Lysim eter investigations. II. Com position of rain w ater at Geneva, N .Y ., for a 10-year period. R. C. C o l l i s o n and J. E. M e n s c h i n g (New York S tate Agric. Exp. Sta. Tech. Bull., 1932, No.
193,19pp.).—The annual average pptn. contained 9 lb.
of N (> 8 6 % of this as N H 3 and rem ainder as N 0 :i'), 41 lb. of S, and 16 lb. of Cl per acre. Variations in the proportion of S per annum were less th an those of N. H C 0 3' occurred a t th e rate of 12—92 lb. per acre. The m ineral contents of rainfall are sufficient to necessitate th eir consideration in lysim eter trials.
A. G. P.
Conductivity of B elgrade drinking water.
P. S. T g t u n d £ i 6 (Bull. Soc. Chim. Yougoslav., 1931, 2, 77—95).—The content of dissolved substances may be deduced from th e conductivity of drinking water.
R. T.
Mineral w ater of R ogaske Slatine. A. R e z e k
(Bull. Soc. Chim. Yougoslav., 1931, 2, 213—223).—
The tem p, and composition of th e w aters of two springs have not changed since 1907. R. T.
Conductivity of M akisch and Sava River water.
P. S. T u t u n d £ i 6 (Bull. Soc. Chim. Yougoslav., 1932, 3, 33— 42).—The conductivity m ethod for determ in
ation of salt content gives good results for river and
other natural waters. R. T.
Salts in subterranean w aters around Palm yra.
V. F r o l o w (Compt. rend., 1932, 194, 2153—2155).—
The total salts in the w aters of a spring a t Palmyra, and of two wells, determ ined throughout a year, vary between 1-27 and 2-29; 1-27 and 3-07; and 1-61 and 6-97 g. per litre, respectively. C. A. S.
M icrobiological lim e precipitation in tropical seas. W . B a v e n d a m m (Arch. Mikrobiol., 1932, 3, 205—276).—The calcareous sludge from waters sur
rounding th e Baham as contains S bacteria, cellulose- and carbamide-decomposing organisms, S 0 4-reducing and N-fixing bacteria. Chalk pptn. is essentially a biological process, th e mechanism of which is dis
cussed. A. G. P.
Liquid carbon dioxide in the depths of the ocean. H. W a t t e n b e r g (Nature, 1932, 130, 26).— A crit. discussion relating to the occurrence of plank
ton.' L. S. T.
“ Rain of ashes ” at B ucharest in February, 1929. A. S t e o p o e (Bui. Chim. Soc. Rom anc Stiinte, 32, 1932, 51—54).—A yellow dust which fell together with snow in a gale.o f wind in various parts of Roumania consisted m ainly of S i0 2, and was in many respects sim ilar to a volcanic tuff. The presence of humic acid, however, indicated th a t the dust originated from wind-swept fields bare of snow.
C .I.
Volatile constituents in m agm a and formation of m agm atic residual solutions. P. N i g g l i (Rec.
trav. chim., 1932, 51, 633—635).—A general theoret
ical discussion. F. L. U.
Minerals containing calcium and antim ony.
G- N a t t a and M. B a c c a b e d d a (Atti R. Accad.
Lincei, 1932, [vi], 15, 389—395).—Various Sb ochres
containing Ca have been examined. Those contain
ing less th an about 4% of CaO consist essentially of p artly hydrated Sb20 4, b u t in those containing
> 12% of CaO the Sb is present as Sb20 5 ; the composition of ochres of this second group ranges from Ca0,Sb20 5,3H20 to 3Ca0,2Sb20 5,8H20 . The X -ray spectra of several such ochres have been determ ined ; the crystals are cubic, with a 10-25—
10-26 A. Vais, of dCaic., ^obs. after heating a t 750°, and no. of mols. in the un it cell are : romeite, 4-98, 4-71—5-07, 4 ; atopite, 5-32, 5-03, 8; Galicia ochre, 5-00, 4-30, 4; Cordova ochre, 4-66, 4-21, 8 ; and China ochre, 4-28, 4-44, 2. H. F. G.
