732
A. F. THOMPSON, JR., N. A. MILASAND IDA ROVNO
nickele as the catalyst. In each experiment after 0.1 mole of the azo compound, 0.25 mole of the aldehyde and 2.0 g. of sodium acetate had been dissolved in 150 cc. of alcohol, from 2.0 g. to 40 g. of Raney nickel was added and the mixture placed in the machine a t an initial pressure of 45 lb. It was found that 10 g. of Raney nickel was best, since it was the smallest quantity which gave a smooth and rapid reduction. The mixture was shaken until no more hydrogen was absorbed, usually from one to two hours, 0.3-0.4 mole of hydrogen being taken up. After the catalyst had been removed by filtration, the solvent was distilled on the steam bath, In the case of the lower molecular weight amines the reaction mixture was acidified before the evaporation of the solvent. The residue, made basic if necessary, was extracted with ether and the ether dried over sodium hydroxide. After the removal of the drying agent, the ether was evaporated and the products obtained by distillation, usually a t reduced pressure. Amines from Azobenzene.-Using the general procedure described above N,n-butylaniline was obtained from azobenzene in 71% yield and identified as the p-bromo(87") Similarly benzenesulfonamide, m. p 55-86 N-n-heptylaniline was obtained in 74% yield and also identified as the p-bromobenzenesulfonamide, m p. 114-115" (115 0).3 N-Benzylaniline was isolated in 49% yield as the hydrochloride, m. p. 210-212 O (214-216").* N,N Dimethyl N',N' - di n butyl p phenylenediamine, prepared similarly from N,N-dimethyl-p-aminoazobenzene and n-butyraldehyde in 76% yield, b. p.
,'
-
-
- -
- -
(6) Covert and Adkins, THIS J O U R N A L , 54, 4116 (1932). (7) Marvel and Smith, ibid., 46, 2696 (1923). (8) Brand, Ber., 42, 3460 (1909).
[CONTRIBUTION N O .
239 FROM
THE
VOl. 03
150-175" (20 mm.), was identified as the picrate, in. p. 121-122O. Anal. Calcd. for C2ZHa10yN6: N, 14.7. Found: N , 14.8. A 7370 yield of n-hutylaniline was also obtained in this reaction. N,N-Di-n-butyl-p-aminophenol was obtained in the same way from p-hydroxyazobenzene and n-butyraldehyde. It was isolated as the benzoate by treatment with benzoyl chloride and aqueous alkali; yield 46%. This benzoate melted a t 232-233' after two crystallizations from acetic acid. Anal. Calcd. for C21H270sN: N, 4.31. Found: N, 4.47. I-(N,N-Di-n-buty1amino)-2-naphthol was prepared in 41 % yield from 1-phenyl-azo-2-naphthol and n-butyraldehyde. It was isolated by adding water to the reaction mixture after half of the alcohol had been distilled, m. p. 106-107O. As it darkened rapidly on standing, it was stored as the hydrochloride, in.p. 225-227'. Anal. Calcd. for ClsH2aONCl: C1, 11.6. Found: C1, 11.5.
Summary Three alkylanilines have been prepared in 49-7470 yield by treating an alcoholic solution of azobenzene and an aldehyde with hydrogen in the presence of Raney nickel and sodium acetate. When an activating group such as hydroxyl or dimethylamino is present in the ortho or para position, a tertiary amine is produced. URBANA, ILLINOIS
RESEARCH LABORATORY O F ORGANIC
RECEIVED DECEMBER 11, 1940
CHEMISTRY O F THE
MASSACHUSETTS INSTITUTE
OF TECHNOLOGY]
The Synthesis of Certain Unsaturated Substances from p-Ionone and Substituted Vinylacetylenes BY A. F. THOMPSON, JR., N. A. MILASAND IDAROVNO' Substances prepared by condensation of Pionone so that the p-ionone ring is retained, and a longer unsaturated side chain results, are of interest for a t least two reasons. First, there is the possibility that such substances may exhibit the physiological activity of Vitamin A, a t least in some degree. Second, the physiological properties of such synthetic substances shed light on the specific structural arrangement necessary for a molecule to possess Vitamin A activity. It was decided to investigate the condensation products of vinylacetylene, and two of its simple (1) Part of the material of this paper is abstracted from a thesis submitted to the Massachusetts Institute of Technology by Ida Rovno in partidl fulfillment of the requirements for the degree of Bachelor of Science
derivatives, with 0-ionone. The condensation product from p-ionone and vinylacetylene itself has already been prepared by Zal'kind, Zonis and Blokhin2 who reported that their product was physiologically inactive. However, the unsaturated carbinol derived from this condensation product by partial reduction of the triple bond has never been reported. And there is no published description of any condensation products of p-ionone with derivatives of vinylacetylene. The series of transformations performed in the present investigation is illustrated by formulas I-VI1 inclusive. It was hoped a t the outset that (2) Zal'kind, Zonis and Blokhin, Compt. rend acad. w i . , U S.
