Nitro-phenyl acetonitrile

Bei der Elektrolyse von 2-Nitro-benzylhalogeniden in Acetonitril wird als Hauptprodukt 1,2-Bis-[2-nitro-phenyl]-dthan gebildet3. Auch Brom-maleinsaure gibt pH-abhan-gig (in waBrigen Pufferlosungen) neben Maleinsaure betrachtliche Mengen an3,4-Dicarb-oxy-2,4-hexadiendisaure (vgl. S. 641)4. 

Methyl-(2-nitro-phenyl)-phosphinsaure-ethylester550 Eine Lbsung von 6,15 g(37,l mmol) 1,2-Dinitro-benzol und 9,20 g (67,6 mmol) Diethoxy-methyl-phosphan in 120 ml Acetonitril wird 20 Stdn. bei 18°belassen. Nach Abziehen des Losungsmittcls wird destilliert Ausbeute 6,50 g (77%) Sdp. 130°/0,0075 Torr (1 Pa). 

Acetonitril (3,5-Dimethoxy-4-nitro-phenyl)- E16d, 288 (H -> N02) Acrylsaure cu-3-(2-Nitro-anilino)- -methylester El6d, 794 (Anilie-rung)... 

Acetonitril Dimethylamino-ethoxy-(3-nitro-phenyl)- E5, 1563 [Ar—C(OR)=NR2 + R-SH] Acrylsanre 3-Amino-3-(2-benzoyl-hydrazino)- -ethylester E15/2, 2101 [RO C(NH2) = CH-COOR + R-CO-NH-NH2] Imidazolidin (4S,5R)-3,4-Dimethyl-1 -hydroxaminocarbonyl-2-oxo-5-phenyl- -oxid E21e, 5580 (Cl - NH-OH)... 

If the photoinitiated autocatalytic chain decomposition outlined in Scheme 12 operates at all, it should be specially important in the photolysis of (4-nitro)phenyl azide where formation of the dehydroazepine is a minor path and the triplet nitrene is formed rapidly. Indeed, Waddell and co-workers [110] report that the quantum yield for disappearance of this azide is 434 when a 0.1 M solution in acetonitrile is irradiated. However, attempts to reproduce this experiment reveal a quantum yield for disappearance of (4-nitro)phenyl azide in acetonitrile solution of 0.7 that is independent of starting azide concentration from 0.001 to 0.1 M [45]. 

MorphoHno-5-(4-nitro-phenyl)-l,3-thiazol880 Eine Suspension von 3.85 g (0,01 mol) N -[Chlor-(4-nitro-benzylthio)-methylen]-N,N-dimethyl-formamidinium-perchlorat in 8 ml Acetonitril wird tropfenweisc un-ter Riihren mit 1,74 g (0,02 mol) Morpholin versetzt und anschlicflend kurz aufgekocht. Nach Zugabe von 2 ml Triethylamin erhitzt man weitere 15 min unter RuckfluB. Nach Abkiihlen wird das Endprodukt abgesaugt und aus Acetonitril umkristallisiert Ausbeute 1,5 g (51%) Schmp. 203-205°. 

These exemples show the kinetic effect of complexation of the substrate itself. A similar study carried out on nitro-substituted phenylacetates revealed that leaving group complexation is less efficient than substrate complexation. It should be borne in mind that the interpretation of complexation effect is complicated by solvent competition. For instance 1,3-dinitrobenzene accelerates the butylaminolysis of 4 -nitro-phenyl-3,5-dinitrobenzoate (A obs/ o>l) in 1,2-dichloroethane and acetonitrile. For 4 -nitrophenyl, 4-NN dimethyl aminobenzoate there is acceleration only in the former solvent (koiyjko =. 55). 

Die Elektrolyse von 3-Nitro-2-phenyl-acrylnitrilen fiihrt in waBrigem Acetonitril iiber die Oxime quantitativ zu 5-Amino-4-phenyl- 1,2-oxazolen. In saurem Acetonitril entstehen infolge Hydrolyse Carbonyl-Verbindungen3 ... 

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 AGhet(R-R ) values observed in acetonitrile are almost identical with A//het(R-R ) values for the compounds [4-6] and [5-6] (Troughton et al., 1984). Thus, provided that this is the case also for a nitro-cyano compound, (tri-t-butylcyclopropenyl)(phenyl)malononitrile [101-102], its AGhet(R-R ) value should be close to the A//het(R-R ) value predicted from (29). In practice, as indicated in Fig. 3, the AG°het(R-R ) observed in acetonitrile is 6kcalmol less than that predicted (Miyabo et al., 1993). Hence this departure from linearity can be most probably ascribed to steric congestion, which is mainly derived from the cation moiety [lOT ] in [101-102]. 

Activated nitro and halo substituents have been efficiently replaced by a variety of alkyl groups via SsAx reaction with carbanions. Examples include the displacement of the nitro group in compounds (10 X = 4-PhCO, 4-MeOCO, 4-CN, 4-N02, 4-PhS02, 3,5-(CF3>2) by the anion of 2-nitropropane in HMPA at room temperature (equation 2),83 and the reaction of p-dinitrobenzene with several ketones, esters and nitriles (RH equation 3) in Bu OK/liquid NH3 at -70 C.84 Interestingly, under the latter reaction conditions, p-chloronitrobenzene gave the product of alkylation rather than of SNAr displacement of chloride, as in equation (4).85 Further examples include the dehalogenation of p-halonitrobenzenes by 9-fluorenyl anions in DMSO at room temperature,34 and dehalogenation and denitration reactions by the carbanions of phenyl- and diphenyl-acetonitrile in DMSO or under PTC conditions.86... 

TSK gel ODS-80-TM 5 mM phosphate buffer pH 5-acetonitrile (3 2) [1 mL/min] and 5 mM bis [4-nitro-2-(3,6,9-trioxadecyl oxycarbonyl)phenyl] -oxalate TDPO and 50 mM-acetonitrile [1.3 mL/min] Chemiluminescent reagent. Separates the drug and dansylated valine. Detection limit under the optimum conditions is 20 amol for dipyridamole. 80... 

Acetonitril (2-Nitro-4-trifluorme-thyl-phenyl)- E6b/1, 566 (COOR -H)... 

The reaction of alkenes with nitronium tetrafluoroborate in anhydrous acetonitrile/dichloro-methane solution at low temperature afforded, after aqueous workup, / -acetamido nitro compounds (Table 6, Method A). These result from preliminary attack of the nitronium ion on the alkene followed by addition of acetonitrile as the nucleophile to the intermediate carbonium ion thus formed, and hydrolytic workup140. Acceptable yields of the adducts were obtained only from phenyl-substituted alkenes141. 

Michael addition of nitro compounds 246 to phenyl vinyl sulfoxides 247 in the presence of DBU in acetonitrile at room temperature gave adducts 248 in quantitative yields (82JOC5017). Other bases, such as triethylamine, potassium fluoride, and tetramethylguanidine, were not so effective as DBU. 

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