Ferro-titaniferous m ineral from Alto E gitto, in the Arabian D esert. A. S t e l l a (Atti R.
Accad. Liticci, 1932, [vi], 15, 336—339).—A detailed description of a m ineral containing about 40% of
T i0 2 is given. H . F. G.
O riginal m aterials of oolites of Lorraine and Luxem burg. J . P. A r e n d (Compt. rend., 1932, 195, 54—56; cf. this vol., 595).—The suggested origin of these deposits is substantiated by analyses of the dried mud deposited from the ferruginous spring a t Mondorf, the accompanying m arls, the dried p arts of molluscs and fish, and of the “ green
layer.” C. A. S.
Form ation of kaolin and alunite in the eastern part of the P olish M ittelgebirge. J . K u h l (Bull.
Acad. Polonaise, 1931, A, 665—675).—The kaolin in the clefts in the shale and quartzite in th e M ittelge
birge was probably formed by the action on the aluminosilicates of traces of H 2SO.„ a decomp, product of the co-existing pyrites. The kaolin contains particles of N a2S 0 4 and A12(S04)3, probably formed by th e fu rther action of H 2S 0 4. J . W. S.
Origin of auriferous deposits of jacutinga.
E. d e O l i v e i r a (Ann. Acad. Brasil. Sci., 1931, 3, 151— 157).—The Au contained in Brazilian jacu tinga deposits is of secondary origin. H 2S 0 4 formed by oxidation of pyrites reacts with the NaCl and M n02 which are also present, and the resulting solution containing free Cl dissolves the Au from the surface deposits and carries it, as AuC13, to the lower strata, where it is reduced to Au by F eS 04. Au is found in jacutinga only when the latter occurs below deposits of auriferous quartz pyrites. H. F. G.
Two nepheline-sodalite-syenites from new localities in Northern Rhodesia. F. D. A D A M S a n d
F. F. O s b o r n e (Canad. .J. Res., 1932, 6, 571—576).—
These rocks, which are similar in chemical composition to lavas found a t the north end of Lake Nyassa, are characterised by a low content of binary oxides and the presence of an aluminous segirine. E. S. H.
T w in structure and surface indications of rock quartz w ith reference to the tem perature of its form ation. 0 . M u g g e (Z. K rist., 1932, 82, 451— 467).—The effect of heating a t 600° on quartz of various origins is examined, and from th e changes effected in the crystal form etc. a m ethod of determ
in-8 3 0 B R I T I S H C H E M IC A L A B S T R A C T S .— A .
ing th e probable conditions as to tem p. etc. of the rocks in which i t occurs is deduced. C. A. S.
Spinel structures, w ith and w ithout varíate atom equipoints. T. F. W. B a r t h and E. P o s n j a k
(Z. K rist., 1932, 82, 325—341 ; cf. A., 1931, 1001).—
The v aríate atom equipoint structure is possessed by MgFe„Oj (a 8-36 Á.), MgGa20 4 (a 8-26), M gln20 4 (a 8-81), TiMg20 4 (a 8-41), T iF e20 4 (a 8-50), and SnZn20 4 (a S-61): the norm al spinel stru ctu re by XA120 4 (X = C o , Fe, Mn, N i, an d Zn). M gln20 4, TiMg20 4, an d SnZn20 4 are prepared b y prolonged heating of th e constituent oxides in the required proportions a t tem p. >1300° for M gln20 4; TiFe20 4 by heating in vac. TiO„, Fc,0.,, and Fe a t 1150°.
2 3 C .A .S .
M agnesium -galliu m spinel. F. M a c h a t s k i (Z.
