P ro g re s s of ste re o c h e m istry in In d ia , an d significance of th e d o ctrin e of sy m m e try . B. K.
Sin g h (J. Indian Chem. Soc., 1933, R ay N o ., 321—
330). ' II. B.
O x id atio n s a n d re d u c tio n s of o rg an ic co m p o u n d s. G. Ur b a in (J. Chim. phys., 1933, 30, 309—318).—Theoretical. Modem electronic ideas of oxidation and reduction arc applied to org. chemistry.
D. R. D.
L iqu id a m m o n ia as a m e d iu m fo r th e stu d y of o rg an ic com p o u n d s. E. W . McCh e s n e y (J.
Elisha Mitchell Sci. Soc., 1932, 48, 33—34).
Ch. Ab s.
S ta b ility of s p a tia l con fig u ratio n s a n d the W alden in v ersio n . R. Ku h n (Inst. int. Chim.
SolVay, Conseil Chim., 1931, 4, 413—422; Chem.
Zentr., 1933, i, 206—207).
P y ro ly tic co n d ensation a n d d eco m p o sitio n of eth an e in p resen ce of h y d ro g en . M. W. Tr a v e r s (J. Indian Chem. Soc., 1933, Ray No., 17—26).—
See A., 1932, 701. H. B.
T rim e th y lp e n ta n e s. K . C. La u g h l in and F. C.
Whitm ore (J. Amer. Chem. Soc., 1933, 55, 2607—
2608).—Physical data for (3(3y- (I), [3(38-, (3yy-, and pyS-trimethvlpentanes are given. (I) of Clarke et al.
(A., 1912, i, 150) contained define. R. S. C.
S y n th e sis o f S -n -p r o p y ln o n a d e c a n e a n d e-n- b u tyleico san e. S. La n d a, J . Ce c h, and V. SlIva (Coll. Czech. Chem. Comm., 1933, 5, 204—210).—
Interaction of E t palmitate with Mg (2 equiv.) and P raBr in E t20 gives S-propylnonadecan-S-ol, m.p.
44-5°, and some (I), converted by ZnCl2 at 110—
llo ° into S-n-propyl-Ay-nonadecene (I), b.p. 204—
804 BRITISH CHEMICAL ABSTRACTS.— A.
206°/10 mm., -\vliicli with H2 and Ni a t 140°/90 atm.
gives 8-n-propylnonadecane, m.p. 6-5°, b.p. 210—
211°/10 mm. The constitution of (I) was proved by oxidation by KM n04 to P r pentadecyl ketone and E tC 02H. C 0Pra2was not detected. s-n-Butyleicosan- c-ol, m.p. 50°, e-n-butyl-tf-eicosene (XI), b.p. 219—
221°/10 mm., and e-n-butyleicosane, m.p. 8°, b.p.
222—223°/10 mm., are similarly prepared. Oxidation of (II) with KMnO, gives Bua pentadecyl lcetone, m.p.
52°, and P r“C02H. H. A. P.
A ction of th e sile n t d isc h a rg e on ethylene. W.
Sz u k ie w ic z.—See th is v o l., 791.1 * A ction of th e sile n t ele c tric d isc h a rg e on eth y len e. I II . R. Stba tta and E. Ver nazza (L’lnd. Chimica, 1933, 8, 698—702).—The condens
ation of C2H2 in mixtures containing up to 20% of an inert gas is proportional to the concn. of C2H2;
if the diluent is H 2, the C,H2 at first disappears more rapidly and then normally. The formation from C2H.j of aeetylenic hydrocarbons by the silent dis
charge decreases rapidly with time, owing to (1) diminution in the concn. of the C2H4 and (2) a secondary condensation of the C,H2. The H2 liberated during th e formation of a hydrocarbon with a triple linking is fixed immediately a t a double linking of the C2H 4, w ith formation of saturated hvdrocarbons (G>He,
CH4, etc.). .. T. H. P.
