Di-D-fructose anhydride III

In 1933, Schlubach and Knoop32 isolated a di-D-fructose dianhydride from Jerusalem artichoke and tentatively identified it as difructose anhydride I [a-D-Fru/-1,2 2,1 - 3-D-Fn / (5)]. Alliuminoside ( -D-fructofuranose- -D-fructofura-nose 2,6 6,2 -dianhydride) was isolated from tubers of Allium sewertzowi by Strepkov33 in 1958. Uchiyama34 has demonstrated the enzymic formation of a-D-Fru/-1,2 2,3 -(3-D-Fru/ [di-D-fructose anhydride III (6)] from inulin by a homogenate of the roots of Lycoris radiata Herbert. 

It has been mentioned that the mixture of trimethyl-D-fructoses from the acid hydrolysis of hexamethyl-di-D-fructose anhydride III, which are now known to be the 3,4,6- and 1,4,6-trimethyl-D-fructoses, shows a specific rotation near that of pure 3,4,6-trimethyl-D-fructose it is to be inferred accordingly that these two trimethyl-D-fructoses do not differ greatly in rotation. Montgomery76 has synthesized 1,4,6-tri-methyl-D-fructose and found its rotation in chloroform to be [a] d = + 29.7°, a value approximating that of 3,4,6-trimethyl-D-fructose (+ 27.7° in the same solvent). Pertinent also are the respective rotations of the acetone condensation products from these two trimethyl-D-fructoses. Montgomery found that 3,4,6-trimethyl-D-fructose under-... 

If di-D-fructose anhydride II has formula XIX, a mixture of 1,3,4-and 1,4,6-trimethyl-D-fructoses would be present in the hydrolytic product. Such a mixture would have a specific rotation of — 10° to — 20° (water) in contrast to the value of + 25 to + 30 found by McDonald and Jackson.76 The rotation of 1,4,6-trimethyl-D-fructose was measured by Montgomery76 in chloroform (+ 29.7°), but it has not been measured directly in water. However, the hydrolysis data of McDonald and Jackson76 for hexamethyl-di-D-fructose anhydride III show that 1,4,6-trimethyl-D-fructose has about the same rotation in water as in chloroform. The argument thus appears to exclude structure XIX. 

The only dimethyl-D-fructose which has been characterized, 3,4-di-methyl-D-fructose, has been prepared by McDonald and Jackson141 from di-D-fructose anhydride I. Tritylation of this anhydride gives the 6,6 -ditrityl derivative which is methylated to 3,4,3, 4 -tetramethyl-6,6 -di-trityl-di-D-fructose anhydride I. Removal of the trityl groups followed by hydrolysis yields liquid 3,4-dimethyl-D-fructose, [ ]d —60.66° in water. It has also been obtained, with 4-methyl-D-fructose, from the hydrolysis of methylated di-D-fructose anhydride III. The structure of this dimethyl-D-fructose follows from its method of preparation from di-D-fructose anhydride I whose structure is known.10 McDonald and Jackson also prepared 3,4-dimethyl-D-fructose from inulin by the following method inulin — monotrityl inulin — monotrityl inulin diacetate — dimethyl monotrityl inulin — dimethyl isopropylidene-D-fructose — methyl dimethyl-D-fructoside —> 3,4-dimethyl-D-fructose. Its structure was confirmed by its oxidation without loss of methyl to the same lactol of the dimethyl dibasic acid obtained from 1,3,4-trimethyl-D-fructose (see page 78). The phenylosazone made from 3,4-dimethyl-D-fructose has m. p. 126° that from 3,4-dimethyl-D-glucose has not been recorded. 

The preparation of liquid 4-methyl-D-fructose, [a]D —87.5°, from di-D-fructose anhydride III has already been mentioned (see page 80). The phenylosazone, m. p. 156°, is identical with that obtained from 4-methyl-D-glucose.14a... 

Taniguchi, T. and Uchiyama, T., The crystal structure of di-D-fructose anhydride III, produced by inulin d-fructotransferase, Carbohydrate Res., 107, 255-262, 1982. 

Ethers and Anhydro-sugars. - 1,6-Anhydro-e-D-mannopyranose, di-D-fructose anhydride III, 1,2-0-(2,2,2-trichloroethylidene)-a-D-glucof uranose (a-D-chloralose), 1,6,2,5-dianhydro-a-L gulofuranose, 2,3,5-0-orthoacetyl-l, 6-anhydro-a-L-gulo furanose, and the rhamnosyl dihydropyrone ether (1). ... 

Historically, the trivial names diheterolevuloson 1, 11, III, and IV have been used to describe the di-D-fructose dianhydrides, which contain one or two pyra-nose rings. Similarly, the names di-D-fructose dianhydride (or difructose anhydride) 1,11, III, IV, and V have been used to describe those compounds in which two furanose rings occur. The names diheterosorhosan I and II have also been coined. Trivial names should not be used in other than a secondary manner for example, they may be listed in parentheses after the IUPAC name. 

A most important theoretical study was presented by Hennig on the possible reaction-mechanisms involved in the formation of cyclic and keto derivatives during acetylation (see Scheme III). When 1 mole of 3,4,5-tri-0-acetyl-l,6-di-0-trityl-fcefo-D-fructose (a) is treated at room temperature with two moles of acetyl bromide in acetic anhydride, 1,3,4,5-tetra-... 

Jackson and Goergen 133) and Jackson and McDonald 134) have isolated three dianhydrides of D-fructose from the nonreducing residue that remains after the removal of D-fructose from the acid hydrolyzate of inulin 135). On the basis of methylation data 136), structure (III) was assigned to difructose anhydride I. Difructose anhydride III was considered 135) to be di-D-fructofuranose l,2 2,3 -dianhydride. Wolfrom, Hilton, and Binkley 129) believe, on the basis of rotational data, that difructose anhydrides II and III are structural units differing only in the configuration of one of the asymmetric centers on the substituted dioxane ring. 

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