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Abstracts from American and Foreign Journals.
American Chemical Journal. AbstraLtor. J 1'
RAmERSHALI.
Ph.D.
A Method f o r the P r o x i m a t e A n a l y s i s of Plants, HENRYB.
PARSONS ( I , 377).-Will
be noticed elsewhere.
On tho Estimution of Phosphot*ic Acid us Mugnesic P y r o phosphate, F. A. GOOCH ( I , 391).--See this JOURNAL ( I , 537).
Lnborutory Note$, ARTHUR MICHAEL( I , 413).
Orb moscoethylphthulate ( I , .il3).--This compound was prepared b y heating equal parts of absolute alcohol a i d ph'thalic anhydride in a flask connected with an upright condenser, for ten hours a t looo, evaporating thc excess of alcohol a t ;t low temperature, dissolving t h e remaining residue in water, and neutralizing it i n the cold with barium carbonate. In this way the barium salts of monoethylphthalate and phthalic acid arc formed, which can b e separated by means of their different solubility in water, t h e phthalate being much t h e less soluble. Barium morioethylphthalate forms long, concentrically grouped needles, which are very soluble ill water, and posBesses t h e formula,
T h e corresponding silver salt is prepared b y precipitating a concentrated aqueous solution of t h e barium salt with silver nitrate ; i t forms beautiful long needles, which blacken on exposure t o t h e light. T h e free monoethylphthalate, which was obtained by treating a solution of t h e barium salt with t h e calculated quantity of sulphuric acid and evaporating thrl filtrate in vacuo, i x a heavy oil, remarkably unstable when heated, even up011 a water-bath. W i t h a view of obtaining the chloride, C g H , ( ~ $ ~ 2 H 5 , equivalent amounts of monoethylphthalate and phosphorus trichloride were heated in a retort over a water-bath. T h e results of this reaction were t h e evolution of chlorhydric acid and ethyl chloride and t h e formation of a heavy oil, which proved t o Le diethylphthalate, C,H,(COOC,EI,),, showing that t h e chloride of monoethylphthalate, first formed, undergoes a condensation, and is decomposed into phthalic anhydride and ethyl chloride, the formation of diethylphthalate being probably due to a portion of the ethyl chloride reacting on unchanged monoethylphthalate.
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On a new fornaatiou of ethyl v ~ u s t a r doil ( I , 41G).-A mixture of ethyl iodide and mercuric sulphocyanate was heated in a tube f o r about t w o hours, a t 1 4 j o , and the resulting compounds brought into a flask connected with a condenser, and treated with steam as lorlg as an oil distilled over. This oil was separated, dried over CaCI,, I t possessed the odor of ethyl mustard oil, and distilled a t 13.5’. and, when mixed with aniline, g a v e a precipitate which, when purified by crystallization from water, possessed the properties of phenylethylsu1phocarl)ainide. T h e amount of ethylsrilpliocyanate formed in the above reaction greatly exceeds that of the ethyl must,ard oil. Both compounds, however, are produced in very small quantities, t h e principal product of t h e reaction being a red mass, previously mentioned by Ychlageiihauffeii,* and probably consistirig of a double cornl,ound of ethyl iriustard oil with mercuric iodide. On the prq~arutiort o f wetliyl wldehyde ( I, 41a).-Monochlorniethyl acetate is first prepared b y passing a current of d r y chlorine gas through methyl acetate for about seven hours, the liquid being placed i n a flask surroiinded by cold water. On submitting the contents of t h e flask to fractional distillation, and separating the portion which passes over between 100-1 20°, a very satisfactory yield of rnonochlormethyl acetate is obtained. This, when mixed with water and placed in a strong closed flask, and heated for about an hour a t looo, furnishes an abundant supply of methyl aldehyde, which is separated by exactly neutralizing t h e contents of t h e flask w h h sodium hydrate, and distilling. T h e above reaction is expressed by t h e equation:
(JII“\O /c1- - OC -CH,
+ H, = CI1,O + 0 + C,H,O, + HCI.
O?L the ‘‘ migration o f utonzs i ~ ithe molecule,” asid Reimer’s chloroform aldehyde rewction ( I , 420).-This article is wholly speculative in character and, not forming a record of personal investigation, possesses only a theoretical interest, On the Oxidution of Substitution Products of Avomatic Hydrocarbons, IRAREMSEN and C. FAHLRERG (I, 426). On the Oxidation of Orthotol2certesull,humi~~e.
Preparation of OrthotoZueneszL~hana~~e ( I , 42G).-The sulphonic acids formed b y , treating toluene with fuming sulphuric acid, were converted by aid of t h e usual reactions into t h e corresponding chlorides, from which the liquid orthotL.uenesulphochloride was
* Ann.
Chem. Phys. (3), 56, 297.
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isolated. This, upon treatment with ammonia, was converted into orthotoluenesulphaniide, which melts a t 153-154’ and, by fusion with potassium hydroxide, yields salioylic acid.
