XVIII.—FERMENTATION INDUSTRIES
XX. —MEDICINAL SUBSTANCES; ESSENTIAL OILS
Action of ultra-violet lig h t on ferric citrate solutions. H. S. Fry’ and E. G. Ge r w e (Ind. Eng.
Chem., 1928, 2 0 , 1392—1394).—When citric acid solutions containing ferric salts are exposed to ultra
violet light, 3 mols. of carbon dioxide are liberated for every mol. of ferric sulphate present. I t is assumed that the photochemical change involves the oxidation of citric acid, with the liberation of 1 mol. of carbon dioxide, to the unstable acetonedicarbonic acid. This also loses 1 mol. of carbon dioxide, thereby giving aceto- acetic acid, which decomposes 'with the formation of acetone and a third molecule of carbon dioxide. The quantitative data obtained confirm these assumptions.
E. II. Sh a r p l e s.
Exam ination of pharmaceutical preparations by the extended capillary diagram and the analytical quartz lam p. Ra p p (Pharm. Ztg., 1928, 7 3 , 1585—
1589).—The following development on the methods of Kunz-Krause and Goppelsroder is described. A glass tube 60 cm. long and 3 cm. in diam, stands in a small cylindrical glass or porcelain vessel of about 20 c.c.
capacity and only just wide enough to fit outside the tube. A piece of fluted filter-paper 56 cm. long and 2 cm. wide is folded lengthways and placed in the tube with the bottom resting in the small vesssel, and only the top of the paper touching the walls of the tube. 3—5 c.c.
of the liquid to be examined are placed in the small vessel and the top of the tube is loosely corked. After remaining thus for a definite time the paper is removed, completely dried, and examined by ultra-violet light.
E.g., a mixture of 0-l% ‘ solutions of the hydrochlorides of quinine, narceine, apomorphine, papaverine, and pilocarpine gave a “ capillary s tr ip 1’ 25-5 cm. long which, after drying and examination with the quartz lamp, showed the first 14-7 cm. marine-blue (apomor- phine), then 3-7 cm. bluish-black (apomorphine and narceine), 2 cm. bluish-grev (quinine and papaverine), 4-1 cm. yellow (papaverine and pilocarpine), and, finally, 1 cm. fluorescent-blue (quinine). In other cases the bands vary in size, colour, and structure, and the method has been successfully applied to the study of the following: (a) deterioration of alkaloid solutions on keeping ; differences in capillary behaviour were noticed with solutions of apomorphine, narcophine, physostig- mine, pilocarpine, and scopolamine after keeping" for 6 months : (b) stability of “ Ysat ” preparations ; (c) differentiation of pure chemical substances and their proprietary equivalents; thus, differences were noticed between aspirin and acetylsalicylic acid in ether
B r i t is h C h e m ic a l A b s t r a c t s — B .
Cl. 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 O ils. I l l
solution, and between veronal and diethylbarbituric acid in both alcohol and ether solution ; (d) marked variations in colour and appearance which occur in the capillary values of 10 commercial digitalis preparations and 5 ergot preparations ; (e) comparison between preparations from plants and drugs and commercial extracts and galenical preparations having similar names. Application of the method for detection of adulteration, for routine pharmaceutical control, and other possible uses is referred to, together with an outline of future work. E. H. Sh a r p l e s.
D eterm ination of calcium carbonate in calcium glycerophosphate, lactophosphate, and the m ono- and di-acid phosphates. E. Le t u r c (Ann. Ealsif., 1928, 21, 534—536).—About 0-5 g. of the dried glycero
phosphate, thinly spread over a porcelain crucible, is calcined to a slightly grey ash, and 0-4 c.c. of hydro
chloric acid (“ officinal ” ) and 3 c.c. of water are added.
After dissolution the liquid is filtered hot. If there is any black residue, the filter must be ashed again. 30 c.c.
of water and 20 c.c. of 50% acetic acid, followed by 1 g.
of sodium acetate, are then added, and after dissolution 1 g. of oxalic acid is added. After heating and rotating the liquid, the calcium oxalate formed sinks to the bottom and is removed by filtration, dried, and weighed.
Calcium lactophosphate is treated similarly. For the mono- and di-acid phosphates the French Codex method is followed a t first, and, after the washing by décanta
tion, the residue is dried, calcined, taken up with 0-5 c.c.
of hydrochloric acid (officinal) and 3 c.c. of water, dissolved, and filtered, and the method described for the glycerophosphate then followed. D. G. He w e r.
Preparation of liquor alum inii acetici. A.
