Nitrosugar

Everninornicin D is the principal component from cultures of M.icromonospora carbonacae (10). Its stmcture (5) was elucidated using extensive chemical degradation coupled with spectroscopic analysis and it was the first reported instance of a natural product containing a tertiary nitrosugar. X-ray analyses of both the olgose residue (9) and the nitrosugar (16) have been reported as has a complete mass spectral analysis of everninornicin D (8). 

N-Nitro-N-methylglycolamide nitrate 2-Nitro-2-methylpropanol nitrate m-Nitrophenyldinitro methane Nitrosugars (dry)... 

Henry reaction of the (V-acetyl-D-glucosamine derived nitrosugar 1 with 2,3-O-cyclohexylidene-D-glyceraldehyde (2) furnishes a single product 3 in 85-90% yield7. 

Nobel Co, at Schlebusch-Manfort, and published works on NG, Nitrosugar, Dinitroglycol, coal mine expls, etc. He was also the author of books dealing with expls, such as Scheiss-und... 

A cordeau detonant contg a compn prepd by thoroughly mixing NG or Nitrosugar with NC, mononitronaphthalene, dinitrobenzene, di- or tri-. nitrotoluene, K dichromate K femcyanide (FrP 237447 of 1894) (Ref 1, pp 158-159) 1894 Smokeless powders prepd by blending NC and Nitromannite, with or without dinitro-benzene (DNB), No 1 NC 60, Nitromannite 40 No 2 NC 60, Nitromannite 20, DNB 20 ... 

Plastomenites. Propints, patented in Ger by Guttler in 1889—90, consisting of NC, Nitro-lignine, Nitrosugar, Nitrostarch, etc, gelatinized by the addition of nitrated aromatic compds such as benz, toluene, phenol, naphthalene, etc. Inorganic nitrates, chlorates, chromates, picrates, etc, could be added to the mixt... 

Domino reactions increasingly gain importance in the search for new drugs. Especially appropriate is the use of multi-component reactions in solution combinatorial chemistry. In such a process described by Wessel et al.1231 an alkoxy-nitroenone 48 was treated with different anilines 49 to give ketene-NO-acetals which in the presence of aromatic aldehydes and TfOH are transformed into 50 (scheme 10). The substrate 48 is readily available by oxidation of the nitrosugar 47. 

Reaction of nitromethane and monosaccharide-derived dialdehydes is a useful tool that has been broadly used for the preparation of nitro and amino sugars, and carbocycles.30 Dialdehydes can easily be obtained by oxidative cleavage of conveniently protected monosaccharides with sodium periodate. Their subsequent Henry reaction with a nitroalkene, commonly nitromethane, usually gives isomeric mixtures that require the isolation of the major isomer.31 Thus, treatment of the D-ribose derivative 27 with sodium periodate gave dialdehyde 28, which was subjected to a Henry reaction with nitromethane, to afford nitrosugar 29 as an epimeric mixture (Scheme 11).32... 

Treatment of D-glucose with nitromethane and sodium methoxide afforded nitrosugar 46 which, on reduction of the nitro group, protection of the resulting amine with Fmoc-Cl and TEMPO oxidation afforded 47 in a three-step sequence. 

In a recent application of this strategy, nitrocyclohexane 143 (prepared from nitrosugar 142 by intramolecular Henry reaction) was subjected to a radical denitration by HSnBu3, after protection of the hydroxyl groups to avoid side reactions. Inositol 146 was selectively obtained in good yield, once the hydroxyl protecting groups were removed (Scheme 45).101... 

Over the last decade, dialdehyde-nitromethane cyclization has established itself as a generally applicable and preparatively satisfactory method for the synthesis of nitrocyclanols, nitrosugars and nitrosugar nucleosides which on hydrogenation are easily converted to the corresponding amino-derivatives... 

Anomeric triphenylphosphonium salts have been used as well as phenylsul-fides,but in the latter case extra stabilization is necessary (see below). Anomeric nitrosugars, which have been extensively studied in C-glycosylation reactions by Vasella, will be covered in Sect. 2.2.1 and ester enolates derived from 3-deoxy-2-ketoulosonic acids (sialic acid and KDO derivatives), which bear a structural similarity to 2-deoxy pyranosides, will be covered in Sect. 4.4. Deprotonation of anomeric phenylsulfones has been discussed in Sect. 2.1.1 and additional transformations on closely related compounds are presented in Scheme 14 [20]. Alkylation of phenylsulfone 54 with epoxide 55 provides adduct 56 which eliminates benzenesulfinic acid at room temperature to give the C(l)-alkylated glycal 57 a similar elimination is also observed with adducts derived from... 

Hubner Powder. Smokeless powder prepd by gelatinizing NC with a solution of potassium xanthogenate in alcoholic ether and adding 2-5% of nitronaphthol and nitromolasses or nitrosugar Ref Daniel (1902), 378... 

Kolf s Blasting Powder. Ger mining expl patented in 1892. A mixt of equal parts of NC, Nitrolignin Nitrostarch 50, Nitrosugar 38,... 

Rinkenbach (Ref 7) patented blasting explosives consisting of PGcDN and 1,1,1-Tris(bydroxymetbyl)-etbane Trinitrate. These mixts were of low sensitivity and practically nonfreezing in winter and were claimed to be suitable replacements for mixts based on NG—NGc or NG-Nitrosugars Refs 1) Beil 1, 2199i (PGc) 2) Beil, not found (PGcDN) 3) C. Spaeth, USP 1883045 (1931) CA 27, 845(1933) 4) C. Spaeth,... 

Note SON (Nitrosugar) must be separated chromatographically before NG can be detd by the periodic acid oxidation procedure A detailed description of periodic acid oxidation procedure is given in Hercules pamphlet D90 (Ref 17), Rev 5-10-61, ppl2-13 periodic Acid Oxidation Method... 

Note Instead of NGc, nitrosugars may be used as antifreezing components. In European... 

The explosive properties of nitrosugars have been examined by Monasterski [13]. This author reported that saccharose octanitrate developed a heat of explosion of 950 kcal/kg, and produced in the lead block an expansion of about 300 cm3. In the drop test it exploded from the impact of a 2-kg weight falling from a height of at least 20 cm. Maltose octanitrate, in the lead block, caused a net expansion of some 260 cm3. 

As with epoxides, carbanions can add in a 1,4 fashion to enones or nitrosugars. Nitromethane anion has been used [64], Dithiane anion has been successfully used in the addition to nitroolefins [65] and to enones [66], Accordingly, C-5 branched-chain glucose derivatives 47 and 48 have been prepared from nitroolefin 46 (Scheme 20) [67,68], Sugar-derived enones have been also used as acceptors in free radical reactions to trap alkyl radicals as well as anomeric radicals (see Schemes 29 and 30). 

J. Dupuis, B. Giese, J. Hartung, M. Leising, H.-G. Korth, and R. Sustmann, Electron transfer from trialkyltin radicals to nitrosugars The synthesis of C-glycosides with tertiary anomeric carbon atoms, J. Am Chem. Soc. 107 4332 (1985). 

CA 40, 206 (1946) (Continuous production and stabilization of NC, NS, DEGDN, PETN Nitrosugar) 21a)E.Berl, ChemMetEngrg 52, 202, 204 206(Way 1945) (The problem of batch versus continuous operation in the explosives industry is primarily concerned with improvements in safety of operations) 2lb)AA.Swanson et al, PB Rept... 

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