6- Methyl-2-nitromethyl

Methyl-nitromethyl- E16d, 187 (C,Ar-Aufbau) E19a, 604 (H CH2-N02) Benzhydroxamsaure 4-Methyl-VIII, 687... 

Dinitro Methyl Anisole (4-Nitro-2-nitromethyl anisole, 3-Nitro-6-methoxynitromethyI toluol. or Methyl-[5-nitro-2-nitromethylphenyl] -ether). CH3.0.(N02)C6H3.CH2N02, mw 212.18, N 13.21%, OB to C02 —113.11%, cryst, mp 93—94°. Prepd from 4-nitro-2(lodomethyl) anisole in ether-ben2ene soln by treatment for 3 days at RT with Ag nitrate. The sodium salt explodes violently on heating Refs 1) Beil, not found 2) G. Bendy,... 

Vasella has used deoxy-nitro sugars for the synthesis of various biologically important carbohydrates,10 and the radical nitromethylation of deoxy-nitro sugars has been used for synthesis of fructose 6-phosphate11 and 6-C-methyl and 6-C-(hydroxymethyl)analogues of V-acetylneuraminic acid (see Scheme 7.2).12... 

Thermolysis of a stable radical 4-[(hydroxyimino)nitromethyl]-2,2,5,5-tetra-methyl-3-imidazolin-l-oxyl 13 gives the corresponding spin-labeled nitrile oxide. It was also identified in isoxazolines formed in cycloadditions with olefins (88). 

Among heteroaromatic compounds able to react with nitrile oxides as dipo-larophiles, furan, probably, is the best known. Recently, a novel nitrile oxide was generated from a sulfoximine and converted in situ to a cycloadduct with furan (Scheme 1.25) (287). The starting racemic N-methyl-S-nitromethyl-S-phenylsul-foximine 124 was prepared in 87% yield via nitration of N,S-dimethyl-S-phenyl-sulfoximine. Reaction of 124 with p-chlorophenyl isocyanate and a catalytic quantity of triethylamine, in the presence of furan, afforded dihydrofuroisoxazole 125, the product of nitrile oxide cycloaddition, in 42% yield (65 35 diastereomer ratio). The reaction of 125 with phenyllithium and methyllithium afforded compounds 126, which are products formed by replacement of the sulfoximine group by Ph and Me, respectively. 

The addition to alkenes of radicals derived from an a-nitroketone is also catalysed by manganese(III) [30]. During the reaction between a-nitroacetophenone 8 and m-but-2-ene, the stereochemical relationship between the methyl substituents is not preserved. The process terminates with the formation of a nitrone. A related process will generate nitromethyl radicals from nitromethane and these add to benzene to give phenyinitromethane [31],... 

Die Seitenketten-Nitrierung von substituierten Toluolen mit elektronenziehenden Substi-tuenten in ortho- bzw. para-Stellung liefern mit dem System Alkalimetallamid/Ammoniak/ Salpetrigsaure-ester die entsprechenden Nitromethyl-benzole in Ausbeuten von 40-55%. Die Methode wird bei 2- und 4-Cyan-, 4-Dimethylaminosulfonyl-, 4-(4-Methyl-phenylsulfonyl)-toluolen, bei 4-Methyl-benzophenonen und sogar bei so schwachen C,H-Sauren wie Diphenyl-methan angewandt1 ... 

Methyl-4-nitro-butanal 2- (6-Methoxycarbonyl-hexyl)-3-nitromethyl-1-oxo-cyclopentan 4-Hydroxy-2- (6-meth-oxycarbonyl-hexyl)-3-nitromethyl-l-oxo-cyclopentan... 

Bei der Umsetzung von 6-Acetoxy-3,6-dimethyl-3-nitro-l,4-cyclohexadien mit katalyti-schen Mengen Schwefelsaure erhalt man in Deutero-trichlor-methan neben 40% 1,4-Di-methyl-2-nitro-benzol noch 40% l-Methyl-4-nitromethyl-benzol, 15% Essigsaure-(4-me-thyl-benzylester) und 5% 4-Methyl-benzaldehyd4. 

Nitromethyl-l-oxo-cycloalkane bzw. 1-Nitromethyl-cycloalkene lassen sich mit Pyrro-lidinen oder (S,)-2-Methoxymethyl-pyrrolidin bzw. -piperidin in Acetonitril bei 20° unter Austausch der Nitro-Gruppe in guten Ausbeuten in 2-(Pyrrolidino-methyl)-l-oxo-cycloalkane3 bzw. l-(Piperidino-methyl)-cycloalkene8 uberfuhren (s.a. S. 378) ... 

Addition of nitromethane to 7-(4,6-0-benzylidene-3-0-methyl-/ -D-arahmo-hexopyranosyl-2-ulose)theophylline (8) and 6-chloro-9-(3,4-0-isopropylidene-/ -L-h/xo-hexopyranosyl-2-ulose)purine (35b) afforded, respectively, 7-[4,6-0-benzylidene-3-0-methyl-2-C-nitromethyl-/ -D-gluco (or manno)pyranosyl]theophylline (96) and 6-chloro-9-(3,4-0-iso-propylidene-2-C-nitromethylene-/ -L-h/xo-hexopyranosyl)purine (98), both isolated in high yield.66 Treatment of 96 with acid permitted the... 

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