Nitro hexane

Nitro-n-hexane. Use 41 g. of dry silver nitrite, 51 g. of n-hexyl iodide (35-5 ml.) and 100 ml. of sodium dried ether. Reflux on a water bath for 8 hours decant the ethereal solution and wash the sohd well with sodium dried ether. Distil the residue, after the removal of the ether from the combined extracts, from 5 g. of dry silver nitrite, and collect the fraction of b.p. 190-192° (13 g.) as 1-nitro -hexane. The pure compound is obtained by distilling under diminished pressure b.p. 81 6°/15 mm. 

Konovalov [15] nitrated aliphatic hydrocarbons in sealed tubes at 120-130°C, using dilute nitric acid of concentration 6.5-19%. From normal hydrocarbons he obtained secondary nitro compounds in yields varying from 40% (2-nitro-hexane from hexane) to 49-50% (2-nitrooctane from octane). Aromatic hydrocarbons with an aliphatic substituted group when nitrated under the same conditions gave nitro derivatives with a nitro group in the side chain. For example, ethylbenzene, when nitrated with 12.5% nitric acid at 105-108°C, gives phenyl-nitroethane in 44% yield. The optimum yield is obtained with 13% acid. 

When lower reaction temperature (e.g. 220-230°) was used, the total yield of nitro compounds was lower ca. 20%, but the proportion of primary nitro-hexane was higher. Also the yield of the non-volatile fraction with a higher nitrogen content was higher (ca. 30%). 

X)ml), The reaction mixture was stirred for 24 h. Nearly all of the solvent was removed in vacuo and the residue dissolved in CH2CI2. The solution was washed with 5% NHj, 1N HCl and brine. The organic layer was dried (NajSOJ and the solvent evaporated in vacuo. The residue was purified by chromatography using CHClj-hexane to give the product (28.0 g, 86%) along with a little 3-[2-nitro-2-(indol-3-ylmethyl)ethyl]indole (2.8 g. 5%). 

A mixture of 6.65 g of 3-chloro-6-nitroacetanilide, 3.2 ml of propylmercaptan, 5.6 g of 50% sodium hydroxide and 100 mi of water Is heated at reflux overnight. The cooled mixture is filtered to give the desired 2-nitro-5-propyithioaniline, MP 69.5°-71.5°C after recrystailiza-tion from ethanoi then hexane-ether. NMR (CDCi3) 40%. 

Removal of the solvent gave an oil which was taken up In ether and filtered through a pad of Woelm grade I alumina. The eluent was concentrated and the residue was crystallized from methylene chloride/hexane yielding 1-methyl-7-nitro-5-(2-fluorophenyl)-3H-1,4-benzo-diazepin-2(1 H)-one as pale yellow needles melting at 166° to 167°C. 

A mixture of 40 mmol or the a-nitro alcohol 1, 48 mmol of (terf-butyldimethyl)chlorosilane or chlorotri-mcthylsilanc, 6.8 g (100 mmol) of I /(-imidazole and 10 mL of DMF is stirred at 20 C for 12 h. Water is added and the mixtnre is extracted with hexane. The combined extract is washed wilh water and sat. aq NaCl and dried over MgS04. Exaporation gives the O-silyl nitro alcohol as an oil which is distilled (bulb-to-bulb) yield 45 - 97%. If unreacled starting material is present in the distillate, it can be removed by chromatography over silica gel (30 g/ l g of product) with l,t,0/pcntanc 1 9 as eluant. 

N 16.09% OB to C02 —119.42% the cis form is v unstable, hence all measurements are of the trans isomer mobile, pungent colorl liq bp 37° at 10mm d 1.0661g/cc at 20/4° RI 1.4527, 1.4545, 1.4559 (sep measurements). Sol in Na acetate soln, ethanol and hexane. Prepn is by boiling an ethereal soln of j3-nitro isopropyl acetate and K bicarbonate and then recovering the prod by shaking with eth. The trans monomer is unaffected by ambient storage for one year and will not react with w (Ref 3)... 

