Purification of m ethyl fluoride. Quantitative g a s analysis by high-dispersion infra-red spectroscopy. W. H. B e n n e t t (J. Amer. Chem.
Soc., 1929, 51, 377—381).—Pure m ethyl fluoride may be prepared by heating 2 parts of anhydrous potass
ium fluoride with 5 parts of potassium methyl sulphate
a t 140—200°, passing the gas successively through concentrated sulphuric acid (to remove methyl ether), concentrated potassium hydroxide solution, soda-lime, and calcium chloride, and finally con
densing in liquid air. This gas is free from methyl ether and ethylene. The quantitative analysis of
ORGANIC CHEM ISTRY. 421 m ethyl fluoride fo r th ese tw o im p u ritie s b y high-
dispersion m easu rem e n ts of th e in fra -re d sp e c tra of th e gas is described. S. K . Tw e e d y.
Catalytic activity of alum inium chloride. G.
D o u g h e r t y (J. Amer. Chem. Soc., 1929, 51, 576—
580).—The author’s view th a t the catalytic activity of aluminium chloride is due to the formation of ionogenic additive products is confirmed by the observation th a t the halogens in mixtures of halogeno- paraffins are readily interchangeable in presence of a little aluminium chloride (cf. Walker, J.C.S., 1904,105, 1082). Thus, in equimolecular proportions, methyl iodide and ethyl bromide give methyl bromide and ethyl iodide, ethylene bromide and ethyl iodide give ethyl bromide (70% of theory), ethyl bromide and chloroform a t the ordinary tem perature give 35% of dichlorobromomethane, and ethylene chloride and bromide give an equilibrium m ixture containing 50% of ethylene chlorobromide. The same m ixture is obtained from ethylene chlorobromide
H. E. F. No t io n. Reactivity of carbinols. W alden inversion.
P. A. L e v e n e and A. R o t h e n (J. Biol. Chem., 1929, 81, 359—368).—The velocity of substitution of Br for OH on heating a number of carbinols under standard conditions with hydrogen bromide was observed. The greatest difference was found between the rapidly reacting mixed aliphatic-arom atic car
binols and the slowly reacting aliphatic compounds.
In the aliphatic series, the normal prim ary alcohols reacted more rapidly th an those with branched chains, and the prim ary alcohols as a whole more rapidly than the secondary; methylcycZohexylcarbinol re
acted much more slowly th an any other compound studied. The unexpected fact th a t Walden inversion takes place principally in the mixed aliphatic- aromatic series in spite of the high speed of sub
stitution m ay be accounted for by the great mobility of the groups in these compounds.
C. R . Ha r in g to n. Synthesis of m ethyl alcohol. E. A x j d i b e r t .— See B., 1929, 162.
D erivatives of aliphatic glycols. G. M. B e n n e t t and F. H e a t h c o a t (J.C.S., 1929, 268—274).—
Treatment of glycol monomethyl ether, in dimethyl- aniline solution, with thionyl chloride conveniently gave methyl p-chloroethyl ether, b. p. 90-5°/747 mm., d'f 1-031. An attem pt to repeat Foran’s preparation of bromodiethyl ether gave vinyl bromide as the only isolable product.
The reaction of sulphur monochloride on tri-, tetra-, and penta-methylene glycols has been exam
ined. y-Chloropropyl 3 : 5-dinitrobenzoate h a s ' m. p.
77°. Trimethylene glycol, by the successive inter
action of acetic anhydride and sulphur chloride, gives y-chloropropyl acetate, b. p. 66°/14 mm., in good yield. Treatm ent of the last substance with propyl mercaptan and aqueous-alcoholic sodium hydroxide leads to y-hydroxydipropyl sulphide, b. p. 112°/16 ram., d f (vac.) 0-9794, n f 1-47789 (phenylurethane, p. 36°). p-Hydroxyethyl butyl sulphide yields the isomeric phenylur ethane, m. p. 44-5°.
Tetrametliylene glycol (corresponding di-a-naphthyl- urethane has m. p. 198°) gave, by treatm ent with
sulphur chloride, crude 8-chlorobutyl alcohol, b. p. 86°/
15 mm. (decomp.), from which the a-naphthylurethane, m. p. 66°, was isolated. S-Chlorobutyl acetate, b. p.
87°/17 mm., d f (vac.) 1-0803, n f 1-43811, was obtained either by heating tetramethylene glycol with sulphur chloride and acetylating the product or by the inter
action of the glycol and acetyl chloride under pressure;
8-Chlorobutyl acetate reactcd with ethyl mercaptan in methyl-alcoholic-aqueous solution, giving ethyl h-hydroxybutyl sulphide, b. p. 120°/19 mm., d f (vac.) 0-9794, n f 1-48118 {phenylurethane, m. p. 37°);
similar use of thiophenol led to phenyl S-hydroxybutyl sulphide, m. p. 24° {phenylurethane, m. p. 68-5°).
Pentamethylene glycol (corresponding diplienyl- urethane and di-o.-naphthylurethane, in. p. 174° and 147°, respectively) interacted with sulphur chloride to give crude e-chloroamyl alcohol, b. p. 114°/16 mm.
(^.-naphthylurethane, m. p. 92°). z-Chloroamyl acetate, b. p. 103718 mm., d f (vac.) 1-0648, ri* 1-43791, was converted by methyl m ercaptan and methyl-alcoholic- aqueous potassium hydroxide into methyl t-hydroxy- amyl sulphide, b. p. 121°/16 mm., d f (vac.) 0-9846, n f 1-488185 {phenylurethane, m. p. 43-5°). Phenyl z-hydroxyamyl sulphide has m. p. 31-5° (phenyl- urethane, m. p. 59°).
A ttention is directed to the general fact th a t an alternation of m. p. occurs in the diurethanes when the lengthening chain is term inated by large polar groups, whilst the in. p. fall with but slight alternation if the highly polar group is a t one end only.
R. J . W. Le Fe v r e. Action betw een copper sa lts and glycerol.
B. K. Y a id y a (Nature, 1929,123, 414).—When copper salts, except cupric chloride, are heated with glycerol a t 150—200°, metallic copper and free acid (which m ay undergo further decomposition) are produced, together with ethyl alcohol, acraldehyde, carbon di
oxide, methane, and small quantities of carbon mon
oxide and hydrogen. Cupric chloride 3delds cuprous chloride quantitatively. Glycol, erythritol, and man- nitol give analogous results. Probably the decom
position is catalysed by the copper, which is pure and finely divided. A. A. E l d r i d g e .
Diacetylenic heterocyclic compound. L e s- pieaxj (Compt. rend., 1929, 188, 502—503).—By condensation of dichloromethyl ether with mag
nesium acetylide the compound O^QH^Qic-CH2-^®
is formed, m. p. (with deflagration) 180°. When heated slowly, it turns yellow, shrinks, and does not melt or deflagrate below 200°. I t forms a precipitate with mercuric chloride, and absorbs 4 atoms of bromine from an ethereal solution.
B. W. An d e r s o n. Cyclic acetals. I. R. D w o r z a k and T. M.
L a s c h (Monatsh., 1929, 51, 59—72).—The formation of cyclic acetals by the interaction of a series of glycols with various aliphatic aldehydes is investig
ated. Contrary to experience in the case of cyclic benzylidene derivatives, the yields obtained are approximately the same whether the m ixture is heated with concentrated hydrochloric acid in a sealed tube or condensed a t 0° by the action of anhydrous hydrogen chloride. Contrary to H ibbert
