1-butene, 2-nitro, reaction with

Irie and co-workers have reported a synthesis of ( )-tecomanine (55) based on a cyclopentenone annulation of 1,4-diketones (Scheme 17) (205). Treatment of 1,3-dimethylpiperidone (246) with lithium diisopropylamide (LDA) and 2-nitro-2-butene, and reaction with 10% hydrochloric acid (Nef reaction) afforded the substituted piperidine 1,4-diketone 247 (a homolog of 230 in Scheme 14) in 87% yield. Reaction of the mixture of isomers with K3PO4 at 55°C for 55 h gave a single cyclized product 248, whose... 

Furalazine, Acetylfuratrizine, Panfuran-S. Heating nitrovin in butanol or dimethylformamide at 100—130°C affords furalazine, 6-[2-(5-nitro-2-furanyl)ethenyl]-l,2,4-triazine-3-amine (34). An improved synthesis originates with 5-nitro-2-furancarboxaldehyde and acetone, proceeds through 4-(5-nitro-2-furanyl)-3-buten-2-one followed by a selenium dioxide oxidation to the pymvaldehyde hydrate, and subsequent reaction with aininoguariidine (35). Furalazine, acetylfuratrizine (36), and the A[-A/-bis(hydroxymethyl) derivative, Panfuran-S, formed from the parent compound and formaldehyde (37), are systemic antibacterial agents. 

When nitrosyl cyanide adduct 1 is reacted with ( , )-l,4-diphenyl-1,3-butadiene in refluxing benzene, the expected cycloadduct 2 is obtained with total diastereoselectivity, whereas by reaction with nitrosyl cyanide itself, prepared from nitrosyl chloride and silver cyanide, only 3-chloro-4-nitro-1,4-diphenyl-l-butene and l-nitro-l,4-diphenyl-l,3-butadiene are recovered in low yield34,35. 

Clark and Heimkamp found that deamination of meso- and d/-2,3-dimethyl-aziridine by reaction with 3-nitro-N-nitrosocarbazole is highly stereospeciflc. The >.vo-isomer (I) afforded c(. -butene-2 of 99.9% purity and the d/-isomer gave 99%... 

Nitropropene (Scheme 14) undergoes a,a-double-deprotonation to give a dianion that reacts with carbonyl compounds at the a-nitro carbon to form nitro alcohols, whereas 4-nitro-l-butene (Scheme 15) produces an a,P-abstraction product that reacts with alkyl halides and carbonyl compounds to give a mixture of the P- and 8-adducts. The 8-isomer can be separated and converted to an a,P-unsaturated aldehyde by Nef reaction with TiCb (equation 9). 

SYNTHESIS To a solution of 45 g 3,4,5-trimethoxybenzaldehyde in 1.2 L IPA, there was added 125 g nitropropane and 67.5 g t-butylammonium acetate and the reaction mixture was held at reflux for 16 h. This was poured into 6 L H20, and extracted with 2x250 ml hexane. The pooled extracts were stripped of solvent under vacuum giving a residue that slowly set to a crystalline mass. On filtering, there was obtained 9.4 g of a crude yellow product which, on recrystallization from hexane provided 8.7 g of slightly sticky bright yellow crystals of 2-nitro-1-(3,4,5-trimethoxyphenyl)butene-1, with a mp of 71-73 °C. A second recrystallization from hexane gave fine yellow crystals with a mp of 72-73 °C. Attempts at the preparation of this nitrostyrene by the more conventional methods with ammonium acetate in acetic acid led either to the formation of a white product C23H30N2O8 which was composed of a molecule of the nitrostyrene, one of the benzaldehyde itself, and a molecule of ammonia, or to 3,4,5-trimethoxybenzonitrile, from reaction with the decomposition products of nitropropane. 

Another example of the formation of a rearranged product is the palladium(0)-catalysed reaction of the enolate ion of 2-methylcyclohexanone with 3-methyl-3-nitro-l -butene... 

