When crotonic acid is heated with 20% hydro

chloric acid about 80% is converted into a mixture of I

1424 BR ITISH CHEMICAL ABSTRACTS.---- A.

¡3-hydroxy- and -chloro-butyric acids. With boiling 5, 10, or 20% sulphuric acid hydration to (3-hydroxy- butyric acid occurs to the extent of 53—70% after

4—5 days. H. Bu r t o n.

C onductivity titration of solu tion s of th e so d iu m sa lts of th e lo w er fatty acid s. M.

Ge h r k e and H. H. Wi l l r a t h (Z. angew. Chem., 1929,

4 2 , 9S8—990).—Exôéss of 0-lAT-hj'drochloric acid is added to the solution and the acidified mixture titrated with 0-liV-sodium hydroxide. Two dis- continuities are shown by the conductivity curves corresponding with the beginning and end of the neutralisation of the' fatty acid. Formic acid is exceptional in that one angle is flattened and the position is obtained by extrapolation. The method is general for acids having dissociation constants for O-liV-solution greater than 5 x K H and also to

phenols. C. Ir w i n.

T etra m eth y lm a rg a ric acid and tetra m eth y l- stearic acid. R. Ku h n and H. Su g in o m jé (Helv.

Chim. Acta, 1929, 12, 915—921).—Phytyl iodide [a-iodo-yrfAo-telmmethylhexadecane], b. p. 152— 154°/

0-12—0-22 mm., d f 1-0791, nf, 1-4799, is prepared by saturating diliydrophytoi (Willstiitter and Mayer, A., 1908, i, 383) at —20° with hydrogen iodide and heating at 70—-80° in a sealed tube. The bromide, b. p.

147°/13 mm., 161°/0-8 mm. (cf. Karrer, Helfenstein, and Widiner, this vol., 49), is obtained by heating dihydrophytol with liydrobromic acid at 2 1 0—2 2 0°.

Condensation of the bromide, or, preferably, the iodide, with ethyl potassiomalonate yields ethyl phytylmalonate, b. p. 191—192°/0-34 mm., converted into £ivp-tetramethylstearic acid, b. p. 182°/0-22 mm.

(tribromoanilide, m. p. 63-5—64-5 ). Treatment of the Grignard compound of phytyl bromide with carbon dioxide yields SOiL-z-tetramethylmargaric acid, b. p.

169°/0-21 mm. (tribromoanilide, m. p. 62—63°).

R. K. Ca l l o w.

S ulp hon ated oils. V. P rep aration of ricin - o leic acid su lp h uric ester fro m ricin oleic and su lp h uric acids. K . Ni s h i z a w a and M . Sin o z a ic i

(J. Soc. Chem. Ind. Japan, 1929, 32, 779—783;

cf. Grün and Woldenberg, A., 1909, i, 284).—

Sulphuric acid (100 g.) is gradually added during 3 hrs. to a mixture of 100 g. of ricinoleic acid (prepared from castor oil) and 1 0 0 g. of ether with vigorous agitation at 25°, the mixture is preserved for 2 hrs. ; when 150 g. of ether are used, the mixture is preserved for 2—17 hrs. The product is colourless and almost pure and is isolated by acidification or as potassium hydrogen salt. K . Ka s h i m a.

P h otoch em ical d ecom p osition of lactic acid.

G. R. Bu r n s (J. Amer. Chem. Soc., 1929, 51, 3165—

3171).—Aqueous solutions of lactic acid are decom­

posed by radiations of wave-lengths shorter than 2500 A. in absence of oxygen. The main products of the decomposition arc carbon dioxide and alcohol;

the alcohol formed is, however, 19% in excess of the amount required by the chango CHMe(0H)-C02H— >- E t0 H + C 0 2. Other products of the decomposition are carbon monoxide (3-82% ; the percentages are of the total gaseous products), methane (2-18%), ethane (2-18%), and unsaturated hydrocarbons (prob­

ably ethylene, 0-89%). Anetaldehyde or hydrogen

peroxide could not be detected. Tho ratio between the energy absorbed and the carbon dioxide produced corresponds with a quantum yield of approximately 0-65. The results agree in tho main with those of von Euler (A., 1911, ii, 452; 1912, ii, 407 ; 1913, ii, 544; cf.

