Isethionic acid as a sulphonic acid is distinguished from the isomeric monethylic sulphate: C2H6SO1 = C2H5.0.SO2.OH and HO.C2H,.SO2.OH. Monethylic sulphate. by its greater stability. Isethionic acid. 515. Dry potassic isethionate readily reacts with phosphoric chloride, forming hydrochloric acid, phosphoric oxychloride, and isethionic chloride or ethylene sulphon chloride: The latter boils at 200°, and combines the properties of an alcohol radical chloride with those of an acid radical chloride, only the latter being attacked on boiling with water and formation of ethylene chloro-sulphonic acid: 516. Ethylene disulphonic acid, or disulphethiolic acid, is formed by the oxidation of ethylene dithio-glycol, ethylene sulpho-carbonate, and of ethylene dithio-cyanate with concentrated nitric acid : further by decomposition of propionitril by concentrated sulphuric acid, and by boiling ethylene dibromide with normal potassic sulphite: C2H,Br2+2K.SO2.OK = 2KBr + C2H (SO2.OK)2. Separated from its lead salt by hydric sulphide, or from its baric salt by sulphuric acid, it is obtained on evaporation of the solution in form of colourless crystals, melting at 94° and readily soluble in water. The baric salt, | CH2.SO2.0. >Ba, crystallises in hexagonal tables, insoluble in concentrated nitric acid, but can be recrystallised from boiling dilute nitric acid and is also soluble in water. NITROGEN COMPOUNDS OF ETHYLENE. Amine Bases of Ethylene. 517. In the action of ethylene haloids upon ammonia, or the alkylamine bases, similar reactions occur to those in the formation of the alkylamines, but in consequence of the divalency of ethylene -with far greater complications of the products simultaneously formed. Of these only the simpler and more important will be mentioned. 518. On heating ethylene dibromide with alcoholic ammonia there are principally formed, in consequence of the union of ethylene with the nitrogen of two ammonia groups, the hydro-bromides of the ethylene diamine bases. The first and simplest reaction yields, by direct union of a molecule of C2H1Br2 with two molecules NH3, ethylene diammonic dibromide : 4 Br.CH2.CH2.Br + 2NH, = 2 CH2.CH2 N=H3 H1EN Br Br The process, however, does not stop at this stage, but proceeds diethylene diammonic dibromide and triethylene diammonic dibromide being simultaneously formed. Ammonic bromide first crystallises out of the solution, then ethylene diammonic dibromide, and later follow the other salts. If the whole mass of salts obtained by evaporation be distilled with solution of potassic hydrate: C2H,(NH,Br)2 + 2KOH= 2KBr+ 2H2O + C2H,(NH2)2, &c., and the mixture of free amine bases dried by means of solid potassic hydrate, the single compounds can be separated on submitting to fractional distillation. 4 519. Ethylene diamine, C2H,(NH2)2, is a colourless, strongly alkaline liquid of faint ammoniacal odour, boiling at 123°, and has a vapour density of 2. It forms salts with two equivalents of acids. Ethylene diammonic dichloride, C2H4(NH2)2Cl2, crystallises in beautiful needles of silvery lustre. Another method of preparing ethylene diammonic dichloride con sists in conducting cyanogen gas into hydrochloric acid in which granulated tin is dissolving : CEN EN + 4Sn + 10HCl = 4SnCl2 + | CH2.NH2.HCI CH2.NH2.HCI Nitrous anhydride converts ethylene diamine into ethylene oxide, nitrogen being evolved: By heating with ethylic iodide and decomposition of the product with potassic hydrate, ethyl groups can be introduced. In this way there have been prepared Diethyl ethylene diamine, C2H,[N(C2H5)H]2 and tetrethyl ethylene diamine, C2H1[N(C2H5)2]2• The latter unites with ethylic iodide, forming Hexethyl ethylene ammonic iodide, CH2.N(C2H5),I CH2.N(C2H5)зI Ethylene diamine, diethyl ethylene diamine, &c., combine directly with a molecule of water to form ammonic oxides, which on evaporisation decompose into their constituents, but are again formed on condensation. The water is removed on distillation over fused potassic hydrate : CH2.NH2 CH2.NH3 +H,O=CH,NHO, ethylene diammonic oxide; CH2.NH3 CH,NH, CH2.N(C2H5)H + H2O = | CH2.N(C2H ̧)H CH.N(C2H5)H2 diethyl-ethylene The latter solidifies to a stearine-like, brittle mass. 10 2 "diammonic oxide. 