minimised by working in an atmosphere of nitrogen.
With 4% sodium hydroxide solution for 5 days a chloroform-soluble syrup is obtained which appears to be a condensation product of 3 mols. of lactaldehydo with loss of 1 mol. of water. The product reduces Fehling’s solution slightly in the cold. Lactaldehyde is oxidised by aqueous copper acetate to pyruv-
aldehyde. ' H. B u r t o n .
Inosinic acid. IV. R ibophosphoric acid.
P. A. L e v e n e and T. M o r i (J. Biol. Chem., 1929, 81, 215—219).—Ribophosphoric acid undergoes lactone formation slowly, indicating the formation of an aS-iactone and the attachment of the phosphoric acid
residue in the e-position ; the suggestion of Robinson (A., 1927, 960, 1225) is therefore not accepted.
C. R. H a r i n g t o n . P recip ita tion of carbohydrates and g lu co sid es b y alkaloid p récip itan ts. L. R o s e n t h a l e r (Pharm. Acta Helv., 192S, 3, 93—96 ; Ghem. Zentr., 1928, ii, 374).—Under the conditions employed, potato, wheat, maize, rice, barley, arrowroot, and sago starches gave with bromine and hydrobromic acid, silicotungstic acid, and phosphomolybdic acid more or less precipitate, and with tannin a turbidity.
Aloin, convallamarin, digitalin, gitalin, and stroph- anthin gave a positive test with silicotungstic and phosphomolybdic acids; Crypsophila saponin reactcd similarly, but was not precipitated by tamiin or by bromine and hydrobromic acid. Thus precipitation of carbohydrates and glucosides can occur if the basicity due to the bridge oxygen atom is not too much weakened by hydroxyl or other acid groups.
A. A. El d r id g e. Influence of su g a rs on th e sta b ility of hydrogen, su lp h ite so lu tio n s. E. H I g g l u n d (Ber., 1929, 62,
\_B], 84—90).—The action of dextrose on the stability of sodium hydrogen sulphite solutions at 135° has been investigated. About 4— 5 hrs. after the maximal temperature has been attained, the sulphur dioxide content suddenly diminishes and the amount of sulphuric acid increases rapidly. At this period, a rapid increase in the amount of " loosely combined ” sulphurous acid is observed but this subsequently diminishes greatly. At this stage, considerable amounts of dithionic and, possibly, polytliionic acids are present which are transition products in the con
version of sulphurous into sulphuric acid. Under similar conditions in the absence of dextrose the sulphur dioxide content diminishes at a slower rate and the amount of sulphuric acid increases very slowly. The sugar content, as judged by the behaviour towards Fehling’s solution, diminishes considerably, probably owing to oxidation. In
stability of the hydrogen sulphite solutions increases with increasing sulphite concentration oxactly as would be expected with solutions free from sugar.
The catalytic efiect of mannose, xylose, and arabinoso is approximately the same as that of dextrose, whereas lævulose is less, but distinctly, effective.
The acceleration of the decomposition of sulphite by sugars depends on the réactivé carbonyl group of the latter. It is certain that the production of sulphuric acid is not due to reduction of the sugar by sulphur dioxide. The catalytic effect is due in the main to the facilitated formation of such intermediate products of the sulphite reaction, particularly thiosulphate ions, which cause and accelerate the decomposition.
H i Wr e n. O xidative d ecom position of su gar. I. A ction of “ ch loram in e-T " on dextrose. K. B e r n h a u e r and K. S c h ô n (Biochem. Z., 1928, 202, 159—163).—
The oxidation of dextrose (1 mol.) using sodium p-tolueuesulphonchloroamide by eight equivalents of oxygen giving rise to 2 mois of acetic acid and 2 mois, of carbon dioxide (Bleyer and Braun, A., 1927, 341) could not be quantitatively confirmed. Acetic acid caimot be detected and considerable amounts of formic acid are obtained. Gluconic acid is not
29S B R IT IS H CH EM ICA L A BSTRA C TS.---- A .
formed initially, since this substance is not attacked by
“ chloramine-T.” P. W. C l u t t e r b t j c k . O xidation of d extrose in alkaline solu tion w ith form ation of carbon m on oxide. M . N i c l o u x (Compt. rend. Soc. Biol., 192S, 99, 226—228; Chem.
