Page images
PDF
EPUB

lises with mol. H2O in needles, the platinochloride in yellow rhombic plates, melting with decomposition at 234-244°.

The oxy-compound crystallises in long needles containing 2H2O, which is given off at 100°. It is soluble in boiling water, alcohol, and chloroform, sparingly so in boiling benzene and ether. The anhydrous substance melts at 63°. It is not decomposed by concentrated hydrochloric acid even at 180°, nor by boiling alcoholic potash, nor is it reduced by long-continued boiling with tin and hydrochloric acid. The hydrochloride forms white, glistening needles soluble in water; the platinochloride, yellow scales melting with decomposition at 220°. When heated, this oxy-compound melts to a clear liquid, and at a slightly higher temperature explodes, leaving a thick brownish liquid, and a small quantity of methylethenyldiamidotoluene. When heated with zinc-dust or with soda-lime, the decomposition takes place. more quietly, methylethenyldiamidotoluene being the chief product. Boiling acetic anhydride appears to act in a similar way, an acetoderivative of the non-oxygenated base being formed. Concentrated sulphuric acid has no action on the oxy-compound at 100°.

Metanitroparethylacetotoluide resembles the methyl-compound, and volatilises with difficulty in a current of steam. Ethylethenyldiamidotoluene (monethylanhydracetodiamidotoluene) has been already described by Hübner, Kronberg, and Tubbe (Abstr., 1882, 505). The hydrochloride forms a gummy mass; the mercurochloride crystallises in needles; the picrate forms crystals sparingly soluble in alcohol. The oxy-compound was not isolated, and if formed at all was only produced in very small quantities. When ethenyldiamidotoluene is heated with methyl iodide and methyl alcohol, it yields methylethenyldiamidotoluene methiodide, soluble in alcohol and water, crystallising in needles, and melting at 221°. When heated with strong potash, the methiodide yields the corresponding hydroxymethide. This ammonium base crystallises in thin scales which soften at 115° and melt at 135°. It is a strong base, is insoluble in alkalis, and is not decomposed by heating with concentrated hydrochloric acid. The hydrochloride, platinochloride, and picrate are all crystalline. From the stability of the base, the author is inclined to consider its NMe formula to be C&H,Me<;

NMeCMeOH.

:

Tetramethyldiamidotoluene, CH,Me(NMe), [Me: NMe, NMe2 = 1:34], is formed when toluylenediamine is heated in closed tubes at 120-130°. It is a colourless, mobile liquid of strongly basic odour. It boils at 225.5° (uncorr.) under 717 mm. pressure. It is easily miscible with the usual solvents, sparingly soluble in water. The platinochloride, picrate, and mercurochloride are crystalline. Nitrotetramethyldiamidotoluene, formed by the action of nitrous acid on the base, crystallises in hexagonal prisms, is easily soluble in alcohol, ether, and benzene, and melts at 63°. It is still basic in properties. It is soluble in phenol, but sulphuric acid added to this solution only causes a slight lilac coloration, showing that no nitroso-group is present. L. T. T. Nitrosalicylaldehydes. By W. v. MILLER (Ber., 20, 1927-1931). Mazzara has (this Journal, 1877, i, 597) described an a- and a ẞ-nitro

salicaldehyde. The a-aldehyde (true m. p. 109°) when oxidised in acetic solution with chromic acid gives 1: 2: 3 nitrosalicylic acid, and is therefore 1: 2: 3 nitrosalicaldehyde, [COH: OH: NO2 = 1:2:3]. The B-aldehyde (true m. p. 126°) when similarly treated gives 1: 25 nitrosalicylic acid, and is therefore 1: 2: 5 nitrosalicylaldehyde. L. T. T.

Nitrocoumaraldehydes. By W. v. MILLER and F. KINKELIN (Ber., 20, 1931-1934).-Tiemann and Kees described (Abstr., 1885, 1073) orthocoumaraldehyde, but were unable to obtain it by the condensation of salicylic and acetic aldehydes. The authors find that the introduction of a nitro-group into salicaldehyde renders the condensation possible.

:

=

1:25 Nitrocoumaraldehyde, [C2H, COH OH NO, 1:2: 5], was obtained by dissolving 100 grams of the sodium salt of 1: 2:5 nitrosalicylaldehyde (preceding Abstract) in 2 litres of water, and adding 60 grams acetaldehyde, and 150 grams of 10 per cent. alcoholic potash. It is soluble in alcohol and acetic acid, very sparingly so in boiling water; it crystallises in yellow needles, and melts with decomposition at 200°. The phenylhydrazide crystallises in oran re scales melting at 235°; the sodium-derivative forms red plates easily soluble in water.

1:23 Nitrocoumaraldehyde, from 12:3 nitrosalicaldehyde, crystallises in glistening yellow needles, melts at 133°, and is easily soluble in alcohol and acetic acid, sparingly so in ether and boiling water. Its phenylhydrazide crystallises in red scales, and melts at L. T. T.

157°.

Nitrosalicylaldehyde and Nitrocoumarin. By C. TAEGE (Ber., 20, 2109-2110).—A summary of the author's inaugural dissertation, which was published previously to the appearance of v. Miller's paper (preceding Abstract). Salicylaldehyde, when nitrated either with fuming nitric acid in a freezing mixture, or by boiling with dilute nitric acid, yields nitrosalicylic acid and two isomeric nitrosalicylaldehydes. The latter can be separated by means of their barium-derivatives, since on treatment with barium hydroxide the aldehyde melting at 107° crystallises first in orange crystals with 2 mols. H2O, and that melting at 125° forms yellow spangles with 3 or 6 mols. H2O, and separates from the second crystallisation. The sodium hydrogen sulphite compound of the former does not crystallise, that of the latter is solid, whilst the phenylhydrazides melt at 165° and 186° respectively.

The nitrocoumarin obtained by direct nitration with fuming nitric acid melts at 183°, and the corresponding amido-derivative formed by reduction with ferrous sulphate melts at 161°; on oxidation with potassium permanganate in alkaline solution, it yields nitrosalicylic acid, [COOH: OH: NO2 = 1:25] (m. p. 228°). A dibromonitrocoumarin, melting at 271°, is formed by the prolonged action of bromine-vapour.

=

When nitrosalicylaldehyde (m. p. 125°) is boiled with acetic anhydride and sodium acetate, nitrocoumarin melting at 183° and iden

=

tical with the preceding derivative is obtained; if, however, a lower temperature is employed in the reaction, an acetyl-derivative of nitrosalicylaldehyde results; this melts at 112°, and loses its acetylgroup on boiling with water. Under similar conditions, nitrosalicylaldehyde (m. p. 107°) yields a compound, probably a nitrocoumarin, from which a nitrosalicylic acid (m. p. 145°) was obtained on oxidation, and at a lower temperature forms an acetyl-derivative; this melts at 110°, and is also decomposed into nitrosalicylaldehyde on boiling with water. W. P. W.

=

Isophthaldehyde. By V. MEYER (Ber., 20, 2005). — Isophthaldehyde, CHO2, crystallises in long needles melting at 89–90°, has a very slightly aromatic odour, and reduces silver solution with difficulty; it can be distilled in small quantities without decomposition. The oxime crystallises from hot water in needles, which melt at 180°. When the latter is left in contact with twice its weight of acetic chloride for 12 hours, dicyanobenzene is formed (compare this vol., p. 482). N. H. M.

Benzoylaldehyde. By L. CLAISEN and L. FISCHER (Ber., 20, 2191 -2193).—Benzoylaldehyde, CH,Bz·COH, is obtained as a sodiumcompound when a mixture of acetophenone and ethyl formate in molecular proportions is added to a dilute alcoholic solution of sodium ethoxide (1 mol.) cooled in ice, and separates as a colourless or pale-yellow oil, on treatment of the aqueous solution of the salt with acetic acid. Its alcoholic solution gives an intense red coloration with ferric chloride. The copper salt, (C,H,O2)2Cu, crystallises in dark-green, glistening, flat prisms. On adding a solution of a salt of the corresponding base to the aqueous solution of the sodium compound of benzoylaldehyde, the following derivatives are obtained: the anilide, CH,BzCH: NPh, crystallising in short, prismatic or scaly yellow forms melting at 140-141°; the paratoluidide, CH2BZ CH: NC,H,, crystallising in small, yellow forms melting at 160 -163°, and the B-naphthalide, CH,BzCH: NC10H1, crystallising in small, bronze-coloured forms, melting at 180-182°. The anilide could not be converted into a quinoline-derivative either by heating alone or with concentrated sulphuric acid, and on dry distillation passes over for the most part unchanged. W. P. W.

Aromatic Ketones. By K. ELBS (J. pr. Chem. [2], 35, 465— 509; compare Abstr., 1886, 461).--Ditolyl ketone is prepared as follows: 50 grams of aluminium chloride, 60-70 c.c. of toluene, and 50 c.c. of carbon bisulphide are put into a strong half-litre flask; 10-12 c.c. of carbon bisulphide saturated with carbon oxychloride is added, and the flask closed with a cork provided with a glass tap drawn out to a fine capillary, which is fastened with wire. The whole is slightly warmed with steam for 15 to 30 minutes, allowed to cool, and the pressure relieved. It is then treated with more carbon oxychloride as before; this is repeated three or four times, and the product treated as previously described (loc. cit.). The yield is 40 to 50 per cent. of the theoretical.

Orthoxylyl phenyl ketone, CH,Me2 COPh [Me: Me = 1:2], prepared from benzoic chloride and orthoxylene, crystallises from alcohol in groups of white, matted needles; it melts at 47-48°, boils at 340-2° under 744 mm. pressure, and is readily soluble in the usual solvents, except water.

2

Orthoxylyl phenyl carbinol, C,H,Me2 CHPh·OH, is readily obtained by reducing the ketone with zinc-dust and potash. It crystallises in groups of white needles, which dissolve readily in the usual solvents, except water; it melts at 68°, and boils at 336° under 744 mm. pressure with slow decomposition.

Metaxylyl phenyl ketone, forms a rather thick colourless oil boiling at 321.2° under 744 mm. presence. In solubility, it resembles the ortho-compound. When boiled for 12 hours, a small amount of B-methylanthraquinone melting at 170-172° is formed; when the ketone is boiled in presence of metaxylyl carbinol, B-methylanthracene is obtained.

Metaxylyl phenyl carbinol, C15H160, is best purified by distillation. It melts at 57° and boils at 330-8°, under 744 mm. pressure.

Paraxylyl phenyl ketone, [Me : CO : Me = 1: 2: 4], separates from its alcoholic solution in large, clear, well-formed prisms, very readily soluble in ether, alcohol, and acetone, sparingly in glacial acetic acid, more soluble in benzene; it melts at 36°, and boils at 317.2° under 744 mm. pressure. When boiled, it yields methylanthracene melting at 199-200°. The disulphonic acid is obtained by dissolving the ketone in pyrosulphuric acid; the barium salt, a yellow crystalline substance, is readily soluble in water. When the ketone is heated with nitric acid (sp. gr. 1·15) at 170° to 180° for six hours, it is oxidised to benzoylterephthalic acid.

Paraxylyl phenyl carbinol crystallises in prisms which melt at 88°, dissolve very sparingly in water, readily in alcohol, ether, acetone, and benzene.

Dipararlyl phenyl methane, CHPh(CH,Me2)2, is prepared by Hemilian's method (this Journ., 1875, 152, and Ber., 16, 2360); it crystallises from light petroleum in colourless prisms which melt at 92.5°, boils above 360°, and dissolves in the usual solvents except water. The solutions show a blue fluorescence.

Dixylyl phenyl B-pinacoline, CPhBz(C,H,Me2)2, is obtained by Thömer and Zincke's method (Ber., 11, 65 and 1396). It forms almost colourless prisms, rather readily soluble in alcohol, ether, benzene, and light petroleum; it melts at 146°. When heated with soda-lime, diparaxylyl phenyl ketone is formed.

