D iethyl ether. I. Products of autoxidation. H.
Ki n g (J.C.S., 1929,738—750).—Titration of deteriorated ether with 0- liV-potassium permanganate in presence of AT-sulphuric acid and manganese sulphate determines the amount of free and labile hydrogen peroxide present ; in four cases the amount varied from 2-8 to 5-6 g. per litre. Distillation of such an ether through an efficient column causes no loss of peroxide. Qualitative detection of hydrogen peroxide in ether is carried out by shaking a mixture of ether (9 c.c.), water (1 c.c.), 22V-sulphuric acid (1 drop), and 0-5iV-potassium dichromate (1 drop) for 30 sec. ; the ethereal layer shows a faint blue colour a t a dilution of 1 in 400,000. The test is untrustworthy in presence of acetaldehyde. Treatment of an ethereal solution of hydrogen peroxide with acetaldehyde and subsequent evaporation in a vacuum yields di-ac-hydroxy- ethyl peroxide (I), which could not be obtained crystal
line. When this is decomposed by gentle boiling with dilute sulphuric acid, the evolved acetaldehyde absorbed in standard sodium hydrogen sulphite solution and determined by ' back-titration with iodine, and the residual hydrogen peroxide redetermined by perman
ganate, a ratio of 1 ■ 82—1 - 91 :1 for aldehyde : peroxide is found. Further treatm ent of I with acetaldehyde and subsequent redetermination of the ratio gives values of 2-1—2 - 2 :1 . Similar determinations of the alde- hyde-peroxide ratio in deteriorated ethers gives values of 1-13—1 -2 4 :1 . These are not materially affected by previous washing with sodium hydrogen carbonate solution to remove formic and acetic acids. The per
manganate titration on the distillation residue of washed and unwashed ether is usually larger than direct titration by about 10%, indicating the presence of a small amount of a more stable peroxide. Treatment of deteriorated ether with acetaldehyde causes an increase of the aldehyde-peroxide ratio to 2-1—2-2 : 1.
This fixation of acetaldehyde by the peroxide present in ether is consistent with Wieland and Wingler’s view of an acetaldehyde-hydrogen peroxide combination (A., 1923, i, 650), but does not agree with Clover’s
formulation (A., 1922, i, 619).' I t is suggested th a t the peroxide present is essentially a-hydroxyethyl hydrogen peroxide and not a mixture of I and hydrogen peroxide (cf. Wieland and Wingler, loc. cit.), since three-fold extraction of the ether with one tenth of its volume of water gives an extract with an aldehyde-peroxide ratio of 1-43 :1 . The distribution ratios of acetaldehyde, I, and 1% hydrogen peroxide, between ether and water are 1 : 2-45, 1-5 :1 (cf. Clover, loc. cit.), and 1 :16 (Clover, loc. cit.), respectively. Formaldehyde could not be detected among the decomposition products of the ether peroxide when distilled with A-sulphuric a c id ; s-dihydroxydimethyl peroxide (II) affords formaldehyde under the same conditions. Aqueous solutions of I and II give a blue coloration with a 10% alcoholic tincture of guaiacum or a 1% solution of benzidine in 50% alcohol, in presence of peroxidase. A mixture of acetaldehyde or formaldehyde and aqueous hydrogen peroxide gives a direct reaction with benzidine, but not with guaiacum.
The reaction becomes negative when the solutions are kept for 2—3 days (cf. Wieland and Wingler, loc. cit.), indicating th a t the coloration is due to an intermediate peroxide consisting of molecular proportions of the aldehyde and hydrogen peroxide, A positive test is given by an aqueous solution of the peroxide from deterior
ated ether ; heptaldehyde and benzaldehyde suspended in water also give positive tests owing to their peroxide content. Butyl, ¿sooctyl, and amyl alcohols show a reaction with benzidine or guaiacum in presence of peroxidase, but methyl, ethyl, tsopropyl, and benzyl alcohols do not. In many of these tests a drop of a solution of a ferrous or ferric salt can replace the enzyme.
