Assay of m ercury oxycyanide and m ercury cyanide pastilles. E. Sc h u l e k and A. St a s ia k
(Arch. Pharm., 1928, 266, 638—641).—Hydrocyanic acid may be determined by the bromine-iodometrio method, previously described (A., 1925, ii, 327, 606).
provided th at sodium chloride or potassium bromide is first of all added to the solution. The solution containing mercuric cyanide is treated with phosphoric acid and bromine water, followed by sodium chloride or potassium bromide. Excess of bromine is subse
quently removed with phenol and the cyanogen bromide is finally determined by titrating with O-OOlA-sodium thiosulphate solution the iodine set free from potassium iodide solution. The method described by Rupp and Lewy (A., 1928, 860) gives low results.
S. Co f f e y.
S tab ility of m orphine in aqueous solution especially during sterilisation. R . Di e t z e l and W. H uss (Arch. Pharm., 1928, 266, 641—667).— Aqueous solutions of morphine hydrochloride decompose on heating, and the change may be followed spectro
scopically since morphine shows distinct absorption bands in the wrave-length region 3000 — 4400 A. As the time of heating is increased the absorption band is gradually shifted towards the visible region and becomes less well defined. The stability of aqueous solutions of morphine depends to a marked extent on the hydrogen - ion concentration. Alkaline solutions (^H > 7) undergo a change a t room temperatures ; approximately neutral
B r i ti s h C h e m ic a l A b s t r a c t s — B .
148 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.
solutions are relatively unstable a t higher temperatures, whilst acid solutions (pa <[ 7) are more stable. No decomposition is observed when solutions (pH 5- 5-5) are heated at 100° for 1 hr. or longer. The change is due to the oxidation of morphine to tj;-morphine, and the two components may be determined in a solution By comparing the absorption curve with those obtained with known mixtures. S. Co f f e y.
Rapid detection of extract of A tr a c ty lis g u m m i- fera in liquorice extract. P. Co n d o r e l l i(Atti II Cong.
Naz. Chim. pura appl., 1926,1353—1355 ; Chem. Zentr., 1928, ii, 592).—The extract (5 g.) is treated with boiling water (50 c.c.) containing a little ammonia, t ooled to 20°, and acidified with dilute sulphuric or hydrochloric acid, whereby it is considered that, a glucoside, atractylic acid, is precipitated. The precipi
tate, when heated with 2—3 drops of concentrated sulphuric acid, gives an odour of valeric acid (Angelico's reaction) ; it may also be oxidised by Bertolo’s method.
A. A. El d r i d g e.
Detection of industrial spirit in pharmaceutical tinctures. W. Me y e r (Pharm. Ztg., 1928, 73, 1600—
1602).—Tinctures suspected to contain inferior spirit may be prepared in part from alcohol distilled from industrial spirit originally rendered non-potable by addi- tion of pyridine to fully rectified alcohol. Distillation by means of hot water at 90° of spirit rendered non- potable in this way yields a product containing no methyl alcohol or acetone, and only -traces of pyridine, A microchemical method of testing for such traces of pyridine by means of its double compound with cadmium chloride is described. S. I. Le v y.
Commercial evaluation of cloves. W. A. N.
Ma r k w e l l and L. J. Wa l k e r (Perf. Ess. Oil Ilec., 1928, 19, 496—497).—Five existing methods for the assay of cloves to be used for oil distillation are reviewed, and the following new7 method is described. About 0-5—1 g. of the cloves reduced to a No. 20 powder is weighed into a tared Petri dish with lid. It is heated at 110° until of constant weight, and from the difference in weights is subtracted the amount of moisture deter
mined by Dean and Stark’s method. The percentage of volatile substances other than water is thus obtained.
Results agreeing well with yields given by commercial distillations arc obtained. E. H. Sh a r p l e s.
E ssential oil of T r ila b u m S u p . S ile r. B . Ru t o v s k i
and K. Gü s s e v a (Riechstofihid., 1927, 230; Chem.