Influence of te m p e ra tu re on th e iso m e ris a tio n of b u ten es in th e p resen ce of a lu m in iu m [oxide]. C. Ma t ig n o n, H . Mouretj, and M. Do d£ (Compt. rend., 1933, 1 9 6 , 1560—1563).—The amount of A^-butenc produced by dehydration of BuQOH by A1203 is increased by previous heating of the catalyst to 450° or 650° or by elimination of adsorbed sulphates by heating to 650 rather th an by neutralisation by alkali. By regulation of these and other factors (cl.
this vol., 693) the Aa- or As-isomeride m ay be pro
duced at will. R. S. C.
B e h a v io u r of p en ten es w ith b ra n c h e d c h ain s to w a rd s h y d ro ch lo ric acid a n d a lu m in iu m ch lo rid e a t low te m p e ra tu re s . P re p a ra tio n of y-m ethyl-A “-b u te n e . J . J . Le e n d e r t s e, A. J.
Tu l l e n e r s, and H. I. Water m a n (Rec. trav. chim., 1933, 5 2 , 515—524).—Dehydration of commercial amyl alcohol by A1203 at 350—450° affords a m ixture of pentenes (I), hydrogenated (Pd-C) to (3-methyl- butane. (I) with dry HCl at —80° during hr.
affords, when fractionally distilled, mainly p-chloro- P-methylbutane; also y-methyl-A<I-butene (II) [which reacts with dry HCl at —80° in presence of A1C13 to give y-chloro-P-methylbutane and a monochloride m ixture formed from the polymerides of (II) and HCl] and S-mcthyl-Aa-butene (III). (II) with BaCl2 and soda-lime at 350—400° affords ¡3-methyl-A0-”
butene and (III). J. L . D.
S te re o iso m e ric m eth y le th y le n e s. D eh y d ratio n of S -m ethylpentan-S -ol b y a lu m in a . 8-M eth y l- A^-pentene. S-Methyl-A“-pentene a n d its d e riv ativ e s. H. v a n Ris se g h e m (Bull. Soc. chim. Belg., 1933, 4 2 , 219—228, 229—242).—Dehydration of S-methylpentan-p-ol by A1203 a t about 360° leads to a mixture of S-methyl-A°-pentene, b.p. 53-9—54-1°
(dibromide, b.p. 80-5°/17 mm.), p-methyl-A^-pentene,
b.p. 66-8—67-6° [nitrosochloride, m p . 74-05—74-2°
when slowly heated; niirosate, m.p. 93° (decomp.)], oxidised by KMnO., to COMe2 and E tC 02H, and cis- and trans- 8-methyl-A^-pentene detected by their Ram an spectra but not isolated.
Interaction of CH^CH-CHaBr and MgPr^Br leads to 8-methyl-Aa-pentene (I), b.p. 53-8—54-2°/7 6 0 mm., and an unidentified hydrocarbon, b.p. 5 T 5—52-0°/760
mm., hydrogenated to ¿sohexane. (I) is reduced to isohexane and converted by Br in 0HC13 into a[3- dibromo-8-methylpentane, b.p. 86-9°/22 mm., tran s
formed by boiling K O H -EtO H into 8-methyl-Aa- pentinene, b.p. 61-1—61-2°/760 nnn., f.p. — 105°, and a bromoliexene, b.p. 134—136-5°/750-2 nnn.
8-Methyl-A“-pentene and HBr yield [i-bromo-8-mcthyl- pentane, b.p. 6S-6—69-2°/90 mm., f.p. —94-6°.
H. W.
S tru c tu re of M a lb o t's diisobutylene. A. D.
Petr o v, L. I. An z o h s s e, and D. N. An d r e e v (Bull.