II. Bu r t o n.
Exam ination of tablets of acetylsalicylic acid containing m agn esia. A. Ho f f m a n n (Dansk Tidsskr.
Farm., 1929, 3, 81—102).—The tablets should be tested for their content of acetylsalicylic acid and for salicylic acid produced by hydrolysis of this. Methods available for the former determination are : (a) warming with O'5A7-sodium hydroxide, followed by rapid titration of the cooled liquid with 0 -liV-hydrochloric acid, using alizarin-yellow as indicator ; (b) extraction of the acetyl
salicylic acid with ether, the dissolved acid being hydrolysed by warming with 0-5A7-sodium hydroxide after removal of the ether, and the excess of alkali titrated with 0 • 5AT-hydrochloric acid, using phenolphthalein as indicator; (c) the material is warmed with sodium hydroxide, excess of hydrochloric acid added, and the whole warmed for 10 min., any separated salicylic acid being redissolved by the addition of alcohol and determined in an aliquot part of the solution by Kolt- hoff’s bromate method (A., 1921, ii, 466), with the modification th a t the liquid is allowed to remain 30 min.
before addition of the potassium iodide. To determine free salicylic acid the tablet is treated with 1 c.c.
of 4iY-sulphuric acid, 10 c.c. of a mixture of ether'and pentane (1 :1 ) are added, and the whole is shaken.
The organic layer is separated, and 5 c.c. of this are evaporated. The residue is dissolved in 20 c.c. of 25%
alcohol, and after addition of 0-5 c.c. of 2% ferric chloride solution the colour produced is compared with th at of similar standard solutions of the acid.
H. F. Ha r w o o d.
B r i t i s h C h e m ic a l A b s t r a c t s — B .
452 Cl. X X.—M e d i c i n a l S u b s t a n c e s ; E s s e n t i a l O i l s .
Evaluation of liquor cresoli sapouatus. H.
Ka is e r (Apoth. Ztg., 1928,68, 026—627 ; Chem. Zentr., 1928, ii, 2047),—A simple procedure based on direct distillation is described. A. A. El d r id g e.
Synthetic drugs. IV. Synthesis of sulphur com pounds. V. Preparation of benzyl com pounds.
H. P. Ka u f m a n n (Arch. Pharm., 1929, 267, 192—211, 212—219; cf. A., 1927, 155, 663, 1083).—IV. [With
E. We b e r.] Kaufmann and Oehring’s method of
“ rhodanation ” (A., 1926, 392) is improved and its usefulness in preparing sulphur derivatives discussed.
The solvent used is methyl alcohol or a volatile ester ; it is saturated with sodium bromide or ammonium chloride according as the halogen to be added is bromine or chlorine; and a great excess of thiocyanate is added.
The use of such solvents allows the reaction to be performed a t a low temperature so th at the thiocyano- derivative can be isolated in cases where formerly the thiazole was produced (cf. Kaufmann, A., 1928, 653).
y-Thiocyanoaniline is obtained in excellent yield either by adding bromine to a solution of aniline and an excess of sodium thiocyanate in methyl alcohol saturated with sodium bromide, or by passing chlorine into a similar solution containing ammonium thiocyanate and ammonium chloride. p-Thiocyanoacetanilide can
not be directly obtained from acetanilide in this way.
Phenacetin likewise remains unattached, but jj-phcnetid- ine is smoothly “ rhodanated ” in methyl alcohol to the 2-iAi'oc//«)!o-derivative, m.p. 67—68°, which, however, is rapidly converted at about its m.p. into 2-amino-6- ethoxybenzthiazole, and yields the diacetyl derivative, m.p. 245°, of this compound on acetylation. 2-Thiocyano- p-phenetidine gives 2 : 2'-diamino-5 : b'-diethoxydiphenyl disulphide, m.p. 101°, when cautiously warmed with dilute alcoholic sodium carbonate solution. The follow
ing thiocyano-derivatives, prepared by direct “ rhodan
ation,” are also described: formyl-p-thiocyanophenyl- hydrazine, m.p. 132°, and the analogous acetyl, m.p.
