santonin. G. Ba n c h i (Gazzetta, 1928, 58, 77—
95).—Largely a sum m ary of th e work th a t has been done on refractivity of organic substances and its application to the structure of molecules. The various formulas proposed for santonin are discussed. The refractive indices and densities of solutions of santonin and of its derivatives mentioned above in chloroform have been determined. I t is stated th a t th e results agree best with the structural formuloe for santonin p u t forward by Francesconi and by Angelo and Marini.
O. J. Wa l k e r. M em b ran es of sp ores and pollen. I. Lyco- podiuhi clavatum, L. F. Z e ts c h e and K. H u g g l e r (Annalen, 1928, 461, 89—108).—E xtraction of Lycopodium clavatum spores with acetic acid does not remove hydrocaffeic acid or albumins (cf. A., 1927, 767); these are removed, however, b y a subsequent extraction with hydrochloric acid or alkali. A ltern
atively, they m ay be removed in one stage by extraction with alkali. The membrane remaining (25% of the original spores) contains no lignin, and when treated w ith diacetylorthonitric acid gives pure cellulose (about 2% of the crude spores). By boiling th e crude spores with 5% alkali and extracting with alcohol and w ater (both boiling) a residue corre
sponding with 23—25% of the spores is obtained.
This after prolonged digestion with hydrochloric acid, followed by boiling w ith 5% alkali, affords a new brownish-yellow substance, sporonin, (C,0H 16O0)j.
This appears to be a chemical individual, since the reactions which can be effected w ith it are reproducible with great exactness. Sporonin contains 1-26%
OMe and forms about 21% of the crude spores. I t is insoluble in all common solvents, contains neither carbonyl nor carboxyl groups, and is very stable tow ards m ineral acids, alkalis, and heat, beginning to decompose first a t 300°, W hen heated in glycerol w ith potassium hydroxide, it affords ankydrosporonin, C90H 132O31. Bromine converts sporonin in cold carbon tetrachloride into bromosporonin I, whilst free bromine gives bromosporonin II. These, unlike sporonin, are not readily attacked by nitric acid.
Bromosporonin I is converted by cold alkali into bromosporonin II I, the la tte r being brom inated in carbon tetrachloride to bromosporonin IV. Hydrogen peroxide oxidises sporonin in glacial acetic acid solution to oxidosporonin, CgoH 1(10 31, or C?0H 148O31.
Boiling acetic anhydride converts sporonin into a compound containing 13% Ac, which, however, on hydrolysis gives a substance other th an sporonin.
M ethjd sulphate and alkali transform sporonin into a substance containing 2-2% OMe. E. E. T u r n e r .
P ectin su b sta n ces. I l l —VII. K . Sm o l e ń s k i
and W . We o s t o w s k a (Rocz. Chem., 1927, 7, 591—
692).—II I. The composition of beetroot pectin is given, and of a num ber of galacturonides and arabans,
ORGANIC) C H E M ISTR Y . 525 extracted by various m ethods from pectin. These
substances contain various proportions of protein, liexuronic acids, galactoside and galacturonide groups, araban, galactan, methoxy- and acetoxy-groups, and mineral m atter, the galactan fraction of th e extract rising as more energetic methods of extraction are applied.
IV. On acid hydrolysis of galacturonides and araban, the acetic acid is first eliminated, then m ethyl alcohol, then araban and galactan, and finally galact
uronide groups. Very energetic hydrolysis yields a strongly-reducing polymeride of galacturonic anhydride, (C6H 8O0),„ [a]D +216°, insoluble in 75% alcohol, not possessing acetoxy- and methoxy-groups, free from galactan, and containing more th an 90% of galact
uronic acid. Among the products of hydrolysis were found galactose and arabinose, the la tte r originating mainly from arabans, which p a rt from then' arabinose groups far more readily th an do galacturonides.
V. Alkaline hydrolysis eliminates acetic acid and m ethyl alcohol, yielding sodium pectinate, containing galacturonic acid, araban, and galactan in th e same proportions as the original galacturonide. Sodium pectinate, on acidification, loses its araban and galactan groups; thus warming for 4 hrs. w ith sulphuric acid yields poly galacturonic acid, (C6H 80 6),„
[a]D +250° {methyl ester, [a]D +228°), containing more than 90% of galacturonic acid, and free from galactan.
This differs from th e above-mentioned potymeride of galacturonic anhydride in its smaller solubility in water, in no t reducing Fehling’s solution, and in optical rotation.