Zentr., 1928, ii, 1077).—The consumption of oxygen and the yield of carbon monoxide are maximal at 85°.
Lmvulose, lactose, galactose, and maltose, but not sucrose until inverted, are similarly attacked. The effect of various salts is examined.
A. A. E l d r i d g e . C olorim etric d eterm in ation of d extrose. A. B.
S c h a c h k e l d i a n (J. Russ. Phys. Chem. Soc., 1928, 60, 1517— 1520).—The method is based on the red coloration, due to the formation of picramic acid, which is developed when a solution of dextrose is treated with picric acid in the presence of alkali. The intensity of the colour depends on the concentration of dextrose, and can be compared with a standard scale. Disaccharides do not give the reaction, whilst lsevo-hexoses produce a more intense colour. If chlorine ions are present, the coloration is fainter, and a special solution containing chlorides must be used as a standard of comparison.
M. Zv e g in t z o v. H exosediphosphate. P. A. L e v e n e and A. L.
R a y m o n d (J. Biol. Chem., 192S, 80, 633—638).—
Hydrolysis of the methylglucoside of hexosediphos
phate (cf. Morgan, A., 1927, 749) at 100° with 0-liV- hydrochloric acid consisted of initial rapid rupture of the glueosidic linking followed by much slower liberation of 1 mol. of phosphoric acid; the hexoscdi- phosphate is therefore a y-derivative, and the stable monophosphate of Neuberg (A., 1913, i, 423) is i-lsevulosephosphate. C. R . H a r i n g t o n .
Pityrol. VIII. D istillation of su crose. Y.
H i d a k a (Mem. Coll. Sci. Kyoto, 1928,11, 549—551).
—Pure sucrose when distilled from an iron retort at 240—610° gave a distillate consisting of water 75%, neutral portion 4-5%, acidic substance 1-5%, and humus 8-5%. Furfuraldehyde, methylfurfuralde- hyde, and hydroxymethylfurfuraldehyde were identified as the neutral constituents, and formic and laevulie acids in the acidic portion.
B. W. A n d e r s o n . C onstitution of daphnin. F. W e s s e l y and K.
S t u r m (Ber., 1929, 62, [5], 115— 119).—The gluco- daphnetin obtained by Leone (A., 1925, i, 12S3) from (3-acetobromogIucose and 7 : 8-dihydroxycoumarin is considered to have the glucose residue substituted in the S- rather than in the 7-hydroxyl group of 7 : 8-di
hydroxycoumarin. Until direct comparison can be made, the identity of this synthetic with the natural glucoside is not regarded as established and the present work refers to the synthetic material. Tetra- acetyldaphnin, m. p. 217°, [a]g —31-64° in methyl alcohol, and daphnin, m. p. 216—217°, [a]” -f29-36°
in methyl alcohol, are prepared by Leone’s method.
Treatment of tetra-acetyldaphnin with diazomethane followed by hydrolysis of the product affords S-hydroxy-l-methoxycoumarin, m. p. 175° (corr.) after slight previous softening, which is similarly prepared from daphnin. S-Hydroxy-7-ethoxycoumariti, m. p. 145 (corr.) after slight softening, is obtained
analogously. Treatment of S-hydroxy-7-methoxy- eoumarin with diazoethane in absolute alcohol gives an 80—90% yield of l-methoxy-S-ethoxycoumarin, m. p.
85-5° (corr.) [8-methoxy-7-ethoxycoumarin has m. p.
80-5° (corr.)], which is converted by successive treat
ment with sodium methoxide and ethyl alcohol and with ethyl iodide into 4-m ethoxy-2; 3-diethoxy- cinnamic ester, hydrolysed to 4z-mellwxy-2 : 3-dietlioxy- cinnamic acid, m. p. 157— 158°. Oxidation of the acid by permanganate yields ‘i-methoxy-2 : 3-diethoxy- benzoic acid, identical with the acid, m. p. 75° (corr.) after softening, obtained by treatment of methyl 4-methylpyrogallolcarboxylate with ethereal diazo- ethane and hydrolysis of the product. H. W r e n .