171° ; benzoyl, m.p. 164° ; and phthaloyl compounds, m.p. 213° ; acetyl-]rp'-dithiocyanodiphe7iylhydrazine, m.p.
160°, and the analogous henzoijl compound, m.p. 160°.
i-Thiocyano-l-hydroxyquinoline (4-thiocyanocarbostyril) has m.p. 141°; i-thiociyano-8-hydroxyquinoline has m-p.
134°. Thymol yields 4-thiocyano-6-Mopropyl-»i-cresol, already described by Kaufmann and Gärtner (A., 1924, i, 840), which is a potent disinfectant, o- and m-Cresols yield the 5-thiocyano- (1-6-cyano- from m-cresol) deriva
tives, m.p. 71° and 76°, respectively. p-Cresol yields the M c / ^ S ,
compound ^>C:NH, m.p. 105°, hydrolysed by
\ / °
alcoholic hydrochloric acid to the cyclic carbonate of the mercaptocresol, m.p. 83°.
V. [With 0. Ri t t e r.] The pharmacological pro
perties of compounds containing benzyl groups are exhaustively discussed, with copious literature references, particularly to the developments from Macht’s work on benzyl alcohol. Tho preparation of the following com
pounds is described. i-Dibenzylamino-l-phenyl-2 : 3- dimethyl-5-pyrazolone, m.p. 102° ; ~N-ct-bromoisovaIeryl- W-benzylcarbamide, m.p. 134° (from benzylcarbamide and a-bromoi'sovaleryl bromide); pp
'-diethoxydiphenyl-phenylethenylamidine, m.p. 113°, obtained by heating phenylacet-p-phenetidide, m.p. 128-5—130°, with phos
phorus oxychloride in benzene solution; oo'-dibenzyl- phenolphlhalein, m.p. 175° (diacetyl derivative, m.p. 134°), prepared in the usual way from o-benzylphenol; pp'- dibenzyldiphenylphthalide, m.p. 123°; ■p-thiocyano-'N- benzylaniline, m.p. 78°, by direct “ rhodanation,” yielding on treatment with alcoholic potassium hydroxide the corresponding disulpliide, m.p. 92°; -p-thiocyano-N- benzylmethylaniline, m.p. 63° (disulphide, m.p. 86—87°);
;p-thiocyano-N-benzylethylaniline, m.p. 54° (disulpliide, m.p. 76°). W. A. Si l v e s t e r.
Variation in activity of different sam p les of strophanthin. P. Wo k e s (Quart. J. Pharm., 1928, 1, 513—516).—Nine commercial samples of strophanthin were compared with the official ouabain of the United States Pharmacopoeia X by the cat method. The average potency of eight samples was 47-3% of the standard; seven samples were within 25% of this
average. E. C. Ha p p o l d.
Detection of holocaine. L. Ek k e r t (Pharm. Zentr., 1929, 79, 120).—Holocaine may be distinguished from novocaine, stovaine, and other related compounds by the different colorations given with resorcinol and sul
phuric acid. S. I. Le v y.
Comm ercial utilisation of Java citronella oil.
B. O ’Do n o g iiu e, J. Drum, and II. Ry a n (Sci. Proc. Roy.
Dubl. Soc., 1928, 19, 113—120).—The more valuable constituents of Java citronella oil (citronellal, geraniol, and citronellol) may be obtained as follows : the crude oil (dir> 0-8918, ax)—2° 48', aeetylatable content 83-3%, aldehyde content 45%) is treated with 30% sodium bisul
phite solution for 4 hrs. at 0°, the citronellal bisulphite, which contains 1—2% of the double bisulphite, is collected, washed with ether, decomposed with dilute alkali, and the citronellal steam-distilled. The aldehyde is further purified by distillation in a vacuum, but pro
bably contains some wopulegol; the product has b.p.
