m<coS^c:N'co‘NHM e’ (L)
X. The conversion of the active diphcnylsuccinic anhydrides into the corresponding substituted amic
314 B R IT IS H CH EM ICA L A BSTRACTS.---- A.
sodiocyanoacetate in ethyl-alcoholic solution gave the monohydrate of diethyl ixy-dici/ano-$-benzylglutaconate, C02Efc<!(CN):C(eH^Ph)-CH(CN)-C02E<i> 'in. p. 131°, whilst methyl sodiocyanoacetate yielded the morio- hydrdte of methyl ethyl txy-dicyano-p-benzylglutacojiaie, m. p. about 115°. An isomeride of the last-named, m. p.
about 115°, was produced by the condensation of methyl a-cyano-p-cthoxy-y-phenylcrotonate and ethyl sodiocyanoacetate. In the above monohydrates, it is supposed that a cyano-group is hydrated to a carb-
amyl group. A. I. V o g el.
P h en ylsu ccinic acid series. IX. R esolu tion of r-diphenylsuccin-x- and -[3-naphthylamic acid s into th eir op tical antipodes. X. R a cem is- ation phenom ena observed during th e action of w a ter and b a ses on optically active diphenyl- su ccin ic anhydrides. H. W ren and E. W rig h t (J.C.S., 1929, 136—138, 13S—141).—IX. r-Diphenyl- succin-a-naphihylamic acid, m. p. 217—219° (decomp.) (obtained by interaction of equivalent quantities of r-diphenylsuccinic anhydride and a-naphthylamine), was resolved into its optical antipodes by quinine in alcoholic solution, the salt of the d-acid being the more sparingly soluble. a-Diphenylsuccin-cc-naphthylamic acid has m. p. 206—207“, [#jg +205-S° in acetone.
l-Dipkcnylsuccin-z-naphtkylainic acid, m. p. 206—207°, [oc]jJ —206-6° in acetone, was separated by means of cinchonidine in alcohol from the crude Z-acid obtained during resolution of the r-acid by quinine, a-Di- phenylsuccin-oi-naphthil, m. p. 145°, [a]1,? +139-2° in acetone, [a]‘J -¡-123-3° in chloroform (prepared by action of 3% ethyl-alcoholic hydrogen chloride on the corresponding acid), was readily racemised by alkali.
*-Diphenylsuccin-$-naphthylaniic acid, m. p. 188°, Mb'* +386-9° in acetone, was obtained by resolution of the corresponding r-acid, m. p. 2 0 1—2 0 2°, by quinine in alcoholic solution. a-Diphenylsvccin-
$-naphthil, m. p. 17S—179°, [a]g +104-9° in acetone, is described.
The marked diminution in specific rotation oc
casioned by conversion of the acids into the corre
sponding substituted imides and the irregularity of influence of aryl groups ((3-naphthyl, phenyl, p-tolyl, a-naphthyl) on the specific rotations of the substituted diphenylsuceinamie acids and diphenylsuccinimides are pointed out.
X. The conversion of the active diphcnylsuccinic anhydrides into the corresponding substituted amic acids by aniline, p-toluidine, a- or S-naphthylamine in cold benzene solution was not accompanied by any marked racemisation. The optical activity of the diphcnylsuccinic acids which resulted from the action of water on the active anhydrides was found to be greatly influenced by the presence of a mutual solvent; thus from aqueous acetic acid, aqueous ether, aqueous acetone, and aqueous pyridine, acids were derived with the respective specific rotations -3 6 4 -7 ° (from Z-anhydride), +232-7°, +116-7°, and +22-4° (from (Z-anhydride) whereas the homogeneous acids had [a]D +383°. The partly racemised products always contained some mesodiphenylsuccinie acid.