Soc. clhm., 1933, [iv], 5 3 , 327—330).—Fractionation of the diisobutylene (I) [Malbot et al. (A ., 1889, 842; prep, improved by using high pressure at 300—
330° with smaller amounts of ZnCl2)] gives a fraction b.p. 108—112°/760 mm. which by reduction witli H 2-NiO at 200° under pressure affords two fractions, b.p. 102—107° and b.p. 107—113°. Comparison of this result with those obtained by reduction of p[iy- (II) (Clarke and Jones, A., 1912, i, 150) and ppS- (III) (A ., 1930, 1553) -trimethyl-Av-?i-pentene suggests th a t (I) is a m ixture of (II) and (III). The acid products of oxidation of (I) appear similar to those from (II) and (III), but fractional crystallisation of the semicarbazone of the ketonic product from (I) indicates the presence only of CMe3'CH2Ac, whereas absence of aldehyde or ketone products in oxidation of (II) w ith Cr03 is explained by the predominance of the form CMe,-CHMe,CH!CH2 and the ease with which the aldehyde initially formed is further oxidised.
J . W. B.
S tru c tu re of th e acid s o b tain e d by o x id ation of triiso b u ty le n e . J . B. Co n a n tand G. W . Wh e l a n d
(J. Amer. Chem. Soc., 1933, 5 5 , 2499—2504).—, Butlerow’s acid, m.p. 66—70°, supposed to be C nH2202 (A., 1880, 230), obtained from triisobutylene by H2Cr207 (modified procedure), is a mixture of about equal quantities of two acids, C12H240 2, (I) m.p. 88—89° [chloride, b.p. 120—123°/40 m m .; Me ester, b.p. 117—120°/40 mm.; ■p-chloroanilide, m.p.
187—187-5°; amide, m.p. 140—141°, resistant to NaO H-EtO H, but regenerates (I) with H N 0 2, and with ICOH-Br gives the carbamide, CO(NH-C11H 23)2, m.p. 164— 165° (stable to boiling KOH-EtOH)], and (II), m.p. 129° [chloride, b.p. 128—133°/50 mm., regenerates (II) with aq. NH3; Me ester, b.p. 115—
120°/30 m m .; p -chloroanilide, m.p. 166-5—167°].
Both are highly substituted acetic acids, since they are very weak acids, only very slowly esterified, and cannot be brominated. If the Buy groups are still intact, they a r e : (I) CMe3-CH2-CMe(CMe3)-C02H, and (II) (CMe3)2CEt-C02H, R. S. C.
H y d ro g en atio n of m ix tu re s of u n s a tu ra te d h y d ro ca rb o n s w ith o u t a d d itio n of a c a ta ly st.
H. I. Waterm an and C. v a n Vlod ro p (Rec. trav.
chim., 1933, 5 2 , 469—477).—Hydrogenation of
octene and of mixtures of unsaturated hydrocarbons does not occur even at 360°/110—120 kg. per sq.
cm. if no catalyst is present, although some poly
merisation occurs. Previous reports to the contrary are ascribed to the presence of impurities on the walls of the autoclave; with a new autoclave the result is completely negative. H. P. G.
P la n t co lo u rin g m a tte r s . L I. P u re « -carot
e n e . P. Ka r r e rand 0 . Wa l k e r (Helv. Chim. Acta, 1933, 1 6 , 641—643).—Complete separation of a-(I) from ¡3- (II) -carotene is effected by filtration of its ligroin solution through air-dried Ca(OH)2 or CaO, (II) being found in the dark reddish-yellow upper layer and (I), m.p. 187—188° (corr.), [a]J?
+315°, bands at 509 and 477 mjx in CS2, in the lower yellow layer. Other methods of separation arc unsatisfactory. W ith SbCl3 (I) gives only the 542 mu, and (II) only the 590 mu, band. J . W. B.
Iso m e ric fo rm s of ca ro ten e a n d th e f u rth e r p u rific a tio n of v ita m in -y l. P. Ka r r e r, O.