205—206°, »¡J,8'3 1 -472, d19'5 0-8845, ax> + 2 ° 24', and the yield is about 43%. The oil remaining after removal of the citronellal is hydrolysed with alcoholic potassium hydroxide for 1 hr., and geraniol is separated as the double compound with calcium chloride ; after washing with light petroleum, the compound is decomposed with water, and the alcohol, b.p. 114—115°/12 mm.,
%,8’3 1-4768, <Z19’5 0-8811, ccD 0°, is obtained by steam-distillation. The residual oil still contains some geraniol together with citronellol and terpenes ; attem pts to separate the citronellol as the phthalate were unsuc
cessful. Citronellol, containing some isopulegol, is obtained by reduction of citronellal with iron and acetic acid at 15° ; the use of 5% sodium amalgam in faintly acid (acetic acid) solution below 5° is preferable and gives a product of b.p. 110—112°/10 mm., 3 1-468, at19-5 0-8542, a B + 2 ° 49', in 70% yield ; aluminium amalgam in aqueous-alcoholic solution a t 60—70°
also affords citronellol in 70—75% yield. Preliminary experiments on electrolytic reduction of citronellal indicate th a t with lead electrodes and sodium hydroxide solution as electrolyte, using a current of 8—9 amp.
for 10 hrs. a t 50—60°, an 80% yield of citronellol can be obtained readily. The preparation of geranyl acetate,
B r i t i s h C h e m ic a l A b s t r a c t s — B .
C l. X X .—Me d i c i n a l Su b s t a n c e s ; Es s e n t i a l Oi l s. 453
b.p. 127—129715 mm., «I?'3 1-4637, d19'5 0-907, a-o 0°, citronellyl acetate, b.p. 119—121°/15 mm., n},8 3 1-457, d10'5 0-9035, ccd + 0° 30', and of geranyl metliyl etber are described. C. W. Sh o p p e e.
Detection of sm a ll quantities of alcohol in cassia oil. Sc h im m e l & Co. (Deut. Parfümcrieztg., 1928, 14, 405—407 ; Chem. Zentr., 1928, ii, 2079).—The flash point is determined in a Pensky-Martens apparatus.
Tables give the flash points of cinnamaldehyde and cassia oil with varying amounts of added alcohol.
A. A. El d r i d g e.
D eterm ination of ethereal oils in gentian spirits.
T. v o n Fe l l e n b e r g (Mitt. Lebensmittelunters. Hvg., 1928, 19, 242—251 ; Chem. Zentr., 1928, ii, 2079).—
The spirit (5 c.c.), diluted to 30% of alcohol, is shaken with light petroleum (b.p. 29—45°, 5 c.c.), the extract is heated with lôN-sulphuric acid (1 c.c.) at 100° for 1 min., and the brown residual liquid is compared in a microcolorimeter with a specified (inorganic) comparison
solution. A. A. El d r i d g e.
P ine-stum p oil. Sc h im m e l & Co. (Ber. Schimmel, 1928, 100; Chem. Zentr., 1928, ii, 2077).—The oil, obtained by distillation in steam, had d15 0-8599,
«D +22° 43', «î? 1-46993; it contains ¿-a-pinene and pS-pineue (35—40%) and 40—50% of A3-carene.
A. A. El d r i d g e.
D ill top o il. Sc h im m e l & Co. (Ber. Schimmel, 1928, 23 ; Chem. Zentr., 1928, ii, 2077).—The oil has d15 0-8752, «d +108° 35', n f 1-47691. The chief con
stituent is phellandrene ; carvone is apparently absent.