This was true also for the mixtures derived from r-diphenylsuccinic acid, although, in certain cases, the
proportion of ?>i&so-acid obtained from the /--anhydride greatly exceeded that derived from the active anhydr
ides under identical conditions. The authors con
sider, therefore, that even in dilute solution the /•-compound does not behave as a simple mixture of fZ- and Z-forms. \-Diphenylsuccin-(3-naphthylamicacid, m. p. 188— 18S-5°, [a]*D7'5 -3S 8-2°, is described.
R. J. W. Le F&vee. S y n th e sis of ¡\soopianic acid. S. N. Chakra- v a r t i and W. H. P erkin , jun. (J.C.S., 1929, 193—
196).—5-Nitro-2 : 3-dimethoxycinnamic acid (niethyl ester, m. p. 154— 155°) is obtained either by nitrating 2 : 3-dimethoxycimiamic acid or by con
densing malonic acid and o-nitro-2 : 3-dimetlioxy- benzaldeliyde in the presence of piperidine. It is smoothly reduced by ferrous sulphate and ammonia to o-amino-2 :3-dimethoxycinnamic acid, m. p. 233°
(decomp.), which is converted through the diazo- compound into o-cya>w-2 : 3-dimethoxycinnamic acid, m. p. 251°. The cyano-acid is oxidised by potassium permanganate in presence of benzene to 5-cyano-2 :3- dimethoxybenzaldehyde, m. p. 135°, which when heated with hydrochloric acid is converted into /soopianic
acid. R. J. W. L e Eevre.
A ld eh ydes fro m acetylenic carbinols. IV.
3 - M eth yl - 6 - isopropylci/cJohexylideneacetalde- hyde. H. Rupe and A. Gassmann (Helv. Chim. Acta,
1929, 12, 193—204).—The action of acetylene on iZ-menthone in presence of benzene and sodamide yields 3 - methyl - 6 - isopropyl -1 - ethinylcyclohexan-1 - d, b. p. 101-5— 102-5°/12-5 m m , d f 0-9257, [ajg +5-08°
(silver derivative), which when heated with 5 parts of 71% formic acid changes to 3-methyl-6-isopropyl- cydohexylideneacetaldehyde (I), b. p. lll°/1 2 -5 mm., d f 0-9115, [ocjfj +82-9° (semicarbazone, m. p. 146—
147°), the oxime, m. p. 101°, [a]ft +103-09° in benzene, of which is hydrolysed by aqueous oxalic acid, form
ing menthone. Magnesium ethyl bromide converts I into a mixture of 3-methyl-6-isopropylcyc\ohexylet}iyl- carbinol, b. p. 125°/12 mm., and a-3-methyl-G-isopropyl- cyclohexylidene-W-butene, C]0H jg:CH-CH:CHMe, b. p.
99°/12 mm. Oxidation of I with alkaline potassium permanganate yields ¡3-methyladipic and S-wobutyryl- p-methyl-M-valeric acids (semicarbazone, m. p. 152°), whilst reduction with hydrogen and a nickel catalyst gives 3-7nethyl-G-hoj)ropylcyc\ohexylacetaldehyde, b. p.
106— 107°/12 mm., d f 0-9032, n“ 1-46111, OJS -51-28°, purified through its semicarbazone, decomp.
222° (oxime, in. p. 102°, [ajg +34-11°), together with the corresponding alcohol. H. B urton.
A rylidene 2 : 4-d iph en ylsem icarb azon es from aldehydephenylhydrazones and phenylcarb- im id e. G. M i n u n n i and S. D ’U r s o [with S.
G u g l i e u i i n o , P. S a l a n i t r o , D . T o r r i s i , and 31.