Wa l k e r, K . Sch o pp, and R. Morf (Nature, 1933,
1 3 2 , 26).—Chromatographic adsorption with CaO or Ca(0H)2 separates a- (I) from p.- (II) -carotene. (I), m.p. 187°, in SbCl3 shows only one absorption band (542 mix) and (II) only one band at 590 mix. Highly conc. vitamin- A can be similarly purified and separates into a main fraction (III), C20H30O, which gives absorption a t 328 mjx, and a smaller fraction (IV), a t 270 m(x. Vitamin-J. preps, purified by old methods give two bands in SbCl3, but after purification by adsorption on Ca(0H)2, (II) shows one band at 620 mpt and (IV) initially one a t 580 m ¡j. and then a second a t 620 m[i.. (Ill) yields geronic acid with 0 3.
L. S. T.
H y d ro g e n a tio n of acetylene d eriv ativ es. XEX.
D ependence of d ire c tio n a n d co u rse of h y d ro g en a tio n on th e ch em ical n a tu re of th e c a ta ly st.
J . S. Sat.ktnd, M. N. Vis c h n ja k o v, and L. N. Mo rev
(J. Gen. Chem. Russ., 1933, 3 , 91—113).—The pro
cess of hydrogenation is independent of the method of prep, of colloidal P t or Pd, or of the nature of the substances taken as carriers for these catalysts.
Colloidal Pd, stabilised by starch, gum arabic, gum tragacanth, Na protalbuminate, or casein, in all cases catalyses chiefiy reduction of C:C to C!C in tetramethylbutinenediol (I), further reduction of C!C to C-C proceeding far more slowly. In the case of CH:C-CMe2-OH, the velocities of the former and latter reactions are equal, whilst in the case of CPhjCH th a t of the latter reaction is greater. Similar results are obtained in the presence of Pd deposited on B aS04, CaC03, C, Fe(OH)3, S i02 gel, or Ni. Similar experiments with P t catalyst gave analogous results, i.e., no selective action on either reaction was in any case found. The relative yield of a-form of tetra- methylbutylenediol from (I) is proportional to the velocity of reaction, which, again, depends on the concn. of catalyst, and on the nature of the solvent ( E t0 A c > E t0 H > E t20). The catalytic action of Pd is a consequence of its chemical properties, and not of its state of dispersion, or of the nature of protective colloids or carriers present; Pd has, and P t has n o t,'a special affinity for triple linkings.
R . T .
C hlorofluoroethylenes. H. S. Bo o th, P . E.
Bu r c h f ie l d, E. M. Bi x b y, and J . B . McKe l v e y (J. Amer. Chem. Soc., 1933, 55, 2231—2235).—The prep, is described of C2C1F3, m.p. —157-6°, b.p.
—27-9°/760 mm., s-C2C12F 2, m.p. -1 1 2 °, b.p. 20-9°/
760 mm., and C2C13F, m.p. —82°, b.p. 70-0°/740-8 mm. These compounds are hvdrolysed slowly by
H ,0 . ’ J. G. A. G.
P e ro x id e effect in th e a d d itio n of re a g e n ts to u n s a tu ra te d com p oun d s. I. A dd ition of h y d ro g en b ro m id e to allyl b ro m id e . M. S. Kh a r a sc h
and F. R. Ma y o. I I. A d dition of h y d ro g en b ro m id e to vinyl b ro m id e . I I I . A d d ition of h y d ro g en b ro m id e to pro py lene. M. S. Kh a r a s c h, M. C. McNa b, and F. R. Mayo (J. Amer. Chem.