Zentr., 1928, i, 267).—The oil, obtained in a yield of 3-27%, had d-o 0-8886, otD +131-65°. n% 1-4862, acid value 1-05, ester value 41-58, ester value after acétylation 59-3, and contained a-limonene (about 55% ; tetrabromide, m.p. 103°) and a-perillaldehyde (about 40% ; semicarbazone, m.p. 197° ; oxime, m.p. 102°).
The presence of a-pinene and azulene was conjectured.
E. H. Sharp l e s.
Determ ination of ionone. R. D. He x d r ik s z and A. Re c l a ib e (Perf. Ess. Oil Rec., 192S, 19, 493).—The following modification of the method of Reclaire and Spoelstra for the. determination of citronellal (B., 1928, 426) is applied to ionone determination. 5 c.c. of ionone
are refluxed for 2 hrs. with a solution obtained by dissolv
ing 15 g. of hydroxylamine hydrochloride in 37-5 g. of water, and adding to this solution 18 g. of potash in 37-5 g. of water. The mixture, still hot, is poured into a separating funnel, the aqueous layer separated, and the oximated oil washed three times with hot brine and filtered as hot as possible. In about 0-5—1 g. of the dry oil the nitrogen is determined by the Kjeldahl- Gunning method. The ionone content is calculated from the formula x = 53-82a./(14—0-012a), in which a — c.c. 0-2Ar-sulphuric acid required for 1 g. of oxini-
ated oil. E. H. Sh a r p l e s.
Sesam in and sesam olin. W. A d rlani (Z. Unters.
Lebcnsm., 1928, 56, 187—194).—Sesamin, found in sesame oil to the extent of 1%, was crystallised repeatedly from alcohol to a constant m.p., 122-5°. The pure material did not give the Baudouin reaction with furfur
aldéhyde and hydrochloric acid. I t had [a] + 6S-23° in chloroform. Elementary analysis and mol. wt. deter
minations indicated the formula C20H18O6. Sesamolin found in sesame oil to the extent of 0-3% had m.p.
93-6° and [ot]+218-4° in chloroform. The formula CooIIjgO, found by Malagnini and Arnianni (Chem.- Ztg., 1907, 31, 884) was confirmed. I t is hydrolysed by concentrated hydrochloric acid according to the equation CgflHigO-+ H 20 = C 7H b0 3 (sesamol) + C13H140 5. Sesam- ol, the phenolic substance to which the Baudouin reaction of sesamolin is due, was found to have m.p.
65-5° instead of 57° as found by Malagnini and Armanni (he. cil.). The name sarnin is suggested for the substance C13H140 5 now isolated for the first time. I t formed colourless crystals, m.p. 103° [a] +103° in chloroform, and did not give the Baudouin reaction.
AY. J . Bo y d.
See a ls o A., J a n . , 49, Sodium and potassium tetrabism uth tartrates ( Ko b e r). 72, Nopinene ozonide (Br u s a n d Pe y r e s b l a u q u e s) . 74, Pyridine and quinoline derivatives ( Ra t h a n d Pr a n g e).
76, Histidine (Ch e m n i t i u s). 79, Microchemical reactions of homatropine (Wa g e n a a r). Absorption spectra of ergot alkaloids ( Ha r m s m a). 81, Mor
phine alkaloids : thebaizone and products of ozonolysis ( Wie l a n d a n d Sm a l l). 82, S tr y c h n o s alkaloids (Le ü c h s, Be x d e r, a n d We g e n e r). H elle- bo ru s group : new alkaloids from H . v irid is
(Ke l l e r a n d Sc hOb e l). U nsym m etrical arseno- compounds ( Pa l m e r a n d Re s t e r). 83, Pyridine-3-arsinic acid (Bi n z, Ra t h, a n d Ga n t e). Derivatives of 1 : 4-benzfsooxazine (Ne w b e r y, Ph i l l i p s, a n d St ic k in g s). 84, Derivatives of 4-am ino-3-hydroxy- phenylarsinic acid (Ba l a b a n). O rgano-selenium compounds (Ta k a m a t s u). 8 6 , Determ ination of colouring m atter ( Ho f m a n). 8 6 , Reactions of colchicine (Ek k e r t). 96, Cicatrising agents ( Ju s t i n - Mu e l l e r). 97, A ssays of Chinese ephedrine ( Fe n g a n d Re a d). 101, Purification of diphtheria toxin.