VI. From the final products of the hydrolysis of galacturonides and araban, a-galacturonic acid hydrate, poH io ° 7.H 20. m - P- 110—112°, [a]D +49-9°, was isolated. This has a reducing power of 80% of th a t of galactose, and on oxidation w ith nitric acid yields 85% of the quan tity of mucic acid given by galactose.
F urther hydrolytic products are acetic acid amounting to 11-5% of simple and 5—5-5% of compound galacturonide, m ethyl alcohol, in q u antity correspond
ing with 5% of compound and 7% of simple galact
uronide, a small quantity of glyoxylic acid, rf-galact- ose, and Z-arabinose, the last-nam ed being the sole product of the acid hydrolysis of arabans. Dextrose and glycuronic acid are no t found.
VII. The following are the probable constituents of beet pectin : arabano-galactano-galaduronidc, a poly
meride of the calcium magnesium salt of the mono- methyl ester of arabo-galacto-acetyldigalacturonic -acid, (C2fSH380 22),i; araban-a, (C5H 80 4)n, easily dis
integrated by acid hydrolysis; araban-b, difficultly hydrolysed by acids; a degradation product of the first-mentioned su b stan ce; simple galacturonide, which is a polymeride of the calcium magnesium salt of the methyl ester of acetyldigalacturonic acid, (C15H j0O13),„
and finally galactan, (C6H 10O5)„. Alkaline hydrolysis of the arabano-galactano-galacturonide yields pectinic acid, {[C5H |O 4-CO2H ]2-(CGH 10O5)-(C5H 8O4)}„, a polymericie of arabo-galacto-digalacturonic acid, (L,3H310 21)(1j whilst alkaline hydrolysis of the simpler galacturonide or acid hydrolysis of pectinic acids yields polygalacturonic acid, a polymeride of digalacturonic acid, [(C5H ;0 4-C02H )2]u, or (C12H l 0O12)„.
R . Tr u s z k o w s k i.
O xidation of reactive m eth y len e grou p s. W.
Tr e ib s and H. Sc h m id t (Ber., 1928, 61, [i?J, 459—
465).—Hydrocarbons containing an ethylenie linking in the ring are oxidised by a solution of chromium trioxide in acetic anhydride (carbon tetrachloride or other suitable diluent m ay be employed if required) m ainly with production of unsaturated alcohols and ketones, the methylene group vicinal to the double linking being attacked. I n spite of th e use of an excess of the reagent, a portion of th e hydrocarbon remains unattacked, whilst another portion suffers further oxidation. Thus, a-pinene yields verbenol and verbenone, whilst carveol and carvone are obtained from dipentene. cyclollexene affords c//c?ohexenol and an unsaturated ketone. 1 : 2 : 3 : 4-Tetrahydro- naphthalene yields 1-keto-l : 2 : 3 : 4-tetrahydronaph- thalene and the corresponding alcohol. Terpineol gives an unsaturated glycol, C10H 18O2, b. p. about 165°/20 mm. W ith terpenes containing a hemicyclic double linking, oxidation m ainly attacks the linking itself. Thus sabinene and sabinol yield cuminaldehyde, f'sopropylci/cZohexenone, and cymene.
Camphene affords eamphenilone, camphenilamalde- hyde, and camphenilanic acid. Similarly, fencho- camphorone, fenchenilanaldehyde, and fenchenilanic acid are obtained from a-fenchene. [3-Pinene gives a saturated acid, C10H ir>O2, and an aldehyde. A«.- Octene gives octoic acid, (?) a ketonic aldehyde, C8H 140 2, and unsaturated alcohols. a-Phellandrene affords cuminaldehyde, unsaturated alcohols, C10H 1(iO, and cymene. The products from sabinene, camphene, and fenchene are similar to those obtained by au to
oxidation. H. W rest,
R e im er-T iem a n n reaction in th e alicy clic ser ie s. O. F e r n a n d e z (Anal. F is . Quim., 1928, 26, 33—39).—If substances of th e typ e of m enthol are first treated w ith sodium, a reaction takes place with chloroform or bromoform in the cold in presence of powdered caustic alkali. Carbon monoxide is evolved on warming, and this is thought to be evidence of the initial form ation of an unstable aldehyde. The final products of the reactions are lialogenated com pounds considered to be dichloro- or dibromo-methyl ethers.
