEDAUGUST9, 1946