V a s t a ] (Gazzetta, 192S, 5 8 , SOS—820).—The inter
action of benzaldehydephenylhydrazone and phenyl- carbimide to give benzaldehvde-2 : 4-diphenylsemi- carbazonc, GHPhiN-NPh-CO-XHPh (cf. Busch and Walter, A., 1903, i, 522), proceeds readily in benzene solution. In hot solution,- the semicarbazone (new m. p. 174— 175°) and some s-diphenylcarbamide are obtained; in the cold the former is produced more slowly', but in better yield, together with two yellow secondary products, one, a mixture, having m.
p-175—188°, and the other ra. p. 194— 196°. The semicarbazono is readily reduced to a-diphenylcarb- amide, with a substance, m, 116— 118°; when treated with phenylhydrazine it yields benzald.ehyde- phenylhydrazone and other products.
o- and »i-Nitrobenzaldehydephenylhydrazones do not react satisfactorily in benzene; with phenyl- carbimide alone the corresponding semicarbazones are formed, m. p. 190— 192° (decomp.) and 206—208°
(decomp.), respectively, identified by reduction to the carbamides. The p-isomeride reacts very slowly in benzene, and more rapidly without solvent, giving the corresponding semicarbazone, m. p. 199—201°;
pipcronalphenylhydrazone gives, in cold benzene, piperonal-2 : 4-diphcnylse7nicarbazonc, ra. p. 169—
169-5° (decomp.). E. W . Wig n a l l. Action of b rom in e on so m e h ydrazones. II.
R. Ciusa and P. Mega (Gazzetta, 1928, 58, 831—
840).—The compound described by Ciusa and Vec- chiotti (A., 1916, i, 437) as p-bromobenzaldehyde-2:4-rlibromophenylhydrazone is found to be <a-bromo- benzaldehyde-2 : 4-dibromophenylhydrazone, since its aliphatic bromine atom will react with aniline, or can be determined by titration after boiling with sodium acetate in alcohol; the formation of jj-bromo- benzoic acid during oxidation must be attributed to bromination during the oxidation process, since benzoic acid is also formed. Similarly, anisaldehyde gives rise to co-bromoanisaMehyde-2 : 4-dibromophenyl- bjdrazone, m. p. 135°, and benzaldehyde-p-nitro- phenylhydrazone to benzaldeliyde-2-bromoA-nitro- phenylhydrazone, m. p. 171°; in each of these com
pounds the bromine may be determined as above, the second giving, with sodium acetate and acetic acid, the O-acetyl derivative of N -benzoyl-^'-2-bromo- imlrophenylhydrazim. The benzoyl group of the last compound may be removed by boiling with hydrochloric acid and alcohol, giving rise to 2 -bromo-i-nitrophenylhydrazine, m. p. 143° (benzaldehyde-2- bromo-4-nitrophenylhydrazone, m. p. 166°). w-Nitro- bcnzaldehyde-jj'-nitrophenylhydrazone is brominated to a-bromo-m-nitrobenzaldehyde-2-bromo-4;-nitropheiiyl- hydrazone, m. p. 212—213°, from which the above hydrazine may again be prepared. Finally, the same hydrazine is synthesised by brominating the benzoyl derivative of p-nitroaniline, hydrolysing the product, and diazotising and reducing the 2-bromo-4-nitro- aniline thus obtained. E. W. WlGNALL.
Trichloro- and tetrab rom o-nitrobenzalde- hydes, h exach loro- and octabrom o-in digotin s.
G. v a n d e B u n t (Rec. trav. chim., 1929, 4 8 , 121—
146).—3 : 4 : o-Tribromocinnamic acid, m. p. 215—
216°, and its 2-ftifro-derivatrve, m. p. 264— 265° (de
comp.), are obtained from the corresponding benz- aldehydes by the Perkin reaction. Treatment of both these acids with warm absolute nitric acid yields 3 : 4 : o-tribromo-2-a>-dinitrostyrene, m. p. 228—
230° (decomp.), which could not be reduced success
fully to tribromoindole (cf. van der Lee, A., 1926, 179). When 3 : 4 : 5-tribromobenzaldehyde is treated with a mixture of absolute nitric and concentrated sulphuric acids at 10 0°, 3 : 4 : 5-tribromo-2 : 6-dinitro- benzoic acid, m. p. 245—-248° (decomp.), is obtained.
When crystallised from boiling alcohol this acid elimin
ates carbon dioxide, yielding 4 : 5 : 6-tribromo-l : 3- dinitrobenzene. Chlorination of p-aminobcnzalde- hyde hydrochloride in 75% acetic acid solution gives 3 : b-dichloroA-aminobenwldehyde, m. p. 144° [phenyl- hydrazone, m. p. 156— 157°; p-nitropkenylhydrazone, m. p. 288— 289° (decomp.); semicarbazone, m. p.
248—250° (decomp.); semioxarnazone, m. p. 269—
270°; azine, m. p. 285—286°], chlorinated further to 2 : 4 :6-trichloroaniline, and converted by the Sandmeyer reaction into 3 : 4 : Ci-trichlorobenzaldehyde, m. p. 90—91° [phenylhydrazone, m. p. 147°; Tp-nilro- phenijlhydrazone, m. p. 342° (decomp.); semicarbazone, m. p. 252—254°, resolidifying with m. p. 284°;
semioxarnazone, ra. p. 297—298° (decomp.); azine, m. p. 289—289-5°]. Nitration of this with cold absolute nitric acid yields 3 : 4 : b-tricldoro-2-nitro- benzaldeliyde (I), ra. p. 118-5—119° {phenylhydrazone, yellow and red, m. p. 229° (decomp.), modifications;
p-nilrophenylhydrazone, m. p. 293—294° (decomp.);
semicarbazone, m. p. 278—279° (decomp.); semi- oxamazone, m. p. 303—304° (decomp.); azine, m. p.
287—288° (decomp.)], oxidised by alkaline potassium permanganate to 3 : 4 : 5 -trichloro- 2 -nitrobenzoic acid, m. p. 181— 181-5°, and converted by absolute nitric and concentrated sulphuric acids into 3 : 4 : 5 - trichloro-2 : G-dinitrobenzoic acid, m. p. 219—221-5°.
This acid also eliminates carbon dioxide in boiling alcoholic solution, forming 4 : 5 : 6-trichloro-l : 3-di
nitrobenzene. 3 : 4 : 5-Triehlorobenzoic acid has m. p.
210—210-5° (lit. 203°).
Nitration of 2 : 3 : 4 : 5-tetrabromobenzaldchyde with a mixture of absolute nitric and concentrated sulphuric acids at 50—60° affords 3 : 4 : 5 : 6-tetra- bromo-2-nitrobenzaldehyde (II), m. p. 225—227° (de
comp.) after previous darkening and sintering, whilst oxidation with potassium permanganate gives 2 : 3 : 4 : 5-tetrabromobenzoic acid, m. p. 234° (slight decomp.). This last compound is nitrated to 3 : 4 : 5 : G-tetrabromo-2-nilrobenzoic acid, m. p. 238—
240° (decomp.), which does not lose carbon dioxide when its alcoholic solution is boiled. 2 : 4 -Dichloro-3 : 5-dibromobenzaldehyde, m. p. 110— 111°, prepared by the Sandmeyer reaction from the 2-chloro-4-amino- compound, is nitrated to 4 : (i-dichloro-3 : 5-dibromo-2-nitrobenzaldehyde (III), m. p. 19S— 199°.
Conversion of the halogeno-2-nitrobenzaldehydes into the polyhalogenated indigotins is effected by warming with acetone and sodium hydroxide solution. Thus, 5 : 5': 6 : 6' : 7 : 7'-hexachloro-, 4 : 4' : 5 : 5' : 6 : 6': 7 : 7'-octabromo-, and 4 :4' : 6 : 6'- letrachloro-5 : 5' : 7 : 1'-tetrabromo-indigotins are ob
tained from I, II, and III, respectively.
