G. UT.HUFFMAN, B. A. LEWIS, F. SMITH .WD D. R. SPRIESTERSBACH
4346
of sodium (0.3 g.) in methanol (20 ml.) was added and the mixture allowed t o stand overnight. After neutralization with carbon dioxide, the solution was evaporated to dryness and repeatedly extracted with light petroleum. T h e solvent was evaporated and the residue sublimed in vucuo yielding 1.1 g. (70%) of IX, m.p. 109". mo-Inositol (X).-The anhydroinositol I S (415 mg.) was heated on the steam-bath with 0.1 ,V sulfuric acid18 ( 5 ml.) for three hours. The substance dissolved in a few minutes (with loss of acetone) and after about 30 minutes crystals began t o separate. They were filtered and washed with iFater giving 160 mg. (52%) of neo-inositol. For analysis it was recrystallized from mater. It decomposes and iublimes on slow heating but when dropped on a heated block i t melts a t 315'. I t has no optical activity. Anal. Calcd. for C6HlzOe: C, 40.0; H, 6.7. Found: C, 40.3; H, 7.2. The hexaacetate, prepared by acetylation with sodium ncctate and acetic anhydride, rras crystallized from ethanol m d melted at 253 O . (18) Heating v i t h hydrochloric acid gives chlorodeoxyinositols as by-products; their presence can he shown b y paper chromatography in acetone-water ( 8 : Z v . / v ).
[COSTRIBL3"L'OS FROM THE
Vol. 77
Anal. Calcd. for C18H2401~: C, 50.0; H, 5.6. Found: C, 50.3; H , 5.65. The acid mother liquor of neo-inositol was mi.ted with ail equal amount of ethanol resulting in a precipitate (6 mg.) which was shown by paper chromatography t o consist of a mixture of neo- and ( - )-inositols. The clear liquor was decanted and neutralized with barium carbonate and filtered; the filtrate was evaporated to dryness and the residue crystallized from aqueous ethanol to give 103 mg. (347,) of ( - )-inositol which, after another crystallization, had m . p . 242-243', [@Iz5D -64.5 zk 2' ( c 1.0, water);o reported for (-)-inositol is the m.p. 246" and [WID -69 (water).
Acknowledgments.-The authors wish to express their gratitude to Dr. G. Lindstedt, the Swedish Tanning Research Institute, Stockholm, and to Dr. R. H. Smith, The Rubber Research Institute of Malaya, Kuala Lumpur, for generous gifts of pinitol and quebrachitol, respectively. Financial assistance by the (*lustralian) Commonwealth Science Fund to one of us ( N , K . l I . ) is gratefully acknowledged. SYDNEY, AUSTRALIA
DEPARTMEXT O F AGRICULTURAL BIOCMEMISTRY, ~ ~ X I V E R S I TOYF h l I S S E S O T A ]
Periodate Oxidation in the Synthesis of Some Partially Methylated Sugars1 BY
G. is7. HUFFBIAN, BERTHAx.LEWIS,F. SMITH XND D. R . SPRIESTERSBACH RECEIVED FEBRUARY 19, 1955
Cleavage of the carbon chain between positions C, and C2 by periodate oxidation, under acid conditio~isto preserve the intermediate formyl group produced from C1, has provided a means of synthesizing 2 - ~ - m e t h y l - ~ - a r a b i n o s2-U-methyle, D-threose and 2,5-di-~-methyl-~-arabinose from 3-O-inethyl-~-glucose, 3-0-methyl-D-xylose and 3,6-di-U-inethyl-~-glucose, respectively. Scission of CI from the hitherto unknown 3,5-di-0-methyl-D-glucoseby periodate oxidation has yielded 2,4-di0-methyl-D-arabinose. A similar oxidation of 1,2-O-isopropylidene-3-O-methyl-~-glucose followed by reduction and hydrolysis provides an additional route to 3-~-rnethyl-~-xylose.
Methylation studies applied to polysaccharides sunie the expected quantity of periodate.9--11This require partially methylated sugar derivatives as incomplete oxidation has been attributed to an inreference compounds. X a n y of these partially termediate stable formyl ester formed by preferenmethylated sugars are incompletely characterized, tial cleavage of the carbon chain between C1 and CZ some are known only in an impure state while oth- without rupture of the acetal linkage. Support for ers have never been synthesized. I t is shown herein this theory was forthcoming from the observation that oxidation of well-characterized partially nieth- that oxidation of 3-0-niethyl-~-glucosewith periylated sugars or their derivatives with periodic acid odic acid gave the well-defined 4-0-formyl 2-0provides a simple and convenient route for the syn- inethyl-~-arabinose. '' thesis of certain methylated sugars. By utilizing the stability of the intermediate Cleavage of 1,2-glycols by periodic acid,2 a reac- formyl ester produced by periodate cleavage of the tion which proceeds rapidly to completion unless glycol grouping a t CI and Cz,the following rnethylthe glycol is of the fixed t r a m t ~ p e ,has ~ 'been ~ util- ated sugars have been prepared : 2-O-methyl-~ized previously both for structural studies of simple arabinose, 2-0-methyl-D-threose and 2,s-di-0and coniplcx c a r b ~ h y d r a t e s ~and - ~ for synthetic methyl-D-arabinose from 3-O-methyl-D-glucose, 3purposes.8 0-niethyl-D-xylose and :~,R-di-O-methyl-D-glucose, Certain partially methylated sugars, when sub- respectively. jected to oxidation with periodic acid, do not conii7hereas the formyl esters of some sugars were stable a t room temperature, t h a t formed from 3 - 0 (1) P a p e r N o . 3320, Scientific Journal Series, XIinnesota Agricult u r a l Experiment S t a t i o n , University of Minnesnta, S t . Paul, Minnemethyl-D-glucose underwent hydrolysis and further sota. cleavage of the carbon chain occurred unless the (2) L. Malaprade, Birll. soI. Abdel-Akher, J . E. C a d o t t e , Bertha .I. Lewis, K. M o n t jomery, F. Smith and J. 17. Van Cleve, XVatiLre, 171, 474 (1933). ( i j 11.?.l~del-Akher, 1. K . Iianiilton, I:
