Aug., 1946
SUGAR INTERCONVE RSION [CONTRIBUTION FROM
THE
UNDER
REDUCING CONDITIONS
1443
CHEMICAL LABORATORY OF THEOHIOSTATE UNIVERSITY ]
Sugar Interconversion under Reducing Conditions. 111'~2 B Y 11.L. WOLFROIT, B.iv. LEW3 AND R. A T r l X GOEPP,JR.4 In a preceding communication,' the following components were reported as present in a commercial product, designated product B, manufactured by the electroreduction of D-glucose ay. pH 10-13 : sorbitol,6 2-desoxysorbitol, D-mannitol, and 1-desoxyD-mannitol. It was shown that the formation of these substances was easily explained by a mechanism of 1,2-enolization followed by the electroreduction of the carbonyl group to the hydrocarbon stage. In addition, the formation of l-desoxysorbitol as a component OS the mixture was predicted. In the present work 1desoxysorbitol and several useful derivatives of i t were synthesized and employed for nucleation but it was not -found in any of the fractions studied. 1-Desoxy-D-mannitol was likewise not encountered in the present work. Our results (the preponderance of 2-desoxyhexitols over l-desoxyhexitols) verify the known fact that ketose:; are more readily reducible than aldoses.'j The hexitols isolated likewise may have arisen mainly from the ketoses rather than the aldoses. Cmtor and Peniston:' have shown that the ease of reduction of a number of aldohexoses a t the dropping mercury cathode was in the following decreasing order : L-dlose, D-galactose, D-mannose and Dglucose. The fact that D-glucose occupies the lowest position would also augur for the prezence of smaller quantities of 1-desoxysorbitol in the product under immediate investigation. Caution is, however, required in accepting concluijions based upon tlie isolation or non-isolation of products from such a complex and difficultly separable mixture as product B. 1-Desoxysorbitol (syn. L-gulomethylitol) has been described by Muller and Reichstein8 and its pentaacetate by Gatzi and R e i ~ h s t e i n . ~I n the present work 1-desoxysorbitol pentaacetate was synthesized by the high-pressure catalytic reduction of 1-desoxy-keto-r-fructose tetraacetatelowith (1) Preceding communication in this series: M. L. Wolfrom, F. B. Moody. 31. LiiliiipsI)?ri: aud R . 11. Goepp, Jr., THISJ O U R X A L , 68, 578 ( 1 9 4 6 ( 2 ) I're,ented i n p a r t before t h e Division of Sugar Chemistry a n d Technology a t t h e 107th Meeting of t h e American Ch-mica1 Society, Cleveland, Ohio, April 6, 1944. ( 3 ) .4tlas Porvder Company Research Associate of T h e Ohic S t a t e L'niversity Research Foundation, 1041-1945. f t ) Research Drpartment, Atlas Powder Company, W i l m n g t o n Delorvxe. (5j \Ye dcnote a s mrliitol t h e common form of t h i i hevitol as obtained by the rcdi,rtirin of I>-gIuco>e. Carbon one nf this horliitul corresponds t o 11, I)rewrsiir in o-glucose. (6) J FCeyro\.ski. and I Smoler, Coll. Cwchixlui.. Cherc. C o i i , m i i i ~ . , 4, 2 2 1 ( 1 9 3 2 ti) S. 11. C ~ i n t ma n t i Q P Peniston, Tiirs J t r u l i s a r . , 6 2 , 211.3 ~1!l40). ( h ~€1 111:!lv) ; I J ~ 'T ~ I I t i . i c t i ~ t r i i ~IIclim ('iiiiii . - ! , / i i . 21, 2:q I I ! ) R X I . I!)) K ( : i i t T i i i i t i 'I' i < c i r h \ t e i n i b z d , 21, !I21 1 I!l:iXl (10) XI. 1- \Vollrum .in11 I