H . Bu r t o n. P ro d u cts w ith an odour of m u sk and carbon rin g s con tain in g a la rg e n um ber of lin k in g s. L.
R u z i c k a (Bull. Soc. chim., 1928, [iv], 4 3 , 1145—
1173).—A lecture surveying recent work on the constitution of muscone and civetone, and the syn
thesis and behaviour of carbon ring systems con
taining a large number of linkings (cf. A., 1926, 614, 615, 726, 727, 1142; 1927, 1189; 1928, 642, 8S7).
In further elucidation of the constitution of muscone, it is shown that neither the ¿-p-methyltridecane-av- dicarboxylic acid, ra. p. 69°, obtained by condensation with benzaldehyde and treatment of the
benzylidene-316 B R IT IS H CH EM ICA L ABSTRA CTS.— A.
muscone with ozone and chromic acid nor its methyl ether can be racemised, and the inactivity of the mixture of two acids, C16H30O4, obtained by oxidation of muscone is consequently due to mutual compens
ation of the two acids. Muscone is thus regarded as /-2-methylcyc/opentadecanone (cf. A., 1926, 1143).
dl-2-Melhyltridecane-av-dicarboxylic acid obtained by synthesis has m. p. 76° (anilide, m. p. 133°), but shows no depression of in. p. when mixed with the degradation product of muscone. The molten acid on solidifying has m. p. 10° lower. Oxidation of exaltone with persulphuric acid affords the lactone of o-hydroxypentadecoic acid (exaltolide).
R. Br ig h t m a n. 3 : 5-D iphenylci/ciohexenone. A. D. Pe t r o v (J.
Russ. Phys. Chem. Soc., 1928, 60 1441— 1445).—
The reactions of 3 : 5-diphenylci/c?ohexenone with hydrogenating and dehydrogenating agents have been investigated. By hydrogenating the ketone at 240°/50 atm. in presence of nickel oxide as catalyst,
1 : 3-dicyc/ohexylcyc/ohexane was obtained in two isomeric forms, m. p. 66° and b. p. 202°/14 mm., respectively. By heating the ketone at 300° in presence of platinised charcoal, 3 : 5-diphenylphenol, m. p. SS—92°, was obtained, whilst reduction with absolute alcohol and metallic sodium gave a 50% yield of 3 : 5-diphenylcyc/ohexanol, m. p. 127°, easily oxidised to 3 : 5-diphenylci/c/ohexanone, m. p. 139—
140". M. Zvegintzov.
U s e of zirconiu m tetrachlorid e in organic sy n th esis. P. Kr is h n a m u r t i (J. Madras Univ.,
192S, [Reprint], 5 pages).—Zirconium tetrachloride may be used in place of aluminium chloride in condensations involving (a) elimination of hydrogen chloride (preparation of acetophenone, benzophenone, anisaldehyde, and diphenylmethane), (6) elimination of water (phenolphthalein), (c) elimination of alkyl halide (demethylation of anisole), and (d) con
densations of phenylcarbimide with benzene and its derivatives. It is more easy to handle and more readily preserved than the older reagent.
J. W. Ba k e r. R eduction of phenyl n aphthyl k eton es b y th e b in ary sy stem , m a g n e siu m -m a g n e siu m iodide.
W. E. Ba c h m a n n and R. V. Sh a n k l a n d (J. Amer.
Chem. Soc., 1929, 51, 306—309).—Phenyl a-naphthyl ketone is reduced by the above system to an equili
brium mixture (I) of the green Iceiyl -CPh(C10H-)-OMgI, and its dimeride, which is converted by water into
■x$-diphenyl-i'i-di-x-naphihylethylene glycol (II), m. p.
220° (decomp.). When heated with acetyl chloride this is almost quantitatively converted into benzoyl- phenyldi-oL-naphthybnethane, m. p. 216—217°, the naphthyl group wandering in preference to the phenyl.
The second a5-diphenyl-:i3-di-a-naphthylethylene glycol, m. p. 15S° (Cohen, A., 1919, i, 124, 210), may
be transformed into II by treatment with a Grignard reagent, when the radical formed by dissociation of the resulting iodomagnesium glyeoloxide changes into I and is then decomposed by water. The second isomeride is converted by acetyl chloride into a sub-stance, C^H^O, m. p. 232% which is also formed from phenyl i-naphthyl ketone, zinc, and acetyl chloride and, unlike most pinacolins, is only slightly
attacked by boiling alcoholic potassium hydroxide.
Phenyl ¡3-naphthyl ketone is reduced by the binary system, or by zinc and acetic acid to <x$-diphenyl-y.§.
di-^-naphthylelhylene glycol, m. p. 175°, which under
goes naphthyl wandering in presence of acetyl chloride, giving benzoylphenyldi-fi-naphthylmethane, in. p. 181—
182°. H. E. F. N otton.
O rganic com pou n ds of sulphur. XI. Com
p a rison of th e tendency of p o ly m eric thioketones tow ard s d issociation w ith th a t oi th e corre
sp on d in g com pounds of th e ethane series. A.
Sc h o n b e r g (Ber., 1929, 62, [J5], 195— 1 9 9 ; cf. A., 1928, 896, 1375).—Replacement of the phenyl groups of hexaphenylethane by hydrogen or methyl causes a stabilisation of the ethane Unking; the same effect is observed when the phenyl groups of the hypo
thetical hexaphenyltrithian arc substituted by hydro
gen or methyl. In both series the effect of hydrogen is more marked than that of methyl. If two phenyl groups of triphenj’lmethyl are replaced by the sub
stituted methylene residue, radicals are obtained which cannot exist “ free ” ; this is also the case with thioketones. Complete or partial replacement of the phenyl groups of hexaphenylethane by the radicals, p-0Me-CGH4- , Ph-C6H4- , C6H4< ° > C GH4, o-OMe-C6H4- , NMe.2-CGH4- , C6H4< ® > C6H4, leads to compounds with a tendency towards dissociation similar to or greater than that of hexaphenylethane itself. As expected, replacement of the phenyl groups of thiobenzophenone by these radicals leads to compounds which, like thiobenzophenone, do not tend to polymerise. In the ethane series, the sub
stituted vinyl group behaves similarly to the phenyl group; this is also the case with thioketones. If one or two phenyl groups of thiobenzophenone are replaced by substituted vinyl groups, thioketones are produced which do not tend to polymerise. On the other hand, attempts to convert eyefohexanone into the corresponding thioketone give trithiocycZo- hexanone, which does not become depolymerised when heated. The close analogy can be explained only by the hypothesis that the dissociation of ethanes and polymeric thioketones is produced and regulated by the same causes. H. Wren.
B en zoin anil anilide and benzoin-p-tolil-p- tolu idid e as am m ono-b en zoin acetals. H. H.
S tra in (J. Amer. Chem. Soc., 1929, 51, 269—273).—
The formulation of these compounds as ammono- acetals of benzoin (cf. A.. 1928, 1134) is in accordance with the following reactions. Benzoinanilanilide is hydrolysed by boiling alcoholic hydrochloric acid to benzoinanilide and aniline, and benzoin-y-tolil- /j-to lu id id e to benzoin-p-toluidide and p-toluidine.
They are nitrised by iodine in liquid ammonia, or in benzene by a current of air, to the ammono-benzils, benzildianil and benzildi-p-tolil. Ammonolysis by liquid ammonia at 130° for 10 hrs. affords a small y ie ld of te tra p h e n y lp y T a z in e , m. p. 252°. The mechanism proposed by Bischler (A.. 1S93, i, 519) for the formation of 2 : 3-diphenylindole from benzoin and aniline is confirmed by the almost quantitative conversion of benzoinanilanilide into this compound in benzene in presence of hydrogen chloride at ISO—200°.