(Ab t). 102, Extraction of hormone of corpora lu tea
(Gl e y). T esting of ovarian preparations ( Ko c h-
m a n n). Preparation of oestrus-producing hormone
( Al l a n a n d o th e r s ) . Regulation of production of insulin (Gr a f e a n d Me y t h a l e b). 103, Separation of
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. B r i t i s h C h e m ic a l A b s t r a c t s — B .
149
vitam in fraction from cod-liver oil ( J Ia r c u s).
Determ ination of vitam in-,4 (Ne l s o n a n d Jo n e s).
104, Conversion of vitam in-B into automatin by radiation (Zw a a r d e m a k e r). Purified ergosterol and its esters ( Bil l s a n d Ho n e y w e l l). Vitasterol-D
( Je n d r a s s i x a n d Ke m e n y f f i). 106, Glucosides of digitalis leaves (Wi n d a u s). Glucosides of A donis vern a lis ( Fr o m h e r z). O enanthe sarrnentosa (Go o d r ic h a n d Ly n n). Extract from Sphacele p arvifto ra
( Ha s e n f r a t z). 110, Extraction of cholesterol and its esters from tissu es and body fluids (Mu l l e r).
M icro-determination of cholesterol (Ho r i y e).
Euphorbium resin. Ba u e r a n d Sc h e x k e l.— S ee
XIII.
Pa t e n t s.
Extraction of theobrom ine. A. Bo e h r ix g e r
(B.P. 302,207, 12.9.27).—Natural products containing theobromine (cacao, cacao waste, cacao husks) are treated with dilute alkaline solutions (e.g., excess of alkaline-earth hydroxides), ¡it not above 50-—60°, in a countercurrent diffusion battery (or, especially in the case of finely-ground materials, a countercurrent decanta - tion or classification battery). E.g., using milk of lime, 90—95% of the theobromine is recovered on treating the extract with hydrochloric acid ; or the material is treated with a limited quantity of alkaline-earth hydroxide, and the residue extracted with 2—5% soda lye. the extract in the latter solvent being then treated with alkaline-earth hydroxide, the impurities separated, and the liquid acidified. The materials may receive an initial treatm ent with water. Materials which have been soaked before extraction are lixiviated with water at varied temperature and pressure. B. Pu l l m a n.
Extraction of theobrom ine from natural pro
ducts. N. V. Soc. Ch e m. In d. “ Iv a t w i j k” (B.P.
287,507, 21.3.28. Holl., 22.3.27).—The ground material is intimately mixed with a large excess of magnesia or alkaline-earth hydroxide and water is added in such amount th a t the mixture remains solid. Either im
mediately or after 24 hrs., further water is stirred in at, e.g., 70° to give an extract of the desired concentration, which is filtered and decomposed in known manner.
R . Br ig h t m a n.
Removal of nicotine from tobacco. H. Fe d e r m a n x
(B.P. 302,560, 17.7.28).—Tobacco, in a slowly-rotating perforated metal drum, is treated in closed cycle for some hours with the same quantity of gaseous ammonia heated a t a low temperature (42°) and a t a pressure only slightly above atmospheric. After passing through the tobacco the ammonia is freed from nicotine by passage through trichloroethylene or carbon tetrachloride and recirculated. W ater vapour is supplied to maintain the natural moisture of the tobacco. After the ammonia treatm ent the tobacco is treated with carbon dioxide to remove the ammonia. B. Fu l l m a n.
Manufacture of am inoalkyl ethers of oxim es and their salts. A. Ca r p m a e l. From I. G. Fa r b e n i n d. A.-G.
(B.P. 301,956, 9.9.27).—Water-soluble products, suitable for subcutaneous injection, are obtained by heating oximes with 3-diethylaminoethyl chloride and alcoholic
sodium ethoxide. The fi-dielhylaminoethyl ethers of oximes of cyclohcxnnone, b.p. 135°/15 mm. (hydrochloride, m.p. 95°), camphor, b.p. 150—160°/14 mm. (hydro
chloride, m.p. 172°), and anisaldehyde (hydrochloride, m.p. 145°) are described. C. Ho l l i n s.