A. A. El d r i d g e.
Cistus leaf oil. Sc h im m e l & Co. (Ber. Schimmel, 1928, 16 ; Chem. Zentr., 1928, ii, 2076—2077).—The oil of Spanish cistus leaves had d30 0-9560, 1-49592, acid value 28-0, ester value 42-9. A. A. El d r e d g e.
B oth a-grass oil. Sc h im m e l & Co. (Ber. Schimmel, 1928, 8 ; Chem. Zentr., 1928, ii, 2076).—Two samples of the oil (apparently identical with Rao, Sudborough, and Watson’s bode-grass oil) had d15 0-9321, 0-9303 ; ap - 1 8 ° 28', - 2 0 ° 45' ; < 1-48693, 1-48587 ; acid value 2-2, 2- 2; ester value 46-7, 40-1 ; ester value after acétylation 112-9, 110-1. A. A. El d r i d g e.
[Oil of] Carline th istle. Sc h im m e l & Co. (Ber.
Schimmel, 1928, 24 ; Chem. Zentr., 1928, ii, 2077).—
Oil from the root of Carlina acaulis, L., has dir> 1-0334, ap —5° 22', «§} 1-56548, acid value 1-1, ester value 7-5, ester value after acétylation 24-3.
A. A. El d r i d g e.
Oil of E u c a ly p tu s d iv e s . Sc h im m e l & Co. (Ber, Schimmel, 1928, 46 ; Chem. Zentr., 1928, ii, 2077).—
The following constituents were isolated : 4-terpineol (b.p. 208—212°/760 mm. ; 79—81°/5—6 mm. ; cP5 0-9275, aD — 22° 3 0 '; w" 1-47740; oc-naphthyl- urethane, m.p.. 105°), 1 : 4-terpin, m.p. 137—138°.
Oxidation with permanganate a t a low tem perature gave the glycerol of 4-terpineol, m.p. 113—115°. The sublimate from this, m.p. 129°, when distilled in steam with hydrochloric acid, gave carvenone (semicarb- azone, m.p. 197—198°) and p-cymene. Oxidation with alkaline permanganate gave a mixture of acids, m.p.
190—195°, passing by loss of water into the dilactone, m.p. 64—66° ; the acid mixture contained the
dihydroxy-dicarboxylic acid C10H18O6, m.p. 200°. The new alcohol js converted by hydrogen chloride into terpinene dihydrochloride, m.p. 51°. Piperitone is not present.
A. A. El d r i d g e.
Oil of D a c r y d iu m F r a n k lin ii, Hook. S c h i m m e l &
Co. (Ber. Schimmel, 192-8, 23 ; Chem. Zentr., 1928, ii, 2077).—The oil of the Huon pine had d15 1-0406—
1-0470, old + 1 ° 21' to - 1 ° 16', n l 1-53037—1-53446.
A. A. El d r i d g e.
Oil of C r y p to m e r ia ja p ó n ic a . S c h i j i m e l Co.
(Ber. Schimmel, 1928, 23 ; Chem. Zentr., 1928, ii, 2077).
—Oil from the root wood of the Japanese cedar had b.p.
270—300°, d15 0 - 9 3 2 5 - 0-9431, aD - 8 ° 20' to -2 0 ° 49', nz£ 1-50910 — 1-51075, acid value 0 — 0-3, ester value 0-9—9-3, ester value after acetylation 36-4—57-9. A. A. E l d r i d g e .
Terpenes and terpene alcohols. I. Vapour pressure-tem perature relationships. 0 . A. Pi c k e t t a n d J. M. Pe t e r s o n ( I n d . E n g . C h e m ., 1929, 21, 325—
326).—D a t a a r e g iv e n f o r a- a n d (3 -p in en e , d i p e n t e n e , t e r p in o le n e , f e n c h y l a lc o h o l, a n d o c-te rp in e o l, d e t e r m i n a t io n s b e in g m a d e b y a m o d if i c a t io n o f t h e R a m s a y a n d
Y o u n g m e t h o d . F . R . En n o s.
