Glucitol 3,6-anhydro

Glucitol, 1,5-anhydro-D- 4.6- phenyl- 4.6- pheny 1-2,3-( diphenyl- 176-177 -80 1,4-dioxane 3... 

Methyl 6-deoxy-6-[3,4,5-trihydroxy-2-(hydroxymethyl) -1 -piperidinylJ-a-D-glucopyranoside, 9CI, MDL 73945, 1, 5-Dideoxy-l, 5- [(6-deoxy-l-0-methyl-6-a-D-glucopyranosyl)imino J-D-glucitol. 1, 5-Anhydro-5-aza-5-deoxyglucitolfN - 6) -methyl-a-D-glucopyranoside [127214-23-7]... 

A series of sorbitol-based nonionic surfactants are used ia foods as water-ia-oil emulsifiers and defoamers. They are produced by reaction of fatty acids with sorbitol. During reaction, cycHc dehydration as well as esterification (primary hydroxyl group) occurs so that the hydrophilic portion is not only sorbitol but also its mono- and dianhydride. The product known as sorbitan monostearate [1338-41 -6] for example, is a mixture of partial stearic and palmitic acid esters (sorbitan monopalmitate [26266-57-9]) of sorbitol, 1,5-anhydro-D-glucitol [154-58-8] 1,4-sorbitan [27299-12-3] and isosorbide [652-67-5]. Sorbitan esters, such as the foregoing and also sorbitan monolaurate [1338-39-2] and sorbitan monooleate [1338-43-8], can be further modified by reaction with ethylene oxide to produce ethoxylated sorbitan esters, also nonionic detergents FDA approved for food use. 

Treatment of l,4 3,6-dianhydro-D-glucitol with boron trichloride gives l,6-dichloro-l,6-dideoxy-D-glucitol (20). Although methyl 6-chloro-6-deoxy-a-D-glucopyranoside (isolated as the tribenzoate) could be isolated from the reaction of methyl 3,6-anhydro-a-D-glucopyranoside with boron trichloride (21), the application to the isomeric furanoside derivative led to complex results. 

Anhydro-2,3,4,6-tetra-0-methyl-D-glucitol-1-ide 2-Carb-32.4. Radical ions... 

Support for this result was obtained from the taste of 1,5-anhydrohexitols, which, only for purposes of comparison, can be regarded as 1-deoxyal-dopyranoses. 1,5-Anhydro-D-glucitol (that is, the incorrectly named 1-deoxy-D-glucopyranose ) (14), 1,5-anhydro-D-mannitol ( 1-deoxy-D-mannopyranose or 2-deoxy-D-fructopyranose ) (15), and 1,5-anhydro-D-galactitol ( l-deoxy-o-galactopyranose ) (16) are all purely sweet, without any trace of bitterness. Furthermore, the complete absence of bitterness of 1,5-anhydromannitol (16) clearly indicates that the anomeric... 

The influence of other radicals in the stabilization of dihydroxytetrahy-drofuran rings should also be considered, as, for example, the p-toluene-sulfonic esters.41 When the compound LXI is hydrolyzed by acids, it gives the 2,5-anhydro derivative (LXII), whereas the compound LXIII gives D-glucitol. 

Brigl and Griiner45 reported the isolation of three products when 1,6-di-O-benzoyl-D-mannitol (29) was heated in boiling 1,1,2,2-tet-rachloroethane in the presence of p-toluenesulfonic acid as the catalyst. These compounds were assigned mono- and di-anhydro structures, and were later shown by Hockett and coworkers46,47 to be 1,4-anhydro-D-mannitol dibenzoate (30), l,4 3,6-dianhydro-D-man-nitol dibenzoate (31), and 2,5-anhydro-l,6-di-0-benzoyl-D-glucitol (32). The latter compound, which can be readily isolated from the... 

Sugihara and Schmidt49 reported the isolation of 2,5-anhydro-D-glucitol in crystalline form its preparation on a relatively large scale has been described in the patent literature,50 and consists in the thermal dehydration of D-mannitol. The process leads to the formation of 1,4-anhydro-D-mannitol, 1,5-anhydro-D-mannitol, 1,4 3,6-dianhydro-D-mannitol, and 2,5-anhydro-D-glucitol, which is isolated as the crystalline 1,3-O-isopropyIidene derivative (35). 

Intramolecular cyclization can also be effected with acyclic intermediates derived from such readily available alditols as D-mannitol. Kuszmann and Vargha63 reported the formation of 2,5-anhydro-l,6-dibromo-l,6-dideoxy-4-0-(methylsulfonyl)-D-glucitol (63), in 73% yield, by boiling 3,5-di-0-acetyl-l,6-dibromo-l,6-dideoxy-2,4-di-0-... 

Miiller and Vargha65 reported that treatment of 1,6-di-O-benzoyl-D-mannitol (29) with p-toluenesulfonyl chloride gave 2,5-anhydro-l,6-di-0-benzoyl-3,4-di-0-p-tolylsulfonyl-D-glucitol (67). The formation of this compound may be the result of a favored p-toluenesulfonyla-tion at the 2(5)-hydroxyl group, followed by intramolecular cycliza-tion and subsequent esterification by the excess of the reagent. This... 

The sugar alcohol anhydride polygalitol, 1,5-anhydro-D-glucitol, may be prepared from the root of Poly gala Senega L.49 The process is, however, a time-consuming one and chemical synthesis of the substance by Raney... 

Phenyl l-thio-/S-cellobioside heptaacetate to 1,5-anhydro-4- (d-D-gluco-pyranosyl)-D-glucitol heptaacetate... 

Phenyl l-thio-0-D-glucopyranoside tetraacetate to 1,5-anhydro-D-glucitol... 

Methyl 2-methyl-3-methylthio-4,6-benzylidene-/S-i>-idoside to methyl 2-methyl-3-de8Oxy-4,6-benzylidene-0-D-idoside Methyl 3-methylthio-5-L-xyloside to methyl 3-desoxy-/J-o-xyloside Ethyl thiol-D-ribonate tetraacetate to aldehydo-D-ribose tetraacetate Methyl thiol-D-gluconate pentaacetate to D-glucitol hexaacetate Ethyl tetraacetyl-0-D-glucopyranosyl xanthate to 1,5-anhydro-D-glucitol tetraacetate... 

Anhydro-L-gulono-1,4-lactone (62) was prepared100 in 62% yield by the platinum-catalyzed oxidation of 1,4-anhydro-D-glucitol. Methyl 3,4,5-tri-0-acetyl-2,6-anhydro-L-gulonate (63, R = H) was obtained from D-glucuronic acid by way of the tetraacetate (63, R = OAc) and the thioglycoside101,102 (63, R = SPh) (76%), followed by reduction in the presence of Raney nickel to afford 63 (R= H) (68%). 

When 1,5-anhydro-l-phenyl-D-glucitol (64, R = CH2OH) was stirred in nitric acid, 2,6-anhydro-6-deoxy-6-phenyl-L-gulonic acid (64, R = C02H) was formed in 22% yield.103 On treating 3,4,5-tri-0-acetyl-2,6-... 

Anhydro-L-xylose, characterized as the benzimidazole derivative formed from the corresponding 2,5-anhydro-L-xylonic acid and o-phenylenediamine, has likewise been prepared92 by the action of one molar equivalent of periodic acid on 1,4-anhydro-D-glucitol. 

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