K rist., 1932, 82, 348—354; cf. th is vol., 12, and preceding abstract).—The distribution of cations in MgGa20 4 is different from th a t required by strict stru ctu re theory, Ga and Mg being largely in te r
changeable. This m ay be due to rapid cooling of th e artificial crystals, or to th e two cations having
O rganic
Co-ordinative theory of the constitution of organic com pounds. G. U r b a i n (Compt. rend., 1932, 194, 1993— 1997).—The electrovalency of C in org. compounds varies from + 4 (as in CC14, where C has lost all its peripheral electrons) to —4 (as in CH4, where C has 8 electrons in its second group). Various
examples are discussed. H . B.
Sim ple organic com pounds of radial structure.
H . J . B a o k e r (Natuurwetensch. Tijds., 1932, 14, 175— 177).—R adial compounds CX4 are characterised by. sm all mol. cohesion, stab ility of the cryst. phase, sm all tem p, range of the liquid phase, simple cryst.
form, inertness, and tendency to ring formation.
H . F . G.
Active product of the reaction of sodium vapour w ith alkyl halides. M. P o l a n y i and D. W. G.
S t y l e (Naturwiss., 1932, 20, 401—402).—-When th e reaction products of N a vapour on MeBr or E tB r (cf. A., 1931, 174) are im m ediately swept into an atm . of Cl2 or I the corresponding alkyl chloride or iodide is formed, th u s affording additional evidence of th e m om entary existence of the free alkyl radical.
A. R, P.
Therm al decom position of isopentane in pres
ence of silica gel. M a i l h e and C r e u s o t (Compt.
rend., 1932, 194, 2220—2222).—Therm al decomp, of 1000 g. of isopentane in presence of silica gel a t 680°/
atm . pressure affords 750 litres of gas containing CH4, C2H 4, C3H 8, and butadiene and 245 g. of liquid, b.p. < 2 0 ° to > 2S 0° (condensed by solid C 0 2), rich in ethylenic and arom atic hydrocarbons. J . L. D ’S.
Polym erisation of diolefm es w ith olefines. I.
Isoprene and A^-pentene. C. A. T h o m a s and W. H. C a r m o d y (J. Amer. Chem. Soc., 1932, 54, 2480—2484).—Isoprene and A&pentene (I) react in presence of A1C13 to form hydrocarbon-sol. and
nearly identical space requirem ents, b u t is certainly no t uncommon in sim ilar compounds (cf. A., 1930,
1137). C. A. S.
Spanish vanadinite. F . M. M a r t i n (Anal. Fis.
Quim., 1932, 30, 377—383).—A specimen of van
adinite from Albunuelas had d15 6-94 an d contained P b 71-98%, V 0 4 22-33%, A s0 4 2-33%, and Cl 2-49%.
The A s0 4 content is th us interm ediate between the am ounts found in vanadinite from Arizona (5-2%) and in th a t from Sierra Grande (1-6%). V should not be determ ined as V20 5 if As is present.
H . F. G.
P resence of germ anium in Brazilian metallic m eteorites. H . E . d e A r a u j o (Rev. Soc. Brasil.
Chim., 1931, 2, 365—369).—0-1% of Ge sulphide was isolated from a m eteorite from Sta. Lucie de Goyaz, where it occurs in th e “ graphitic fraction.” Ge was also found and identified spectroscopically in two other m eteorites and m ay be of more general occur
rence. E. L.
C ollinsics of m inerals. XXII. H . C o l l i n s
(Chem. News, 1932,144, 427—430).
C h em istry.
-insol. polym erides. The q u a n tity of the sol. poly
mer ¡deformed is afun ctio no f th e am o un tof (I) present, w hilst its hardness is an inverse function of the quan t i ty of (I) used. The q u a n tity of th e insol. polymeride is also an inverse function of th e (I) present. The sol. resin polymeride, exposed in a th in film to air, slowly oxidises, thereby becoming h a rd e r; the I val.
gradually decreases w hilst th e acid val. increases;
0 3 is rapidly absorbed by th is polym eride in CC14, b u t th e product, after absorption ceases, has an I val.
