or of the salts of the so-called Reiset's second base (platosodiamine): -N(CH3)H2Cl whilst the soluble second salt corresponds to Reiset's first salts (platotetramine salts): CHINH, Ethylamine is at low temperatures a colourless, mobile liquid, of sp. gr. 696 at 8°. It boils at + 18° and has a vapour density of 1.577. Liquid ethylamine can be mixed with water in every proportion. With metallic salts it behaves similarly to methylamine, except that in excess, like the caustic alkalies, it also dissolves aluminic hydrate. On passing chlorine gas into a dilute aqueous solution, ethyldichloramine, N(C2H5)Cl2, separates as a heavy oily liquid, boiling at 91°. It is Ethylammonic chloride, N(CH)H3.Cl, crystallises in deliquescent plates, which melt at 80° and boil with decomposition at 320°. soluble in alcohol even when containing ether. Its platino-chloride, [N(C2H5)H3]2PtCl, crystallises in orange yellow rhombohedrons. With platinous chloride it yields compounds corresponding to those described above of methylamine. 269. It will be sufficient to give the formula and boiling points of the higher homologous primary amines. 270. Only a few bodies of the series of secondary amines have been prepared in the pure state and thoroughly investigated. Their formation from the primary amines has been already mentioned, as has their general chemical behaviour. With nitrites they behave in completely different manner to the primary amines and ammonia. By heating their nitrites, obtained by mixing their hydrochlorides with potassic nitrite, water and a nitroso body are found. For example, if an aqueous solution of diethyl ammonic nitrite be heated, an oil, boiling at 177°, separates, which is nitroso-diethylamine or nitroso-diethyline: C2HS CH N-C2H5 + HO.NO = H2O + NC2H5 (nitroso-diethylamine). H NO Dimethylamine, N(C2H5)2H, metameric with ethylamine, boils at between 8 and 9°. Its hydrochloride gives with platinic chloride a double salt, crystallising in beautiful needles, [N(CH3)2H2]2PtCl. Diethylamine, N(C,H,), H, metameric with the butylamines, boils at 57°, and is miscible with water in every proportion. The above-mentioned nitroso-diethylamine is converted by alcoholic potassic hydrate into monethylamine; the reaction is complicated, but inay probably be represented by the equation: 4N(C2H)2(NO) + 8KOH = 4N(C2H5)H2 + 4NH ̧ Treated with sodium amalgam, it is reconverted in presence of water into diethylamine, nitrous oxide being evolved: 2N(C2H5)2(NO) + 4H = 2N(C2H ̧)H + H2O + NO. Dibutylamine, N(CH2.CH2.CH2.CH3)2H, boils at 158°-160°. Diisoamylamine, N(C,H11)2H, is an oily liquid, which floats on water, boils at 170°, and forms difficultly soluble salts with acids. Tertiary Amines. 271. Nitrous acid acts with difficulty on these compounds; their nitrites also are more stable than those of the less substituted bodies. Trimethylamine occurs ready-formed in herring pickle. From this it can be obtained mixed with ammonia by distillation with sodic hydrate. The distillate is saturated with hydrochloric acid, evaporated to dryness, and the residue extracted with strong alcohol, in which ammonic chloride dissolves but little. The filtered alcohol solution is then evaporated, and the trimethylammonic chloride distilled with potassic hydrate. Trimethylamine also occurs in the stinking goose-foot (Chenopo dium vulvaria), in the flowers of Crataegus oxyacantha, in coal-tar oil, and in animal oil. It boils at +9-3° (the metameric propylamine at 49°-50°), dissolves readily in water, and smells at once of herrings and ammonia. Triethylamine, N(C,H)3, is obtained readily by heating a mixture of diethylamine and ethylic bromide; the mixture soon solidifies to fibrous crystals of triethylammonic bromide, from which triethylamine can be obtained, by distilling with an alkali, as a colourless, strongly alkaline liquid, little soluble in water. It boils at 89°. By long heating with a concentrated solution of potassic nitrite its hydrochloride is converted into nitroso-diethylamine.. Normal tributylamine, N(CH2.CH2.CH.CH3)3, is an oil boiling at 208°. Triisoamylamine, N(C5H11)3, boils at 257°. Diethyl-isoamylamine, N(C,H5)2(C5H11), is a mixed tertiary amine; it boils at 154°. 2 Methyl-ethyl-isoamylamine, N(CH3)(C2H ̧)(C5H11), boils at 129°. Tricetylamine has been obtained by slowly passing ammonia gas into cetylic iodide heated to 180° : 3C16H33I4NH3 = N(C16H33)3 + 3NH,I. Much ammonic iodide separates, from which the melted tricetylamine is decanted; it solidifies on cooling to a crystalline mass. By repeated crystallisation from hot alcohol tricetylamine is obtained in colourless needles, which melt at 39°. Its salts, though insoluble in water, dissolve readily in alcohol and ether. Tetralkylammonic Compounds. 272. The tetralkylammonic haloids are the last products of the action of ammonia on the haloid salts of the alcohol radicals. The iodides are generally prepared by heating a tertiary amine with an alkylic iodide to 100°. Both unite to form a crystalline compound: N(CnH2n+1)3 + CnH2n+1I= N(CnH2n+1)1I, which by stronger heating can be reconverted into the tertiary amine and alkylic iodide. Potassic hydrate does not exert a marked decomposing action on these bodies on boiling; by shaking their aqueous solutions with freshly precipitated argentic oxide argentic iodide separates, and the now strongly alkaline liquid contains the corresponding hydrate: N(CnH2n+1)+ AgOH = AgI + N(CnH2n+1)4.OH. These hydrates behave chemically like the strongest alkalies. By evaporation in vacuo they can be obtained in crystals, which deliquesce in moist air and are caustic in strong solution. They saponify fats, precipitate metallic oxides or hydrates from metallic salts, dissolve alumina, zincic hydrate, &c., like potassic hydrate (they do not, however, dissolve chromic hydrate), and combine with the acids (even carbonic) to form salts which correspond to those of the alkalies. Their iodides unite with further quantities of iodine, forming periodides. 273. Tetramethylammonic iodide, N(CH3), I, crystallises in colourless prisms, which are separated unchanged by addition of potassic Secondary Amines. -CnH2n+1 270. Only a few bodies of the series of secondary amines have been prepared in the pure state and thoroughly investigated. Their formation from the primary amines has been already mentioned, as has their general chemical behaviour. With nitrites they behave in completely different manner to the primary amines and ammonia. By heating their nitrites, obtained by mixing their hydrochlorides with potassic nitrite, water and a nitroso body are found. For example, if an aqueous solution of diethyl ammonic nitrite be heated, an oil, boiling at 177°, separates, which is nitroso-diethylamine or nitroso-diethyline: 2 5 5 C2H NCH + HO.NO H2O + N-CH, (nitroso-diethylamine). ΝΟ H = Dimethylamine, N(C2H5)2H, metameric with ethylamine, boils at between 8 and 9°. Its hydrochloride gives with platinic chloride a double salt, crystallising in beautiful needles, [N(CH3)2H2]2PtCl6. Diethylamine, N(CH), H, metameric with the butylamines, boils at 57°, and is miscible with water in every proportion. The above-mentioned nitroso-diethylamine is converted by alcoholic potassic hydrate into monethylamine; the reaction is complicated, but may probably be represented by the equation: 4N(C2H)2(NO) + 8KOH= 4N(C2H5)H2 + 4NH3 + 2C2H1 + 4K,CO3. Treated with sodium amalgam, it is reconverted in presence of water into diethylamine, nitrous oxide being evolved: 2N(C2H5)2(NO) + 4H = 2N(C2H2)H + H2O + N2O. Dibutylamine, N(CH2.CH2.CH.CH3)2H, boils at 158°-160°. Diisoamylamine, N(C5H11)2H, is an oily liquid, which floats on water, boils at 170°, and forms difficultly soluble salts with acids. Tertiary Amines. CnH2n+1 271. Nitrous acid acts with difficulty on these compounds; their nitrites also are more stable than those of the less substituted bodies. Trimethylamine occurs ready-formed in herring pickle. From this it can be obtained mixed with ammonia by distillation with sodic hydrate. The distillate is saturated with hydrochloric acid, evaporated to dryness, and the residue extracted with strong alcohol, in which ammonic chloride dissolves but little. The filtered alcohol solution is then evaporated, and the trimethylammonic chloride distilled with potassic hydrate. Trimethylamine also occurs in the stinking goose-foot (Chenopo dium vulvaria), in the flowers of Crataegus oxyacantha, in coal-tar oil, and in animal oil. It boils at +9.3° (the metameric propylamine at 49°-50°), dissolves readily in water, and smells at once of herrings and ammonia. Triethylamine, N(C,H)3, is obtained readily by heating a mixture of diethylamine and ethylic bromide; the mixture soon solidifies to fibrous crystals of triethylammonic bromide, from which triethylamine can be obtained, by distilling with an alkali, as a colourless, strongly alkaline liquid, little soluble in water. It boils at 89°. By long heating with a concentrated solution of potassic nitrite its hydrochloride is converted into nitroso-diethylamine.. Normal tributylamine, N(CH2.CH2.CH2.CH3)3, is an oil boiling at 208°. Triisoamylamine, N(C5H11)3, boils at 257°. Diethyl-isoamylamine, N(C2H5)2(C5H11), is a mixed tertiary amine; it boils at 154°. Methyl-ethyl-isoamylamine, N(CH3)(C2H5)(C5H11), boils at 129°. Tricstylamine has been obtained by slowly passing ammonia gas into cetylic iodide heated to 180° : 3C16H33I4NH3 = N(C16H33)3 + 3NH,I. Much ammonic iodide separates, from which the melted tricetylamine is decanted; it solidifies on cooling to a crystalline mass. By repeated crystallisation from hot alcohol tricetylamine is obtained in colourless needles, which melt at 39°. Its salts, though insoluble in water, dissolve readily in alcohol and ether. Tetralkylammonic Compounds. 272. The tetralkylammonic haloids are the last products of the action of ammonia on the haloid salts of the alcohol radicals. The iodides are generally prepared by heating a tertiary amine with an alkylic iodide to 100°. Both unite to form a crystalline compound: N(CnH2n+1)3 + CnH2n+1I= N(CnH2n+1)4I, which by stronger heating can be reconverted into the tertiary amine and alkylic iodide. Potassic hydrate does not exert a marked decomposing action on these bodies on boiling; by shaking their aqueous solutions with freshly precipitated argentic oxide argentic iodide separates, and the now strongly alkaline liquid contains the corresponding hydrate: N(CnH2n+1)4I + AgOH = AgI + N(CnH2n+1)4.OH. These hydrates behave chemically like the strongest alkalies. By evaporation in vacuo they can be obtained in crystals, which deliquesce in moist air and are caustic in strong solution. They saponify fats, precipitate metallic oxides or hydrates from metallic salts, dissolve alumina, zincic hydrate, &c., like potassic hydrate (they do not, however, dissolve chromic hydrate), and combine with the acids (even carbonic) to form salts which correspond to those of the alkalies. Their iodides unite with further quantities of iodine, forming periodides. 273. Tetramethylammonic iodide, N(CH3), I, crystallises in colourless prisms, which are separated unchanged by addition of potassic |