Thiocyanogen value of fats. Ka u p m a n n a n d Br o c e e.—S e e X II. Vapour pressure of nicotine.
Yo u n g a n d Ne l s o n.—S e e X X III.
Pa t e n t s.
Preservation of ether. E. M a l l i n c k r o d t , t u n . ,
and H. V. F a r r , Assrs. to M a l l i n c k r o d t C h e m . W o r k s
(U.S.P. 1,697,320, 1.1.29. Appl., 17.11.27).—The tinned interior surface of the container is oxidised, e.g., with potassium permanganate, or coated with varnishes insoluble in ether or with lead or other metal which does not catalyse the oxidation of ether.
R . Br ig h t m a n.
Medicinal com pound. C. N. An d e r s o n, Assr. to
Pa r k e, Da v i s & Co. (TJ.S.P. 1,703,377, 26.2.29. Appl., 6.2.28).—Tetrachloroethylene in anthelmintic capsules for administration to animals is stabilised i against actinic rays by incorporation with an oil-soluble red dye, e.g., Oil Soluble Red O. R. B r i g h t m a n .
Purification of organic com pounds [chiorophen- arsazine], D. B . Br a d n e r (U.S.P. 1,696,539, 25.12.28.
Appl., 25.6.25).—Crude chlorophenarsazine, made for example from djphenylamine and arsenic trichloride at 160—250°, is washed with water only. C. Ho l l i n s.
Manufacture of soluble plant extracts. F.
Go e d e c k e (B.P. 308,403, 24.1.28).—Inositolhexaphos- phoric acid and vitamins are extracted together from comminuted plants by means of very dilute hydro
chloric acid, and the former are precipitated by addition of calcium carbonate as neutral salts, from which they are recovered by means of (oxalic) acid. The vitamin solution may be mixed with the pure inositolhexaphos- phoric acid in solution and concentrated in a vacuum for use in foodstuSs. C. Ho l l i n s.
B a s i c q u in i n e s o l u t i o n . A. L i e b r e c h t , Assr. to
C h e m .- P h a r m . A.-G. Ba d H o m b u r g (U.S.P. 1,692,900, 27.11.28. Appl., 17.1.28. Ger., 4.11.25).—Quinine base is dissolved in solutions of quinine hydrochloride, formate, lactate, etc., preferably with the addition of
B r i t i s h C h e m ic a l A b s t r a c t s—B .
454 Cl. X X I.— P h o t o g r a p h i c M a t e r i a l s a n d P r o c e s s e s . Cl. X X II.— E x p l o s i v e s ; M a t c h e s .
solubilisers such as antipyiine, wovaleramide. In presence of antipyrine quinine base is soluble in -water.
The solutions are suitable for injections. C. Ho l l i n s.
N ew em etine s a lts . Ch e m. Fa b r. v o r m. Sa n d o z
(B.P. 233,533, 12.1.28. Switz., 12.1.27).—Emetine salts of bile acids, especially cholic and deoxycholic acids, are described. C. Ho l l i n s.
Manufacture of vaccines. W. We i c h l e i n (B.P.
282,780, 24.12.27. Ger., 24.12,26).—Immunising sera of high strength are produced by combining the virus or germ culture in physiological salt solution -with aniline dyes (magenta, brilliant-green, etc.) at 37° during 24—48 hrs. Examples are vaccines for swine erysipelas and for chicken cholera. C. Ho l l i n s.
Manufacture of soporifics containing at least one alkinyl group. M. Bo c k m u h l, I I . Sc h w a b e, a n d G.
Eh r h a r t, Assrs. to Wi n t h r o p Ch e m. Co. (U.S.P.
1,682,062, 28.8.28. A ppl, 15.12.26. Ger., 11.6.25).—
See B .P . 285,598; B „ 1928, 389.
Manufacture of com plex antim ony com pounds.