as high as 1 4 0 (in some cases). The insol. polymeride, (C5H 8L, begins to depolymerise about 1 1 6 ° ; it is decomposed by strong acids and gives reddish-violet colorations (with decomp.) w ith phenols. No insol.
polym eride is form ed when (I) is treated with A1C13-C. J . W. (b) Preparation of pure octene. H. I. W a t e r m a n
and T. W. T e N u y l (Rec. trav . chim., 1932,
51, 5 3 3—5 3 7 ) .—The preps, of octan-£S-ol from castor oil and thence of octene, b.p. 121-6—1 2 3-6°/760-2 m m ., are described. Octan-a-ol gives an octene sim ilar in physical properties. R. S. C.
Fluorine derivatives of chloroform. H. S.
B o o t h and E. M. B i x b y (Ind. Eng. Chem., 1 932, 24,
6 3 7 — 6 4 1 ) .—CHC12F , b.p. 1 3 -5 — 1 5 -5 ° , m.p. - 1 2 7 ° , is prepared from CHC13 (containing a little CS2), SbF3, an d a little SbCls a t room tem p., whilst chhrodifiuoro- methane, b.p. — 3 9 - 8 ° , m.p. — 1 4 7 ° to — 1 4 6 ° , is formed from CHC13, SbF3, and SbCl5 a t 1 0 0 ° under pressure.
CHF3 could n o t be obtained from CHC13, SbF3, and SbCl- a t 2 0 0 ° (bath) under pressure. The toxicity (towards guinea-pigs) of th e above compounds decreases w ith increase in th e no. of F atoms
su b stitu ted for Cl. H. B .
Action of ultra-violet ligh t on halogenated hydrocarbons. I. Action on tetrachloroethane.
E. M u l l e r and A. L u b e r (Ber., 1932, 65, [5], 985—9S7).—Irra d ia tio n of CHC12-CHC12 through which m oist air is passing results in th e production of HC1, CHCU’CChH, and octachlorobutane, m.p. 81°.
The hypothesis th a t the p rim ary change is loss of HC1 w ith form ation of CHClyCCl, which combines with activated 0 to produce CHClyCOCl, is supported by the production of CHClyCO-NH, b y th e action of NH3 on the solution rem aining when d ry air is used. H3C204 is produced in sm all am ount. C2H2C14 appears stable tow ards 03 a t room tem p. Similar irradiation of CHC13 produces COCU and C2C1G.
H . W.
Synthesis of aliphatic alcohols by catalytic reduction of carbon m onoxide. G. N a t t a and R. R i g a m o n t i (Giorn. Chim. Ind. Appl., 1932, 14, 217—225; cf. B., 1931, 874).—The catalytic reduc
tion of CO b y H2 under pressure and in presence of ZnO and IvOAc ydelds MeOH, higher aliphatic alcohols, about 0-9—1-1% of aldehydes and ketones, 0-02—0-5% of hydrocarbons, 1-4—2-4% of free acids, and 2-5—2-6% of esters. The proportion of alcohols higher th an MeOH m ay be increased som ewhat by increasing th e am ount of alkali m etal in th e catalyst, but the effect is sm all over the range 14— 9% K20 . The m ethods used for separating and identifying the different alcohols are described in detail. Besides MeOH, the following are formed : BuH)H, 51-3—46-6;
PrOH, 131— 11-6: C H M eEt-C H /O H , 4-9—4-8:
EtOH, 3-3—4-2: Pr*OH, 2-6—3-7 ; CHMePr-CHyOH, 2-5; BuOH, 1-8—2-0; w-C5H n -OH, 0-4, and (3-methyl- hexanol, T6% ; y-m ethylpentanol, iso-C-H, ,-O'H, CHMePr^-CHo-OH, G HEtPrf-OH, CHPr% OH, CHPrPr^-OH, ierf.-BuOH, an d <eri.-C5H n -OH,“all in small proportions. The alcohols formed contain 94-7—9S-4% or, excluding MeOH, 87-5—90-1% of primary alcohols. Among the norm al-cliain alcohols, those w ith odd nos. of C atom s predom inate, and among th e ones w ith branched chains, those with the Me in th e p-position to the OH. T. H. P.