422 B R IT ISH CH E MICAL ABSTRACTS.— A.
and Timm’s experience (A., 1924, i, 710), the yield of cyclic acetal increases with increasing mol. wt. of the aldehyde used. Acetals could be obtained only with a ¡3- and ay-glycols (yieldmg live- and six-membered rings) (cf. Pranke and Gigerl, A., 1928, 759) and no definitely characterised, halogen-free compound could be isolated from the product of the action of I'sobut- aldehyde with pentane-aS-, octane-aO-, nonane-ou-, and dccane-a«-diols. By the above methods from the appropriate glycol and aldehyde arc obtained the cyclic methylene derivatives of p-methyl-|3-ethylprop- ane-ay-diol, b. p. 150—152° (yield 30%) ; (3(3-di-mcthylpropane-ay-diol (30%) (cf. Apel and Tollens, A., 1S96, i, 115) : th e cyclic ethylidene derivatives of pS-methyl-[3-ethylpropane-ay-diol, b. p. 156—160°
(30%) : the cyclic isobutylidene derivatives of pp-di- methylpropane-ay-diol, b. p. 159—161° (67%) ; p- methylpentane-ay-diol, b. p. 69—70°/12 mm. (69%) ; butane-ay-diol, b. p. 42-5—43°/10 nun. (63%) ; (iS-di- methylpentane-pS-diol, b. p. 67—73°/21 mm. (25%) ; (îy-dimctliylbutane-Py-diol (pinacol), b. p. 59°/13 mm.
(6S%) ; and yS-dimethylhexane-yS-diol, b. p. 81—
83°/10 mm. (66%) : and the cyclic heptylidene deriv
ative of S3-dimethylpropane-ay-diol, b. p. 234—239°
(78%). ‘ J . W. Ba k e r.
E sters of phosphoric acid. I. Phosphates of cetyl alcohol, cholesterol, chloroethyl alcohol, and ethylene glycol. II. A ction of ethyl m eta
phosphate on alcohols, am m onia, and som e am ino-com pounds. R. H. A. P lim m e r and W. J. N. B u r c h (J.C.S., 1929, 279—291, 292—300).
—I. The interaction of phosphoryl chloride and cetyl alcohol in chloroform gave barium monocetyl -phos
phate monohydrate (from which monocetyl dihydrogen phosphate was isolated), calcium monocetyl phosplmte, and dicetylphosphoryl chloride (hydrolysis of which yielded barmm dicetyl phosphate and dicetyl hydrogen phosphate, softening a t 46°). The action of 1 mol.
of phosphoryl chloride on 1 mol. of cetyl alcohol a t 100° gave cetene as the only isolable product. Tri- cetyl phosphate was obtained by the interaction of cetyl alcohol and phosphorus pentacldoride and by boiling excess of cetyl alcohol with phosphoric oxide in presence of ether. I t gave sodium dicetyl phos
phate when boiled with aqueous sodium hydroxide.
The interaction of phosphoryl cldoride and chol
esterol in chloroform solution gave barmm mono- cholesteryl phosphate tetrahydrate (from which mono- cholesteryl dihydrogen phosphate and its lead, silver, copper, and sodium salts were obtained) and barium dicholesteryl phosphate (whence dicholesteryl hydrogen phosphate was prepared). Tricholesteryl phosphate was obtained by treatm ent of cholesterol with phos
phorus pentachloride.
Analogous reactions with phosphoryl chloride and ethylene chlorohydrin led to tri-fi-chloroetkyl phos
phate, b. p. 140°/40 mm., d 1-39, barium p-hydroxy- ethyl phosphate, and barium di-fi-hydroxyethyl phos
phate dihydrate. The interaction of ethylene chloro
hydrin and phosphoryl chloride in cold pyridine resulted in good yields of barium chloroethyl phos
phate monohydrate\ the corresponding brucine salt
|C23H.,(;0.1No,(C2H4C1)H2P 0 4,4H„0] was converted into barium (3-hydroxyethyl phosphate. Barium
chloroethyl phosphate was also obtained by the action of ethyl metaphosphate on ethylene chloro
hydrin. Treatm ent of a saturated aqueous solution of trisodium phosphate with ethylene chlorohydrin resulted in the isolation of disodium $-liydroxyethyl phosphate hexahydrate, m. p. 61°. A very soluble salt, probably sodium ethylene phosphate,
C2H 40 2IP 0 ,0N a, was formed by th e action of phos
phoryl chloride on the disodium derivative of ethylene glycol.