Diparaxylyl ketone, CO (CH,Me); [CO: Me2 = 2:1:4 and 5: 1:4], is prepared in a manner similar to diparaxlylyl ketone. It is a thick, pale-yellow liquid, boiling at 325-327° (uncorr.). When boiled, it gives up the elements of water, and is converted into trimethyl

CH
|

[ocr errors]

anthracene, C,H,Me C,H,Me [Me, 1 : 4 and Me 2]. The

CH

latter crystallises in colourless plates, which show a blue fluorescence and melt at 227°. It sublimes below 100°, dissolves readily in ether and benzene, very sparingly in cold alcohol.

Diparaylyl carbinol, CH(C,H,Me2), OH, crystallises from alcohol in white needles melting at 131°. In solubility, it resembles its homologue.

Tripararlylmethane, CH(C&H3Me2)3, is prepared by boiling a solution of diparaxylyl carbinol in paraxylene with phosphoric anhydride in a reflux apparatus for four hours. It crystallises from alcohol in colourless crystals which melt at 188°, and are moderately soluble in alcohol, readily in ether and benzene. It boils above 360°.

Mesityl phenyl ketone (Louise, Abstr., 1883, 577; 1884, 905) is best prepared by the general method previously described (loc. cit.); an excess of mesitylene need not be used. It melts at 35° and boils at 318-319°; no anthracene-derivative could be obtained from it. The carbinol (Louise, loc. cit.) is best prepared by reducing the ketone with zinc-dust and potash. When the ketone is heated with strong sulphuric acid in a water-bath, mesitylenesulphonic acid and benzoic acid are formed; when the temperature does not rise above 50°, mesitylphenylketonesulphonic acid is formed; the barium salt is a yellow powder. When 2 grams of the ketone is dissolved in 30 c.c. of nitric acid (sp. gr. 145) and 10 c.c. of pyrosulphuric acid, two isomeric trinitro-compounds are formed; the one crystallises in slender, colourless needles which melt at 188°, almost insoluble in alcohol; the other crystallises from alcohol, in which it is rather readily soluble, in colourless needles melting at 145°. Nitric acid (sp. gr. 1·1) at 200° converts the ketone into a mixture of acids from which benzoyl uvitic acid, COPh•CH2Me·COOH [Me: CO (COOH), = 1 : 2 : 3:5 or 5:2 1: 3], was isolated; this crystallises from hot water in slender white needles melting at 245°.

Pseudocumyl phenyl ketone, COPh C,H,Mes, boils at 328-329°; when boiled, no dimethylanthracene but dimethylanthraquinone is formed; sulphuric acid converts it into benzoic and pseudocumenesulphonic acids. When bitrated, two isomeric trinitropseudocumyl phenyl ketones are obtained; both crystallise in slender needles; the one is sparingly soluble and melts at 185°, the other which is rather readily soluble melts at 155°. When oxidised with dilute nitric acid, benzoyltrimellitic acid, CH2Bz(COOH)3 [Bz: (COOH), = 5 : 1 : 2 : 4] is formed together with other products.

Paracymyl phenyl ketone (Kollarits and Merz, Ber., 6, 546 and 1264), prepared in a manner similar to the other ketones, is a readily soluble thick oil boiling at 175°. When boiled for eight days, a small amount of ordinary anthracene is formed.

Paracymyl phenyl carbinol forms a thick, pale-yellow oil.

Paraxylylparacymylphenylmethane, CH,Me, CHPh·C,H,MePr, is prepared by adding 20 grams of phosphoric anhydride to a solution of 30 grams of paracymi phenyl carbinol in 30 grams of paraxylene, and boiling the whole for five hours. It is a thick, reddish-yellow oil which boils above 360°.

Dinitroparacymyl phenyl ketone, CH1O(NO2)2, is obtained by adding potassium nitrate to a solution of the ketone dissolved in 10 parts of sulphuric acid; it forms white flakes rather readily soluble in ether, acetone, and benzene, &c., and could not be crystallised.

« PreviousContinue »