Menthol yielded (?) dichloromethyl mentliyl ether, b. p.
128°/14 mm., unsaponifiable by alkali, and n o t reduced by zinc and acid. Borneol and terpineols yielded im pure products apparently containing small am ounts of similar compounds. Benzovlacetone yielded only benzoic acid under the conditions of reaction. Allyl alcohol yielded dibromomethyl allyl ether, b. p. 90— 110°/15 mm. R. K . C a l l o w .
C on stitu tion of In dian tu rp en tin e fro m Pinus longifolia, R oxb . IV. P . P . P i l l a y and J . L.
S im o n s e n .— See B., 1928, 274.
G enetic re la tio n sh ip s in th e sylvestren e grou p . O. Asch a n (Annalen, 1928, 4 6 1 , 1—26, and Svensk K em .Tidskr., 1927, 39,16 5—178).—Careful fractional distillation of Finnish pine oil, of balsam turpentine oil which had previously been strongly superheated with steam, and of “ sulphate ” turpentine oil (sulphate- cellulose m anufacture) showed th e presence of the tw o terpenes isodiprene and pinonene. The former has iff 0-8561, [a]^ 4-5-37°, and nD 1-47536 and is apparent
ly identical with Simonsen’s A3-carene (J.C.S., 1920,
526 B R IT IS H CH EM ICA L A B S T R A C T S .----A .
1 1 7 , 570; 1925,1 2 7 , 2494), whilst the latter is appar
ently A4-carene (Simonsen, loc. cit.) (oxidation gives pinonic acid). The pinonene was converted into a monohydroc-hloride, b. p. 75—S0°/11 mm. (affording sylvestrene when boiled with aniline), and dipentene dihydrochloride. Similarly, the isodiprene, b. p.
167'—170°, gave a monohydrochloride, b. p. 80—85°/
10 mm. (converted by boiling aniline into sylvestrene), together with dipentene dihvdrochloride. The nitros- ate of isodiprene has m. p. (taken rapidly) 146° (cf.
Simonsen, loc. cit., 1920).
[With I. Iv ro hn.)—Diprene, prepared by Aschan (A., 1924, i, 1212) from isoprene, gives a dihydro
chloride (m. p. now given as 52-5°), which is identified as th a t of sylvestrene and (1) is convertible into a terpin, rri| p. 127°, identical with Baeyer’s terpin from carvestrene, and (2) is converted by a boiling acetic acid solution of potassium acetate into carvestrene.
R epetition of Baeyer’s original synthesis of carvestrene from carone showed th a t Baeyer’s crude carvestrene was a mixture, from which a definite substance, re-named carveprene, b. p. 183— 186°, has been isolated. Carveprene gives the same diliydrobromide, m. p. 48—49°, as diprene, so th a t diprene also is a jnefa-cymene derivative.
The author concludes (cf. Simonsen, 1925) th a t sylvestrene is formed as a result of the treatm ent to which turpentine oils are subm itted and is not necessarily an original constituent of the natural oil.
The m atters referred to in the title are discussed
briefly. E. E. Tu r n e r.
Products of the ad dition of chlorine and brom ine to pinene and th eir de-chlorination.
I. L. Ko n d a k o v (Ber., 1928, 6 1 , [B ], 479—481;
cf. A., 1905, i, 798).—A theoretical comment on the work of Aschan (this vol., 296). H. Wr e n.
Cam pherol. T. As a h i n a and M. Is i i i d a t e (Ber., 1928,6 1 , [ 5 ], 533—536).—Campherol, m. p. 216—217°, [«]8 +38-9° in ethyl alcohol, present as the glycuronic acid derivative in the urine of dogs to which camphor has been administered and isolated therefrom by hydrolysis with hydrochloric or sulphuric acid, is reduced by sodium amalgam and water to camphor in satisfactory yield, bu t when oxidised with nitric acid gives only small amounts of camphoric acid. The camphorquinone derived from it by treatm ent with dichromate in glacial acetic acid is a m ixture of isomerides, one of which affords camphoric acid when oxidised with hydrogen peroxide in alkaline solution, whereas the other remains intact and is identified as 5-ketocamphor. Campherol is therefore a m ixture of 3- and 5-hydroxvcamphor (cf. Magnus-Levv, A .,
1907, i, 228). * H . Wr e n.
R eaction of caryophyllene. D. T. Gib s o n
(J.C.S., 1928, 750—751).—When caryophyllene is treated with a solution of ethyl di'azoacetate in caryophyllene in presence of finely-divided copper a t ISO—200°, there is formed a cf/c/opropane ester (cf.