W ifflLK (Dansk Tidsskr. Farm., 1928, 2, 320—323).—
In order th a t the resulting solution shall be stable on keeping, it is necessary th a t exactly equivalent quantities of aluminium sulphate and calcium carbonate be used in its preparation, and it is recommended th at the sulphate content of the former and the purity of the latter should both be determined volumetrieally before
use. II. F. H a r w o o d .
Manufacture of argentum proteinicum , argen
tum colloidale, and other organic silver com pounds. J. Sc h w y z e r (Pharm. Ztg., 1928, 73, 1549—
1553, 1568—1570).—The preparation from casein of lysalbinic and protalbinic acids, the conversion of the latter into silver sodium anhydroprotalbinate, and the final preparation of argentum proteinicum are described in detail, with special reference to the methods of control. The specifications of the pharmacopoeias of different countries are discussed, and amendments and additions suggested. An apparatus and method for dialysis on the large scale are described, but no really satisfactory system is yet known. The manufacture of argentum colloidale is discussed, and the view is advanced th a t this is, as regards almost the whole of the silver content, a definite silver compound, the characteristic opalescence being due probably to only 1 or 2% of the silver content actually present as colloidal metal. Teste for alkalinity (determined on the ash) and solubility in water are described and suggested for inclusion in the pharmacopoeias. A brief description is
also given of several less important preparations of silver with protein acids. S. I. Le v y.
A ssay of ointm ents of m ercuric oxide and amm oniated m ercury. N. L. Al l p o r t (Quart. J.
Pharm., 1928, 1, 23—27).—Mercuric oxide ointment (yellow, 5 g., or red, 1 g.) is warmed at 50° with 100 c.c.
of a mixture of benzene 13, acetic acid 2, and 90%
ethyl alcohol 5 pts. The resulting d ear solution is saturated with hydrogen sulphide, the mixture heated a t 50°, the precipitate collected in a Gooch crucible, washed with hot benzene and a little alcohol, and dried at 100°. Ammoniated mercury ointment (2-5 g., or 1*5 g. of B.P. 1898 preparation) is heated at 70° with 100 c.c. of a mixture of benzene 9, acetic acid 10, 90%
ethyl alcohol 1 pt., the resulting clear solution being then treated as above. Ch e m ic a l Ab st r a c t s.
Evaluation of rhubarb. A. Tsc h ir c ii and P.
Schmitz (Pharm. Acta Helv., 1928, 3, 88—92; Chem.
Zentr., 1928, ii, 375—376).—Determinations of chryso- phanic acid showed no difference between Chinese rhubarb and rhubarb of the Palmcitum group cultivated by the authors. When kept for a long period the material gives lower values, whilst the rhizomes of old plants give higher values than those of young ones.
A. A. El d r id g e.
Evaluation of Peru balsam . A. Tsc h ir c h [with H. Ro s e n t h a l and G. Fr ie d l a n d e r] (Pharm. Acta Helv., 1928, 3, 85—88 ; Chem. Zentr., 1928, ii, 375).—
The analytical characteristics of Peru balsam are de
scribed. The material has d15 1-145—1-167, and gives a clear mixture with 1 vol. of 90% alcohol, but turbidity on addition of a further 7 vols. of alcohol; 3 g. ot balsam give a clear mixture with 1 g. of carbon disul
phide, and yield a brown resin on addition of 9 g. of carbon disulphide. The characters of the portions soluble or insoluble in ether and light petroleum are described.
These and other analytical tests are preferred to deter
minations of the acid and saponif. values of the crude
product. A. A. El d r id g e.
Volumetric process for the determination of phenazone. J. Ra e(Pharm. J., 1928,121,575).—Excess of picric acid is added, the solution filtered after 10 min., and the excess of acid determined by titration with 0-lA-sodium hydroxide solution. S . I. Le v y.
Action of Schiff’s reagent on pyram idone. A.
Va l d ig u ie (J. Pharm. Chim., 1928, [viii], 8, 506—510).
—By the addition of Schiff’s reagent to an aqueous or alcoholic solution of pyramidone the solution is coloured red, more or less intense according to the proportions of the reactants. Antipyrine does not give the reaction, but many samples of pyramidone of varied origin, the camphorate, salicylate, hydro
chloride, and sulphate, all form the red colour. 2 mg. of pyramidone in 10 c.c. of water give a very distinct rose colour with 3 or 4 drops of the reagent. The colour is stable to air and light, is intensified on heating, and persists on cooling, but it is destroyed by strong acids, alkalis, and reducing agents. I t is not due to aldehydic
impurity. E. H. Sh a r p l e s.