Soc., 1933, 55, 2468—2496, 2521—2530, 2531—
2533).—The peroxide content of CH2!CH'CH2Br (I) (modified p rep .; 90—95% yield) controls the direction of addition of HBr. Ignorance of this factor in validates all previous results. (I) slowly forms peroxides (NH4CNS test) when kept or when 02 is bubbled through it. Presence of peroxides (notably when an org. peroxide is added) causes reaction with HBr to give rapidly ay-dibromopropane (II) (reaction A ) ; in the absence of 02 or, better, presence of anti
oxidants ct[3-dibromopropane (III) is formed (reaction B ) ; the amount of each product formed varies from 0 to 100%, according to the conditions. Solvents very greatly affect the velocity of the additions without altering the ratio of (II) and (III) in the product, but this effect bears no relation to the * of the solvent (cf. lit.). Rise of temp, in presence or absence of solvent increases greatly the velocity of both reactions, but the temp, coeff. of reaction A is 1-5—2 times as groat as th a t of B, so th a t even a low peroxide content leads to much (II). Light of all X (including infra-red and ultra-violet), par
ticularly th a t of short X, increases greatly the rate of reaction A . Anhyd. FeCl3 or A1C13 increases greatly the rate of reaction B, but Cu salts arc almost
•without effect. The reaction is homogeneous, since glass, Pyrex, asbestos (freed from Fc), and S i02 gel surfaces are without effect. AcOH acts as a n ti
oxidant, thus leading to apparently anomalous results with this solvent. The amounts of (II) and (III) in the product are estimated within 5% by deter
mining 7i [after removal of (I) by NPhMe2 in EtOH]
and controlled by the b.-p. range.
II. Results with CH2ICHBr (IV) and HBr con
firm those obtained with (I) in all respects, CHMeBr2 being the “ normal ” product, and (CH2B r)2 the product of the peroxide reaction. (IV) forms per
oxides very rapidly, and their effect can be completely eliminated only by the use of powerful anti-oxidants.
I II . CHMeICH2 does not readily form peroxides and with HBr gives “ normally ” Pr^Br, but addition of Bz0 2H or ascaridole leads to nearly 100% yields of PraBr. The results in general confirm those above.
R. S. C.
C atalytic ox id atio n of b u ty l alcohol to b u ta ld e - h y d e. A. M. Rt jbin sch t e in, A. A. Ba l a n d in, B . A.
Dolqoploska, K . A. Morozov, and L. I. Va g r a n sk a ja
(J. Appl. Chem. Russ., 1933, 6, 278—288).— Bu«OH is converted into Pr°CHO and Pr°C02H at 350—
806 BRITISH CHEMICAL ABSTRACTS.— A.
380° in presence of catalysts, the activity of which increases in the o rd e r: Cr203< C r2034-Fe20 3<
M n02-j-Fe203 < M n 02 < F e203 < V205 < Ag gauze <
42-5% Ag+7-5% Cu+50% asbestos (I) < 4 0 % Ag + 60% (I) < 7 5 % Ag + 25% (I). The most active catalysts, in which Ag is pptd. on (I) by CH20, may be used repeatedly without loss in activity.
V205 differs from other catalysts in giving the highest relative yields of Pr°C02H, and in catalysing oxidation
in an atm. of C02. R. T.
P r e p a ra tio n of b u ty l a n d bex yl alcohols fro m th e b y -p ro d u c ts of sy n th esis of div in yl fro m eth y l alcohol. I II . B. A. Ka z a n s k i, A. A.
Ba l a n d in, 1. M. Tser k o v n ik o v, K . A. Iv a n o v a,
and E. N. Staro vjerova (J. Appl. Clicm. Russ., 1933, 6, 266—273).—Considerable quantities of by-products are obtained in the Lebedev process for prep, of divinyl from EtOH. Of these, the “ butyl fraction,” b.p. 115— 120°, consisting chiefly of un- saturated alcohols, is readily hydrogenated at 120° (Ni catalyst) to yield practically pure B u °O H; under similar conditions the “ hexyl fraction,” b.p. 153—
160°, cannot be completely hydrogenated, and does not yield a homogeneous product. R. T.
G lycerol p -m o n o brom o h yd rin . L . Sm it h and J . La u d o n (Ber., 1933, 6 6, [£], 899—901).—T reat
m ent of allyl alcohol with Br-H20 affords a mixture of glycerol a- (I) and P- (II) -bromohydrin containing about 65% of (I). Condensation of the mixture with COMe2 containing 1% of HBr and finally with C0Me2-P „ 05 preferentially removes (I), leaving (II), b.p. 106°/6 mm., in which about 2% of (I) remains.
H. W.
M o bilities of alk y l ra d ic a ls in th e ir ch loro- su lp h ite s. P. CARRib (Compt. rend., 1933, 196, 1806—1809).—Action of SOCl2in C5H 5N on CH?Ph-OH and on allyl alcohol produces the cliloro-derivatives directly below —10°, whilst the decomp. temp, of the chlorosulphites formed in small amounts in the same reaction fall in the expected order compared with other radicals (cf. A., 1932, 719). Substitution of Cl, Br, C02R, and Ph in various radicals gives chloro
sulphites of greater stability in accordance with the increased negative character of the migrating groups.
A. A. L.
M ethylene disu lp h o n es. D. T. Gib s o n (J.
Amer. Chem. Soc., 1933, 55, 2611—2612).—The reaction of S 02R-CH2Ac (4) with S 02R'-SMe (2?) gives S 02R*GHAc-SMe if A is in excess, and S 02R '-CHAc-SMe if B is in excess, provided th a t R and R ' are both alkyl or both aryl. Exchange takes place if R is alkyl and R ' aryl, but not vice versa.
Exchange is of SOaR for S 02R ', and not of R for R '.
R. S. C.
A cid ch lo rid es a n d d iazo m eth an e. C arbonyl a n d su lp hon y l. F. Ar n d t and H. Scholz (Ber., 1933, 6 6, [£], 1012—1014).—i>C6H 4Me-S02Cl does not react with CH2N2 (I). MeSOX'l causes slow, catalytic decomp, of (I), but itself remains unchanged.
The action between acid chlorides and (I) (R’COCl-f- CH2N2=R-C0-CHN2H-HC1) is not therefore simply double decomp.j but involves the formation of a primary, additive compound such as R*S02C1 is incapable of producing. Similar additive compounds
are considered to be formed from (I) and aldehydes
or ketones. H. W.
P re p a ra tio n of eth yl a cetate fro m acetaldehyde.
M. J. Kag an and I. A. Sobolev (J. Chem. Ind.
Russ., 1933, No. 2, 35—37).—The conversion of MeCHO into EtOAc is catalysed not only by Al(OEt)3, but also by other more easily preparable A1 alkyl - oxides. Al(OBua)3 and Al(OBu^)3 are prepared by dissolving commercial A1 foil (pure A1 does not dissolve) in the corresponding anhyd. alcohol, con
taining 2-5% of A1C13. A1 woamyloxidc is prepared by dipping A1 in aq. HgCl2, when the amalgamated metal readily dissolves in the alcohol; the same method can be applied to BuaOII and Bu^OH. Yields of 80% of EtOAc are obtained using catalyst solutions containing A1C13, as compared with about 50% in its absence. About 7 g. of A1 and 2 g. of A1C13 are required to produce 1 kg. of EtOAc. R. T.
C h a ra c te risa tio n of h ig h e r fatty acids a s th e ir m o n o c a rb a m id e s . N. St e n d a l (Compt. rend., 1933, 196, 1810—1812).—The E t esters of fatty acids react with carbamide and conc. N aO Et-EtO H in the presence of C5H 5N at room temp, to give the car&amiifo-derivatives (90—100% yield) of stearic, m.p. 176-8°, erucic, m.p. 161-5°, octoic, m.p. 191-3°, decoic, m.p. 187°, arachidic, m.p. 172°, oleic,, m.p.
161°, and undocenoic acid, m.p. 175°, hydrolysed to the acids by KO H-EtOH . A. A. L.