Deussen, this vol. 70), hydrolysed by alcoholic potass
ium hydroxide to the corresponding acid,
Ci6H25'C 0 2H, m. p. 165°, [ct]5161 —40° in alcohol.
The presence of caryophyllene in supa oil (B., 1927, 172) is dem onstrated by this reaction.
H. Bu r t o n.
C yclic d erivatives of aceton ed ica rb ox ylic acid.
II . J . Li t y n s k i and R. Ma e a c h o w s k i (Rocz.
Chem., 1927, 7 , 579—5S4).—M éthylation of 4 : 6-di- hydroxy-a-pyrone by means of diazom ethane yields 4 : Q-dimethoxy-a.-'pyrone, in. p. 105-5—106°, which on heating w ith m ethyl alcohol yields dimethyl fi-methoxy- glutaconate, b. p. 138°/1S mm. The m onomethyl deriv
ative was obtained as follows : 6-hydroxy-4-acetoxy- ec-pyrone yielded on m éthylation G-niethoxy-i-acetoxy-
;x-pyrone, m. p. 66—67°, which on hydrolysis gave i-hydroxii-G-methoxy-x-piirone, m. p. 146—147-5°.
R. Tr u s z k o w s k i. B eh aviour of d ixan th ylen e w h en h eated. A.
Sc h ö n b e r gand O. Sc h ü t z (Ber., 1928, 6 1 , [jB], 478—
479).—Dixanthylene is colourless a t the tem perature of liquid air, pale yellow with a greenish tinge a t the ordinary tem perature, and green a t 2S0°. I t melts to a dark greenish-blue liquid. Its behaviour is thus analogous to th a t of dianthrone. W izinger’s hypo
thesis (A., 1927, 764) th a t the behaviour of the latter substance is dependent on the presence of the carbonyl group is therefore doubtful. H. Wr e n.
A b sorp tion sp ectra of flu orescein, fluoran, and related com pou n ds. W. R. Or n d o r f f, R. C.
Gi b b s, and C. V. Sh a p ir o (J. Amer. Chem. Soc., 1928, 50, 819—828 ; cf. A., 1926, 884).—The red and yellow forms of fluorescein (A., 1927, 671) have identical absorption spectra in neutral alcoholic solution. Both forms are quinonoid, since their absorption curves differ entirely from those of lactonoid compounds such as fluoran, 3 :6-dichlorofluoran, arid fluorescein diacetate, the absorption curves of which resemble one another.
The absorption spectra of fluorescein in 75% formic acid, 93% sulphuric acid, and in an alcoholic solution of hydrogen chloride are all very similar, probably owing to salt formation in each case. In alcoholic solution with 1 mol. of potassium hydroxide the absorption is similar to th a t in neutral solution, bu t excess of reagent causes a m arked change in absorption, owing to form ation of the dipotassium salt. In 33%
aqueous potassium hydroxide fluorescein gives an orange solution which changes to purple and finally to pink on long keeping. The absorption alters during these colour changes (cf. Baeyer, A., 1910, i, 249), which are attrib u ted to (i) opening of pyrone ring, (ii) possible production of carbinol followed by further
disruption. A. McGo o k in.
Z-Hydroxyproline and l-p roline. J . Ka p f-
h a m m e r and R. Eck (Z. physiol. Chem., 1927, 1 7 0 , 294—312).—Z-Hydroxyproline and /-proline are precip
itated by Reiriecke’s salt (cf. Terada, this vol., 542) from hydrolysed gelatin solution from which arginine has been removed as fiavianate. The precipitated salts are shaken w ith warm copper sulphate solution through which sulphur dioxide is passed and the cuprous “ Reineckate ” is removed by filtration.
The filtrate, after being freed from thiocyanate and chromium, is evaporated to dryness in a vacuum ; Z-proline is extracted with absolute alcohol, leaving /-hydroxyproline undissolved. From 200 g. of gelatin are thus obtained 172 g. of mixed Reineck- ates,” giving 7-5 g. of pure Z-proline, [a]“ —84-9“
(in water), —95-2° (in alkali), —54-5° (in hydrochloric acid) [picrate, m. p. 152 — 154°; “ R eineckate”
O RG ANIC c h e m i s t r y. 527
C5H 90 2N,C4H 7N GS4Cr, m. p. 199° (decomp.)], and 14 g. of Z-hydroxyproline, [a]^ —80-6° (in w ater;
[hydrochloride, decomp. above 190°; picrate, in. p.
