Nitromethane, Benzoyl

Furoxan dialdehyde 105 has been prepared from the bisaldoxime 14 by des-oximation with nitrous acid. The bisaldoxime 14 was prepared by a two-step procedure from nitromethane [25LA7] (Scheme 55). The benzoylated oxime 106... 

The condensation of arylsulfonyl acetonitriles 369a-c with 22a proceeds via addition of the in-situ formed anion 370 to the arylsulfonyl acetonitriles 369 to afford the dimers 371, in 69-94% yield, and hexamethyldisiloxane 7 [136]. Furthermore, y9-dicarbonyl compounds such as ethyl acetoacetate 372 a or ethyl benzoyl-acetate 372b are O-silylated by 22 a or 22 c to rather stable alkyl 3-O-trimethylsilyl-oxycrotonoate 373a and alkyl 3-0-trimethylsilyloxy-3-phenyl acrylate 373b [130]. Aliphatic nitro compounds such as nitromethane are O-trimethylsilylated and further transformed into oligomers [132] (cf Section 7.6) and are thus unsuitable reactants for silylation-C-substitutions (Scheme 4.50). 

The cycloaddition of A-benzoyliminochloromethanesulfenyl chloride and 3,3-dimethyl-2-butene in nitromethane and in the presence of lithium perchlorate involves addition of the electrophile at the double bond and 1,2-methyl shift. Unusually, the ring closure is accompanied by elimination of the benzoyl group (Equation 16) <2002CHE1150>. 

A number of anhydro sugar derivatives have been prepared by treatment of orthoesters with mercuric bromide in nitromethane. Among them are 3-0-acetyl-l,5-anhydro-2-0-benzoyl-/3-L-arabinofuranose,68... 

Examples of very highly sensitive substances are mixture of chlorates-red phosphorus, paper cracker, lead azide, and DDNP. High sensitivity substances are dynamite(powder), PETN(powder), HMX(powder), RDX(powder), tetryKpowder), picric acid(powder), TNT(powder), and benzoyl peroxide (powder). Medium-sensitivity substances are the modem safety industrial explosives (slurry explosives, ammonium nitrate explosives), black powder, AIBN, and t-butyl-benzoate. Among low sensitivity substances are non-cap explosives dinitro benzene, dinitropentamethylenetetramine, ANFO, ammonium nitrate, nitromethane, dinitrotoluene, and cast TNT. 

Reaction of 2,2 -diformyldiphenyldisulfide (27) with nitromethane in the presence of triethylamine gives 2-nitrobenzothiophene (28) (29%).25 Addition of benzoyl peroxide (0.5 mol) increases the yield to 77%. A similar reaction of the pyrazole derivative 29 leads to the thieno[3,2-d]pyrazole 30.25... 

The reaction51 of 5-methyl-2,4-diethoxypyrimidine with per-benzoylated D-arabino-, D-xylo-, and D-lyxofuranosyl bromides in polar solvents (acetonitrile, nitromethane) proceeds stereospecifically with the formation of C- -C-2 -trans derivatives whereas in poorly polar solvents (e.g., toluene) the corresponding C-l -C-2 -cis derivatives are also formed. 

O) 1—benzoyl fluoride 2—nitromethane 3—nitrobenzene 4—benzo-nitrile S—acetonitrile 6—propanediol-1, 2-carbonate 7—ethylene sulfite 8—Water 9—trimethyl phosphate 10—dimethylformamide 11—N, N-di-methylaoetamide 12—dimethyl sulfoxide 13—hexamethylphosphoric amide. 

A solution of 6.6 g. of tetra-O-benzoyl-a-D-glucopyranosyl bromide, 1.6 g. of f-men-thol (dried over phosphorus pentoxide), and 2.5 g. of mercuric cyanide in 20 ml. of dry nitromethane was refluxed for 7 hr. with exclusion of moisture. The sirup obtained on evaporation under diminished pressure was dissolved in 20 ml. of hot benzene. On cooling, the mercury salts separated and were Altered. The residue after evaporation was crystallized from methanol (100 ml.) 5.6 g. (75% of the theoretical) twice recrystallized from ethanol m. p. 139-140°. 

Aminotriazole, and some of its 5-substituted derivatives, when fused with 1,2,3,5-tetra-O-acetyl- or -benzoyl-/ -D-ribofuranose, gave a 1 1-mixture of 2- and 3-ribofuranosyltriazoles (76USP3968103). 4-Acetamidotriazole-5-carboxamide, mercuric cyanide, and tri-0-benzoyl-/ -D-ribofuranosyl chloride, when refluxed in nitromethane, furnished 4-acetamido-l- 2, 3, 5-tri-O-benzoyl-/S-D-ribofuranosyl)triazole-5-carboxamide (3 hr, 48%), from which the benzoyl groups were removed in methanolic ammonia (0°C, 3 days, 54%) (72BCJ2577). Occupation of the 1 position in this and other ribosylations was unexpected but was carefully verified. 

AUylation. Scandium(III) triflate promotes allylation of aldehydes (in the presence of ketone moieties) with allylgermanium reagents in aqueous nitromethane. By adding primary amines as the third component, such reactions deliver homoallylic amines (in such cases the aldehydes react too slowly to cause any chemoselectivity problem) Benzoyl hydrazones react accordingly. ... 

Direct glycosylation of 3-amino-5(7)/7-[l,2,4]triazolo[4,3-ft][l,2,4]triazole (17) with 1-D-acetyl-2,3,5-tri-(7-benzoyl-D-ribofuranose (18) in the presence of trimethylsilyl triflate gives the 1-(2,3,5-tri-0-benzoyl-) -D-ribofuranosyl) derivative (20). The same product (20) results from the high temperature glycosylation with boron trifluoride etherate in nitromethane as well as from the reaction of the triazolotriazole sodium salt with 2,3,5-tri-(7-benzoyl-D-ribofuranosyl bromide (19) (Equation (1)) <87Mi 80i-0l>, When 3-amino-5(7)/7-[l,2,4]triazolo[4,3-6][l,2,4]triazole (17) is treated with l-0-acetyl-2,3,5-tri-0-benzoyl-D-ribofuranose (19) and stannic chloride a mixture of four products is obtained. In addition to (20), the l-(2,3,5-tri-f -benzoyl-a-D-ribofuranosyl) derivative (21), the 3-imino-2,3-dihydro-7//-2-(2,3,5-tri-0-benzoyl-/ -D-ribofuranosyl) derivative (22), and the 3-(2,3,5-tri-0-benzoyl-)S-D-ribofuranosylamino) derivative (23) are isolated (Equation (1)) <93JHC1289>. 

Benzoylation In the presence of TMEDA, this ketone benzoylates alcohols and amines in high yield. The reaction with nitromethane results in a-nitro-acetophenone, C6H5COCH2NO2, in 52% yield. 

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