P ro d u c ts of c ra c k in g of oleic acid in th e p resen ce of a lu m in iu m ch lo rid e. N. D. Ze l in s k i
and R. D . Le v in a (J. Appl. Chem. Russ., 1933, 6, 20—30).—Oleic acid when heated at 150° during 2—
3 hr. with 30% of A1C13 yields 61% of volatile pro
ducts, of which 40% has b.p. 60—150°, and contains 25-6% of unsaturated aliphatic (I), 13-7% of un
saturated cycZohexane (II), 17-8% of unsaturated cyc/opentane (III), 4-1% of aromatic (IV), 2-2% of saturated cydoliexano (V), 1-7% of saturated cyclo- pentane (VI), and 34-6% of paraffin (VII) hydro
carbons. The corresponding figures for the fraction, b.p. 150—200°, a re : (I) 35-2, (II) 9-9, (III) 10-4, (IV) S-l, (V) 3-1, (VI) 3-8, (VII) 29-5%, and for the fraction, b.p. 200:—250° : (I) 19-6, (II+ IV ) 19-6, (III) 20, (V) 4, (VI) 8-3, (VII) 28-5%. R. T.
O zonisation of oleic acid a n d lin se e d oil, a n d th e gaseo u s ozonisatio n p ro d u c ts. E. Br in e r, C. De n z ie r, and H. Paillard (Helv. Chim. Acta, 1933,16,800—807).—0 3 acts as an oxidation catalyst for linseed oil (I) at 60°, but not a t 20° or 100°, nor for oleic acid (II). The ozonide of (II) gives gases containing H2 33, C02 20, CH4 23-4, CO 4-6, and 02 2-5%, and those from the ozonide of (II) contain H2 55, CH4 14, C02 12-5, 02 1-0%, and unsaturated substances 0-5%. The formation of the ozonide of (II) is exothermic (+279 kg.-cal.). R. S. C.
E stérifica tio n . II. E stérifica tio n of olive oil a n d carboxylic acid s. R. Od a (J. Soc. Chem. Ind.
Japan, 1933, 36, 292—296b).—The esterification of olive oil and CH2C1-C02H is accelerated by a small amount of H 20 and by rise of temp, to 170°. W ith Ac20 , the esterification is not affected by addition of H20 . Esterification with BuOH, H3C20 4, and aromatic and OH-acids is also described. F. R. S.
E lasostearic a cid s. I I . P o ly m e risa tio n of th e elasostearic ac id s. E. Ro ss m a n n (Fettchem.
Umschau, 1933, 4 0 , 96—102, 117—123).—Polymeris
ation at < 300° does not proceed beyond the dimeric stage. The cjclomonoelceostearic acid (I), b.p. about 200°/4 mm. ( = “ elteolic a c id ” of Cloez, A., 1876, ii, 102), formed in variable amount during heating (or distillation) of a- and p-elacostearic acids, is charac
terised as -r\-2-butyl-A3:5-cyclohexadienyloctoic acid.
The corresponding Me ester is formed during the dis
tillation of a- or ¡3-Me elseostearate. These mono- cyclic isomerides are sol. in most org. solvents and give red or violet colorations with cone. H N 03 or with H2S 04 and EtOH. Besides (I), a dimeride, cyclodielccostearic acid, has been separated from tung oil th a t had been gelled and further heated at 290° for £ hr. A tung oil gel th a t has not been over
heated can be re-liquefied by heating to 350° ; similarly, on heating the polymerised Me esters obtained from such a gel, some depolymerisation occurs at the expense of the dimeride, and polymeric esters of p-elseostearic acid and of (I) are formed. The isomerism of elseostearic acid into (I) is irreversible.
I n strongly heated tung oil gels, further cycZopoly- merides are formed, which cannot be depolymerised by heat before the onset of excessive decomp.
E. L.
P o ly m e ris a tio n of th e m eth y l e s te rs of the h ig h e r u n s a tu ra te d fa tty ac id s. X II. S tru c tu re of th e in tra m o le c u la r re a c tio n p ro d u c ts of m eth y l clu p an o d o n ate. K . Kin o (Sci. Papers Inst. Phys.