Carvacrol. A. Wa g n e r (Pharm. Zentr., 1928, 60, 757—763, 773—-777).—An account is given of the his
tory, constitution, occurrence, formation, preparation,
B r itis h C h e m ic a l A b s t r a c t s — B .
1)2 Cl. X X .— J Ik 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.
properties, reactions, detection, and determination of the product, with an exhaustive bibliography.
S. I . Le v y.
Colours of som e newer dyestuffs used in m edi
cine at different hydrogen-ion concentrations.
H. W. VAN Uric(Pharm.Weekblad, 1928,65,1227—1230).
—Tables are given showing the colours for the pn range 1—12 of the acridine derivatives trypaflavine and rivanol, of the sodium compound of tetraiodoplienolphthalein (“ Iodotetragnost ” ), and of the sodium salt of the mercury compound of dibromoiluorescein (“ mercuro-
chrome 220 ”). S. I. Le v y.
Solutions of quinine in ethylurethane. II. M . Gio r d a n i (Annali Chim. A ppl. 1928, 1 8 , 479—485;
cf. A., 1928, 907).—Spectrographic measurements in the ultra-violet show th at dissolution of quinine hydro
chloride in presence of ethylurethane is accompanied by the formation of molecular complexes, which cause a marked change in the absorption spectrum, and con
firm the view th a t the product of the transformation is quinotoxiu (cf. Schmidt, Physikal. Z., 1900, 1, 466;
Fischer. “ Die ultravioletten Absorptionespektren der Ckina-alkaloide,” 1925). T. II. Po p e.
Stability of solutions of cocaine and ^-cocaine.
E. Sa d o u n (Dansk Tidsskr. Farm., 1928, 2 , 309—315;
cf. A., 1927, 264).—A 1% solution of cocaine hydro
chloride undergoes hydrolysis to the extent of only 10% on keeping for a month at the ordinary tempera
ture, and no further hydrolysis takes place within a y e a r;
the results are the same if either water or 0 • OOOl/V- hydrochloric acid is employed as solvent. Cocaine is more resistant to alkalis than ip-cocaine. The latter is completely hydrolysed on shaking with 0-lAT-sodium hydroxide for 5 hrs. a t 20°, whilst cocaine requires 9—10 hrs. under similar conditions. Using 1% sodium bicarbonate solution in place of sodium hydroxide, 20%
of the cocaine and 30% of '.jj-cocame is hydrolysed at the end of the above periods. H . F. Ha r w o o d.
Strychnine hydrochloride. J. E. Dr iv e r and S . P.
Th o m pso n(Quart. J. Pliarm., 1928,1, 37—43).—Strych
nine hydrochloride crystals, in equilibrium with moist air a t the ordinary temperature, have the composition C21H2202N2,HC1,1-75H20 ; commercial samples con
tain > 1-5 < 1-75 IIoO. The solubility of the salt is greatly diminished by the presence of hydrochloric acid or metallic chlorides. The solubilities in water and hydrochloric acid solutions have been determined.
Ch e m ic a i Ab s t r a c t s.
M icrochem ical reactions of scopolam ine. M.
Wa g e n a a r (Pharm. Weekblad, 1928, 6 5 , 1226—1227).
—The most sensitive reactions are those with bromine and gold chloride. The crystals obtained are de
scribed. S. I. L ev y .
Pharm acological a ssa y of d igitalis. J . W . Tr e v a n,
E. Boock, J. II. Bu r n, and J. H . Ga d d u m (Quart. J.
Pharm., 1928, 1, 6—22).—Agreement between the results obtained by various methods was fairly good with a strong leaf, but unsatisfactory with a weak leaf.
The international standard powder is a practical standard for digitalis leaf and tincture in Great Britain.
Ch e m ic a l Ab s t r a c t s.
Lemon oil. J. Pr it z k e r and R. Ju n g k u n z
(Pharm. Acta Helv., 1928, 3, 79—83; Chem. Zentr., 1928, ii, 193).—Fresh or suitably preserved lemon oil has n20 70—76 ; values above 77 indicate th a t the oil is old and altered, unless it is free from terpenes.
Old lemon oil changes colour and deposits a brown mass ; with hydrochloric acid, d 1-19, the acid layer becomes dark brown or black, and the oil layer brownish. A residue on steam distillation of over 4% is abnormal.
The normal Eibner-IIue value is 0-6—1-2.