H. Ha h l, Assr. to Wi n t h r o p Ch e m. Co., In c. (U.S.P.
I,703,732, 26.2.29. Appl., 28.11.27. Ger., 22.4.26).—
See B.P. 288,370 ; B., 1928, 427.
Production of pyridine derivatives [3 :5-di-iodo-2-hydroxypyridine]. M. Do h r n and R. Di r k s e n,
Assrs. to Sc h e r in g- Ka h l b a u m A.-G. (U.S.P. 1,706,775, 26.3.29. Appl., 23.2.28. Ger., 31.3.27).—See B.P.
288,133; B., 1929, 37.
A lkyl- and aralkyl-resorcinolcarboxylic acids (U.S.P. 1,697,332).—See III. Curative cream s (B.P. 309,012).—See X II.
XXI.— PHOTOGRAPHIC MATERIALS AND PROCESSES.
Photographic action from m etals, w oods, etc.
J. G. St r a c h a n (J. Roy. Tech. Coll., Glasgow, 1929, 2, [1], 20—29).—In close proximity to a photographic plate zinc produces a blurred image in the dark after 2 h r s .; the intensity of the image is increased by highly polishing the zinc or by amalgamating it (although mercury alone produces no effect) and is diminished by rasping the surface. Boiled linseed oil, alcohol, and benzene have a similar action to zinc, but light petroleum is without action (cf. Russell, B., 1897, 825; 1904, 998).
A . R . Po w e l l.
Determ ination of ripening silver in photographic em ulsions. F. We i g e r t and F. Lt>BR (Z. Elektrochem., 1929, 35, 209).—Polemical against Kieser (B ., 1929,
227). H. T. S. Br i t t o n.
Pa t e n t s.
Production of photographic colour prints and transparencies. J. C. Ca r t e r (U.S.P. 1,706,107, 8.1.27).—Positives are printed from the separate colour-impression negatives on to collodion emulsion plates, and these are dyed their respective colours, stripped, and superposed on a suitable base to give the colour print. J. W. Gl a s s e t t.
Making of negatives. W. He in e c k e (U.S.P.
1,700,262, 29.1.29. Appl., 6.5.27).—Impressions are made from engraved plates or the like on a sensitised film, which is then developed in a bath containing
sodium sulphite, formaldehyde, and quinol, rinsed, dipped into an alkali bicarbonate solution to remove the ink used in making the impression, and finally
fixed. A. R. Po w e l l.
XXII.— EXPLOSIVES; MATCHES.
Specifications for cellulose for use in the manu
facture of sm okeless powder. F . O l s e n ( I n d . E n g . C h e m ., 1929, 21, 3 5 4 — 3 5 6 ).— T h e c u r r e n t s p e c if ic a tio n s f o r c e llu lo s e t o b e u s e d i n t h e p r e p a r a t i o n o f n i t r o c e llu lo s e h a v e b e e n d r a w n u p w i t h p a r t i c u l a r re fe re n c e t o c o t t o n liu t e r s . T h e r e a r e , h o w e v e r , o t h e r s o u rc e s o f c e llu lo s e w h ic h , w h ile n o t c o m p ly in g w i t h th e s e s p e c if ic a tio n s — p a r t i c u l a r l y t h a t o f t h e l i m i t i n g a m o u n t of a lk a li- s o lu b le m a t e r i a l — y e t y ie ld a n e q u a l l y s ta b le p r o d u c t ; o t h e r t r u s t w o r t h y c r i t e r i a w o u ld s e e m to b e c a lle d f o r w h ic h a r e a d a p t e d t o t h e p a r t i c u l a r fo rm o f c e llu lo s e c o n c e r n e d . F. R. E n n o s .
Determ ination of diphenylam ine and diphenyl- nitrosoam ine in the presence of their derivatives.
