Mannitol and derivs

Nitromannite (Nitromannitol). See in this Vol under Mannitol and Derivatives, M13-Lff... 

Anhydro-D-mannitol has been converted to the corresponding 1,6-diazido derivative ( H n.m.r. data for which are claimed to correct previously reported data see Vol.16, p.177, ref.29), and hence to 1,6-diamino-l,6-dideoxy-2,5-anhydro-D-mannitol and derivatives, which were incorporated into some chiral macrocyclic poly-26... 

Etherification. The reaction of alkyl haUdes with sugar polyols in the presence of aqueous alkaline reagents generally results in partial etherification. Thus, a tetraaHyl ether is formed on reaction of D-mannitol with aHyl bromide in the presence of 20% sodium hydroxide at 75°C (124). Treatment of this partial ether with metallic sodium to form an alcoholate, followed by reaction with additional aHyl bromide, leads to hexaaHyl D-mannitol (125). Complete methylation of D-mannitol occurs, however, by the action of dimethyl sulfate and sodium hydroxide (126). A mixture of tetra- and pentabutyloxymethyl ethers of D-mannitol results from the action of butyl chloromethyl ether (127). Completely substituted trimethylsilyl derivatives of polyols, distillable in vacuo, are prepared by interaction with trim ethyl chi oro s il an e in the presence of pyridine (128). Hexavinylmannitol is obtained from D-mannitol and acetylene at 25.31 MPa (250 atm) and 160°C (129). 

Nonionic Surface-Active Agents. Approximately 14% of the ethyleae oxide consumed ia the United States is used in the manufacture of nonionic surfactants. These are derived by addition of ethylene oxide to fatty alcohols, alkylphenols (qv), tall oil, alkyl mercaptans, and various polyols such as poly(propylene glycol), sorbitol, mannitol, and cellulose. They are used in household detergent formulations, industrial surfactant appHcations, in emulsion polymeri2ation, textiles, paper manufacturing and recycling, and for many other appHcations (281). 

Summarizing the results of many investigations, monosaccharides and such derivatives as D-mannitol and D-glucitol are rather weak acceptors. Disaccharides, including such acceptor products as isomaltose, are much better acceptors, except for certain molecules, for instance leucrose, which is not an acceptor.29,46,47 The decrease of enzyme activity with time has been described in terms of a first-order reaction. The inactivation parameters have been calculated for the immobilized enzyme. The inactivation constants kd were 0.0135 (1/d) when maltose was the acceptor (stabilizing), and 0.029 (1/d) when fructose was the acceptor.38... 

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). 

The crystallization energy, extrapolated for the warming rate zero is calculated for mannitol (13.5 kJ/Mol) and forNa-cefazolin (39,1 kJ/Mol). These data agree with measurements by other methods. The activation energies are generated with certain assumptions to be 335 kJ/Mol for mannitol and 260 kJ/Mol for Na-cefazolin. DeLuca L1.31J derived at with slightly different data at a warming speed of 0.625 °C/min, he found 16.3 kJ/Mol for mannitol and 41.8 kJ/Mol for Na-cefazolin. 

Another proof of the configuration of D-mannitol and also of D-manno-n-manno-octitol (XVI), which is likewise dependent on the experimental proof of the equivalent symmetry of D-mannitol is the following. D-Mannose has been converted, by successive cyanohydrin syntheses, first to a mannoheptose and then to a mannooctose which on reduction yielded a mannooctitol whose octaacetyl derivative is optically inactive. (It was not possible to examine the octitol itself because of its very low solubility in water.)87 The meso character of the octaacetate shows that the mannooctitol must possess a meso configuration, with a plane of symmetry between carbon atoms 4 and 5. To write its formula, the hydroxyl at carbon atom 7 is placed on the... 

The acetates of the l,4 3,6-dianhydrohexitols may also be useful as plasticizers both 2,5-diacetyl-l,4 3,6-dianhydro-D-mannitol and the analogous D-sorbitol derivative have been described.97... 