Formation oj’ bemoic
[email protected] amide thus obtained was heated for ten hours on a water-bath, together with potassic permaganate, the excess of permanganate reduced b y adding alcaohol, t h e solution filtered, arid hydrochloric acid added t o the concentrated filtrate. T h e precipitate formed, gal e, on analysib, figures corresponding t o the formula, C,H,O,NS, which differs from t h e normal sulphamine acid produced from the corresponding para compound, in t h a t it contains a nioleuule of water less. This body niay be rcgardetl as :t condensation product, having the fortnulit,
T h e authors note that a similaf grouping of a carboxyl and an amido group, is a characteristic feature of some coml)ounds allied to indigo, such as iflatine, and suggest, as a proper designation of such compounds, the term sulphinides. Uenzoic sulphinide (or anhydrosulphaminebenzoic acid) crystallizes in short prisniatir. forins, which fuse at 220’. It is difiicultly soluble in c,old wiiter. b u t dissolves readily in alcohol and in ether. It possesses (i marked w r z t tmte, hei7cg much sweeter thnu citue sugur. 1Sy fusion with potasdiiiin Iiydroxide, benzoic sulphinide is easily and completell. converted into sdicylic acid. B y neutralizing its aqueous solution with various carbonates, t h e corresponding salts were ol)taiued. 111 this manner tlie barium, magnesium, lead, potassium and :tininoniuni compounds werc prepared. O h o s u Q k oheizzo ic ucitl.--O ti f u r tiler ev :ipor:tt i ng t h c ~ fil trate obtained in the preparation of benzoic Liiilphinide, ;1 C I sium salt separates out, whicli is purified frotu tlie :tcuompatiying potassium chloride b y recrystallization. T h e niialysis gave figures / SO:,K corresponding to rnoriopotassiurnsulphobenzoate, C,11 ‘\CO,H This compoilnd belongs t o t h e ortlio series, as is shown by t h e formation of salicylic acid when it is fused with potassium hydroxide. It is precipitated from concentrated solutions by :idtiition of hydrochloric acid and, upon recrystallization, forins beautiful, large rhombic plates. Benzoic sulphinide i n d orthosulphobenzoic acid a r e formed in about equal quantities by t h e oxidation of ortliotoluenesulphamide, i. e., from two molecules ( I f t h e latter otic2 niolccule of each of t h e former compounds is obtained. Orthosulphobenzoic
/”O,H acid, C,H,.,S02H
crystallizes in fine large plates, which fuse at 2-io”,
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223
undergoing decomposition ; i t is easily soluble in water, b u t scarcely dissolves in alcohol or in ether. A c i d hwiwn orthosicll,hohenzonte crystallizes in needles, which suffer partial decomposition a t 250’. 0rthosulphobenzoic:iobenzoic acid can he !)repared from benzoic siilphinitle by heating this comporirid in a sealed tube t o 150”, with concentrated hydrochloric acid. I n areverse manner, when t h e neutral potassium salt of orthosulphohenzoic acid is treated with phosphorris pentachloride, t h e prodrict treated with ammonia, and hydrochloric acid is added, a precipitation of benzoic snlphiiiide occurs. Phthalic acid, when submitted t o the above treatdiffering, merit, yields an imide of t h e formula, C,H, /‘O\NLI, \CO/ however, in properties from Laurent’s phthalimide. T h e anthors further mention an iinsriccesufril a t t e m p t to convert orthosiilphobenzoic acid into phthalic acid, b y treatment with sodium formate. O n ( c i i riritcszcnl Ca.oe of Eledvolysis, J. W. MALI.ET(I,438).T h e author iioteh that a Sniee’s galvanic battery, not being in I M , was laid aside, when the plates, which were originally raised out of t h e acid, accitlcntly became immersed in t h e liquid, whicli was of uiinsual strength. I t was afterwards found t h a t t h e ziiic plates were very much corroded, and that one of the sheets of platinized silver foil was thickly coated with zinc, of which over 30 grmq were removed. The battery liquid liad doubtless tirst become converter1 into zinc bulpliate, which had subsequently acted as a ‘‘ decomposing cell,” and metallic zinc was electrolytically deposited from its salt.
Bericlite der Deutsclien Cliemisclien Gesellschsft. Abstractor, A K N O BEHR,Ph.D.
OILMetlbyluted DiethUle?ieamiitee, H. F. MORLEY(13, !?22).-
Monometliyldioxethyleneamine and dimethyloxethylenearnine were prepared b y t h e action of chlorhydrine (CJ14~l.011),on methylamine and dimethylamine respectively. O n t?ce Oxidntion of Substiticted Pihenoh, G . MAGATTI
(13, 224).-The
acetylated compound of tetrahromparadiphenol, dissolved in glacial acetic acid, is oxidized b y fuming iritric acid. T h e result is a crystalline body of t h e formula of tetrabrotndiphenylquinone, C,H,.C,H,.Br40,. Tliis is a simple analogue to cedriret, a colored substance found in wood-tar.