A. A. El d r id g e.
Coumarin and um belliferone m eth yl ether in lavender products. A. El l m e r (Riechstoffmd., 1927, 206—210, 220—222; Chem. Zentr., 1928, i, 268).—
An extracted lavender oil, on extraction with a con
centrated aqueous barium hydroxide solution, gave 0-9% of umbelliferone methyl ether and 3-4% of coumarin, whereas a distilled oil on similar treatm ent gave only 0-8% of coumarin. Probably the difference is due to the destruction of enzymes bysteam-distillation, and the coumarin present in the distilled oil represents that originally formed together with th a t liberated by the boiling water. In the extracted oil further action of the enzymes on the glucoside is still possible, thus accounting for the higher yield of coumarin. A method for the isolation and determination of coumarin by means of concentrated aqueous barium hydroxide solu
tion is described. E. H. Sh a r p l e s.
Caucasian bay leaf oil. B. Ru t o v s k i and N.
Ma k a r o v a- Se m l j a n s k a j a (Riechstoffmd., 1927, 218—
219; Chem. Zentr., 1928, i, 268).—An average sample of the oil, obtained in a yield of 0-915%, had d-° 0-9167,
<xd — 19-6° , nfj 1-4690, acid value 1-1, ester value 47-6, ester value after acetylation 67-3,solubility in 90% alcohol 1 in 0-4 vol., in 80% alcohol 1 in 2 vols. I t contained ciueole (50%), eugenol (benzoyl derivative, m.p. 69°), aeetyleugenol, a-pinene (nitrochloride, m.p. 90°; semi- carbazone of the pinonic acid, m.p. 201°), i-a-terpineol (nitrochloride, m.p. 99°; nitropiperididc, m.p. 151°;
phenyluretliane, m.p. 110°), and a sesquiterpene, b.p.
118—1220/12 mm., d20 0-9335, aD up to + 1 6 -S 0, n f 1-4902 (nitrosochloride, m.p. 113°).
E. H. Sh a r p l e s.
E ssential oil of C a ch rys a lp in a , M B . B. Ru t o v sk i
and .T. Vin o g r a d o v a (Riechstoffincl., 1927, 194—195;
Chem. Zentr., 1928, i, 268).—Steam-distillation of the fresh material gave 0-98% (2-7% 011 dry plants) of oil, having d2n 0-8456, ocd + 4-04°, Wg i-4868, acid value 0-26, ester value 3-9, ester value after acetylation 15-23, and was insoluble in 90% alcohol. The half
dried roots of the plant gave 0-4% of oil having d20 0-8671, ocn-f-6-640, 1-4972, acid value 1-6, ester value 4-56, ester value after acetylation 67-62, solu
bility in 90% alcohol 1 in 0 • 1 vol. Oil was obtained from the above-ground part of the plant in a yield of 0-8—
1-52% on the dried material; it had d20 0-8618, ocd 4 • 16°, 1-4880, acid value 0-79, ester value 11-88, ester value after acetylation 29-87, and was insoluble in 90%
alcohol. I t contained pinene, limonene, terpinolene, cymol, and a terpene and sesquiterpene of unknown constitutions. E. G . Sh a r p l e s.
D eterm ination of caffeine in tea. Go b e r t.—See X IX .
B r i t is h C h e m ic a l A b s t r a c t s — B .
C l. X X n . —Ex p l o s i v e s ; Ma t c h e s. C l. X X III.— Sa n i t a t i o n ; Wa t e r Pu r i f i c a t i o n. 113
Pa t e n t s.
Preparation of a nutrient m edium [for absorp
tion through the skin]. K . St e j s k a l (B.P. 271,120, 17.5.27. Austr., 17.5.26).—The product consists of a lion-aqueous emulsion containing a fat or oil, e.g., olive oil, and a water-binding liquid capable of being consumed by the body, e.g., glycerol, together with carbohydrates and/or proteins or their decomposition
products. L. A. Coles.
Production of trim ethylam ineglycol m onobor
ate. K. LIdbckb (B.P. 293,438, 9.2.28. Ger., 8.7.27).—
An aqueous solution containing 1 mol. of trimethyl- amineglycol and 1 mol., or between 1 and 3 mols., of boric acid is concentrated to a syrup a t about 30—60°
in vacuo, and trimethylamineglycol monoborate is deposited in a crystalline form ( + 1II20), m.p. above 300°, by the addition of a liquid in which it is insoluble, e.g., acetone. Alternatively, the syrup is dissolved in alcohol before the addition of the acetone, or the original constituents are brought to reaction in alcohol instead of in water. The product is of therapeutic value.