The various esters of phosphoric acid were com
pletely hydrolysed by dilute acids. The mono- and di-esters of the aliphatic alcohols with phosphoric acid were not hydrolysed, and the triester was hydrolysed to the diester, by dilute alkali. The mono-, di-, and tri-phenyl phosphates were com
pletely hydrolysed by dilute alkali. Sodium dicetyl phosphate is also described.
II. E thyl metaphosphate and absolute ethyl alcohol interacted in chloroform solution to give barium ethyl phosphate monohydrate and barium di
ethyl phosphate. n-Propyl alcohol and ethyl m eta
phosphate similarly gave barium ethyl phosphate, barium di-n-propyl phosphate, and barium dipropyl pyrophosphate (whence barium propyl phosphate was obtained). Cetyl alcohol and ethyl tnetaphosphate yielded barium mono- and di-cetyl phosphates with barium mono- and di-cthyl phosphates. Phenol and ethyl metaphosphate formed barium ethyl phosphate, barium phenyl phosphate, barium diethyl phosphate, and barium diphenyl phosphate tetrahydrate. Similar treatm ent of cholesterol with ethyl metaphosphate gave barium ethyl phosphate and barium cholesteryl phosplmte tetrahydrate, cholesteryl ethyl ether, b. p.
237°/20 mm., being also formed. Passage of an
hydrous ammonia through a chloroform solution of ethyl metaphosphate gave ammonium ethyl hydrogen phosphate identical with the product obtained directly from ethyl alcohol and phosphoric oxide. Diammon
ium ethyl phosphate and ammonium diethyl phosphate were prepared by the action of ammonium sulphate on barium ethyl phosphate and barium cliethyl phos
phate, respectively.
The product of the interaction of ethyl metaphos
phate and hydrazine (Strecker and Heuser, Ber., 1924, 57, 1364) is hydrazine ethyl dihydrogen phos
phate, which reacted with copper sulphate to give hydrazine copper sulphate and copper ethyl phosphate.
Similarly, ethyl metaphosphate formed with phenyl- hydrazine, alanine, and guanidine, respectively, phenyl hydrazine ethyl dihydrogen phosphate, alanine ethyl pyrophosphate (which formed alanine ethyl dihydrogen phosphate on treatm ent with water), and guanidine diethyl pyrophosphate; in no case were- any compounds isolated in which nitrogen is directly linked to phosphorus.
The use of ethyl metaphosphate for the preparation of phosphoric esters has no advantage over the alcohol-phosphoric oxide reaction.
R. J. W. Le PiVRE.
S ilv er sa lts of esters of hexosem onophos- phoric acids. F. W e i n m a n x (Biochem. Z., 1929, 204, 493—494).—The silver salt of Neuberg’s hexose- monopliosphoric ester, obtained in 81% yield from the barium salt, is a faintly yellow powder easily
OTtOANIO CHEMISTRY. 423 soluble in cold water" and, when prepared from satis
factory material, stable towards light. Its solution soon gives a silver mirror when heated. The silver salt of Robison’s ester is, in solution, more sensitive than, but otherwise very similar to, the salt of the isomeric ester. W. McCa r t n e y.
H exosem onophosphate (Robison). P. A.
L e v e n e and A. L. R a y m o n d (<T. Biol. Chem., 1929, 81, 279—283).—The rate of hydrolysis by 0-liV- hydroehlorie acid of the methyl glucoside of the hexosemonophosphate of Robison (A., 1923, i, 86) indicates th a t the latter has the structure of a y- lactone; the phosphoric acid residue m ust therefore be attached to the e-carbon atom. C. R. H a r i n g t o n .
3-Hydroxyetliyl allyl sulphide and its deriv
atives. S. M. Sc h e r e i n and V. V. V a s i l e v s k i (J. pr.
Chem., 1929, [ii], 121, 173—176).—See this vol., 293.
Refractom etric determ ination of form ic acid in the presence of acetic acid. J. Brain, (Chem.
Listy, 1929, 23, 25—26; cf. ibid., 1920, 14, 6, 45).—
Objections raised against this method by St’astny are shown to be unfounded, fairly accurate results (0-2 g.
of formic acid per 100 c.c.) being attained provided th a t no substances other than the above acids and water are present in the solution. R. T rtjs z k o w s k i.
