'rABLB
111
A C E T O L Y S I S O F Cis-CYCLOPEXTYL-2-d
TOSYLA~E
'knip. 50.0'; [ROTS] = 0.0965; [NaO.lc] = 0.1170; calcd. infiiiity titer, 1.762 i d . ; found, 1.779 ml. Time, min.
Titer, ml.
0 108 9 209.2 315.3 384.5 488.0 555.8 G16.7
7.609 6.066 4.858 3.920 3.393 c>
-.,LaI
I .
2.356 2.082
lOSk, sec. -la
3.46 3.55 3.50 3.50 2.32 3.52 3.50 __ 8 . 5 1 =k 0 ,02'
Using equation for a first-ordei- rcaction. squares k = 3.502 X sec.-l.
The least
per 1nolecule).~5 The tosylate iras prepared as above, m.p. 28-29'.
Cyclopentanol-1-d.-Cyclopentanone was reduced with lithium aluminum deuteride using the procedure detailed above for the reduction of IV-dr; yield 3 g. (37%) of alcohol, b.p. 140.5-141.5", dZ50.9547 (corresponding to 1.07 deuterium atoms per m ~ l e c u l e ) . ' ~The tosylatc prepared as above had m.p. 25.5-26".
Kinetics.--Anhydrous acetic acid WdS prepared by treating reagent grade acetic acid, which had been analyzed for water b y the Karl Fischer method, with a n amount of acetic anhydride calculated to give a lY0 excess. Freshly fused sodium acetate and dried p-toluenesulfonic acid were used t u make up stock solutions in acetic acid. I n most of the runs about 2 g. of the tosylate was dissolved in sodium acctate stock solution in a calibrated 100-ml. volumetric flask. The flask was placed in a thermostat at 50.00 i 0.05' and aliquots were removed periodically with a calibrated 5-1d. automatic pipet and titrated potentiometrically with stock p-toluenesulfonic acid solution iu acetic acid. The procedure for the cyclopentyl-1-d tosylate runs was similar except that the solution was placed in sealed tubes which were periodically withdrawn and titrated. Infinity titers generally agreed with the calculated titers ivithin 1-270. A typical run is shown in Table 111; a suinniary of rate constants calculated by the method of least squares is presented Table 11.
Acknowledgment.-%'e are indebted to Professors W. D. Gwinn, I(. S . Pitzer, H. S . Johnston, G. C. Pimentel and W. E. Doering for discussions and suggestions which greatly assisted the formulation of some of the concepts and arguments presented in this paper. We thank Professor William H. Saunders, Jr., for exchange of information in advance of publication. BERKELEY 4, CALIF.
[ C O N T R I B U T I O N FROM THE DEPARTMENT OF CHEMISTRY, UNIVERSITY O F S O U T H E R N C A L I F O R S I A ]
Heterocyclic Compounds. VI.
Reduction of 3-(3,4-Methylenedioxyphenyl)-4-nitro1-phenyl- 1-butanonel
BY MILTON C . KLOETZEL AND
JACK
L. PIXKUS
RECEIVED NOVEMBER 11, 1957 Reduction of 3-(3,4-xnetl~ylenedioxyphenyl)-4-nitro-l-phe1~yl-l-butanone (I) by catalytic hydrogciiation 01 cr platitiurll black or Raney nickel, or by zinc dust and aqueous ammonium chloride, yields 4 - ( 3 , 4 - m e t h y l e i i e d i o x y p h e n y l ) - 2 - p l ~ e 1 ~ ~ ~ - ~ ' pyrroline (VI). Chemical and physical evidence clearly supports a A*-pyrroline structure for 1'1.
Pyrrolidines and Ai-pyrrolines have become increasingly recognized as characteristic reduction products from aliphatic y-nitro However, despite the fact that aromatic nitroketones frequently have been reduced t o N-oxygenated derivatives of indole or quinoline, l 2 oxygen-containing reduction products from aliphatic y-nitro ketones have remained elusive. Kohler and Drake2 reported the only products from catalytic hydrogenation of 3- (3,4-methylenedioxyphenyl) -4-nitro-1-phenyl-1-butanone (I) over platinum black, to be amino ketone IT, pyrrolidine I11 and an hydroxylated pyrroline to which (1) Partially abstracted from a portion of the P h . D dissertation of Jack L. Pinkus. (2) E. P. Kohler a n d N . I.. Drake, 1'HrS J O L J K N A I . , 45, 9144 ( 1 9 2 3 ) . ( 3 ) A . Sonn, B e y . , 68, 148 (1035); 72, 2150 (1039). (1) J . Dhont and J. P. Wibaut, Kcc. Lyav. chiwt., 63,81 ( l < I W ) . ( 5 ) X I . C. Kloctzel, T H I S JouRNnr., 69, 2271 (1947). ( 0 ) P. h l . Maginnity and J. B. Cloke, ibid., 73,49 ( l 9 . j l l . ( 7 ) P. G. Bordwell a n d M. Knell, i b i d . , 73, 2354 (1951). ( 8 ) I,. I . Smith and E. R . Rogier. ibid., 73, 3837 (1931). (9) B. Witkop, ibid , 76, 5597 (1954). (10) X I . L. Stein a n d A. Burger, i b i d . , 7 9 , 154 (1957). (11) 14. C. Kloetzel, J. L. Pinkus and R. M. Mashburn, ibid., 79, 4222 (1957). (12) A . Reissert, Bev., 30, 1030 (1897); S. Gabriel and W. Gerhard, i b i d . , 64, 1007 (1921); l i . I , McCluskey, THISJ O U R K A I . , 4 4 , 3873 ( 1 9 2 2 ) ; S. (:&hiel and K Wu , 2445 ( l 9 2 : j ) I Mcisetilieimcr u u d I < , S l u l z , i b i c i . , 68, ~
they ascribed structure IV or V. Prior to our reduction studiesi3 this was the only instance in which an oxygenated pyrrole nucleus had been obtained by reduction of an aliphatic y-nitro ketone.I5 For this reason it appeared of interest to include nitro ketone I in a series of nitro ketones whose behavior upon reduction we have been studying. In our hands, reduction of I by hydrogen over platinum black or Raney nickel, or by zinc dust and aqueous ammonium chloride, yielded only 4-(3,4methylenedioxyphenyl) - 2 - phenyl - AI - pyrroline (VI). We obtained none of the products (11-V) reported by Kohler and Drake.2 Pyrroline V I was characterized by forination of a crystalline picrate, hydrochloridei6 and oxalatc. (13) Stein and Burgerlo recently reported the preporativn o f i i n oxyKen-containing base by reduction of an nliphatic nitro ketone b u t did not ascribe t o i t 0 structui-e. Sliortly thereafter, Brown, Clark and Todd" reported the syuthesis of two :dicyclic nitrones Ihy reductivc