Scharz, Arch. ges. Physiol., 1918, 1 7 0 , 650) but not with those of Neuberg (A., 1912, i, 314) and Baudisch (A., 1920, ii, 461). H . Bu r t o n.

A cetoacetic ester condensation. S. M.

Mc-El v a i n (J. Amer. Chem. Soc., 1929, 5 1 , 3124—

3130).—An excess of ethyl acetate, propionate, butyrate, or isobutyrate is treated with dry sodium ethoxide (0-5 mol.) and the reaction mixture distilled periodically to remove excess of ester , and the alcohol formed during the reaction (the distillate is replaced with ester until no more alcohol distils). Refracto- metric determinations of the alcohol in the distillate, formed according to the reaction 2CH2R-C02E t + NaOEt — > CH2R-C(0Na):CR-C02E t+ 2 E t0 H , give values of 0-83, 0-97, 1-03, and 0-03 mol., respectively.

Tho yields of isolated keto-esters are 0-34, 0-405, 0-38, and 0 mol., respectively. The results support Claisen’s mechanism (A., 1887, 583), which is reversible (cf. Higley, A., 1907, i, 461). Scheibler and Marhen- kel’s postulate of an intermediate enolate as an essential step in the reaction (A., 1927, 1167) is not upheld by the results with ethyl jsobutyrate. I t is suggested that the ethyl acetate-sodium ethoxide additive product may undergo decomposition either into the original components or sodium hydroxide and keten acetal (cf. Scheibler and Marhenkel, loc. cit.).

H . Bu r t o n.

D eterm in ation of con figu ration in th e terpene series. TV. O ptically active isop ro p ylsu ccin ic acid s. J. v o n Br a u n and W . Re i n h a r d t (Ber., 1929, 6 2 , [£], 2585—2587; cf. this vol., 679).—

rfZ-isoPropylsuccinic acid, b. p. 130°/15 mm. with considerable conversion into the anhydride, readily obtained from ethyl a-bromoisovalerate and ethyl sodiomalonate, is resolved with some difficulty into its optical antipodes by treatment with strychnine in aqueous solution. The more sparingly soluble alkaloidal salt affords ( + ) - i sop ropylsuccinic acid, m. p.

87—88°, [a]u. +24-01° in water (anilide, m. p. 200°, [a]jJ —36-5° in alcohol). The mother-liquors from the salt of the (+)-acid yield (—)-isopropylsuccinic acid, which, after purification through the ethyl ester, b. p.

119—120°, d20 0-9896, [ajg -1 5-05 °, had m. p. 85—90°, [a]D > 2 1 ° in w-ater. H. Wr e n.

R edu ction of m e th y l e ste r s of p oly m eth y len e- d icarb oxylic acid s w ith fifteen to tw enty-on e carbon a to m s b y so d iu m and alcohol. P. Ch u i t

and J. Ha u s s e r (Helv. Chim. Acta, 1929, 1 2 , 850—

859).—Glycols, OH-[CH2]„-OH (71=15—21), have been prepared by reduction of the methyl esters of the corresponding acids (A., 1926, 499) by sodium and alcohol. Certain of the related compounds (cf. this vol., 677) have been prepared in a greater state of purity by improved methods. av-Dicyanotridecane, m. p; 31—31-5°, b. p. 215—216° (from av-dibromo- tridecane), yields tridecane-av-dicarboxylic acid, the methyl ester of which is reduced to pentadecane ao-diol, m. p. 87°, which yields with hydrobromic acid ao-dibromopentadecane, m. p. 27-2—27-5°, b. p.