C onstitution and p rop erties of fraxin. F.
W e sse ly and E. Demmer (Ber., 1929, 62, [23], 120—
126).—Fraxin, obtained by extraction of the young bark of Fraxinus excelsior with boiling water, pre
cipitation of the extract with lead acetate, decom
position of the precipitate by hydrogen sulphide, and crystallisation of the glucoside from alcohol, forms pale yellow, hydrated crystals, m. p. 205° (corr.) when slowly heated. It is readily hydrolysed by hot, dilute sulphuric acid to fraxetin and dextrose and belongs to the (3-series, since it is attacked by emulsin.
Since the constitution of fraxetin has been elucidated (Wessely and Demmer, A., 1928, 893) the possible positions of the glucose residue and the methyl group in the 6 : 7 : S-trihydroxycoumarin structure of fraxin are S : 6 or 7 : 6; the decision in favour of the former is reached as follows. Fraxin is converted by successive treatment with ethereal diazomethane and hydrolysis into S-hydroxy-G : 7-dimethoxycoumarin, m. p. 195° (con1. ; decomp.), which with diazoethane affords 6 : 7-dimethoxy-S-ethoxycoumarin, m. p. 10S-50 (corr.). B y a similar series of changes fraxin is con
verted into S-hydroxy-6-methoxy-l-ethoxycoumarin, m. p. 153—154° (corr.; decomp.), and 6 : 8-dimethoxy- 7-ethoxycoumarin, m. p. 82° (corr.). Dimethyl- daphnetin is oxidised by potassium persulphate in alkaline solution in the presence of ferrous sulphate to a hydroxydimethoxycoumarin (cf. Bargellini, A., 1916, i, 490) which must be 6-hydroxy-7 : S-dimethoxy- eoumarin, since it is methylated by diazomethane to 6 : 7 : 8-trimethoxycoumarin, m. p. 103— 104° (corr.), identical with dimethylfraxetin. Diethyldaphnetin, b. p. 160°/0-2 mm., m. p. 67—78° (corr.), prepared by treating daphnetin with diazoethane, is oxidised to (i-hydroxy-7 : 8-diethoxycoumarin, b. p. 170°/0-2—0-4 mm., m. p. 149—150° (corr.), which is methylated to 6-methoxy-7 : 8-diethoxycoumarin, m. p. 80—Sl°
(corr.), identical with diethylfraxetin (A., 1928, 893).
Oxidation of 7-methoxy-8-ethoxycoumarin affords 6-hydroxy-7-methoxy-S-ethoxyc&u)narin, m. p. 156—
157° (corr.), methylated to 6 : 7-dimethoxy-8-ethoxy- coumarin, m. p. 108-5° (corr.), identical with the compound obtained from fraxin. H. W ren.
S esa m in . J. B o e s e k e n and W. D. C o h e n (Biochem. Z., 1928, 201, 454— 463).—Sesamin, m. p.
122-5°, [a]1,? +68-6° in chloroform, is shown to have the composition C20H 18O0. It is not reduced at 250°/100 atm. by hydrogen, and on oxidation no intermediate stages could be detected. The six oxygen atoms are held in ether linkings, and it contains the
methylene-dioxy-group attached to a benzene nucleus. Nitration with a mixture of nitric and acetic acids yields dinilrosesamin, C20H 1GO10N2, m. p. 235—245° (tin salt of reduction product, C20H22O6N2Cl6Sn, has [<x]|5 +60-0°), 4-nitro-l : 2-methylenedioxybenzene, and a little nitropiperonal (cf. Sal way, J.C.S., 1909, 95,
1163).