T horium form ates. H. R e i h l e n and M.
D e b u s (Z. anorg. Chem., 1929, 178, 157—176).—
The compound [Th3(HC02)G(0H )5]SCN,7H20 ob
tained by Weinland and Stark (A., 1926, 498) by the action of potassium thiocyanate on thorium formate is now shown to be potassium hexaformiato-oo:ytelra- hydroxythiocyanalotrithoriate,
K[SCN(0H)40(H C 02)6Th3],7H20 . In a vacuum it loses 7H20 rapidly and a further 2 H ,0 after being heated for 24 hrs. a t 61°, being converted into the
¿nory-compound, [Th3(HC02)G0 3SCN]K. When thor
ium formate is added to a half-saturated solution of potassium thiocyanate until it ceases to dissolve, the compound
3K[SCN(0H)40 (H C 0 2)GTh3],2K„[(SCN)2(0H),0.>
‘ (HC02)GTh3],30H„0 crystallises on cooling to 0°. The following com
pounds have been obtained in a similar manner from thorium formate and solutions of alkali nitrate, chlorate, or perchlorate:
Na[Th3(HC02)G0(OH)4N 0 3],10-5H20 ; Na[ClO3(OH),O(HCO2)0Th3],13H2O ; Na[Th3(HC02)G0 (0 H )4C104],9H20 ; N atN 03(0H )40 (H C 02)6TK^,[N03(0 ffi5(HC02),)Th3],
21H20 ; 2K[N03(0H )40(H C 02)GTh3],[N 03(0H )5(HC02)GTh3],
30H20 ; K[C103(0H )40(H C 02)GTh3],2[(0H)20(H C 02)6Th3],
29-5H20 . Dissolution of thorium hydroxide in formic acid yields crystals of thorium form ate; as this compound is not an electrolyte it should be formulated as [Th3(HC02)12],9H20 ; when treated with pure formic acid on the water-bath the hydrate with 3-5H20 is obtained, but with water under the same conditions hydrolysis ensues with separation of the complex [Th3(HCO2)G(OH)0],4H2O. Interaction of aqueous solutions of thorium nitrate and sodium formate affords two basic formates which are most satisfac
torily formulated as [Th3(HCO2)10(OH)2],7H2O and [Th3(HCC)2)9(OH)3],10H20 . Electrical conductivity measurements of solutions of the neutral formate [Th3(HC02)12],9H20 show th a t the conductivity increases very rapidly with rise of tem perature; this is ascribed to decomposition of the complex with the formation of the complex formate
[(H20 )3Th(HC02)3Th(HC02)3Th(H20 )3](HC02)G.
A. R. POWELL.
Products of partial hydrogenation of higher m onoethylenic esters. T. P. H i l d i t c h and N. L.
V i d y a r t h t (Proc. Roy. Soc., 1929, A, 122, 552—
563).—Methyl oleate, palmitoleate, and erucate were treated with hydrogen a t 114—220° in the presence of nickel mounted on kieselguhr (15% Ni), the con
centration of metallic nickel present with respect to the ester being about 0-5%, until their iodine values were reduced by about 30%. The products of hydro
genation were examined by oxidation with potassium permanganate in hot acetone solution, with form
ation of free monocarboxylic acids and monomethyl ethers of dicarboxylic acids, together with neutral (non-oxidised) m aterial of negligible iodine value.
The evidence afforded by the identification of the dicarboxylic acids (and to a smaller extent of the monocarboxylic acids) indicates th a t the isomeric acids produced during hydrogenation consist in each case of a m ixture of acids in which the ethylenic linking is adjacent to the position occupied in the original compound, and th a t these acids, together with the original position isomeride, are almost certainly present in both cis- and tram-loxms in the hydrogenated products. The proportion of iso-acids formed appears to vary -with the length of the carbon chain. The present results are in full accord with the view previously expressed by Armstrong and Hilditch (A., 1925, i, 355). L. L. B irc u m s h a w .