520. Diethylene diamine, CH12N, or NHCH>NH, is a colourless, liquid base, boiling at 170° and of vapour density 2.9. It unites directly with ethylic iodide, yielding diethyl-ethylene diammonic diiodide, from which alkalies separate Diethyl-diethylene diamine, C,H,.NCHN.C2H ̧, as a vola 5 tile amine base; this further unites with two molecules of ethylic iodide, giving tetrethyl diethylene diammonic diiodide : C6H12N2 NC2H5 I CH2.CH2 CH2.CH2 521. Triethylene diamine, CH12N2 = N CH,.CH, N, is an oil boiling at 210.. 522. If ethylamine be heated with ethylene dibromide, there are formed, in addition to diethyl-ethylene diammonic dibromide and diethyl-diethylene diammonic dibromide: 2N(C2H¿)H2 + C2H,Br2 = C2H,<N(C2H.) H2Br : N(C2H5)H2Br also bromides of other ammonium bases, containing more than two nitrogen atoms. Decomposed by potassic hydrate, there pass over, above 200°, strongly caustic thick-liquid compounds which are soluble in water, and from whose mixture can be isolated. These give salts with two or three equivalents of acid. 523. By the action of trialkylamine bases upon ethylene dibromide, trialkyl-ethylene bromide ammonic bromides are formed: CH2.CH2.Br N(C2H2n+1)3 + Br.CH2.CH2.Br = N(C2H2n+1)3 Br Triethylamine and ethylene bromide, e.g., give triethyl-ethylene bromide ammonic bromide, N(C2H5)3(C2H,Br)Br. With argentic nitrate it yields triethyl-ethylene bromide ammonic nitrate: [N(C2H5)3(C2H,Br)]O.NO2. By treatment with argentic oxide and water all bromine is removed and replaced, as far as regards that united to nitrogen, by hydroxyl, whilst the ethylene mono-bromide group loses an atom of hydrogen also, and is converted into vinyl, CH2:CH. There thus results triethyl-vinyl ammonic hydrate: CH2.CH2Br CH:CH2 N (C2H5)3 + 2AgOH= 2AgBr + H2O + N=(C2H5)3 Br OH By nascent hydrogen the ethylene bromide group is converted into ethyl, and tetrethyl ammonic bromide is formed: CH2.CH2.Br N (C2H5) CH2.CH3 + 2H = HBr + N=(C2H5) Br 524. The ethylene hydrate amines are closely related to the ethy lene monobromo-bases. In these ethylene is united by one bond with OH, and by its second bond to an ammonia residue. These strongly basic ethylene hydrate amines are formed by the combination of ethylene oxide with concentrated solution of ammonia or substituted amines, the reactions being violent : CH.CH2.OH CH..CH, + NH=N(H H ethylene hydrate amine; 2C,H,O + NH2 = N(CH2.CH2.OH)2 diethylene hydrate amine; 3C2H40+ NH3 = N=(CH2.CH2.OH)3, triethylene hydrate amine. In the form of their salts they are obtained by bringing together ethylene hydrate chloride and ammonia or amine bases, only one molecule, however, generally entering into reaction: and Ethylene hydrate ammonic chloride. N(CH3)3 + Cl.CH2.CH2.OH = NE (CH3)3 They are, therefore, half alcohols and half animes. In order to separate the compounds simultaneously formed, the varying solubility of their hydrochlorides and platino-chlorides is made use of. The mixture, after addition of hydrochloric acid, is evaporated as far as possible to dryness, whereby triethylene hydrate ammonic chloride, N(C,H,.OH)3.HCl, partly crystallises out in prisms, whilst diethylene hydrate and monethylene hydrate ammonic chlorides cannot be obtained in the solid state. The first is insoluble in absolute alcohol, which dissolves both the others; the alcoholic solution is then mixed with platinic chloride. The double salt of diethylene hydrate ammonic chloride, [N(C2H4.OH)2H2C1]2PtC14, crystallising in prisms, first separates, whilst that of ethylene hydrate ammonic chloride, [N(C2H,.OH)H3C1],PtCl, is precipitated later on addition of ether. The platino-chlorides are separated, dissolved in water, and the platinum precipitated by hydric sulphide. On evaporation the hydrochlorides are obtained, which by treatment with moist argentic oxide yield the free bases. The latter are strongly alkaline syrups, which dissolve in alcohol. Monethylene hydrate amine is isomeric with aldehyde ammonia or ethylidene hydrate amine (§ 424): CH2.OH CH3 |