NOTES
Nov., 1948
3953
was evident but the material was largely polymerized to a tar. The rearrangement was achieved with less polymerization by steam distilling the (2) Tiemann and Kriiger, Be?.,¶9,901 (1896). carbinol through 28% sulfuric acid. The resul(3) Fuller and Kenyon, J . Chsm. SOC.,126, 2308 (1924). tant crude cinnamaldehyde in two experiments DEPARTMENT OF CHEMISTRY was converted directly to the phenylhydrazone POLYTECHNIC BATTERSEA (%yoover-all yield). In a third experiment the LONDON S. W. 11, ENGLAND RECEIVED JANUARY 27,1945 aldehyde was converted to a-bromocinnamaldehyde (2 1% over-all yield). Rearrangement of Phenylethynylcarbinol Experimental
phthalic anhydrides has been known for over half a
BY WARRENS. MACGREGOR
Rearrangement of Phenylethynylcarbinol.-Phenylethynylcarbinol (5.4 g.) and 5 cc. of water were placed in a Rupel reported that several tertiary acetylenic 25-c~.distilling flask fitted for steam distillation with the alcohols containing a free acetylenic hydrogen side arm extending nearly t o the bottom of the 50-c~.flask were rearranged upon boiling with 85% formic of a Clark acetyl apparatus’ containing 25 cc. of 28% sulfuric acid. The flasks were heated in oil-baths t o 115O, a acid to the corresponding &-unsaturated alde- steam generator connected to the small flask, and steam hydes. Thus, the ethynylcarbinols from tetra- distillation started adjusting the bath temperatures t o hydrocarvone and fenchone were reported to yield maintain approximately constant volume in the flasks. A water-insoluble oil (3.1g.) separated in the distillate and 5 isopropyl 2 methylcyclohexylidene 1 in 5 cc. of ethanol. A solution of 17.5g. phenylacetaldehyde and 1,3,3-trimethylbicyc10~2,2,1]- dissolved hydrazine hydrochloride and 10.0 g. sodium acetate in 150 heptylidene-2-acetaldehyde, respectively.2 The CC. of water then was added t o the oil and the mixture reaction represents a special case of a Meyer- warmed for fifteen minutes on a water-bath. After filterSchuster rearrangement3 and was considered by ing, washing with water, ethanol and ether, and drying, 3.0 g. (!3%) of crude cinnamalphenylhydrazone (m. p. Rupel to proceed in analogous manner 154-157 ) was obtained. Two recrystallizations from ethanol raised the m. p. t o 168-169’ and a mixed m. p. R(R’)C(OH)-CH +R(R’)C=C=CHOH ---f with an authentic sample showed no depression. A second R(R’) C-CHCHO experiment yielded 1.2 g. (36%) of the crude phenylhydra(m. p., 161-165’) from 2.0 g. of the carbinol. Reinvestigation of several of the reported re- zone The crude cinnamaldehyde from a similar rearrangement arrangements by Fischer and L~wenberg,~ Hurd of 6.2 g. of phenylethynylcarbinol was extracted from the and Christ5 and others demonstrated that the distillate with ether, and upon removal of solvent the oil principal products were unsaturated ketones pre- was taken up in 10 cc. of glacial acetic acid. A solution of 10.7 g. of bromine in 19.9 g. of acetic acid was added dropsumably formed by dehydration of the carbinols wise with stirring and cooling in a n ice-bath until the brofollowed by hydration of the triple bond.s Thus, mine color remained for ten minutes (10.3 g. of the soluI-ethynylcyclohexanol yielded l-acetylcyclohex- tion, corresponding t o 3.0 g. cinnamaldehyde, was reene4J rather than cyclohexylidene acetaldehyde. quired.) Potassium carbonate (1.5 g.) was then added the mixture allowed to stand overnight at room temChanleyG showed that both the ketone and alde- and perature. After refluxing thirty-five minutes, the mixture hyde products resulted from the rearrangement of was cooled and poured into 30 cc. of water, whereupon an 1-ethynyl-1-cyclohexanolsalthough the aldehydes oil separated that partially crystallized upon shaking. The oil and crystals were removed and taken up in 10 cc. of were formed in very low yield (0.8 to 6%). warm ethanol. Upon cooling and seeding 2.1 g. (21%) of The reaction probably involves initial elimina- a-bromocinnamaldehyde, m. p., 71.5-72”, was obtained. tion of the hydroxyl group to form a carbonium Recrystallization from ethanol did not alter the m. p., and ion. The loss of a proton from an adjacent carbon the mixed m. p. with a sample prepared following the difollowed by hydration of the triple bond and keto- rections of Allen and Edens8 showed no depression.
-
-
-
-
-
nization would yield the observed unsaturated ketone. Shifting of the carbonium ion bonds to the allenic structure followed by hydroxylation a t the positive terminal carbon would yield the enolic form of the unsaturated aldehyde which is in equilibrium with the predominantly favored aldehyde. A compound such as phenylethynylcarbinol would yield a carbonium ion that could not form an unsaturated ketone by the above mechanism and hence, barring alternative modes of reaction, should yield cinnamaldehyde as the principal rearranged product. When the carbinol was heated with 3Oy0 sulfuric acid, 85% phosphoric acid or phthalic anhydride the odor of cinnamaldehyde (1) Rupe and Kambli, Helo. Chim. Acto, 9, 672 (1926). (2) Rupe and Keunzy, Hclv. Chi?%.A c f a , 14, 708 (1931). (3) Meyer and Schuster, Ber., 65, 819 (1922). (1) Fiscber and Lowenberg, Ann., 416, 183 (1929). ( 5 ) Hurd and Christ, THISJOURNAL, 69, 118 (1937). (6) Chanley, THIS TOURNAL. TO, 244 (1948).
(7) Clark, Ind. Eng. ChLm., Anal. Ed., 8, 487 (1936). (8) Allen and Edens, “Organic Syntheses,” 26, 92 (1946).
DEPARTMENT OF CHEMISTRY UNIVERSITY O F PORTLAND PORTLAND 3, OREGON
RECEIVEDJUNE 1, 1948
Indium Orthovanadate’ BY
w.0.MILLIGAN,HENRYH. RACHFORD,JR.,
AND
L.
MERTENWATT
Forty-seven years ago Rem2 prepared a gel which he designated as In(VOa)s.2HzOby the addition of a sodium metavanadate solution to an indium chloride solution. The supposed constitution of the gel was based merely upon a chemical analysis, and there does not exist in the literature. (1) Presented before the Texas Regional Meeting of the American Chemical Society held in Austin, Texas, December 7-8. 1945. (2) Renz, Bcr., 84, 2765 (1901).
Vol. 70
NOTES
3954
A.
any definite evidence concerning the constitution or even the existence of indium vanadates. Mole % InzOa VzOs The purpose of this present investigation was to a t t h p t to Standard InzOa prepare a definite indium vanadate. 40 Dry way Experimental.-Seven samples in the system indium triox50 Dry way ide-vanadium pentoxide were prepared by wet and dry meth50 Wet way ods as outlined in the table. The samples were examined by X-ray diffraction 60 Dry way standard methods, using Cr Kcu X-radiation. The K/3 X-radiation was Standard VZOS removed completely by a supplementary filter of vanadium pentoxide. The results of X-ray 5.0 3.0 2.0 1.5 1.2 analysis are likewise summarA. ized in the table. Fig. 1.-X-Ray diffraction patterns. Discussion.-It will be noted that both gels prepared by precipitation are TABLE I Sample Method of preparation Results of X-ray analysis amorphous to X-rays. There is no indication 1 An equimolar amount of Amorphous t o X-rays of the formation of a definite crystalline indium InC13solution (0.1 M ) was vanadate. It is not known whether these gels added rapidly to 100 ml. of consist of an amorphous indium vanadate or of a saturated NHdVOj solumixture of amorphous indium oxide or hydroxide tion a t room temperature. together with amorphous vanadium pentoxide. The yellowish gel was Samples heated to temperatures of 850-1000° washed in a centrifuge and are sub-microscopically crystalline and yield a dried in air diffraction pattern consisting of numerous rela2 A n equimolar amount of Amorphous to X-rays tively sharp lines. This pattern is distinct from those of anhydrous InzOaor Vz06,and is therefore InCla solution (0.1 M)was assumed to be characteristic of a definite indium added .rapidly to 100 ml. of vanadate. Since samples containing excess of NHIVO~solution (satureither component yield diffraction lines from the ated at 90"). The gel was washed in a centrifuge, excess oxide, it is believed that the compound formed is indium orthovanadate, InV04. X-Ray and dried at 120' diffraction patterns for InV04, In203 and V2O5 are 3 Sample no. 1 heated for two Pattern consists of numerous sharp given in chart form in Fig. 1. The data cannot be hours at 850" lines distinct from indexed in the cubic or tetragonal crystal systems. those of In203 or The numerical data of the observed interplanar spacings and visually estimated intensities have VZOS 4 Sample no. 2 heated for two Pattern identical with been tabulated and included in the card index file of the American Society for Testing Materials no. 3 hours a t 1000" 5 Equimolar quantities of dry Pattern identical with (ASTM). 5.0
3.0
2.0
nos. 3 and 4 In(0H)s and dry NHIVOI were ground for two hours in a ,motor-driven agate mortar, and were heated for two hours at 850' 6 Prepared as no. 5, except the Pattern consists of all lines found in no. 5 amounts of dry powders were taken t o give 40 mole plus some weak VSOSlines % In&lsand 60 mole % of VZO~ 7 Prepared. as no. 5, except the Pattern consists of all lines found in no. 5 amounts of dry powders were taken to give 60 mole plus some weak yoof Inn01 and 40 mole % InaO, lines VaOr
DEPARTMENT OF CHEMISTRY THERICEINSTITUTE RECEIVED JUNE23, 1948 HOUSTON, TEXAS
Absorption Spectra of
4-(4-Diethylamino-1-
methylbutylamino)-7-phenoxyquinoline and 4(4-Diethylamino-1-methylbutylamino)-7-ethoxy3-methylquinoline BY FREDERICK C. KACHOD, EDGAR A. STECKAND GALEN W. E W I N G ~
A comparison of the absorption spectra of 4-(4diethylamino - 1- rnethylbutylarnino) - 7 - phenoxy(1) Present address: Depnrtment of Chemistry. Union College, Schenectady 8, N. Y.