Products of partial hydrogenation of som e higher polyethylenic esters. T. P. H i l d i t c h and N. L. V i d y a r t h i (Proc. Roy. Soc., 1929, A, 122, 563—570; cf. preceding abstract).—In the case of higher polyethylenic esters the conclusions to be reached from the acids isolated as scission products from the oxidised esters are complicated by the facts th a t (a) the hydrogenation process is selective, not only as regards the degree of unsaturation present, but also to a considerable extent in th a t each ethylenic linking is not equally attacked, and (b) isomerisation occurs, as previously described (he. cit.), although to a smaller degree. The utility and limitations of the procedure are illustrated by a description of experi
m ents with m ethyl linoleate (from soya-bean and cotton-seed oil) and ethyl linolenate (from linseed oil). I t can be deduced with certainty th a t the un
saturation in linoleic acid is in the A1- and A^-positions, whilst in linolenic acid the positions of the A1 and At* linkings can be fixed, but it can only be indicated th a t the third double linking lies beyond the fourteenth carbon atom of the chain. L. L. B irc u m s h a w .
co-H ydroxyaliphatic acid s ; s y n th e sis of sa b in ic acid. W. H. L y c a n and R. A d a m s (J.
Amer. Chem. Soc., 1929, 51, 625—629).—u-Hydroxy- aliphatic acids are conveniently prepared through their methyl esters, which are formed quantitatively
424 B R ITISH CHEMICAL ABSTRACTS.— A.
by hydrogenating o-aldehydo-esters (cf. A., 1926, 712) in presence of platinum and ferrous sulphate.
The following are described : 0-hydroxy tionoic acid, m. p. 53—54° (methyl ester, b. p. 137—139°/3 mm..
d20 0-9588, nD 1-4438, and its phenylurethane, m. p.
53—54°), which gives a t 220—230° a (?) dimeric intermolecular ester, m. p. 64—66°; t-hydroxydecoic acid, m. p. 75—76° (methyl ester, b. p. 145—147°/3 mm., d20 0-9618, nD 1-4471, and its phenylur ethane, m. p. 54—55°); K-hydroxyundecoic acid, m. p. 65-5—
66° (methyl ester, b. p. 156—159°/3 mm., d20 0-9542,
■«„ 1-4493, and its phenylurethane, m. p. 64-5—65-5°) ; X-hydroxydodecoic acid, m. p. 83—84° (methyl ester, b. p. 164— 166°/3 mm., m. p. 34—35°, and its phenyl
urethane, m. p. 64—65°), which is identical with naturally occurring sabinic acid (Bougault, A., 1909, i, 82; cf. Simonsen and others, A., 1928, 1355), and
¡¿-hydroxytridecoic acid, m. p. 77—78° (methyl ester, b. p. 170—173°, m. p. 40-5—41-5°, and its phenyl
urethane, m. p. 73-5—74°) (ef. Ruzicka and Stoll, this vol., 68). Methyl hydrogen decane-aK-dicarboxylate, m. p. 51-5—52°, is a by-product in the preparation of methyl K-aklehydoundecoate (semicarbazone, m. p.
90—92°). H. E. F. Notto n.
H ydrogen peroxide as an oxidising agent in acid solution. IX. O xidation of keto-acids.
W. H . Ha t c h e r and A. C. Hil l (Trans. Roy. Soc.
Canada, 1928, [iii], 22, III, 211—220).—The methods of analysis of pyruvic acid are studied and compared.
Oxidation by means of alkaline hydrogen peroxide or acid permanganate is preferred. The oxidation of pyruvic and mesoxalic acids by acid permanganate was investigated with special reference to the effect of concentration of mineral acid. The oxidation of these acids with aqueous hydrogen peroxide was also investigated, the effects of tem perature, concentration, alkali, and added mineral acid being given. In the case of pyruvic acid, the formation of a complex CH3,C 0,C02H ,H 20 2 is assumed. This breaks down rapidly to give acetic and carbonic acids. W ith mesoxalic acid there is formed a complex,
C0(C02H )2.2H20 2, which decomposes into carbonic acid, Mesoxalic acid is about one fifth as reactive towards hydrogen peroxide as pyruvic acid.
