CONDENSATION OP CYCLIC ALDEHYDES WITH QUINALDINE.
2309
isolated. When the mixture was heated a t I 50' for a short time no change occurred, but longer heating at this temperature, or for a few minutes a t 153'~gave the I-phenyl-urazole as the sole product.
Summary. (I) A study has been made of the progressive action of primary amines on methyl and ethyl allophanate which has resulted in the isolation of ryl allophanic esters, mono- and di-aryl biurets and mono- and di-substituted ureas. ( 2 ) Phenylhydrazine has been found to give I -phenyl-4-carbethoxysemicarbazide and I -phenyl-urazole. The investigation is being continued in this laboratory. LAWXBNCB, KANSAS.
[CONTRIBUTION FROM THE LABORATORY OF WERNSRDRUGAND CHEMICAL Go.]
THE METHIODIDES OF THE CONDENSATION PRODUCTS SOME CYCLIC ALDEHYDES WITH QUINALDINE AND ALPHA PICOLINE, AND TMEIR POSSIBLE VALUE AS INDICATORS IN ACIDIMETRY. BY LOUISF, WERNER. Received July 16, 1920.
The. aqueous solution of the methiodide of z (3-methoxy-4-hydroxystyry1)quinoline when treated with sodium hydroxide solution was found t o give a deep fuchsine-colored fluid, instead of the anticipated precipitate of the quaternary-ammonium hydroxide. As the hydrochloride of 2 (3methoxy-4-hydroxy-styry1)quinoline under like conditions gave but a milky emulsion of the free base, the color noted must be due to the auxochrome effect of the methyl group attached t o nitrogen. Following up these results, the methiodides of the condensation products of various cyclic aldehydes with quinaldine vvere prepared, and their behavior with sodium hydroxide determined. The methiodides of the condensation products of quinaldine with benzaldehyde, furfural, o-hydroxybenzaldehyde, p-hydroxy-benzaldehyde, protocatechuic aldehyde, and also the condensation product of piperonal with a-picoline, were prepared and studied. The results secured showed that in order that the methiodides of compounds of this type have the properties of an indicator, that there be a phenolic hydroxyl group attached to the neucleus of the aldehyde used in its preparation. Thus in the case of the methiodides of z-styryl-quinoliiie, z (P-furfuryl-vinyl)quinoline, z (4,3-methylene-dioxyl)pyridine,the yellow-aqueous solutions of these salts were rendered colorless upon the addition of sodium hydroxide solution, but the methiodides of 2 (z-hydroxystyry1)quinoline and of 2 (4 -hydroxy-styryl) quinoline gave a blood-red
c /\ HC C---OCH, I1 /I
c-OH
/\
~:-oCI-13
HC,
/I
~
Tic
CH
\/ c I
CH
CH
IT?
7: y
I
Q3H==CXf----C:
C
CR
CH
//k /'\ C TIC C CH 11 I I Ii cw---cI-T1--c c @R \/ \/
/\ //\
~_->
CH
\/ \\s N CH /\
Y\ cir8
CR
CHa I I A lew preliminary tests carried out t o determine the possibility of using these soinpounds a? indicators, indicated that they may be used as s u ~ h , provided that the hydriodic acid first foriued by their hydrolysis in water be ceutrdized with alkali.
Experimental
0
-ur?d'urai,5 g., were heated in the presence of 2 g. of anhydrous zinc chlozide -9pn the boilitag water-bath for 5 hours, Water, and then a slight excess of hydrochloric acid was added, and steam passed into the mixture until all but tar was dissolved. The solution was filtered hot through a wetted fiiter, and conc. hydrochloric acid added to tlre cooled filtrate. The precipitated hydrochloride was filtered out as an orange-colored powder, d ~ s ~ l v e in c l water, filtered, and repvecipitated avith hydroeblorie acid.. The iree base was finally secured by dissolving the hydrochloride in water ruid sarddly adding ammonium hydroxide, fiitering from tke tarry i n puritie3 which precipitate first. The .free base is recrystallized from ligroin, M. p. (corr.) 56'. The base is soluble in a11 the ordinary organic ::c;l.i7ents, Subs., 0 . 3 8 2 3 ' 2 3 4 cc N (over 30'3~ KOH at Clac. for C&IIION. K, 6 33 Found 6 69 2 (P-Fasrfuryl-vinyl)q~noline
27'
and 749 mm ).
methiodide, C4H30.CaH~.CIoKgNI.-$'bis
d x i h x e was prepared by heating 3 g. of 2 (8-furfuryl-vinyl) qtiinoline with an excess of methyl iodide in a sealed tube in the dark, a t a temperature of 1 4 0 ~I ~t was necessary to heat fol- 4 to 5 hours, an oil-bath
being used. The contents of the tube were then recrystallized from
CONDENSATION OF CYCLIC ALDEHYDES WITH QUINALDINE.