The action of magnesium ethyl iodide on sesamin gives a product with two ethyl groups, showing that sesamin lias two metliylenedioxy-groups. Alcoholic hydrogen chloride produces an isojneride, m. p. 95—
98° [a]if +86-6° (in chloroform), probably by a kind of Walden inversion. Acetic acid in presence of sulphuric acid at 60° gives a third isomeride of sesamin, m. p. 118—120°, [a]\8 +73-3°. The following constitution is suggested :
I— O 1
ch,Oo:c6h3-c h-c h2-c h-c h-c h„-c h-c gh3:o2c h2 I---o --- 1 " ( 1 : 2 : 4 )
J. H . B ik k in s iia w . Solanine. G. O d d o (Bcr., 1929, 62, [-£], 267—
271; cf. Oddo and others, A., 1905, i, 455; 1906, i, 527, 980; 1911, i, 671; Colombano, A., 1908, i, 99;
1912, i, 798).—In their criticisms of the work of Oddo and co-workers, Zempldn and Gerecs (this vol., 51) have overlooked the established difference between the glucosidcs oxtracted from Solanum sodomceum (with which Oddo has worked) and S. tuberosum (investigated by Colombano). Zempldn has used a technical variety of solanine of unknown origin, but usually derived from S. tuberosum. H. W r e n .
Methyl salicy la te g lu co sid e of Gaultheria, pvocinnbens, L., id en tical w ith m onotropin. M.
B r i d e l a n d ( M u le .) S. G r i l l o n (B ull. Soc. Chim.
bid., 1928,10, 1326—1335).—See A., 1928, 1224.
Formulae of D igitalis glu co sid es. II. A.
Wixdaus (Naclir. Ges. Wiss. Gottingen, 1927, 422— 420; Chem. Zentr., 1928, ii, 669—670).—The formula CyHjjOg previously ascribed to digitaligenin is replaced by the formula C^H^Oa, which is supported by the fact that oxidation of hexahydrodigitaligenin affords a dicarboxylic acid, C23H340 6, m. p. 286—287°
(dimethyl ester, m. p. 174°), but this conclusion is rendered uncertain by the observation that pure digitaligenin on oxidation yields no toxigenone, but a product, C23H280 3, m. p. 197°. A. A. El d r id g e.
Carbohydrates. VII. S tarch acetate. P.
B r ig l and R. S c h i n l e (Ber., 1929, 62, [B], 99—103).
—Rice starch, swollen with hot water, precipitated by alcohol, and dried with alcohol and ether, is heated with pyridine and acetic anhydride at 80° until a transparent jelly is produced which yields starch tri
acetate, [a],“ +162-40° in chloroform. The product is soluble in chloroform, s-tetrachloroethane, and glacial acetic acid, giving solutions which are very viscous even when dilute. Hydrolysis with alcoholic potassium hydroxide yields starch which appears more freely soluble in water than the original material, but gives the blue coloration with iodine and normal hydrolysis by diastase. The acetate has a high mol.
wt., since it does not appreciably increase the b. p. of chloroform. The constant cannot be determined by Bast’s method. In glacial acetic acid the acetate
does not suffer dialysis under conditions whereby the acetates of dextrose, sucrose, and maltose readily pass through the membrane.
Repetition of the work of Friese and Smith (A., 1928, 1225) on rice and potato starch affords a starch acetate which, contrary to these authors, is soluble in chloroform or glacial acetic acid, yielding colloidal solutions which slowly pass through a Jena glass filter, size < 7 . Intensive desiccation appears to render the acetate less soluble.
Many of the conclusions of Peiser (A., 1927, 753) with regard to the composition of starch acetate and the constitution of starch are invalid, since aeetylation by acetic anhydride in presence of sulphuric acid yields a partly changed product in which free reducing groups are present. H. W r e n .
D isru p tion of the corn [m aize] starch granule and it s relation to th e con stitu en t a m yloses.