L. A. Co l e s.
Phosphatides (B.P. 285,417).—Sec X IX . XXII.—EXPLOSIVES; MATCHES.
Effect of com pression on the explosive properties of explosive gas m ixtu res. A. Ha i d and A. Sc h m id t
(Z . angew. Chem., 1928, 4 1 , 1309—1312).—The explo
sion pressures and brisance values for mixtures of oxygen with hydrogen (1: 2), methane (2 :1), ethylene (3 :1 ), and acetylene (2 -5 :1 ) a t ordinary pressure, and also when compressed at 600 atm., show th a t the compressed mixtures are as powerful as the ordinary solid explosives. Their brisance is comparable with th at of liquid air explosives. Auy practical application is, however, excluded by the difficult and dangerous technique. The uncompressed gases are very inferior in brisance to the solid explosive. S . Bi n n i n g.
Stabilisation of nitroglycerin powders b y di- ethyldiphenylurea. Le c o r c h e and Jo v i n e t (Compt.
rend., 1928, 1 8 7 , 1147—1148).—Notes from a paper already abstracted ( B ., 1928, 656). S. Bi n n i n g.
Determ ination of stab ility of sm okeless powder and guncotton by m easurem ents of hydrogen-ion concentrations. N. L. Ha n s e n (Forh. I l l nord.
kemistmotet, 1928, 227—230).—A method for deter
mining the stability of explosives of the nitrocellulose class has been devised based on the formation of acid when the explosive undergoes slow decomposition. The material (in the case of smokeless powder, after sifting to obtain grains of 0-35—0-8 mm. diam.) is dried in vacuo a t 40° for 8 hrs., or, in the case of guncotton, until the water content is less than 1%. 5 g. of smokeless powder or 2-5 g. of guncotton are weighed out into each of nine glass cylinders, closed by rubber corks carrying a capillary tube and stopcock. Eight of the cylinders are placed in a calcium chloride bath heated a t 110°, and after immersion for 15 min. any condensed moisture is removed. One cylinder is removed each hour, filled with distilled water (free from carbon dioxide) after cooling, and the ]>i± value of the solution
determined a t once without previous filtration, using a quinhydrone electrode ; the p n value of the ninth (unheated) sample is similarly determined. The results are plotted, using values as ordinates and the times of heating in hours as abscissoe, the curves obtained indicating the relative stability of the material under examination. Experiments show th a t in respect to the decomposition of the explosive, 8 hrs.’ heating under the above conditions corresponds to upwards of 30 years’ magazine storage at 10°. II. F. Ha r w o o d.
Determ ination of the friction sen sitivity of ignition m aterials. H. Ra t h s b u r g (Z. angew. Chem., 1928, 4 1 , 1284—1286).—The apparatus consists of a mechanically rotated pestle of steel or porcelain, which turns in a mortar, and is held down by a load of lead weights variable at will. The rate of rotation being kept constant, the friction is maintained for constant short periods under successively increasing loads until detonation occurs. The load required is found to be constant for the same material. With variable rates of rotation, the load required varies; curves are constructed which are characteristic for each material.
S. I. Le v y.
Flame m ovem ent in gaseous explosive m ixtures.
El l i s.—See II.
Pa t e n t s.
D igestion of nitrocellulose. He r c u l e s Po w d e r Co . , Assees. of M . G. Mi l l i k e n (B.P. 301,267, 20.4.28.
U.S., 23.2.28).—Nitrocellulose is digested by being forced under pressure in aqueous suspension through a long pipe of small diameter. The suspension contains 1 pt. of nitrocellulose to 25 pts. of water, the pressure is 80 lb./in.2, and the pipe is 1600 ft. long and 3 | in.
diam. The temperature of the suspension just after entering the pipe may be raised to 160° by injecting steam into a steam jacket surrounding the pipe.
S. Bi n n i n g.
Manufacture of nitroglycerin and the like.
F. E. Sm i t h, A. P . H. De s b o r o u g h, W. T . Th o m s o n,
W. Le d b u r y, and E. W. Bl a i r ( B . P . 301,112, 26.8.27).—
The nitration of polyhydric alcohols such as glycerin, glycol, or their ether derivatives is carried out in two stages either by adding the alcohol to pure nitric acid and then separating the nitrated compound by adding in one or more portions the correct amount of sulphuric acid, or by dissolving the alcohol in sulphuric acid and then precipitating the nitrated compound by adding
nitric acid. S . Bi n n i n g.
M ixing of liquids (B.P. 299,942).—See I.