H. Ry a n, J. Ke a n e, and J. Du n n e (Sci. Proc. Roy.
Dubl. Soc., 1928, 19, 85—100).—Methods suggested by Berger and by Dreger (A., 1909, ii, 708) for determin
ing the “ safe-period ” of nitrocellulose powders stabil
ised by diphenylamine (I) are discussed critically.
The present authors claim th a t accurate results for the total reserve of stability in the powder may be obtained by the following method : after extraction with alcohol, the extractive is reduced with stannous chloride and hydrochloric acid in alcoholic solution, the alcohol removed, and the diphenylamine distilled in steam.
The distillate is extracted with chloroform, and diphenyl
amine is determined volumetrically with bromine.
Diphenylnitrosoamine (II) is thereby quantitatively converted into (I), and nitro-derivatives of (I) into bases the hydrochlorides of which are non-volatile in steam. In this method it is found th a t bromine water cannot be used, as the apparent absorption varies with the light conditions and the concentration of the reagent. These difficulties may be overcome by using a chloroform solution of bromine a t 15° in indirect sunlight, when (I) affords a tetrabromide, (II) a di
bromide, and 4-nitrodiphenylamine (III) a tribrom ide;
4-nitrodiphenylnitrosoamine (IV) and 2 : 4-dinitrodi- phenylamine (V) give monobromo-compounds, whilst 2 : 4'-dinitrodipheny]nitrosoamine (VI), 2 : 4 : 2 ': 4'-tetranitrodiplienylamine (VII), and 2 : 4 : 6 : 2 ': 4 ': 6'- hexanitrodiplienylamine (VIII) exhibit no appreciable bromine absorption. When binary mixtures of the above nitro- or nitroso-derivatives are brominated in chloro
form solution the apparent bromine absorption is greater than the theoretical value by 10% ; if this deduction be made the bromination appears to be nor
mal. Figures are also given for the quantitative action of bromine in alcoholic solution (cf. Dreger’s method) on I, II, III, and a mixture of VI and 4 : 4'-dinitro- diphenylnitrosoaruine (IX). The volatility in steam at 100° and 250° of several of the above compounds and their mixtures are recorded. I t is found th a t I is wholly, and II partly (66%), distillable in steam at 100° from an acid solution, and th a t II distils to the extent of 75% from an alkaline solution (cf. Berger’s
method). C. W. Sh o p p e e.
B r i t i s h C h e m ic a l A b s t r a c t s —B .
Cl. X X III.— S a n i t a t i o n ; W a t e r P u b i f i c a t i o n . 455
T esting of explosives for use in fiery coal m ines (Safety in Mines Res. Board Paper No. 51, 1929, 50 pp.).
—Comparative tests with coal gas, light petroleum vapour, benzene vapour, and methane showed th a t methane was the most suitable for use in the gallery test for explosives. New tests for permitted explosives are proposed which it is hoped will result in more reliable control of coal-mine explosives. S. Bi n n i n g.
E xplosive gas m ixtu res. Pr a u s n i t z.— S ee II.
Erosion of gu ns. Gr e a v e s a n d o t h e r s .—S e e X.
Pa t e n t s.
E xplosives for use in m in es containing firedamp and like ga ses. A. Se c a y (B.P. 299,462, 23.10.28.
Belg., 27.10.27).—Potassium perchlorate, or nitro
glycerin with or without potassium perchlorate, is added to ammonium nitrate, sodium or potassium chloride, and trinitronaphthalene, the last-named being in such amount th a t it is completely burnt by the oxygen in the ammonium nitrate, or at least by the total oxygen present in the mixture. S . Bi n n i n g.
H igh-explosive com position. E. Ol s e n (U.S.P.
1,705,874, 19.3.29. Appl., 30.10.23).—The composition includes ammonium perchlorate, barium nitrate, vege
table ivory meal, ferrosilicon, trinitrotoluene, and graphite. H. Ro y a l- Da w s o n.
Porous m aterial for receptacles for explosive ga ses (B.P. 293,697).—See II.