188°; “ R eineckate,” m. p. 248° (decomp.)].
Z-Proline, unlike Z-hydroxyproline, in alcoholic solution gives, with cadmium chloride, a precipitate of a double compound, C5H 90 2N,CdCI2,H20 ; the copper salt, C10H 16O4N 2Cu, p -toluenesulphonyl deriv
ative, m. p. 130—133°, and 2 : 4-dinitrophenyl derivative, m. p. 136°, are also described. The preparation of Rcinecke’s salt, N H 4[Cr(SCN)4(NH3)2], is detailed. C. Ho l l in s."
C ondensation of p yru vic acid w ith a m in es and aldehydes. II. S. We i l and (Ml l e.) F. Go l d
b e r g (Rocz. Chem., 1927, 7 , 585—590).—Prolonged boiling in alcoholic solution of a m ixture of pyruvic acid, ethyl ^-aminobenzoate, and benzaldehyde yields 4 - p - carbethoxyphenylvm ino - 2 -phenyl -1 - p - carbdhoxy- phenyl-5-keiopyrrolidine, m. p. 203—204°, together with some 2-phenyl-l-2?-earbethoxyphenyl-4 : 5-di- ketopyrrolidine, which also yields the above product on condensation with ethyl jp-aniinobenzoate. By varying the aldehyde used in the above reaction, the following products were obtained : with vanillin, 4-p-carboxyethylpheiiylimino-2-('?> - methoxy - 4 - hydroxy - phenyl)-!-i'i-carbethoxyphetiyl-5-kelopyrrolidine, m. p.
159°; with piperonal, the. corresponding 2 -(3 ': 4'- methylencdioxyphenyl) derivative, m. p. 219°, together with the diketo-derivative, m. p. 156— 157° ; with salicylaldehyde, th e corresponding 2-o-hydroxyphenyl derivative, m. p. 219°, and with p-dimethylamino- benzaldehyde the corresponding 2-j)-dimdhylamino- phenyl derivative, m. p. 176°. R. Tr u s z k o w s k i.
A ction of ai-d i-iod o-n -h exan e on am in es. A.
Mu l l e rand E. Rolz (Ber., 1928, 6 1 , [5],. 570—574).
—c^-Di-iodo-w-hexane, b. p. 141—142°/10 mm., is prepared in 73% yield by the action of red phos
phorus and iodine on n-hexane-a^-diol, obtained by reduction of m ethyl adipate with sodium and alcohol.
I t is converted by m ethylam ine into iV-methylhexa- methyleneimine, identified by direct comparison of the methiodides, in.' p. 265° (corr.; slight decomp.), and the corresponding chloroplatinate, m. p. 233°
(corr.; decomp.), with those of the products derived from a^-dibromo-w-hexane and ^-toluenesulphon- amide (Muller and Sauerwald, this vol., 43). Von Braun’s conception of the product as a derivative of a-pipecoline therefore requires correction. N N - Dimethyl-a-pipecolinium chloroplatinate decomposes a t 246° instead of a t 222°, as recorded by von Braun (A., 1920, i, 821). Ring contraction therefore does not occur during the action of a£-di-iodo-?i-hexane on methylamine. Similarly, a£-di-iodo-?i-hexane and piperidine afford hexamethylenepiperidinium iodide,
|£ H 2]6> K I< [C H 2]5, in .p .273° (corr.; slight decomp.), the constitution of which if confirmed by its formation from hexamethyleneimine and xc-di-iodo->i-pentane.
On the other hand, as-di-iodo-m-pentane and a-pipecol- me afford 2-methylpentamethvlenepiperidinium iodide,
m. p. 268°. H. Wr e n.
Oxidation of Ar-b en zoylh exam eth ylen eim in e.
A. Mitller [with H. Cl o s t e r m e y e r] (Ber., 1928, y l ’ f-8 ], 568—570).—iV-Benzoylhexamethyleneimine is oxidised by potassium perm anganate in w ater a t
50° to s-benzamido-n-hexoic acid, in. p. 80—81°
(corr.), in 44% yield, thus confirming th e constitution assigned to the base (this vol., 43). H. Wr e n.
M anufacture of isa tin s and A7-arylsu lp h on yl d erivativ es thereof. I. G. Fa r r e n i n d. A.-G.—
See B., 1928, 224.