T. C. T a y l o r and C. O. B e c k m a n n (J. Amer. Chem.
Soc., 1929, 51, 294—302).—The discrepancies in the values obtained by previous workers for the propor
tions of a- and p-amylose in starch (cf. Sherman and Baker, A., 1916, i, 767; Ling and Nanji, J.C.S., 1923, 123, 2666) are due to the fact that starch pastes prepared with boiling water at 1 or 2 atm. pressure contain, even after passage through a ball mill or homogeniser, a large proportion of swollen but unruptured granules. The high viscosity of the paste is mainly due to the presence of these gelatinised particles. When dry maize starch is ground in a quartz ball mill the viscosity and apparent a-amylose content of 1% pastes prepared from it gradually decrease until, when unbroken granules can no longer be detected microscopically, these values are identical with those previously obtained for a 1% paste in which the granules had been ruptured by chemical means (cf. B., 1926, 717). This proves that the latter treatment does not alter the relative proportions of st
and (j-amylose in the product. The viscosity of a paste from untreated starch is approximately equal to that of a [3-amylose solution of ten times the concentration. H. E. F. N o t t o n .
A lly lcellu lo se. I. S a k u r a d a (J. Soc. Chem.
Ind. Japan, 1928, 31, 638—642).—B y treating tissue paper with 40—50% sodium hydroxide solution and allyl bromide, the higher cellulose allyl ethers (tri- and di-ether of C6 unit) were directly obtained. The halogen-absorbing powrer of the resulting ether was concordant with the result of elementary analysis, and the double linking remained intact by etlieri- fication. The tetrabromide of cellulose diallyl ether was isolated almost pure. The higher allyl ether is partly soluble in alcohol, benzene, and carbon tetra
chloride, but its solubility is not so great as expected.
Y. T o m o d a . M anufacture of m ix e d acid este r s of cellu lose or e s te r s of cellu lo se ethers. I. G. 1a r b e n i n d . A.-G.—See B ., 1929, 126.
A ction of fatty acid s on cellu lose. C. J. M a lm and H. T. C l a r k e (J. Amer. Chem. Soc., 1929, 51, 274—278).—Prolonged refluxing of native cellulose with acetic acid effects esterification up to a limit (6—7% Ac) which is independent of the source and
300 B R IT IS H CH EM ICA L A B STRA C TS.— A.
molecular complexity (cuprammonium viscosity) of the fibre, and corresponds with the formula
C24H39O20Ac. The same product is obtained more rapidly at higher temperatures. The corresponding propionate and butyrate are obtained similarly.
Cellulose which has been mercerised or regenerated from its nitrate, from viscose, from cuprammonium solution, or from a solution of its acetate yields on similar treatment acetates of the limiting composition C6H,,O^Ac (21—22% Ac). These differ from cellulose in their capacity to retain basic dyes. Cellulose regenerated from cellulose acetate which has retained its original fibrous structure is esterified to a much smaller extent (about 10-8% Ac). These results are regarded as evidence that native cellulose has the unit molecule C^il^Oa,. H. E. F. N o t t o n
C ellulose xan th am id es. T . N a k a s h i m a (J. Soc.
Chem. Ind. Japan, 1928, 31, 629—633).—Cellulose xanthamides were obtained by the interaction of sodium cellulose xanthoacetic acid and ammonia or
amines. Y. T o m o d a .
Influence of p oles and p olar lin k in g s on tau to- m e r is m in the sim p le three-carbon sy stem . I.
P rototrop y and anionotropy in trialkylpropenyl- a m m o n iu m derivatives. C. K. In g o l d and E.
Rotiistees' (J.C.S., 1929, S—14).—Prototropic and anionotropic changes are recorded in the system C-C:C, the facilitating group being the ti’ialkyl- ammonium ion. Dicthyl-y-chloroallylamine, b. "p.
55°/9 mm. (hydrochloride, m. p. 221°; picrate, m. p.
78°), obtained in 57% yield from y-chloroallyl chloride and diethylamine, when treated with ozone yields hydrochloric acid, carbon monoxide, and probably diethylaminoacetaldehyde; with ethyl iodide it yields triethyl-y-chloroallylammonium iodide, m. p.
210° (picrate, m. p. 125°), also prepared directly from y-chloroallyl chloride and triethylamine through the quaternary hydroxide. These salts do not react with triethylamine at 100°. When tricthyl-y-chloroallyl- ammonium chloride or iodide is warmed with alcoholic sodium ethoxide and the product treated with picric acid triethyl-a-ethoxyallylammonium picrate, m. p.