ORGANIC CH EM ISTRY. 1425 197°/2 mm. Hexadecane-a:r-diol yields a^-dibromo-

hexadecane, m. p. 56-2—56-79.

x-Bromoliexadecan-■k-oI, m. p. 53—54° (acetate, m. p. 31°, b. p. 192— 194°/

1 mm.), is obtained in poor yield from hexadecane- ctTr-diol monoacetato and hydrogen bromide. Ilepta- decane-ccp-diol, m. p. 96—96-5°, yields ap-dibromo- heptadecane, m. p. 38—38-4°, b. p. 208—210°/3 mm.

Octadecane-acr-diol, m. p. 98-6—99° (lit. 92°), b. p.

2 1 0—2 1 1 ° / 2 mm., yields aa-dibromoheptadecane, m. p.

63-5—64°, b. p. 205—207°, from which heptadccanc- aapp-tetracarboxylic acid, m. p. 89—90°, may be obtained by condensation with malonic acid. Nona- decanc-a-^-diol, m. p. 101°, b. p. 212—214°/l-5 m m , yields ar-dibromononadecane, m. p. 46-2— 46-5°, b. p.

210—211°/l-5 mm. Octadecane-aa-dicarboxylic acid, m. p. 123° (lit. 124— 125°) (methyl ester, m. p. 65-5—

6 6°, b. p. 223—224°/2 m m .; ethyl ester, in. p. 54-5—

55°, b. p. 230—232°/2 mm.), is obtained by the malonic ester method. Eicosane-a'j-diol, m. p. 103°, b. p.

215—217°/l-5 m m , yields xv-dibromoeicosane, m. p.

67-4—68°, b. p. 220—222°/2 mm. Nonadccanc- ax-dicarboxylic acid, m. p. 123° (lit. 111°, 117°) [methyl ester, m. p. 65-3—65-8° (lit. 56—57°), b. p.

225—228°/3 m m .; ethyl ester, m. p. 57°, b. p. 238;—- 239°/3 mm.], is obtained by the malonic ester method.

Heneicosane-a.<f>-diol, m. p. 105—105-5°, b. p. 223—

224°/l-5 mm. (acetate, m. p. 60°, b. p. 240°/3 mm.), yields a<f>-dibromoheneicosane, m. p. 52-5—53°, b. p.

226— 228°/2-5 mm. The ascending curves of the m. p.

of the series of odd- and even-numbered glycols cross after the fifteen-atom member and then rejoin at the eighteen-atom member to give a single curve. The ascending curves of the m. p. of the dibromo-com- pounds, at first roughly parallel, afterwards converge slightly. The even-numbered compounds in each

case have the higher m.-p. curve. R. K. Ca l l o w.

Constitution, of anhydrotricarballylic acid. R.

Ma l a c h o w s k i (Bull. Acad. Polonaise, 1929, A, 265—

273).—The structure 2™ V h - C H 2-C02H for CU OJdlg

anhydrotriearballylic acid, prepared in 87—91% yield by the action of acetic anhydride below 45° on tri- carballylic acid, is supported by the following experi­

ments. a-Methyl ircms-aeonitate is reduced by platinum-black and hydrogen to a-methyl iricarballyl- ate, m. p. 1 1 1—1 1 2°, and is identical with the ester ob­

tained by tlie aleoholysis of anhydrotricarballylic acid with methyl alcohol or by the treatment of the anhydro- acid with diazomethane in ether with the formation of the a.-methyl ester of the a n h y d r o - a c id , m. p. 59— 60’, followed by ring fission of the latter by w a t e r. Tri- carballylic acid, m. p. 160— 161°, is produced in 87%

yield from ¿raws-aconitic acid, platinum-black, and hydrogen, and, in a less pure form, by the reduction of ci’s-aconitic acid. Attempts to reduce the anhydrides of cis- and ¿ra?«-aconitic acid dissolved in glacial acetic acid with platinum-black and - hydrogen were un­

successful. A -1- Vo g e l.