A. J . Mé e. Configurative relationship of [3-hydroxy- and p-chlorobutyric acids, and of p-hydroxybutyric acid w ith m ethylpropylcarbinol. P . A. L e v e n e and H . L. H a l l e r (J. Biol. Chem., 1929, 425—433).
—1-Aa-Pentcn-8-ol, [<x]i? —6-1° in ether (hydrogen phthalate, [a]^ —4° in ether; a-naphthylcarbamate, m. p.
47—49°, [a]'U +1-37° in alcohol), gave with phosphorus pentachloride d-S-chIoro-Aa-pentene, b. p. 95—97°, [a]'g +11-1° in ether; with ozone the latter yielded d-$-chlorobuiyric acid, b. p. 67—70°/0-35 mm., [x]‘g + 11-5° in ether, [a]f,’ -f 21-5° in water (sodium salt, [“Id +15-7° in water). When reduced with hydrogen and palladium, Z-A°-penten-[3-ol gave Z-pcntan-8-ol, and when oxidised with ozone it yielded Z-¡3-hydroxy- butyric acid; the configurative relationship of the two last-mentioned compounds is thus confirmed (cf.
A ., 1927, 591) and hydroxy butyric acid is con- figuratively related to rf-S-chlorobutyric acid.
C. R. Ha r in g to n.
H ydrates of calcium oxalate. W . F. J a k ó b and E. Ł u c z a k (Rocz. Chem., 1929,9 ,41—48).-—y-Calcium oxalate, CaC20 4,3H20 , is precipitated in rhombic plates or prisms on the gradual addition a t 0° of 1%
ammonium oxalate to 0-007M-calcium nitrate or chloride solutions containing 0-061il/-normal sodium citrate. This modification is unstable a t the ordinary temperature, and is rapidly converted into the mono- hydrate a t 40°. The p-oxalate, erroneously supposed by Souchay and Lenfsen (Annalen, 1856, 100, 30S) to possess 3 mols. of water of crystallisation, has in reality only 2-25H20 . I t is prepared by the addition a t 40—50° of 1% ammonium oxalate to a 0-0241i- solution of calcium salt containing normal sodium citrate (0-061i¥). The crystals thus obtained are flattened octahedra, which lose 0-25H20 a t 80°, but regain this when kept a t the ordinary temperature.
Above 100° a further molecule of water is irreversibly lost, the stable monohydrate being obtained.
R. Tr u s z k o w s k i.
Ferric oxalate and ferric oxalate perchlorate.
R . W e i n l a n d and K. R e in (Z. anorg. Chem., 1929, 178, 219—224).—On keeping a solution of fem e nitrate enneahydrate and oxalic acid in concentrated nitric acid in a desiccator over concentrated sulphuric acid a canary-yellow powder, Fe2(C20 4)3,5H20 , is obtained. The compound dissolves slowly in water, b ut the solution gives no reaction for oxalic acid ; it therefore appears to be a ferric salt of a ferrioxalic acid. When a solution of ferric chloride and oxalic acid in perchloric acid is evaporated on the water - bath a light green, microcrystalline, hygroscopic compound, Fe3C20 4(C20 4H 2)2(C104)5,14H20 , separates.
A solution of tlie compound in water gives reactions for perchloric but not for oxalic acid.
A. R . Po w e l l. M ixed oxalato-fluoro- etc. -anions of tervalent chrom ium , iron, antim ony, and bism uth. R . W e i n l a n d and W . H ü b n e r (Z. anorg. Chem., 1929, 178, 275—288).—Evaporation of a solution of chromic nitrate, oxalic acid, and pyridine over sulphuric acid yields dark reddish-violet leaflets of pyridine tri- oxalatotrinitratodichromiate,
[Cr2(C20 4)3(N 03)3(H20 )3]H3, ( a H 5N)4. Under the same conditions quinoline yields quinoline trioxalato- nitratodichromiate, [Cr2(C20,1)3N 0 3(H20 )4]H,(CpH7N),1.
From a solution of chromic acid, oxalic acid, and
From a solution of chromic acid, oxalic acid, and