Manufacture of basic ethers of resorcincl. A.
Ca r p m a e l. From I. G. Fa r b e n i n d. A.-G. ( B .P . 300,695, 18.8.27).—Basic ethers of resorcinol which have a strong contracting effect on blood-vessels and on the muscles of the uterus are obtained by treating a saturated mono- alkyl resorcinol ether with an aminoalkyl halide in an alkaline medium. Monomethyl resorcinol ether and (3- diethylaminoethyl chloride in presence of sodium eth
oxide afford m-methoxyphenyl dielhylaminoethyl ether, b.p.
160—166°/13 mm. (hydrochloride, m.p. 138—140°). m- Melhoxyphenyl $-dimelhylaminomethylbulyl ether, b.p.
170—172°/12 mm., and m-elhoxyphenyl $-dielliyl- aminoethyl ether, b.p. 171—179°/12 mm., are similarly
obtained. R . Br ig h t m a n.
Manufacture of arylam inoalkylcarbinols [fi- am ino-a-arylethyl alcohols]. W., K., L., W., and F. Me r c k (E. Me r c k) (B.P. 280,574, 10.11.27. Ger., 10.11.26).—Phenacylamine salts are hydrogenated in presence of a nickel catalyst. Phenacylmethylamine hydrobromide, when shaken with hydrogen gas in presence of 10% of nickel catalyst precipitated on pumice or asbestos, affords p-methylamino-a-phenylcthyl alco
hol, m.p. 77°. [3-Amino-a-plienylethyl alcohol (hydro
chloride, m.p. 40°) and p-methylamino-a-plienylpropyl alcohol (hydrochloride, m.p. 189 • 5°) are similarly obtained. * R . Br i g h t m a n.
Manufacture of 2-hydroxypvridine-5-carboxylic acid. C. Ra t h (G.P. 447,303,’ 12.11.24).—2-Chloro-5-cyanopyridine is heated a t 100° under pressure with 20% alcoholic sodium hydroxide solution, or a t 150°
with hydrochloric acid (d 1 -19). The reaction product is diluted and, in the first case, acidified. 2-Hydroxy- pyridine-5-carboxylic acid is precipitated, and on recrys
tallisation from methyl alcohol has m.p. 302—203°.
A. R . Po w e l l.
Manufacture of 8-hydroxyquinoline and deriva
tives thereof. A. Ca r p m a e l. From I. G. Fa r b e n i n d.
A.-G. ( B .P . 301.545, 2.9.27).—8-Hydroxyquinolines are obtained in practically quantitative yield by heating 5-aminoquinoiines with mineral acid or zinc chloride in aqueous or aqueous alcoholic solution a t 180—190 at 5—6 atm. 8-Hydroxyquinoline and 6 : 8-dihydroxy-quinoline, m.p. 153°, b.p. 207°/16 mm. (from S-amino-G- hydroxyquinoline, m.p. 177°, or 8-amino-6-methoxy- quinoline), are described. C. Ho l l i n s.
Manufacture of ethers of 6 :8-dihydroxyquinol- ine. A. Ca r p m a e l. From I. G. Fa r b e n i n d. A.-G.
(B.P. 301,947, 1.9.27).—6 : 8-Dihydroxyquinoline is converted by alkylating agents into mono-ethers, the 6-alkoxyl derivative predominating, or, with excess of the reagent, into di-ethers. The same products are obtained by Skraup’s reaction from 4-aminoresorcinol ethers. A second alkyl group may be introduced into the mono-ethers. The following quinolines are described:
6 : 8-dimelhoxy- (m.p. 56°, b.p. 132—134°/1 m m .;
anti-B r i ti s h C h e m ic a l A b s t r a c t s —anti-B .