Preparation of m ixed ethers. R . T r u c h e t and M. G ra v es (Bull. Soc. chim ., 1932, [iv], 51, 6S6— 689).—The action of alkyl arylsulphonates on Na alkoxides gives 55% ydeld of ethers. A. A. L.
Ethyl ethers of a-glycols, and the ketones obtained by their dehydration. IV. D. Bar d a n (Bui. Chim. Soc. R om ane S tiinte, 1930, 33, 25—32;
cf. this vol., 368).—isoValeryl chloride (from the acid with S0C12) gives the a-Br-derivative, converted into the E t ester, which gives E t a-ethoxyisovalerate, b.p.
"3—76°/31 m m . From th is the following are ob
tained w ith the appropriate Grignard re a g e n t: y- dhoxy-p-methyl-S-ethylhexan-S-ol, b.p. 74—77°/19 mm.
(60%); y-ethoxy-$-methyl-8-propylheptan-8-ol, b.p.
105—109°/20 mm. (70% ); y-ethoxy-$-methyl-8-butyl- octah-8-ol, b.p. 143—145°/26 m m .; and y - e t h o x y - 'inethyl-SS-dipJmiylbutan-S-ol, b.p. 204—209°/17 mm.
Conversion of these substances into the following ketones is best effeoted b y treatm en t w ith P205 in anhyd. pyridine, followed by hydrolysis w ith 20%
^ t^ 0 4 : p.methyl-8-ethylhexan-y-one, b.p. 52—54°/21-5 inm. (yield 80% ); p-methyl-8-propylheptan-y-one, b.p. 74—78°)23 m m . ; (i-methyl-8-bidyloctan-y-one,
b.p. 116—121°/14m m .; andSS-diphenyl-fi-methylbutan- y-one, b.p. 159— 165°/21 mm. A. A. L.
Alkyl peroxides and ozonides. A. R i e c h e
(Aiigew. Chem., 1932, 45, 441—444).—A review.
Glycerophosphoric acids. G. C a r r a r a (Giorn.
Chim. Ind. Appl., 1932, 14, 236—237).—The two free OH of the glycerol residue in «-glycerophosphates are vicinal and, like analogous glycols (Criegee, A., 1931, 461) and unlike ¡1-glycerophosphates, these compounds are readily oxidised by Pb(OAc)4, which is converted into Pb(OAc)2. As th e tetra-acetato liberates I from K I, a-glycerophosphates m ay be determ ined accurately by means of this reaction.
W hen tested in this way, Ca glycerophosphate polv.
F.U .V I (Erba) proves to be the almost pure a-com- pound; it is readily convertible into the Na salt (Charpentier and Bocquet, this vol., 251). The quinine a- and ¡1-compounds show the m.p. given by King and Pym an (J.C.S., 1914, 105, 1238). During th e alkaline hydrolysis of the di-esters of glycero
phosphoric acid, 20—40% of a polvglycerol poly
phosphate (?) is formed. T. H. P.
M etallic compounds of the enolic form s of m onocarbonyl com pounds. XIV. Action of sodium alkoxide on esters, ester-condensation, and substitution reactions of m etallic com pounds of esters. H. S c h e i b l e r (Ber., 1932, 65, [J3], 994—999).—M ainly a reply to Adickes (this vol., 599) and Hiickei (“ Theoret. Grundlagcn d.
organ. Chemie,” 1931, Vol. I, p. 18S). The course of the reaction between BzOEt and N aO Et is represented, B z O E t+ N a O E t—N aO B z+ C2H4+ E tO H . The p ro duction of th e salt is not quantitatively explicable by assuming the action of “ traces of H „0 .” H. W.
Addition of alkali alkoxides to esters. VII.