S te r e o iso m e r ism in p o lycyclic sy ste m s. IV.
T w o ste reo iso m e rid e s of 2 : 3 : 4 : 5 :1 2 :1 3 - h exahydroquinindene. W. H. Pe r k i n, jun., and S. G. P . Pl a n t (J.C.S., 1928, 639—646; cf. this vol., 72).—Elimination of carbon dioxide from 2 : 3- dihydroquinindene-12-carboxyIic acid, m. p. 297°
(decomp.) (lit. 277—278°), yields 2 : 3-dihydroquin- indene, which is reduced by tin and hydrochloric acid in aqueous-alcoholic solution, giving a m ixture of the two stereoisomeric 2 : 3 : 4 : 5 : 1 2 : lZ-hexa- luydroquinindenes (A), m. p. 67° [acetyl derivative, m. p. 102°; benzoyl derivative, m. p. 174°; picrate, m. p. 193° (decomp.)], and (B), an oil, b. p. 284°/762 mm. (acetyl derivative, m. p. S7° ; benzoyl derivative, m. p. 161°; picrate, m. p. 158°). The proportion of (A) to (B) is about 1 to 3. W hen 2 : 3-dihydro- quinindene is reduced electrolytically, the proportion of (A) to (B) is about 1 to 12. No conclusive evidence as to which is the cis- and which the Zrans-isomeride is available. The existence of th e two modifications can be accounted for by th e Sachse-Mohr theory of m ultiplanar rings. The influence of the strain con
ditions existing in th e two molecules on their relative am ounts of form ation is considered. The experi
m ental results are in accordance with the deductions which can be drawn from the space-models.
M. Cl a r k. P rep aration of p yridin e d erivatives [iododi- chlorides] etc. De u t s. Go l d- u. Sil b e r-Sc h e i d e-
a n s t a l t.—See B., 1928, 244.
A ction of eth ox ya cetyl chloride on m a g n esy l p yrro les. A . Sa n n a and G. Cii e s s a (Gazzetta, 1928, 58, 121— 127).—Magnesium 2-pyrryl iodide reacts in ether w ith ethoxyacetyl chloride to give 2-ethoxyacetylpyrrole, b. p. 173°/10 mm. (phenyl- hydrazone, m. p. 163°); 3-magnesium 2-methylindolyl iodide similarly yields 3-ethoxyacetyl-2-methylindole, m. p. 157° (phenylhiydrazonc, m. p. 90°), and mag
nesium carbazyl iodide yields N -ethoxyacetylcarbazole, m. p. 70°. ' ' E. W . Wi g n a l l.
C om pound of (i-alan yl-i-tryptop h an w ith rf-alanyl-I-tryptophan anhydride. E. Ab d e r-
h a l d e n and H. Sic k e l (Z. physiol. Chem., 1927, 171, 93— 100).—During the preparation of (i-alanyl-/- tryptophan by warming (Z-bromopropionvl-Z-trypto- phan with ammonia, a substance was isolated which appears to be the compound, 1 dipeptide 4-1 an hydride, decolorising a t 270°, m. p., after sintering, 280°. I t contains no free amino-group. I t has a mol. w t. corresponding w ith the double molecule. A m ixture of molecular equivalents of the dipeptide and th e anhydride gives an absorption in the ultra-violet very similar to, b u t not quite identical with th a t of the compound. The optical rotato ry power of the m ixture is also slightly different from th a t of the compound. By boiling in methyl-alcoholic solution the compound is quantitatively transform ed into the
anhvdride. H. D. Ra y.
528 B R IT IS H CH EM ICA L A BSTRA C TS.— A.
Preparation of quinoline derivatives. I. G.
Fa r b e n i n d.—See B., 1928, 244.
Q uinoline derivatives. V li. 4 -A m in o -2 - phenylquinoline derivatives. H. John [with E.
W v n s c i i e ] (J. pr. Chem., 1928, [ii], 118, 303—313).
—The following derivatives of 2-phenylquinoIine have been obtained by condensing 4-ehloro-2-phenyl- quinoline (Wenzel, A., 1895, i, 70) with th e appro
priate amine in a sealed tube a t th e tem perature given in parentheses : 4k-diisoamylamino- (150—160°), in. p. 61°; 4-anilino- (180—200°), m. p. 182° (picrate, m. p. 233—234°); 4-p-toluidino- (200—210°), m. p.