1 5 0 Cl. X X . — .Ue d i c i x a l Su b s t a n c e s; Ks s e n t i a l Oi l s.
epilepsin), S-hydroxyS-methoxy- (m.p. 125°; anti
pyretic), 6 : 8-diethoxy- (m.p. 60°, b.p. 153°/2 mm. ; intestinal remedy), S-hydroxy-G-ethoxy- (m.p. 125°),
6-methoxy-S-fi-diethylaminoethoxy- (b.p. 193 °/4 mm.), 6-ethoxy-S-^-diethylaminoethoxy- (b.p. 190°/1 m m .; from 1-$-diethylaminocthoxy-o-phenetidine, b.p. 166—168°/1
mm.). C. H o llin s.
Preparation of cinchophen [2-phenylcinchoninic acid]. R. Pa s t e r n a c k, Assr. to C. Pf i z e r & Co.
(U.S.P. 1,690,128, 6.11.28. Appl., 21.4.27).—Equi- molecnlar quantities of 30% aqueous pyruvic acid, aniline, and benzaldehyde are charged into boiling 95% alcohol at about 100°. Side reactions yielding diketopyrrolidine anil are reduced. R. Br ig h t m a n.
Manufacture of arsenobenzenes. A . Al b e r t (B.P.
300,716, 26.8.27).—Aromatic arsenic compounds con
taining ter- or quinque-valent arsenic, or mixtures of the two, are reduced to arsenobenzenes with hypophos- phorous acid or a hypophospbite in presence of less than 0-33 mol. of sulphurous acid or a sulphite and of hydriodic acid or an iodide if required. With more than 1 mol.
of sulphurous acid colourless arsenobenzenes which contain sulphur probably attached to arsenic are obtained. Thus, in presence of 0-025 mol. of sulphurous acid, the semicarbazone of 2-carboxymethoxy-4-alde- hydophenylarsinic acid affords the corresponding arsenobenzene. With 1 mol. of the same semicarbazone and 1 mol. of the semicarbazone of 4-aldehyde-2- hydroxyphenylarsinic acid, the disemicarbazone of 2-hydroxy-2'- carboxymethoxy-4 : 4'- diahlehydoarseno- benzene, decomp, above 200°, is obtained. The di- setn icarbazones, decomp. 240° aud 230°, respectively, of 2 : 2'-dihydroxy-4 : 4'-dialdehydoarsenobenzene and of 2 : 2'-dihydroxy-4 : 4'-diacetoxyarsenobenzene are similarly obtained. In presence of 1—2 mols. of sulphur dioxide in acetic acid a t 80—85° the semicarbazone of 4-aldehydo-2-hydroxyphenylarsinic acid yields a sub
stance, decomp, a t 225°; similar ■products, decomp, at 220° and a t 230°, are obtained- in alcoholic hydrochloric acid in presence of hydriodic acid and by boiling under a reflux in presence of sulphurous acid. With 1 mol. of sulphurous acid in alcoholic hydrochloric acid in presence of hydriodic acid, 3-amino-4-hydroxyphenylarsinic acid affords a product, decomp, at 230°. R. Br ig h t m a n.
Synthesis of arom atic arsenic compounds con
taining iodine. A. D. M acallum (B.P. 300,286 and 300,538, 4.5.27).—(a) 5-Iodo-3-nitro-4-hydroxyphenyl- arsinic acid on reduction with titanous or ferrous oxide in cold alkaline solution affords 63—66% of the zin c or lead salt of D -iodo-3-am ino-i-hydroxyphenylaTsinic acid.
darkens a t 95°, decomp, in a vacuum at 65°, the -acetyl derivative of which, m.p. 158—159° or 190—191° (from 50% acetic acid), is converted by reduction with sodium hyposulphite a t 55—60° into 5 : 5'-diacetamido-i : 4'- dihydroxyarsenobenzene, m.p. 194°. Treatment of the latter in ether suspension with iodine and hydrolysis of the di-iodide with alkali hydrogen carbonate gives 5-iodo - 3 - acetamido - 4 - k yd roxypkenyla rsen oxide, m.p.