B enzoin-p-tolil-p-toluidide sim ila rly y ie ld s 2 : 3-di- phenyl-5-m ethj'lindole. H. E. F. N o t t o n .
Persistence of op tical activity d u rin g elim in ation of w ater from optically active g ly co ls. II.
Production of optically active k eton es b y se m i- pinacolinic transform ation . R . R o g e r and A.
M cK enzie (Ber., 1929, 62, [B\, 272—284).—Ethyl Z-mandelate is converted by magnesium benzyl chloride into d -l-h yd ro x y-2 -p h en yl-\ : \-dibenzyl- ethanol, m. p. 136— 137°, [a]'D4 +80-3° in ethyl alcohol, [a]1,? +62-3° in chloroform, [a]g +96-8° in acetone. The glycol is converted by concentrated sulphuric acid into r-ay-diphenyl-y-benzylacetone, m. p. 74-5—75-5°; this product is also obtained when the action is effected by boiling, dilute sulphuric acid, but is then accompanied by d-u.y-diphenyl-y-be.nzyl- acetone, m. p. 77—78°, [a]^, - f 208° in benzene, [a ] ^ +202° in chloroform (among other values), and l-phenyl-2-benzylindene, m. p. 10 0—1 0 2°, which appears to become isomerised to a product, m. p.
95—96°, when crystallised repeatedly from ethyl alcohol. The optically active ketone is racemised by concentrated sulphuric acid or by alcoholic potassium hydroxide; the latter change appears to be uni- molecular. (Z-Methykleoxy benzoin is likewise racem
ised by concentrated sulphuric acid. The first phase of the elimination of water from the cZ-glycol appears to consist of a semipinacolinic transformation yielding the iZ-ketone which, after transitory production of the sulphuric ester of the corresponding substituted vinyl alcohol, passes into the optically inactive ketone. The observation that triphenylacetaldehyde is converted by acids into phenyldeoxybenzoin suggests the possibility that aldehydes are intermediate products in the transformation of glycols to ketones in acid media (cf. Danilov and Venus-Danilova, A., 1927,460;
Tifleneau and Orekhov, A., 1926, 171, 172). In the present instance and that recorded by McKenzie and Dennler (A., 1927, 243), the intermediate formation of the corresponding aldehyde is impossible, since the compound would be optically inactive owing to the absence of an asymmetric carbon atom and thus could not give rise to an optically active ketone. The preservation of optical activity during the formation of the cZ-ketone has its parallel in the elimination of the amino-group from optically active amino-alcohols (cf.
McKenzie, Roger, and Wills, A., 1926, 610). I t is suggested that in this transformation an electric charge plays the part of a group, so that the dissymmetry of the molecule remains undisturbed.
/-Benzoin is transformed by magnesium benzyl chloride into l-benzylhydrobenzoin (\-fi-hydroxy-a.fi-di- phenyl-a.-be7izylethanol), m. p. 183— 184-5°, [a ] ^
—61° in chloroform, [ a ] ^ —2 2° in acetone (among other values), which is converted by protracted action of boiling acetyl chloride into 2 : 3-diphenylindene, m. p. 176—177°, isomerised by alcoholic potassium hydroxide to 1 : 2-diphenylindene, m. p. 107— 108°;
the last-mentioned compound is not affected by the protracted action of boiling acetyl chloride.
H. W r e n . E lim ination of th e am in o-grou p fro m tertiary am ino-alcohols. V. S em ip in acolin ic d e-am in - ation and W alden inversion . A. M c K e n z i e and
A. K. M i l l s (Ber., 1929, 6 2 , [B], 284— 2 8 8 ; cf. A.,
1927, 457).—Ethyl Z-phenylaminoacetate hydro
chloride is converted by magnesium benzyl chloridc into d-fi-amino-pi-phenyl-xx-dibenzyldhanol,
(CH2Ph)2C(OH)-CHPh-NH2, m. p. 144— 145°, [ a f t + 5 9 -2 ° in chloroform, which is transformed by sodium nitrite in dilute acetic acid solution into a mixture of (Z-ocy-diphenyl-y-benzylacetone, m. p.