23 I X
water, and the salt was secured as orange colored needles, having a steelblue iridescence when viewed in natural light. The substance is soluble in hot alcohol and hot water, but is practically insoluble in the usual organic solvents. M. p. (corr.) 226.2'. An aqueous solution of this salt is lemon-yellow in color under neutral or acid conditions, and colorless in the presence of alkalies, but the change in color is so slight as to give i t no value as an indicator. Subs., 0.5878: 22.4 cc. N (over 30% KOH a t 27' and 746 mm.). Found: 4.15. Calc. for C I ~ H ~ ~ O N, N I 3.86. : 2 (3,4-Methylene-dioxy-styryl)pyridine methiodide, C711602.CzHz.GeHsNI,---2 (3,4-Methy1ene-dioxy-styryl)pyridine1 and an excess of methyl iodide were heated in a boiling water-bath in the dark for 4 hours. The. contents of the bomb tube were then recrystallized from water, the salt being secured as a lemon-colored microcrystalline powder. It is soluble in hot water, alcohol, and acetone, but is but slightly soluble in the usual organic solvents. M. p. (corr.) 276". An aqueous solution of this salt is yellow in aqueous acid or neutral solution and colorless in alkaline solution, but the substance has no value as an indicator.
Subs., 0.5029: 19.2 cc. N (over 30% KOH a t 27' and 732 mm.). Found: 4.08. Calc. for C I ~ H I ~ O ~N, N I 3.82. :
a-Styryl quinoline methiodide, C6H~.C2H2.C10U9NI.-2-Styryl-quino$ne2 and an excess of methyl iodide mere heated in a sealed tube in t.he dark for 4 hours in a boiling water-bath. The contents of tube were recrystallized from water, and the salt.was secured as acicular bright orangecolored crystals. It is soluble in hot water and alcohol, but only slightly soluble In the common orgarlic solvents. M. p. (corr.) 235.2' with decomposition. A solution of this substance in neutral or acid aqueous solution is a faint yellow, but is rendered colorless by adding alkali. It is of no service as an indicator. Subs., 0.5881: 2 1 ~cc. 4 N (over 30% KOH a t 27' and 735 mm.). Calc. for C1&~NI: N, 3.75. Fouad: 3.91.
C6I-3[dI.CzM~. CloH9NI. an excess of methyl iodide were heated in a sealed tube in the dark a t 135' to 140'. The contents of the tu'be were recrystallized from water, and i t was thus secured as a bright orangecolored crystalline powder. It is soluble in hot water and hot alcohol, slightly soluble in other organic solvents. M. p. (corr.) 236'. Qne cc. of a 0.1% solution in 250 cc. of water was turned to a blood-red 2 (2-Hydroxy-styryl)
quinoline
methiodide,
2 (a-Hydroxy-styryl) quinoline3 and
Thiemich, Ber., 30, 1578 (1897). Wallach and Wuesten, ibid., 16, 200s (1883). * Dzierzgowski, ibid., 27> 1980 (18941,
color irpnn the addition of a d ~ s pof 0.1 iV soclhmi ~ ~ y ~scirution ~ r ob u~t ~ ~ e t h e n:oloa: ~ ~.to pale~leamn ~ rapon s r ~tfor a few ~~ ~ e ~~~o ~Not ~~ ~c l ~ ~ ~ 0.4 cc. op t,he a1ka.E had been a,clded *V"sthe: blood-red color p manen.t. This betlavim is due ~ ~ ~ ~to dthe ~fact~ that ~ a~certain t e ~ ~ y an~ountof alkali ist needed to neutraXze the hydriodic acid formed by the hydrdgsis of the ~akt.1 It was f o ~ ~ n .that c l the blood-red color WBS dits'by 0.1% CT. of 0.1 N h y d r o ~ ~ acid, ~ ~ ~but r ~itcreturned upon addi:tIg aga%lrb0.1 CC. Uf 0.1 nU Sodium. hydroxide §O!UtiOII. T o USE: this Substance 85 an indica.tor, it would be necessary therefore, to ' ~ s e ~the~ ~ . ~ ~ solu-i-ion by the addi.tion of .the proper anaornlrt of sodium hydraxide "io O V ~ : P C O ~ Tthis R ~ acidit.y, analogous to the additisis cd h y ~ ~ acid ~ toc ~ ~ ~ the sedium salt of helianthin (methyl orange). ~~~~~~~~~
¶
Subs., 0.6100: 2 1 , x cc. N (over 30% KOH a t Calc. for CI&IIOOP\TX:N, 3.60. Pourid: 3.81.
