Glucose 3- nitro

Decomposition Water Cellulose, glucose, nitro aniUne, nitrotoluene... 

Aliphatic fluorodenitration has also been applied to mononitro compounds, specifically to an a-nitroepoxide Thus, l,2-anhydro-3 4 5,6-di-O isopropyli dene-1-C-nitro D mannitol and labeled potassium bifluonde give 2-deoxy-2-fluo-ro-3,4 5,6-di-O-isopropylidene aldehydo D glucose [J03, 104] (equation 30)... 

A mixture of methyl 3-deoxy-3-C-methyl-3-nitro-ct-D- and fi-L-glucopyranosides d l is formed by the reaction of nitroethane with the sugar thaldehyde obtained from L-glucose The products are separated and converted into branched-chain fluoro nitro l- and L-sugars fEq 361 ... 

In extending this direct method of synthesis, we next investigated the possibility of preparing similarly constituted halides from 2-deoxy-D-arabino-hexose (2-deoxy-D-glucose) (21). The hexose was subjected to a partial anomerization procedure described by Bergmann and co-workers (1). The solid material obtained by this procedure is a mixture of the anomeric forms of 2-deoxy-D-arabino-hexose low temperature p-nitro-benzoylation of the latter in pyridine resulted in a mixture of crystalline, anomeric tetrakis-p-nitrobenzoates in a ratio of approximately 1 1. They were readily separable by fractional recrystallization, and treatment of either with an excess of hydrogen bromide in dichloromethane, or with... 

Azoxy compounds can be obtained from nitro compounds with certain reducing agents, notably sodium arsenite, sodium ethoxide, NaTeH, NaBH4—PhTeTePh, and glucose. The most probable mechanism with most reagents is that one molecule of nitro compound is reduced to a nitroso compound and another to a hydroxylamine 119-42), and these combine (12-51). The combination step is rapid compared to the reduction process. Nitroso compounds can be reduced to azoxy compounds with triethyl phosphite or triphenylphosphine or with an alkaline aqueous solution of an alcohol. ... 

Chorionic gonadotropin. Follicle stimulating hormone Urea, Uric add. Bilirubin, Cortisol, n-Maimitol. n-Glucose, Sodium pyruvate, 4-hydroxy-3-methoxy mandelic add, 4-Nitro-phenol, 17 Amino adds in HQ, Angiotensin-I, Tripahnitin, Bone meal (8 elements), Bone ash (8 elements), lithium carbonate Luteinizing hormone. Thyroid stimulating hormone... 

Kambe and Yasuda19 discovered the effectiveness of the fluoride as a Henry reaction catalyst. Since then, the use of diverse fluorides is a common method to catalyze nitro aldol condensations, since they provide mild conditions that are particularly convenient for sensitive products as carbohydrates. The most common fluorides are potassium fluoride20 and tetrabutyl ammonium fluoride.21 A recent example relates to the TBAF catalyzed addition of nitroethanol to the D-glucose derivative 18, to give nitro sugars 19 (Scheme 8).22... 

However, this multistep procedure is experimentally complex. A simpler variation described in 199127 consists of the reaction of an aldehyde and a nitro compound in the presence of triethylamine, TBAF and tert-butyl-dimethylsilyl chloride. Under these conditions, nitro sugars are obtained in good yieds and higher diastereoselectivities than those afforded by the standard conditions. This procedure was used in several synthesis of 2-nitro-2-deoxyaldoses, as for the condensation of l,l-diethoxy-2-nitroethane and l,2 3,4-di-0-isopropylidene-a-D-galacto-hexodialdo-l,5-piranose.28 More recently, it was applied to the addition of ethyl nitroacetate to the D-glucose derived aldehyde 18, to give nitro sugar derivatives 26, key precursors of polysubstituted cyclohexane a-amino acids (Scheme 10).29... 

Michael addition of nitromethane to D-glucose based vinyl sulfone 38 to afford nitro sugars 39 and 40 was also recently described (Scheme 15).37... 

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. 

Intramolecular Henry reactions of nitro sugars are usually diastereo-selective sometimes a single isomer results from an epimeric mixture, on account of the reversivility of the Henry reaction, which allows equilibration through open chain intermediates.49 A recent example involving the D-glucose derived nitro acid ester 26 is shown in Scheme 22. 

Michael additions to sugar nitro olefins have received considerable less attention than the Henry reaction involving nitro sugars. Early examples of Michael addition include the synthesis54 of licoricidin by Paulsen in 1982, the addition of phosphorous nucleophiles to a D-glucose based nitro olefin55 by Yamashita in 1987 and the synthesis of the natural antibiotic polyoxin published by Barret in 1990.56... 

Recently, a synthesis of tetrodotoxin from D-glucose was described (Scheme 36). After a Michael addition of the lithium salt of bis(phenylthio)-methane to the nitroolefin 116, the major component (117b) of the resulting epimeric mixture 117a + 117b was subjected to a reaction sequence that involved an intramolecular nitroaldol reaction, to give the complex nitro cyclohexane derivative 118. 

Nitropropanoyl esters of glucose from the roots of Lotus pendunculatus Cav. were determined by analysis of nitrate released on alkaline hydrolysis. This method was validated for quantitation of both total nitro compounds in ethanolic extracts and for individual components from TLC separations557. 

The reduction of a dinitro ketone to an azo ketone is best achieved with glucose. 2,2 -Dinitrobenzophenone treated with glucose in methanolic sodium hydroxide at 60° afforded 82% of dibenzo[c,f [i 2]diazepin-l 1-one whereas lithium aluminum hydride yielded 24% of bis(o-nitrophenyl)methanol [575], Conversion of aromatic nitro ketones with a nitro group in the ring into amino ketones has been achieved by means of stannous chloride, which reduced 4-chloro-3-nitroacetophenone to 3-amino-4-chloroacetophenone in 91% yield [178]. A more dependable reagent for this purpose proved to be iron which, in acidic medium, reduced m-nitroacetophenone to m-aminoacetophenone in 80% yield and o-nitrobenzophenone to o-aminobenzophenone in 89% yield (stannous chloride was unsuccessful in the latter case) [903]. Iron has also been used for the reduction of o-nitrochalcone, 3-(o-nitrophenyl)-l-phenyl-2-propen-l-one, to 3-(o-aminophenyl)-l-phenyl-2-propen-l-one in 80% yield [555]. 

Bei der Herstellung von Azo-Verbindungen ist Glucose das wichtigste Reduktionsmittel fur aromatische Nitro-Verbindungen, das auch technische Anwendung findet. Die Reak-tionen dieses Typs sind bereits in Bd.X/3, S. 347ff. ausfuhrlich besprochen worden. 

In analoger Weise erhalt man aus o-Glucose in 95%iger Ausbeute 112 5,6-Bis-O-isopro-pyliden-3-nitro-3-deoxy-oL-T>-allofuranose2 ... 

H5C CH2 0- . HsCg - CH2 - 0OH H5C8 — CH2 NH- OH o-ch2-c6h5 NO, 2,3,4,6-Tetra-O-benzyl-l-deoxy-l-nitro- glucose 90... 

C3 H, 04 mw 104.06. One of the products of the alkaline saponification of NC and nitro-oxycellulose (Ref 1). Berl and Smith (Ref 3) obtained it, calling it oxypyruvic acid, by the alkaline hydrolysis, not only of NC, but also of nitrates of glucose and levulose... 

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