Kinetics and statics of the decom position of ethyl formate by sodium ethoxide. F. A d i c k e s and G. S c h a f e r [with, in p art, W. B r u n n e r t ] (Ber., 1932, 65, [R], 950—955; cf. this vol., 614).—The course of the change is observed by measurem ent of the CO evolved during th e action of alkali alkoxide on HCOoEt in E tO H . The ra te is independent of the initial concn. of ester and directly proportional to the N aO Et concn. N a ' (H C 02Na, NaOAc) is w ithout catalytic action. K O E t is more powerful th an N aO Et, whilst Ca(OEt)2 is still less active and Al(OEt)3 w ithout action. The results do not throw light on the mechanism of th e change. Solubility d ata of H C 0 2Na in anhyd. E tO H and in N a O E t-
E tO H are recorded. H . W.
Oxidation and degradation of various sugars and their decom position products. XIII. Con
version of acetic into succinic acid. K . B e r n - h a u e r and W. S t e i n (Bioehem. Z., 1932, 249, 219—
222).—Ac OH (50 g.) on oxidation w ith K2S203 gave 0-2 g. succinic acid. The smallness of the yield is due to further oxidation of succinic acid to H C 02H,
AcOH, and C 02. P- W. C.
Preparation of branched-chain fatty acids of high m ol. w t. H. R u f e and E. W i l l (Helv. Chim.
Acta, 1932, 15, 842—853).—Heptaldehyde, COMe2, and 3% NaOH first at 0° and then a t room tem p, give M e $-hydroxyoctyl ketone (I), b.p. 128— 129°/10
S32 B R I T I S H C H E M IC A L A B S T R A C T S . A .
mm., di-$-hydroxyoclyl ketone (3—5% yield), m.p.
S5—86°, and Az-decen-p-one (II), b.p. i05°/10 mm.
(p-semicarbazidosemicarbazone, m.p. 172°) [also formed when (I) is heated in vac. w ith a little I]. (II), when hydrogenated (Ni) in 75% E tO H and subsequently oxidised by Beckm ann’s m ixture, gives n-decan-$- one, b.p. 92°/10 mm., m.p. 2-5° (scmicarbazone, m.p.
126°), which w ith CH2B r-C 02E t and Zn in hot, dry C6H 6 yields E t (3 - h ydroxy-\i - methylundecoate, b.p.
157°/10 mm., dehydrated, best by distillation a t 60—70 mm. w ith anhvd. ZnCl2, to E t [i-methyl-Aa- undecenoate,b.p. 142— 143°/10 mm. This was hydro
genated (Ni), best in 90% E tO H a t 60—70 atm ., to Et ^-methylundecoate, b.p. 134°/10 mm., hydrolysed to' th e corresponding acid, b.p. 165-5°/10 mm. (K , N a, and Cu salts) (together w ith a small am ount of an acid, b.p. 185°/10 mm.), the acid chloride of which, an oil (prepared by S0C12), w ith ZnMe, gives Me fi-melhyldecyl ketone, b.p. 129°/10 mm. (semi- carbazone,m.p. 81-5°). From this by sim ilar m ethods were prepared : E l fi-hydroxy-$8-dimelhyltridecoate, b.p. 170— 175°/11 mm., E t ^8-dimethyl-ka-tridecenoate, b.p. 160°/10 mm., fiS-dimelhyltridecoic acid, b.p.
183— 184°/10 mm. (Et ester, b.p. 153°/10 m m .;
N a s a lt; acid chloride, b.p. 162—163°/10 mm.), M e
$8-dimelhyldodecyl ketone (III), b.p. 162°/10 mm.