2.5'
and 745 mm,),
2 ( ~ - ~ ~ ~ ~ o quinoline x y ~ s ~ ~~ ~e y~ l h) i oCaH50. ~ ~ CzHzI ~ ~CloH9NI , .-Methyl iodide in excess was heated with 2 (4-hydroxy-styryl) quinoline2 in an oil-bath a t 140' in. t h e dark. Recrystallized from water, the. substai~ee:i s as a bright orange-colo~e~~ crystaJIine powder, 1.c:i s soluble in hot alcohol and hot water, but is only slightly soluble in other sokvents, M. p. (corr.) 250.8 O with decomposition. Tested as the preceding compound as to its value as an indicator, e similar results, it giving a lemon-yellow solution in presence of mi in neutral solutions, and a blood-red so1utia:n in the presence of alkalies.
Subs., 0.6181 : 20.2 cr. N (over 30% KOH a t 24' and 743 mm.). Calc. for C I ~ R I ~ O NN, I : 3.60. Found: 3.52.
e ~ ~ o x y - squinoline ~~y~) iodide, 4,3-OH.0CH3.-This substance was pre by heating 2 (4-lzydry-3methoxy-styryl)quinoline3 with an excess of methyl iodide in the dark in a boiling water-bath. The product is a 'brick-red ciystalline powder, sligb.tly soluble in hot water and alcohol, practically irisoluble in other solvents. lit was powdered and purified by extra.cting 3 times with boiling gsyo a1cch.d t o remove tar and any unchanged base. M. p. 267' (corr.) with decomposition.. Upon determining the sensitivity of this compound to acids and bases, it was found that 0.4 cc. of 0.1 sodillin hydroxide solution was required t o seiciire a permanent fuchsine-red colored solution, using a mix.twe oi one cc. of 0.1% solution to 250 ce. of water, but only 0.1cc. of 0.1 N 1 Compounds of this type, despite the common conception that quaternary ammonium compounds are all strong bases, are on the contrary very weak bases, and f.hose containing na phenolic group are readily precipitated from their strong aqueous solv.tions of t.beir salts by ammonium hydroxide. a Wallach and Wuesten, Bey., 16, 2009 (1883). li'encki, ibid., 2~~ r974 (1894).
CONDENSA'I'ION OF CYCLIC ALDEHYDES WI'J?N QUINALDINE.
2313
hydrochloric acid was required to turn it t o the neutral lemon-yellow color. This dye also would require sensitizing with sodium hydroxide solution before i t would serve as an indicator. Subs., 0.6041: 19.70 cc. N (over 30% KOH at 26' and 749 mm.). Calc. for CI8H18O2NI: N, 3.34. Found: 3.59.
ihydroxy-styryl) quinoline, 4,s(OH) 2. C6H3. C2H2~ CRH6N.-This was prepared by heating 4.6 g. of protocatechuic aldehyde, 4.8 g. of quinaldin and 2 g. of zinc chloride upon a boiling water-bath until the mass was nearly solid. The paste was then dissolved in water and a little hydrochloric acid, and filtered hot. The hydrochloride was then precipitated by adding an excess of hydrochloric acid, and cooling, and was recrystallized in this manner several times, and the free base secured in a pure condition by adding 5 .cc. of glacial acetic acid t o the solution, and then carefully adding ammonium hydroxide solution t o the appearance of the first permanent turbidity. Upon cooling and agitating well, the tarry impurities were precipitated, and filtered out. The brilliant clear solution was then treated with steam, resulting in the hydrolysis of the acetate, and the precipitation of .the free base. This is a very pretty example of progressive hydrolysis, as the bright red color of the acetate rapidly fades as the temperature rises, and is followed by the precipitation of the free base. This last operation is repeated, thus securing the compound in a pure condition. M. p. 244.6' (corr.). The base is slightly soluble in dcohol, acetone and benzol, but not sufficiently to be purified by recsystallization. Subs., 0.3390: 15.4 cc. N (over 30% KOM at Calc. for C I T H I ~ O ~N, N :5.32. Found: 5.32.