S.R . , 2, 57 (1935).
March, 1941
-I33
VINYLACETYLENE DERIVATIVES OF 0-IONONE
By slow addition of one mole of hydrogen in the conversion of I11 t o VI11 by a 1,5 shift of the the presence of palladium the carbinols (111) rehydroxyl group could be worked out quite simply sulted from (11). The smooth addition of one by analogy with the ease with which the 1,3 transformation proceeds, making i t so useful for other syntheses in this field? \\ However, the 1,5 shift has not been ji +-- r = - + - g - x found to occur as readily as had been ,sl I' H 11 anticipated. Further work on this I/ 0 g 0 04 Q z 0 aspect of the problem is in progress. 1 I Ill 0 Meanwhile, the present paper reports 0-0 0-0-2 o o-fl-0 0 I 1 ,3: z / * j z the preparation and properties of the o tertiary carbinols. x u 0 I z 11 The condensation of 0-ionone with S I p simple vinylacetylene derivatives has I /I I/ 0 been accomplished by two methods. 0-,w V-F I The condensation took place in the 0 0 x x presence of potassium tertiary amyl$j P ate to furnish small yields of the ter"0 E tiary acetylenic carbinols (11). The /,sl Grignard reagents of the acetylenic hydrocarbons reacted to give SO-SO% yields of the same 1,2 addition prodI 1 ucts (11). Contrary to expectations, 0 the 1,4 product was formed in relatively small amount. The structures 0-5-0 of the carbinols I1 prepared by the -"I/ Grignard reaction were confimed as rn follows. They absorbed five moles of $ 5 - 9 hydrogen in the quantitative hydro03:- p geriation and yielded nearly one mole 0 3: of methane in the Zerewitinoff apparatus. Furthermore, on complete reduction they furnished carbinols (VI) identical to the carbinols prepared ?\ \ from tetrahydroionone by a parallel .-.VP, J / 7 / /---\/ series of reactions. \-A \-A zzz I 1 V I I 1 1 This behavior of the vinylacetylene P' a Grignard reagents, in yielding 1,2 ad6 Y i c9 o i dition products, is in contrast with the p&p z results of Kipping and Wild4 who ob8 ,I 4 '10 tained no evidence of 1,2 addition a F8,F l!l I 0 products from the addition of methyl0 3 It 0I/ - p I 1 I II magnesium bromide and phenylmagI 0"3: 0--_w 0 w Q nesium bromide to p-ionone. The ,X 11 V-F 11 addition of other acetylenic Grignard n p reagents is being investigated to determine whether the different mode of addition is a property of acetylene derivatives, or mole of hydrogen to the triple bond has been is peculiar to vinylacetylene derivatives. demonstrated by many workers, and by Gould and Thompson3' under nearly the same conditions. (3) (a) Gould and Thompson, Tms J O U R N A L , 87, 340 (1935). Contains numerous references t o earlier examples. (b) Gould, Since the compounds (VIII) were not readily J. Bid. Chcm., 144,xli (1936). available, the carbinols (111) were tested for (4) Kipping a n d Wild, J. Chcm. .So