122—123°, is obtained; the corresponding acetate when treated with ozone and then with picric acid yields formaldehyde and triethyleihoxyaMehydomethyl- ammonium picrate, m. p. 1 1 0—1 1 1°, hydrolysed by hydrochloric acid to tncthylhydroxyaldchydomethyl- ammohium picrate, m. p. 195—196°; triethyl-a- ethoxyallylarumoiiium chloride when warmed with concentrated hydrochloric acid yields trielhyl-ci- hydroxyallylammonium chloride, oily (picrate, m. p.
145°; chloroplatinate), and the corresponding acetate when treated with ozone and then with picric acid gives the preceding hydroxy’aldehydo-picrate, m. p.
195—196°. ‘
y-Chloroallyl chloride with alcoholic trimethylamine yields Inmethyl-y-chloroallylammonium chloride, m. p.
193° (picrate, m. p. 141°), which with ozone gives hydrochloric acid, carbon monoxide, and betaine;
neither the chloride nor the picrate reacts with diethyl- or triethyl-amine at 100°. The chloride is converted into trimethyl - k - ethoxyallylarnmonium picrate, m. p. I l l —1 1 2°, and the acetate of this base yields formaldehyde and
trimethyUthoxyaldehydo-methylammonium picrate, m. p. 168°, hydrolysed to tri- methylhydroxyaldehydomethylammoniuni picrate, m. p.
182— 184°. Trimethyl - a - ethoxyaliylammonium chloride when treated with warm hydrochloric acid yields non-crystalline trimethyl-a-hydroxyallylammon- ium chloride (picrate, m. p. 149°), and the acetate of the latter base gives the preceding hydroxyaldehydo- picrate, m. p. 182— 1S4°.
The ease of hydrolysis by acids of the ethoxy-com- pounds described above (which resemble esters rather than ethers) suggests that this effect, as also failure to replace the ethoxy-group by bromine, is due to the electron-affinity of the \NII3® group.
C. W. S h o p p e e . D iam in obu tan es. E . S t r a o k and H. E a n s e l o w (Z. physiol. Chem., 1929, 180, 153— 160).—Various diaminobutanes have been prepared and characterised by the preparation of their m-nitrobenzoyl derivatives.
Putrescine (aS-diaminobutane) yields a m-nitrobenzoyl derivative, m. p. 240°; Py-diaminobutane yields two m-nitrobenzoyl derivatives, m. p. 238° (soluble in methyl alcohol) and 320° (insoluble); ay-diamino- butane m-nitrobenzoyl derivative, m. p. 199°. ap-Di- amiaobutane (m-nitrobenzoyl derivative, m. p. 197°) could not be obtained by Demjanoff’s method (A., 1907, i, 174) and is best prepared by the action of saturated alcoholic ammonia on propaldehyde cyano- hydrin for 3 hrs. at 100° and reduction of the amino- nitrilc with sodium and alcohol, or, in small yield, by the action of saturated methyl-alcoholic ammonia for 24 hrs. at 100° on ap-dibromobutane. ay-Diamino- p-methylpropane (Johnson and Joyce, A., 1916, i, 755) (m-nitrobenzoyl derivative, m. p. 182°) is obtained by similar reduction of methylmalononitrile. afi-Di- amino-P-methylpropane (not obtained by Sidorenko’3 method, A., 1907, i, 270) is prepared by reduction of a-aminoi’sobutyronitrile and yields two m-nitro
benzoyl derivatives, m. p. 145° and 174°, the former being converted into the latter by heating with
alcohol. J. W. B a k e r .
R eaction b etw een carbon d isulphide and som e d ia m in es and gu anid ines. E. S t r a o k (Z. physiol.
Chem., 1929, 180, 198—211).—When an alcoholic solution of tetramethylenediamine is treated with carbon disulphide 8-amirtobuiyldilhiocarbamic acid, NH2,[CH2],,*NH,CSoH, m. p. 173° (all m. p. are uncorr.;
decomp.), is obtained (cf. von Braun and Lemke, A., 1923, i, 6). When an alcoholic suspension of this is heated at 100° hydrogen sulphide is eliminated and tetramcthylenethiocarbamide, NH*[CEL,],\NH, m. p.