Ad-nitro-Verbindungen konnen durch Alkohole zu Oximen reduziert werden, wobei es zweckmaBig ist, die Reduktion bei einem pH-Wert von 3 durchzufiihren und als Re-duktionsmedium Wasser oder organische Losungsmittel einzusetzen (s.Bd. X/4, S. 138). Das Verfahren wird speziell zur Herstellung von Cydohexanon-oxim aus Nitro-cyclo-hexan verwendet (s.Bd. X/4, S. 146). 

Experimental Preparation of 6-nitrospiropyran 2 (R = Bu). Triethyl-amine (2.65 g, 26 mmol) was added to a suspension of 2,3,3-trimethyl-7V-butylindolinium iodide (9.0 g, 26 mmol) and 5-nitro-salicylaldehyde (4.38 g, 26 mmol) in EtOH (100 ml) under stirring. The mixture was refluxed for 2 h, and filtered off. Recrystallization from hexane gave 6-nitrospiropyran 2 (R = Bu). Also, spiropyran 2 was isolated from the filtrate, which was evaporated under reduced pressure and then was chromatographed on silica gel with dichloromethane-methanol (60 1 v/v). Total yield of 2 (8.3 g) is 88%. 

Experimental Preparation of 5, 6-dinitrospirobenzothiopyran 44b. A mixture of 5-nitro-l,3,3-trimethyl-2-methyleneindoline (0.38 g, 1.75 mmol) and 5-nitro-thiosalicylaldehyde (0.22 g, 1.2 mmol) in EtOH (50 ml) was refluxed for 2h, and then evaporated under reduced pressure. The residue was chromatographed on silica gel with benzene-acetone (15 1, v/v) and recrystallized from dichloromethane-hexane to give 44b (R1 = N02, R2 = 6-N02)(0.30 g, yield 65%). 

Photolytic. Synthetic air containing gaseous nitrous acid and toluene exposed to artificial sunlight (Z = 300-450 nm) yielded methyl nitrate, peroxyacetal nitrate, and a nitro aromatic compound tentatively identified as a nitrophenol or nitrocresol (Cox et al., 1980). A n-hexane solution containing toluene and spread as a thin film (4 mm) on cold water (10 °C) was irradiated by a mercury medium pressure lamp. In 3 h, 26% of the toluene photooxidized into benzaldehyde. 

Photolytic. Irradiation of trifluralin in hexane by laboratory light produced a,a,a-trifluoro-2,6-dinitro-A-propyl-jo-toluidine and a,a,a-trifluoro-2,6-dinitro-p-toluidine. The sunlight irradiation of trifluralin in water yielded a,a,a-trifluoro-A, 7 -dipropyl-5-nitrotoluene-3,4-diamine, a,a,a-trifluoro-A/ ,A/ -dipropyltoluene-3,4,5-triamine, 2-ethyl-7-nitro-5-(trifluoromethyl)benzimidazole, 2,3-dihydroxy-2-ethyl-7-nitro-l-propyl-5-(trifluoromethyl)benzimidazoline, and 2-ethyl-7-nitro-5-(trifluoromethyl)benzimidazole. 2-Amino-6-nitro-a,a,a-trifluoro-p-toluidine and 2-ethyl-5-nitro-7-(trifluoromethyl)benzimidazole also were reported as major products under acidic and basic conditions, respectively (Crosby and Leitis, 1973). In a later study, Leitis and Crosby (1974) reported that trifluralin in aqueous solutions was very unstable to sunlight, especially in the presence of methanol. The photodecomposition of trifluralin involved oxidative TV-dealkylation, nitro reduction, and reductive cyclization. The principal photodecomposition products of trifluralin were 2-amino-6-nitro-a,a,a-trifluoro-jo-toluidine, 2-ethyl-7-nitro-5-(trifluoromethyl)benzimida-zole 3-oxide, 2,3-dihydroxy-2-ethyl-7-nitro-l-propyl-5-(trifluoromethyl)benzimidazole, and two azoxybenzenes. Under alkaline conditions, the principal photodecomposition product was 2-ethyl-7-nitro-5-(trifluoromethyl)-benzimidazole (Leitis and Crosby, 1974). 

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