Chem. Res. Tokyo, 1933, 2 1 , 63—68; cf. A., 1930, 1272).—Me clupanodonate at 290—300° in H2 during 20 min. affords a product, b.p. 214—221°/3-5 mm., which with 03 in CHC13 gives succinic acid and probably Cn H1802 (this vol., 145). J . L. D.
A lkalin e d eco m p o sitio n of a lip h a tic (3-hydroxy- ac id s. I I I . D isu b stitu te d p-lactic ac id s. D.
Iv a n o v (Bull. Soc. chim , 1933, [iv], 5 3 , 321—
323).—When heated with 20% KOH in H20 - E t0 H the disubstituted (3-OH-acids (cf. this vol., 157) decompose : 0H-CHR-CHArC02H — > R-CHO+
CH2Ar-C02H, quant, data being given. I f decomp, is effected in the presence of N H2OH, the oxime of the aldehyde is obtained, thus preventing further action
of KOH. J. W. B.
A lkylidene a cetate p y ru v a te s. A. Ktrrm ann
(Bull. Soc. chim., 1933, [iv], 53, 295—301).—The pro
ducts obtained by heating aldehydes with AcCOaH and Ac20 at 100° have the structure O Ac • CHR • O • CO Ac, and not 0Ac-CHR-CH2-C0-C02H as stated by Wohl and Maag (A., 1911, i, 13), since they contain no active H (Zerevitinov), do not form salts, and are readily hydrolysed to the parent aldehyde and acids;
no condensation occurs with AcCOaE t. Thus from the appropriate aldehydes are obtained ethylidene
(I), b.p. 9S°/11 mm. (semicarbazone, m.p. 179°;
j)-nitrophenylhydrazone, m.p. 195°); propylidene (II), b.p. 108— 109°/16 mm. (semicarbazone, m.p. 168°;
l>-nitrophenylhydrazone, m.p. 199°); bulylidene, b.p.
114°/10 mm. (semicarbazone, m.p. 132°; p -nitro- phenylhydrazone, m.p. 177°); heptylidene, b.p. 145°/10 mm. (semicarbazone, m.p. 75°); and allylidene, b.p.
108—109°/19 mm., acetate pyruvate, accompanied by
3h
the corresponding diacetates (butylidene diacetate, b.p. 86°/12 mm.). The hydrolysis of (I) and (II) in 1% aq. solution a t 25°, studied kinetically by (a) determination of the GO group by N aH S03 titration, and (b) a conductometric method, is complete in a
few days. J . W. B.
C hem ical a n d e lectro ch em ical o x id atio n of lasvulic an d s-keto-n-octoic ac id s. F . Fic h t e r
and S. Ltjrie (Helv. Chim. Acta, 1933, 1 6 , 885—
891).—a-Angelicalactone, y-chlorovalerolactonc, and lajvulyl chloride with H202 or B a02 give ketoper-oxides. “ Acetyl-lamilic acid,” OAc-CMe<q^ 2 ^ q 2-and H202 (2 mols.) give the keto-peroxide, (C5H80 4)2.
K kevulatewith K2S20 8givesC02(l-24mol.), COMeEt, and resins. s-Keto-n-octoic acid (I), m.p. 52°, b.p.
175—177°/15 mm. (modified prep.), + C GHg, m.p.
78—S2° (formed only in presence of Ac20), gives by electrolytic oxidation C02 (75%) and ytx-tetradecadione, m.p. 72—74°, b.p. 125°/4 mm. [disemicarbazone, m.p.
181° (decomp.)], and with K ^ O o C02, COEtBua (semicarbazone, m.p. 99—100°), and resins; the E t ester, b.p. 125—127°/12 mm., and H202 give the Tceto-peroxide, C2pH360 8. (I) and S0C12 give a small
181° (decomp.)], and with K ^ O o C02, COEtBua (semicarbazone, m.p. 99—100°), and resins; the E t ester, b.p. 125—127°/12 mm., and H202 give the Tceto-peroxide, C2pH360 8. (I) and S0C12 give a small