21'
and 746 mm.).
2 (3,4-I)ihydroxy-styryl) quinoline methiodide, 4 3 -(OH)a.CBHB.CIOHSNI. -This was prepared by heating 2 (3,4-dihydroxy-styryl-quinoline in a sealed tube with an excess of methyl iodide a t 140' in an oil-bath for 5 hours, protected from the light. The salt was recrystallized from water as a brownish-orange powder, soluble in hot water and alcohol, slightly soluble in cold alcohol and water, and other usual solvents. M. p. 266.8' (corr.) with decomposition. TJpon testing the approximate sensitivity of this salt to alkalies and acids, it was found that to secure a permanent grape-colored solution, 0.4 cc. of 0.1 N sodium hydroxide solution was required in a mixture of one cc. of a 0.1570 solution in 250 cc. of water, which was converted t o the original lemon-yellow colored solution by the addition of 0.1cc. of 0. I N hydrochloric acid. This indicator would also require sensitizing t o fit it for practical use. Subs., 0.6069: 19.0 cc. N (over 30% KOH a t 27' and 749 mm.).
Calc. for 618H1602N1: N, 3.46.
Found: 3.43.
1. w-E* GLAT1'E'ELI.l
2314.
AND C;EOR.GE $. MreLa'bL
I'he work showed. that the a a methyl group to the nitr at,osn of the condensation p r o d i ~ t svl" the ortho- and para-hydroxy zro alc~ehycles"ith qdnaldin gave these compoullds the properi:ies of iradi c~.~QI-s, 'but that coinpounds not possessing these ortho- or jr!cera-phcnol groups did not acqtiire this property. A 1ittl.epreliminary work was d m c to tietermhe the suitability of these coiiilpounds to serve a.s indicators in vo 1umehic analysis ~
I
CUUCINNATI, 5.
[COKTRIBUTION PROM THE KENT CHEMICAI, h B o R A T O R Y , UNIVERSITY OF CRlCAGO. 1
UTYRIC ACID INTO ENTS. THE DERIVAT BY J. W E. GL.ATTFEI.D AND GBORGF: E. MILLER.^ Received July 19, 7920.
The saccharink acids are acids ~vhicliwould result from the oxidation of the H - C = 0 group of an aldo-monosaccharide of th.e formiila 1 to the 0 ,= C - O H group at the expense of one of the G,H,,O, I I G - OH groups which would be reduced to the M -:C - H El ~
I
I
groi.ip. These acids have the same molecular formula as the corresponding aldo-monosaccharides and may thus he loolied upon as the results OS a.3 internal oxidation-reduction reaction. The saccharinic acids formed froni some of the pentoses and hexoses have Seen .the direct subject af study2 by Nef and his students a t various times, and have also entered into consideration in connection. with all the sugar-oxidation experiments coiiducted in this laboratory in resent gears. 'These oxidatims were carried out in alkaline solution, under which. conditions the prod;ict,ioia of saccharink acids was a possibility. In a recent paper from this Ia,boratory3 there w;is reported, in the oxidation of maltose in alkdine. solution, the prod.uction of an acid, the phenylhydrazid of .which gave a perfect analysis for that of a 4-carbon-at.om sacchariaic acid. The properks sf the free acid furthermore were those which would be expected of one of these acids. Its configuration c:oinld not, 'be reported because of iack of 1
The dissertation of which this paper i s a condensation
VI^
presented by Genrgc
E. Miller as part. fulfihent of the requirements for the degree of Doctor of Philosophy in the University of Chicago. The original dissertation is iihrary. 2
Xef, Ann., 376,
I-IZO
(1910).
T H ~ JOWREAL, S 40, 9'73 (1918).
011
file in the TJniversity