(scmicarbazone, m.p. 77°), E t fi-hydroxy-(i8Z,-trimelhyl- pentadecoate (impure), b.p. 203—2 0 5 °/ll mm., E t ¡38£- trimethyl-Aa-pentadecenoate (IV), b.p. 191— 192°/10 mm., [38X,-trimethylpentadecoic acid, b.p. 209—210°/10 mm. (N as a l t ; E t ester, b.p. 189°/10 mm.). (IV) was reduced only a t 50°. ( I ll) w ith MgBu“Br gives im pure z-/)'.-lri?nethylhepladecan-e-ol, b.p. 173—175°/9 mm., yielding (probably) im pure zr,i-trimethyl-As- heptadecene,b.p.168°/10mm. rjis recorded for the new compounds, whence the average val. -j-0-272 X10-3 for log is obtained for th e grouping -OHMe-CHy in agreem ent w ith th e lit. R . S. C.
Fatty acids associated with, cassava starch.
L . L e h r m a n (J. Amer. Chem. Soc., 1932, 54, 2527—
2530).—The fa tty acids liberated during th e hydrolysis of cassava starch (free from extraneous fa tty materials) are palm itic, oleic, linoleic, and linolenic. The detection of small am ounts of linolenic acid in presence of oleic and linoleic acids by brom ination is b etter th an oxidation. The te st for phytosterol was
negative. C. J . W. (6)
U nsaturated fatty acids and their derivatives.
II. Configuration of tetrahrom ostearic acid from linoleic acid. T. M a r u y a m a and B. S u z u k i
(Proc. Im p. Acad. Tokyo, 1932, 8, 186— 189).—The tetrahrom ostearic acid, m.p. 114°, from linoleic acid is trea ted w ith E tO H -K O H a t 0° for 120 hr. or a t 20° or 35° for 20 hr. and th e Me ester of th e resulting B iyacid (I) oxidised by Arm strong and H ilditch’s m ethod (A., 1925, i, 355); Me H sebacate and tartronic [from C H Br(C02H )2] and w-valeric acids are thereby"
obtained. (I) is, therefore, OA-dibromo-A's-octa- deeadienoic acid. Dehalogenation at 50° gives O-bromo-Aw-octadecatrienoic acid (oxidation pro ducts, H 2C20 4, n-valeric and a-hydroxysebacic acid s);
a t 80°, A’A'^-octadecatetraenoic acid (oxidised to H 2C20 4, suberic and w-valeric acids) results. Elim in
ation of H B r occurs sim ultaneously w ith alm ost
equal readiness between th e l- and k- and the u- and v-C atom s to give (I). Linoleic acid is considered, to have th e cis-cis-structurc; th e grouping,
B rB r H H
•CH2-C—C-CHyC— C(e)-CWH,-, probably occurs in the H H B rB r
B iyacid. H. B.
Action of hydrazine polysulphide on oleic acid.
J . V o r i S e k (Chem. Listy, 1932, 26, 285—286).—
N 2H 4 polysulphide and oleic acid yield a mixture of th e hydrazones of oleic an d stearic acid. R. T.
Hydrogenation of linoleic acid. I. Ethyl linoleate. H . v a n d e r V e e n (Chem. Umschau, 1932, 39, 104— 109).—E t linoleate (prepared from linoleic acid tetrabrom ide by7 R o lle tt’s method) was hydrog en ated. a t 200° w ith a N i-kieselguhr catalyst (reduced a t 500°), and th e reaction was followed by thiocyanom etric analysis. The first stage of the reaction converting linoleic into A9-octadecenoic acid was highly selective, < 9 % of stearic acid (checked by th e B ertram m ethod) being formed. Under the given conditions no wandering of th e double linking occurred, th e octadecenoic acids produced consisting of about equal proportions of As-oleic and elaidic acids (cf. Suzuki and Inoue, B., 1930, 956). E. L.
Odour and constitution of som e alkoxy-acids and their esters. I. B. R o t h s t e i n (Bull. Soc.
chim., 1932, [iv], 51, 691—696).—The action of CH2C1,C 0 2H on the appropriate N a alkoxide gives th e following alkoxyacetic acids : n-heptyl-, b.p.
157°/18 mm. (M e ester, b.p. 115°/18 mm. ; Etester, b.p. 123-5°/16 mm.) (60% ); octyl-, b.p. 162°/15 mm.
