2970 NOTES NOTES. Preparation of p- Bromophenylhydroxylamine by the Emulsijication Process. A Modi$cation. By ROBERT DOWNS HAWORTH and ARTHUR LAPWORTH. IT has been found that the reduction of pure p-bromonitrobenzene is often quite unsuccessful if carried out as previously described (J. 1921 119 770). The following modification of the original method however usually gives a yield of p-bromophenylhydroxyl-amine nearly the same as that originally obtained but involves the use of more solvent benzene and preferably also more reducing solution. It is essential that the sodium sulphide crystals used in making the reducing solution should be of good quality. p-Bromonitrobenzene (5 g.) benzene (40 c.c.) the hydrosulphide solution (120 g. prepared as formerly described Zoc.cit. p. 769), and calcium chloride (5 g. in a little water) are emulsified. Crystals soon separate and after 1 i hours solid ammonium chloride (5 g.) is added the whole shaken and the precipitated p-bromophenyl-hydroxylamine (about 2-9 g.) collected and washed with water. The benzene layer of the filtrate is separated washed with wafer, dried over anhydrous sodium sulphate and carefully diluted with petroleum (b. p. 40-60"); a further crop (about 0.5 g.) of the hydroxylamine is then obtained. Three experiments carried out in the above way gave total yields of 2-7 g. 3.4 g. and 3.3 g. respectively of p-bromophenylhydroxyl-amine. With the smaller quantity (52 g.) of sodium hydrosulphide solution previously advised the yields in five experiments were 24-34 g.-THE UNIVERSITY M~NCHESTER.[Received November 24th 1925. NOTES 2971 Action of Hydrazine Hydrate on Phenanthraquinone. A Corre.ectim. IT was stated by Dutt and Sen (J. 1923 123 3420) that phen-anthrone is the sole product obtained from phenanthraquinone by the action of hydrazine hydrate. In subsequent experiments with commercial hydrazine hydrate (50%) 9 10-dihydroxyphen-anthrene (m. p. 147") waa almost exclusively obtained instead of phenanthrone. Fortunately a small quantity of the original " hydrazine hydrate " in a sealed tube was available and this was found to be incorrectly labelled the substance being actually pure anhydrous hydrazine. Further experiments have shown that when anhydrous hydrazine is allowed to react with phenanthraquinone in absolute alcohol phenanthrone is obtained in good yield and that when small quantities of moisture are present or when ordinary com-mercial hydrazine hydrate is employed 9 10-dihydroxyphen-anthrene is almost the sole product.The error was made through unavoidable circumstances but is none the less regretted.-kPERrAL COLLEGE SOUTH KENSINGTON, S.W. 7. [Received November 28th 1925.1 By SIKHIBHUSHAN DUTT. The Alurniniomlutes of same Optically Active Bases. By THOMAS BRUCE CHILD ELWYN ROBERTS and EUSTACE EBENEZER TURNER. COMPOUNDS of the aluminioxalate type derived from the acid H,Al(C,O,), should be capable of resolution into optically active forms. This has been attempted by means of active bases. Strychnine AZuminiozdzte.-Barium aluminioxalate (Burrows and Walker J.1923 123 2738) twice cryatallised from water was warmed with the calculated quantity of aqueous strychnine sulphate. The precipitate of barium sulphate and strychnine aluminioxalate was extracted with boiling water and the extract allowed to crystallise. Different crops had [aE. -24.0" to -21.0" in 50% aqueous acetone and formed slender colourless needles very sparingly soluble in water [Found strychnine 63.0; C,O, 16.6. (C21€&O~2),,H&l(C204)3,16H,0 requires strychnine 63.4 ; C,O,, 16-7%]. When these salts were recrystallised partial decomposi-tion occurred with formation of strychnine oxalate and aluminium hydroxide and no conclusions can be drawn in connexion with any rotational differences observed. When a solution of sodium aluminioxalate was treated with half its equivalent of aqueous strychnine hydrochloride a salt was obtained which had [a%* -19.0" in 50% aqueous acetone.It was treated with aqueous potassium iodide and the precipitated strych-VOL. CxxVTr. 5 2972 NOTES. nine hydriodide removed. The resulting solution of potassium aluminioxalate contained a trace of colloidal aluminium hydroxide, and what optical measurements were possible pointed to the inactivity of the solution. Crystallisation of strychnine aluminioxalate from acetone gave crops of salt having slightly different specific rotations but consistent results could not be obtained. 1-Menthylamine A1uminiomlate.-The barium salt was digested a t 100" with an aqueous solution of the equivalent quantity (10 g.) of I-menthylamine previously dissolved in the calculated quantity of dilute sulphuric acid.SdEcient water was added to keep all the menthylamine salt in solution and after fltration from barium sulphate 17 g. of 1-menthylamine aluminioxalate separated in well-defined prisms which were sparingly soluble in water [Found: I-menthylamine 59-2 ; C204 33.6. (Cl,,H21N)3,H3Al(C204)3,H,requires I-menthylamine 59.9; C,O, 34.0%]. This salt had [aE' -28.5" in 50% aqueous acetone. Recrystallisation which was accompanied by partial decomposition gave no evidence of resolution. Treatment of a concentrated solution of sodium aluminioxalate with one-third of the equivalent quantity of 1-menthylamine sulphate gave a salt having a rotation practically identical with the above. 1-Phenylethylamine A1urniniomlate.-This salt was prepared by digesting the barium salt with the calculated quantity of aqueous I-phenylethylamine sulphate at 100" for about an hour removing the barium sulphate and evaporating to a small bulk under diminished pressure.It crystallised from water in which it was very soluble in colourless prisms. The main bulk of the salt had [a]$* -340" in aqueous solution [Found C,O, 39-1. requires C204 39-1y0]. After it had been recrystallised four times from water its rotation was not measurably affected (Found: I-phenylethylamine 53.0 ; C,04 39.2. Calc. I-phenylethylamine, 53.7 yo). Distrychnine potassium aluminioxalate and d-phenylethylamine dipohsium alurninioxahte were also prepared. Their specific rotations did not change as a result of repeated recrystallisation. Cinchonsine aluminioxulate was obtained as a gummy solid which could not be crystallised. (c~H1~N)3,H3~(c204)3~H20 The authors wish to thank the Research Fund Committee of the Chemical Society for a grant by means of which the expense of this work has been met.-EAST LONDON COLLEGE UNIVERSITY OF LONDON. [Received September 19th 1925.