I___CSJLJ
177°, results. Pentamethylenediamine and carbon disulphide afford s-aminoamyldithiocarbamic acid (cad
mium, barium, and silver salts).
Ethyl-i/i-thiocarbamide hydrobromide reacts with tri-, tetra-, and pcnta-methylenediamines in alcoholic solution, forming <x.-amino-y-guanidinopropane hydro
bromide, m. p. 116° (sulphate, m. p. 265°), and ay-di- guanidinopropane, 111. p. 135° (hydrobromide, in. p. 218°;
sulphate, m. p. 270° after sintering at 260°); aS-di- guanidinobutane hydrobromide, m. p. 212°, after sintering at 205° [sulphate, m. p. 297° (lit. 291°)]
(cf. Kiesel. A., 1922, i, 531); a-amino-z-guanidino- pentanehydrobromide, m. p. 105° (sidphale, m. p. 284p),
and oz-diguanidinopentane, m. p. 173° (decomp.;
hydrobromide, m. p. 217° after sintering at 212°;
sulphate, m. p. 317°), respectively. Guanidine reacts with carbon disulphide in alcoholic solution at 100°
yielding guanidine trithiocarbonate,
CS[SH,NH2-C(:NH)-NH2]?j m. p. 133— 135° after sintering at 125°, also obtainedfrom guanidine sulphate and sodium trithiocarbonate. The production of this salt demonstrates the following changes: CS«-f-2H20 = C 0 2+ 2 H 2S ; CS2+ H 2S=CS(SH )2. The above trithiocarbonate is decomposed by dilute acids, including carbonic acid, into hydrogen sulphide, and when it is treated with aqueous lead acetate lead trithiocarbonate is obtained. The irithiocarbonates obtained from methyl- and ethyl-guanidines, ay-di- guanidinopropane, aS-diguanidinobutane, and ae-di- guanidin open tane have m. p. 153°, 165°, 95° (decomp.), 193° (decomp.), and 190° (decomp.), respectively.
a-Amino-S-guanidinobutane (agmatine) and a-amino- c-guanidinopentane react with carbon disulphide forming the corresponding dithiocarbamatcs, m. p.
210° (deeomp.) after sintering at 200° and 201°, respectively. These compounds are postulated as internal salts CS-NH-[CH2]n-iSTH-C(:NH-)-NH2—HS.
I____:___________________________I The compound previously abstracted as C12H22N4S3 (Wrede, Strack, and Hettche, A., 1928, 5ll), and the compound CI4H30N 8S4 (loc. cit.) are postulated as [CH2< ^ l (J ^ > !s T-CH2-CH2-]2 and
JNUI ■ [CH2 ]3 •i'TH ■ CH2 • CH2
HN:C< I j, respectively.
\ n h - c s - s h J2
H . Bu r t o n. Glutaric series. C. R a v e n n a and 11. N u c c o r i n i (Gazzetta, 1928, 58, 853—804).—The formation of a dipeptide of aspartic acid from asparagine (A., 1920, i, 150) has no analogy in the glutaric series. Beetroot glutamine, m. p. 178— 1S6°, according to" conditions of preparation, when boiled with water for 10 days lost ammonia, but yielded glutamic acid, with pyrrolidonecarboxylic acid, w'hich substances also formed some labile compounds of undefined character.
Ammonium hydroxyglutamate was prepared by pre
cipitation from an ethereal solution of the acid. It
"as converted when heated into the diamide, m. p.
181—182° (decomp.), of glutamic acid, which on further heating at its m. p. lost a molecule of water, furnishing the unimolecular lactone amide,
I O 1
NH2-CO-CH-CH2-CH,-CO, m. p. 87—89°.
E. W. Wignall. A m m onium creatinine picrate. I. G r e e n w a l d (J. Biol. Chem., 1929,81,73—75).—Addition of excess of picric acid to a concentrated ammoniacal solution of creatinine yields ammonium creatinine picraie, m. p.
241°, which, on successive recrystallisations from
241°, which, on successive recrystallisations from