182—183°. (b) 5-Iodo-3-nitro-4-hydroxyphenylarsinic acid is converted (yield 78—79%) by hypopliosphorous
acid in methyl alcohol at 55—60° into 5 : o'-di-todo-3 :3 '- dinitro-4 : i'-dihydroxiyarsenobenzene, which when sus
pended in ether and treated successively with iodine and alkaline hydrogen carbonate solution affords 5<odo-3-nitro-l-hydroxyphenylarsenoxide, m.p. 170—210°.
R. Br ig h t m a n.
Extracts of the internal secretory organs of fem ales. Soc. Ch e m. In d. i n Ba s l e ( B .P . 285,856, 16.2.28. Switz., 23.2.27).—The fresh organs are mixed with an indifferent freezing agent (solid carbon dioxide), if necessary with addition of a dehydrating agent (sodium sulphate), and the product is powdered and extracted with solvents a t ordinary or raised tempera
ture. B. Fu i l m a n.
Separation of the cardio-active glucoside of B ulbu s scillae into two com ponents. R. E . El l i s.
From Ci i e m. Fa b r. v o r m. Sa n d o z (B.P. 300,726,1.9.27).
—The cardio-active glucoside of Bulbus scillce obtained, e.g., by the processes of B.P. 199,400 and 217,247 (B., 1924, 692, 997) is separated in aqueous methyl alcohol by fractional dissolution or precipitation including salting out, or by fractional extraction with an organic solvent, e.g., ethyl acetate, into two components A and B. The less soluble component (A) has af, — 78°, crystallises from methyl alcohol with 6-5% of solvent of crystallisation (lost in vacuo a t 76°), has a physiological activity per mg. of 1050 according to the frog standard of Houghton and Straub, and is readily hydrolysed to aglucone-A, which sublimes in vacuo at 180—200°, losing 1H ,0. Component B is non-crystalline, dextrorotatory, slowly hydrolysed to crystalline aglucone-B, m.p.
228—229° (decomp.), and has a physiological activity per mg. of about 1500—1600 frog doses. The separation may equally be effected on the glucoside-tannin com
pounds with relatively crude m aterial; in such cases a treatm ent with a tannin-precipitating agent is given prior to isolation. R. Br i g h t m a n.
Manufacture of anti-serum for prevention or treatm ent of scarlet fever. I . G. Fa r b e n i n d. A.-G.
(B.P. 276,024, 15.8.27. Ger., 14.8.26).—Scarlet fever bacilli or varieties thereof are cultivated either on solid nutrient media, e.g., solidified Loffler’s serum, or on liquid media, e.g., beef broth containing 2% of peptone, and the bacilli are separated from the medium and made into a suspension for injection. The suspension and culture are alternatively injected subcutaneously or intravenously, e.g., into horses, either with or without previous inoculation of the culture with streptococci, and when immunisation of the animal is complete the serum is recovered in the usual manner.
R. Br i g h t m a n.
Manufacture of phvsiologically-active substances from [secretory] organs [of fem ales]. W. Me r k i,
Assr. to Soc. Ch e m. In d. i n Ba s l e (U.S.P. 1.692,509.
20.11.28. Appl., 26.1.28. Switz.. 23.2.27).—See B.P.
285.S56 : preceding.
Production of rem edies from glandular organs.
G. Sc h r o d e r ( U .S .P . 1,695,612. 18.12.28. Appl..
29.11.26. Ger., 16.12,25).—See B.P. 263,155: B., 1927, 925.
B r i ti s h C h e m ic a l A b s t r a c t s — B .
C l. X X I.—Ph o t o g r a p h i c Ma t e r i a l s a n d Pr o c e s s e s. Cl. X X I I .—Ex p l o s i v e s ; Ma t c h e s. 151
Manufacture of pharm aceutical preparations.
W . S c h o e l l e r a u d K. S c h m i d t , A s s r . to C h e m . F a b k . a u f A c t i e n (v o r m. E . S o b e r i n g ) ( U .S .P . 1,693,055, 27.11.2S. A p p l., 28.7.27. Ger., 2.8.26).—See B.P.
275,213 ; B„ 1928, 83.
XXI.— PHOTOGRAPHIC MATERIALS AND