T e s ts for acetone ;and aldehyde. H. Le f f m a n n

and C. C. Pi n e s (Bull. Wagner Free In st, 1929, 4, 39—41).—For the detection of formaldehyde in the presence of acetaldchyde the most satisfactory results are obtained with a solution of 1 g- of potassium guaiacolsulphonate in. 1 0 c.c. of concentrated sulphuric

acid. Acetone can be readily detected in the presence of formaldehyde by adding a concentrated aqueous or preferably glycerol solution of sodium nitroprusside containing ethylamine to a dilute aqueous solution of the m ixture; a red ring is formed at the contact zone.

A. I. Vo g e l.

M anufacture of chloroacetaldehyde. L G.

Fa r b e n i n d. A.-G.—See B , 1929, 887.

B rom in ation p rod u cts of /sobutaldehyde. R.

D w o r z a k and W. P r o d i n g e r (Monatsh, 1929, 53 and 54, 588— 595).—Bromination of ¿sobutaldehyde (I) at about —1 0° and treatment of the product with alcohol affords a-bromot'sobutaldehyde (IT), its ethyl acetal (III), and bromoparaisobulaldehyde (IV) CjgHjgOaBr, b. p. 128-5°/10 mm. Attempted dcpoly- merisation of IV at 160° gives I, but II could not be isolated. Bromination of I at about 30° and treat­

ment with alcohol gives small amounts of II, III, and IV; the main product is the compound (V), m. p.

82-5°, previously described (this vol., 1166). The stability of V towards various acidic reagents is noted;

but hydrolysis with sodium hydrogen carbonate or alcoholic potassium hydroxide solution gives a-hydr- oxyi'sobutaldehyde. The substance is now considered to be eta -tetrabromodiiBobutyl ether (cf. Stepanov, A , 1927, 42; Hibbert, Perry, and Taylor, this vol., 791).

H. Bu r t o n.

T h e rm a l d ecom p o sitio n of acetone in the g a seo u s state. F. 0 . Ri c e and R . E. Vo l l r a t h

(Proc. Nat. Acad. S c i, 1929, 15, 702—705; cf.

Hinshelwood and Hutchison, A , 1926, 691).—When vaporised acetone was passed with nitrogen at a known rate through a quartz tube heated in an electric furnace, for every 1 0 0 mols. of acetone decomposed approximately 60 mols. of keten were recovered.

Hence the primary reaction in the unimolecular decomposition of acetone is probably the separation of a molecule of methane and the formation of keten, which, at the high temperature, undergoes a bimole- cular decomposition into ethylene and carbon mon­

oxide. If this is the correct explanation, 100 mols. of decomposed acetono should give 1 0 0 mols. of methane, 30 mols. of ethylene, and 60 mols. of carbon monoxide.

This result agrees fairly closely with that of Hinshel wood and Hutchison (loc. cit.) as far as the gases are

concerned. A. J. Me e.

P o ly m er isa tio n and condensation. V. Con­

d en sation p rod u cts of m e th y ley eIod ih yd roxy- acetone. P. A. Le v e n e and A. W a l t i (J. Biol.

Chem, 1929, 84, 39— 47).—The action of methyl alcohol containing 0-5% of hydrogen chloride on commercial dihydroxyacetone led principally to the rr.ethylcycZoacetal of dihydroxyacetone (cf.

Fischer and Taube, A , 1927, 857). The mother - liquor was treated with ethyl acetate and the precipit­

ated oil, after removal of solvents, was acetylated with acetic anhydride and pyridine, the product consisting of diacetoxyacetone and the acetate of the methylcyclo- acetal of dihydroxyacetone, m. p. 135°. The residue from the ethyl acetate mother-liquor was similarly acetylated, yielding acelyldihydroxyacelonylmethyl- cyclodihydroxyacetone, m. p. 184°, When heated at or slightly above its m. p , methylcj/cZodihydroxy- acetone formed