The hexitol anhydrides also have medicinal uses.97 Carr and Krantz98 found that l,4 3,6-dianhydro-D-mannitol was quite non-toxic to man and was a valuable diuretic. The dinitrates of both isomannide and isosorbide" have possible uses as agents for lowering blood pressure, though Burn and Stephenson100 found that the D-sorbitol derivative was twice as active as the D-mannitol derivative in this respect. 2,5-Diam-ino-2,5-didesoxy-l,4 3,6-dianhydro-D-mannitol and -D-sorbitol have been prepared and their sulfanilamido derivatives obtained.101 These however showed no outstanding bacteriostatic activity. 

It should be noted that the following positions are synonymous in D- or L-mannitol and d- or L-iditol 1 and 6, 2 and 5, and 3 and 4. Sorbitol, because of lower optical symmetry, would form even more derivatives. The number of possible acetals is much smaller and that of metallic complexes still smaller. The number of various theoretical permutations of mixed ether-esters, ether-acetals, etc., utilizing readily available reagents, runs into the hundreds of thousands. 

Normally, however, the reaction involving the formation of hydroxy-methylfurfural proceeds less readily than does the hydrogenation of glucose and fructose to mannitol and sorbitol, but its occurrence is detected by the fact that tetrahydrofuran derivatives have been isolated from the hydrogenation products. Thus, we have isolated tetrahydrofuran 2,5-dicarbinol (identified as its ditosyl derivative), 5-methyltetra-hydrofurfuryl alcohol and 2,5-dimethyltetrahydrofuran (VII) together with hydrogenolysis products of these compounds. 

The dianhydrides of mannitol and sorbitol also form two crystalline dinitrates (XXI) and (XXII), both of which are blood-pressure depressants. Curiously enough the sorbitol derivative is twice as active as the mannitol derivative, although both are less active than glycerol trinitrate. Both anhydrides give rise to amino derivatives, 2,5-... 

Uronic acid derivatives are also known among the guanosine 5 -pyrophosphate esters. A mixture of the a-D-mannopyranosyluronic acid ester (20) and, presumably, the /J-L-gulopyranosyluronic acid ester (21) was isolated from the brown alga Fucus gardneri,88 The conversion of the uronic acid in the ester 20 into D-mannitol, and that... 

The configuration at C-2 was established by comparison with the optical activities of 1,5-anhydro-D-mannitol and -D-glucitol and the proton magnetic resonance (p.m.r.) spectra of their acetates.31(b) This reaction is useful for the preparation of C-2 substituted derivatives, but the configuration at C-2 of the products must then be established. 

This reaction was extended to 0-(o-nitrobenzylidene) derivatives of glycerol,67 D-mannitol,68 and D-glucitol.69 Some regioselectivity seems to have been observed, as two acetal groups [of the three for the tri-O-(o-nitrobenzylidene) derivatives of D-mannitol and D-glucitol] were found to have reacted. The identity and the structure of the photo-... 

In the alditol series, examples of acetobrominolysis of O-isopropyl-idene groups of derivatives of D-mannitol and D-iditol were given by McCasland and coworkers.i . i i Thus, the D-mannitol trithioearbonate derivative 157 gave the 1,6-dibromo derivative 158 (yield 55%).160 The same bromation with ring-opening was described for the D-iditol tri-thiocarbonate analog (yield 77%). 

The 2,5-diamino-2,5-dideoxy derivatives of l,4 3,6-dianhydro-D-mannitol and -D-glucitol gave, on deamination, the same product, namely, l,4 3,6-dianhydro-L-iditol, in unspecified yield.176 The product presumably arose from carbonium-ion intermediates, which reacted predominantly with solvent on the less hindered, exo sides of the V-shaped molecule. 

B. Helferich, A. L6wa, W. Nippe, and II. Riedel, Two new derivatives of trehalose and mannitol and an ot-methyl glucoside dichlorohydrin, Berichte der deutschen chemischen Gesellschaft 56 1083 (1923). 

---