996
ROBERT E. LUTZAND ROBERTH.
Vol. 71
JORDAN
the solutions were prepared. The results are tabulated in Table I1 and the complete curves shown in Fig. 1.
phenone hydrochloride," and o-morpholinoacetophenone hydrochloride12 were examined in absolute ethanol solution (see Table I11 and Fig. 3). Using absolute methanol as a solvent, the TABLE I1 spectra of the morpholine hydrochlorides (IV) ABSORPTION SPECTRA O F THE 2-PHENTZ-2-HYDROXYand (VI) and the dimethoxy compound (IX) MORPHOLINES IN HEPTANE were examined. A summary of the results is Molar Maxima Minima given in Table IV and the complete curves are Concn. Morpholines x 104 x,A. x ;o-l x,A. x ;o-a shown in Fig. 4. 15.1 0.60 2.67 2.47 1.24
(1)
(11) (111)
2350 2350 2550 2350 2350
0.63 .66 .51 .92 .98
2260 2260 2300 2340 2340
0.59 .55 .49 .91 .97
w - Dibenzylamino-
acetophenone
TABLE ZV ABSORPTION SPECTRA O F %HYDROXY AND 2-METHOXYMORPHOLINE HYDROCHLORIDES IN ABSOLUTE METHANOL Morpholine
1.50 2390 12.96 2240
10.05
Using heptane as the solvent, the spectra of (I) and (111) were observed in more dilute solutions and compared with the previous results (see Table I1 and Fig. 2). The spectra of the morpholine hydrochlorides (V), (VII), (VIII), and of w-dibenzylaminoaceto-
IV VI IX
Molar concn. X 104
5.32 3.53 4.16
Maxima A,A.
2500 2805 2500
c
Minima
X 10-8
x,A.
0.93 . 26 .49
2260 2280 2240
e
X 10-8
0.11 .04 .02
Summary
1. The reactions of phenacyl bromide with N-substituted ethanolamines have been studied and the desired N-phenacyl-N-substituted TABLE I11 ethanolamines have been found t o have tautoABSORPTION SPECTRA O F 2-HYDROXY AND 2-ETHOXY-2- merized to their respective hemiacetal forms, the PHENYLMORPHOLINE HYDROCHLORIDES IN ABSOLUTE ETH- 2-phenyl-2-hydroxymorpholines. 2. Some acetal derivatives, or 2-phenyl-2ANOL alkoxymorpholines, have been obtained from these Molar Maxima Minima concn. Morpholines x 104 LA. x'10-a x , ~ . x io-@ hemiacetals. 3. Absorption spectra studies have aided in Y 3.67 2500 1.05 2300 0.44 the elucidation of these structures. VI1 3.37 2570 0.31 2300 0.13 4. These results confirm for the N-phenacylVI11 1 . 4 5 2550 0.52 2340 0.25 N-substituted ethanolamines the conclusions Acetophenones reached by Lutz, et al., with the related a-(Nw -Dibenzylaminosubstituted-N-ethanolamino) -desoxyben~oins.~ hydrochloride 1 . 5 4 2480 11.89 2260 5.86
w-Morpholinohydrochloride
(12) Rubin and Day, J. Ore. Chum., 6, 54 (1940).
1.00 2480
[ C~NTRIBUTIONW O M
13.70
THE
..
..
LINCOLN, NEBRASKA
RECEIVED JULY 17, 1948
COBB CHEMICAL LABORATORY O F THE UNIVERSITY OF VIRGINIA]
Ring-Chain Tautomerism of a-(Ethylethano1amino)-acetophenone' BY ROBERTE. LUTZAND ROBERT H. JORDAN^ Because of the ring-chain tautomerism involved in the a-(ethylethanolamino) -desoxybenzoins,* and because of the interest in these compounds as (1) This is the second paper dealing with ring-chain tautomerism of hydroxyalkylamino ketones. This aork, except for the ultraviolet absorptions, was included in a doctorate dissertation by R. H. Jordan, University of Virginia, May, 1948. Some financial support for rnuiurementr and analyacp, from a grant-in-aid by the National Cancer Institute, is acknowledged. (2) Holder of Tenneuee ,Eac.tman Company Fellowship, 19471948. (3) (a) Lutz, Freek and Murphey, Tnrs JOURNAL, 70, 2016 (1948) [an m o r appears in Tnble I, page 2016, where NBI for compound 819 should read NHC~H~N(CiHr)r-P.Ano