77-5— 78°, [a]jj -)-283° in benzene, and cZ-[3-hydroxy- (3-diphenyl-aa-dibenzylethanol, m. p. 136— 137°, [a]'r?
- f 8 1 ° in ethyl alcohol, identical with the product obtained by Roger and McKenzie (preceding abstract).
A further instance in favour of the semipinacolinic transformation and againstthe intermediatcproduction of an aldehyde is afforded, since phenyldibenzyl- acetaldehyde could not yield an optically activc
ketone. ' ~ H. W r e n .
E lim in a tion of the am ino-group from tertiary am in o-alcoh ols. VI. A ction of n itrou s acid on th e am in o-alcoh ols fro m l-phenylam inoacetic acid. A. M c K e n z i e and (Miss) M. S. L e s s l i e (Ber., 1929, 6 2 , [-BJ, 288—295; cf. A., 1927, 457).—Ethyl Z-mandelate is converted by a slight cxcess of magnes
ium ethyl bromide into 1-°,-hydroxy-fi-pJie?iyl-o.y.-di- ethyleilianol, m. p. 48—48-5°, [a|D —26° in ethyl alcohol, [a]D —32° in acetone. From ethyl Z-phenyl- aminoacetate hydrochloride and magnesium ethyl bromide, \-$-amino-$-phenyl-'xa.-dicthylcthanol hydro
chloride, m. p. 225—226°, [a]1,; —2S-7° in water, [a]1,?
— 17° in ethyl alcohol, is derived. The amino-alcohol is converted by nitrous acid into a mixture of r-fi-hydr- oxy-P-phenyl-aa-diethylethanol, m. p. 88—89°, and a substance which is dextrorotatory in ethyl alcohol;
the optical activity cannot be ascribed to the ketone, E t’CO-CHPhEt, formed by semipinacolinic deamin
ation, since it persists unchanged after addition of alcoholic potassium hydroxide.
Ethyl r-phenylaminoacetate hydrochloride is trans
formed by magnesium methyl iodide into v-fi-amino- fi-jdienyl-xz-dimethylethanol, m. p. 82-5—83-5° (hydro
chloride, m. p. 173— 175°), from which methyl a-phenylethyl ketone is obtained by means of nitrous acid. The dissimilar course of the cliangc in the cases of the dimethyl and diethyl derivatives is attributed to the superior saturating capacity of the methyl group, which causes a less firm union of hydroxyl to carbon in the methyl compound. Somewhat unexpectedly, T-fi-am ino-$-phenyl-a.a.-di-n-propylethanolhydrochloride, m. p. 2 1 0—2 1 2° (from ethyl r-phenylaminoacetate hydrochloride and magnesium «-propyl bromide), is converted by nitrous acid into r-3-hydroxy-(3-phenyl- aa-di-n-propylethanol, m. p. 100— 102°. Ethyl (Z-mandelate and magnesium »¡.-prop3Tl bromide afford d-$-hydroxy-$-phenyl-?.x-di-n-p)ropyleUianol, m. p. 67—
68°, [a]p +26-4° in ethyl alcohol. l-[l-Amino-
$-phcnyl-rx.a.-di-\\-propylethanol, m. p. 12 0—1 2 1°, [a]]J
—93-4° in ethyl alcohol (from ethyl Z-phenylamino- acetate hydrochloride and magnesium w-propyl bromide), is transformed by nitrous acid into a mixture of r- and(Z-P-hydroxy-3-phenyl-aa-<fi-n-propyl- ethanol; the presence of the corresponding optically active ketone is excluded, since the activity of the product remains unchanged after treatment with alcoholic potassium hydroxide. H. W r e n .