173° (elhiodicle, m. p. 219°); 4-m-4'-xylidino- (200—
210°), m. p. 151° (picrate, m. p. 237°); i-ip-cumidino- (180—200°), m. p. 188° ; i-a-najrfithylamino- (170—
210°), m. p. 177— 17S° (picrate, m. p. 246°); 4-p- naphthylamino- (180—200°), m. p. 185° (picrate, m. p.
219°), and 4-benzylatnino- (ISO— 190°), ra. p. 147°
{picrate, m. p. 241°). The chloro-derivative gives with o- (230°) arid p- (180—200°) anisidines, sub
stances, m. p. 279° and 183°, respectively; w ith 4-amino-2-phenylquinolino hydrochloride (240°), di-2-phenylA-quinolylamine, m. p. 253-5°, and with hydrazine (150—160°), 2-phenyl-4-quinolylhydrazine, m. p. 143° (acetyl derivative, m. p. 184— 185°), from which beMzaldehyde-2-phenylA-quinohjlhydrazone, m. p.
151°, sintering from 100° (picrate, m. p. 256°), and acetophe7ione-2-plienyl-4:-qumolylhydrazone, m. p. 195—
196° (picrate, m. p. 112°), are prepared. The hydro
chlorides, sulphates, rnercurichlorides, chromates, ferro- cyanides, and periodides of the above bases are described. H. E. F . No t t o n.
T au to m erism in th e pyridin e series. D i- phenylpyridylm ethane and its d eriv a tiv es. A . E . Ts c h it s c h ib a b in and S. W. Be n e v o l e n s k a j a (Ber., 192S, 61, [ j B ] , 547—555).— Phenyl 2-pyridyl ketone is converted by magnesium phenyl bromide in ethereal solution into diphenyl-2-pyridylcarbinol, in. p.
105° [chloroplatinate (-f2 H .,0 ); picrate, m. p. 173°
(decomp.)], which is reduced by hydriodic acid in glacial acetic acid to diphenyl-2-pyridylmethane, in. p.
63° [chloroplatinate, m. p. 182° (decomp.); picrate, m. p. 172°]. Diphenyl-2-pyridylmethane methiodide, m. p. 222—224°, is transformed by concentrated alkali hydroxide into \-methylpyrid-2-miediphenyl- methide, dark reddish-violet needles, m. p. 147°, soluble in water to a strongly alkaline solution; th e presence of the phenyl groups facilitates th e pro
duction of the pyridonemethide and enhances its stability. Diphenyl-i-pyridylcarbinol, m. p. 235°
[chloroplatinate, m. p. 203°; picrate, m, p. 101—103°
(decomp.), prepared analogously from phenyl 4-pyridyl ketone, differs in an unexplained manner from the compound, m. p. 203°, described previously. Both earbinols are stable towards air and potassium per
m anganate, so th a t the possibility th a t the phenyl groups in one of them have suffered oxidation (by air) with production of a fluorene derivative appears excluded. The earbinol, m. p. 235°, is reduced to diphenyl-4c-pyridyhnethane, m. p. 125° (chloroplatinate, ni. p. 201° after darkening; picrate, m. p. 172°), whereas th a t of m. p. 203° affords diphenyl A-pyridyl- meihane, m. p. 111— 112°. Diphenyl-4-pyridyl- methane methiodide, m. p. 159— 161° (from the base,
m . p . 125°), is converted into l-methylpyridA-onedi- phenylmethide, m . p . 113°. H . Wr e n.
D yes derived fr o m quinoline-2 : 3 : 4 -tricarb - oxylic acid. J. D . T jb w a r i and S. D u t t (J.
Ind ian Chem. Soc., 1928, 5, 59—62; see also A., 1927, 969, 1006).— Quinoline-2 : 3 : 4-tricarboxylic acid condenses w ith phenols either alone or in the presence of stannic chloride or sulphuric acid to give the following dyes of the phthalein typ e : phenol-, in. p. above 280°; resorcinol-, m. p. 194° (yellowish- green fluorescence); phlorogluciiwl-, m. p. above 280°;
pyrogallol-, m. p. above 280°; ni-diethylaminophenol- m. p. 220° (brown fluorescence); m-phenylenediamine- quinoline-2 : 3 : i-tricarboxylein, m. p. above 280°
(green fluorescence). The dyes are probably pro
(green fluorescence). The dyes are probably pro