(M e ester, b.p. 119°/15 m m .; E t ester, b.p. 125713 mm.) (A., 1929, 1174); benzyl-, b.p. 180—182715 mm. (M e ester, b.p. 136-5°/15 m m .; E t ester, b.p.
143°/15 nun.); phenylethyl-, m.p. 46°, b.p. 1S3°/14 mm. (loc. cit.) [Me ester, b.p. 145°/13 m m .; Etester, b.p. 153°/16 mm.] (50% ); phenylpropyl-, m. p. 55°, b.p. 198°/15 mm. (M e ester, b.p. 157°/14 m m .; Et ester, b.p. 162— 163°/15 m m .); rhodinyl-, b.p. ISO- 1810/ 16mm. : and geranyl-, b.p. 180°/16 mm., 143°/
0-86 mm. (Et ester, b.p. 155— 157°/16 mm.).
A. A. L.
Electrolytic oxidation of aliphatic dicarboxylic acids. E. A. T o m m i l a (Ann. Acad. Sci. Fennic», 1932, 36, 114 pp.).—The anodic oxidation products of a no. of aliphatic dicarboxylic acids have been determ ined, m ostly in strongly alkaline solutions (5A7-NaOH), b u t in some cases in presence of 2AT-H2S 0 4 or w ithout any addition. Electrodes of polished and platinised P t, Fe, and Ni were used in th e alkaline solutions, and P t and P b 0 2 in the acid solutions. The course of th e oxidation varies with th e composition of th e electrolyte, an d w ith the nature and m aterial of th e anode. In general, the anodic oxidation of malic acid in alkaline solution gives relatively7 large yields of malonic acid (by7 oxidation of th e univalent m alate ion), MeCHO (from the bivalent m alate ion), and H 2C20 4 (especially at Ion potentials and a t anodes of Ni or Fe). Secondary changes and th e mechanisms of th e reactions involved are discussed. In H 2S 0 4 solution the curren efficiency is low, except w ith P b 0 2 anodes, and the
products of oxidation are malonic acid, H C 02H, AcOH, MeCHO, CO, and C 02, no H 2C20 4 being obtained; in th is case the undissociated malic acid is the dcpolariser, ra th e r th an the m alatc ions. The anodic oxidation products of oxaloacetic acid are mainly C 02 and MeCHO in acid solution, b u t in alkaline solution a yellowish-red condensation product of unknown composition is produced. Malonic acid in alkaline solution is oxidised electrolytically mainly to C02, w ith some H 2C20.j and H C 0 2H (probably indicating tartro n ic acid as interm ediate). No CO or hydrocarbon is formed. Alkaline mesoxalic acid gives equiv. am ounts of C 02 and H 2C20 4 in quant, yield, whilst th e acid solution is oxidised to C 02 alone. Succinic acid is oxidised w ith difficulty to C02, accompanied by traces of org. acids. Alkaline solutions of maleic or fum aric acid are oxidised
products of oxidation are malonic acid, H C 02H, AcOH, MeCHO, CO, and C 02, no H 2C20 4 being obtained; in th is case the undissociated malic acid is the dcpolariser, ra th e r th an the m alatc ions. The anodic oxidation products of oxaloacetic acid are mainly C 02 and MeCHO in acid solution, b u t in alkaline solution a yellowish-red condensation product of unknown composition is produced. Malonic acid in alkaline solution is oxidised electrolytically mainly to C02, w ith some H 2C20.j and H C 0 2H (probably indicating tartro n ic acid as interm ediate). No CO or hydrocarbon is formed. Alkaline mesoxalic acid gives equiv. am ounts of C 02 and H 2C20 4 in quant, yield, whilst th e acid solution is oxidised to C 02 alone. Succinic acid is oxidised w ith difficulty to C02, accompanied by traces of org. acids. Alkaline solutions of maleic or fum aric acid are oxidised