Ir-catalyzed alkylation with a nitro compound was applied in a synthesis of flS,2R)-tra s-2-phenylcyclopentanamine, a compound with antidepressant activity (Scheme 9.41) [45]. The reaction of cinnamyl methyl carbonate with 4-nitro-l-butene gave the substitution product with 93% ee in 82% yield. A Grubbs I catalyst sufficed for the subsequent RCM. Further epimerization with NEts yielded a trans-cyclopentene in 83% yield via the two steps, while additional reduction steps proceeded in 90% yield. 

Alkenes can react with nitric acid, either neat or in a chlorinated solvent, to give a mixture of compounds, including v/c-dinitroalkane, jS-nitro-nitrate ester, v/c-dinitrate ester, /3-nitroalcohol, and nitroalkeneproducts. Cyclohexene reacts with 70 % nitric acid to yield a mixture of 1,2-dinitrocyclohexane and 2-nitrocyclohexanol nitrate. Frankel and Klager investigated the reactions of several alkenes with 70 % nitric acid, but only in the case of 2-nitro-2-butene (1) was a product identified, namely, 2,2,3-trinitrobutane (2). 

The reaction of fuming nitric acid with 2-methyl-2-butene (3) is reported to yield 2-methyl-3-nitro-2-butene (4). The reaction of alkenes with fuming nitric acid, either neat or in chlorinated solvents, is an important route to unsaturated nitrosteroids, which assumedly arise from the dehydration of /3-nitroalcohols or the elimination of nitric acid from /3-nitro-nitrate esters. Temperature control in these reactions is important if an excess of oxidation by-products is to be avoided. 

The reaction of alkynes with dinitrogen tetroxide is less synthetically useful as a route to nitro compounds. The reaction of 3-hexyne with dinitrogen tetroxide yields a mixture of cis- and fran -3,4-dinitro-3-hexene (4.5% and 13% respectively), 4,4-dinitro-3-hexanone (8%), 3,4-hexanedione (16%) and propanoic acid (6%). 2-Butyne forms a mixture containing both cis- and fran -2,3-dinitro-2-butene (7 % and 34 % respectively). " ... 

A very short and elegant synthesis of the 16-rtiembered dilactone ( )-pyrenophorin (515) has been accomplished by the dipolar cycloaddition reaction of a trialkylsilyl nitronate (81TL735). Nitromethane was added to 3-buten-2-one and the carbonyl group of the product reduced with sodium borohydride. The nitro alcohol (511) was converted to the acrylate (512) which was then subjected to a dimerization-cyclization reaction by treatment with chlorotrimethylsilane and triethylamine in dry benzene. Hydrogenation of the mixture of isoxazoline products (513) over palladium on charcoal followed by double dehydration of the intermediate bis-/3-hydroxyketone (514) led to ( )- and meso-pyrenophorin (Scheme... 

The reaction of dinitrogen pentoxide with ( )- and (Z)-2-butenes and ( )-l,2-diphenyl-ethylene afforded the corresponding nitro nitrates predominantly by syn addition114. 

However, during the addition of -keto esters onto enals, ytterbium triflate proved to be an efficient catalyst [171] as in the Michael additions of a-nitro esters [172]. Several water-soluble phosphines gave the corresponding phos-phonium salts in good yields when added to a,j9-unsaturated acids [173] or activated alkynes [174]. With alkynes, vinyl phosphine oxides or alkenes were formed depending on the pH of the aqueous solution. Significantly, the reaction of nitroalkanes with buten-2-one is considerably accelerated when going from... 

Nitro-propene or 2-butene and 1 gave ketofuran adduct 130 and 131 (R = Me), respectively (75CC726, 80JOC2945). A stereoisomeric mixture of hydroxyimino dihydrofuran 132 was obtained in the presence of KE Reaction of 1 with l-nitro-l-(phenylthio)-propene in the presence of KF afforded a diastereomeric mixture of dihydrofuran 133 along with... 

Attack of NO3 on isoprene apparently proceeds in much the same manner, but there is considerable controversy about the precise reaction pathway because of the variety of peroxy radicals that can be formed. The products, such as 4-nitroxy-2-methyl-l-butan-3-one and methacrolein, are consistent with the initial addition of NO3 to the terminal carbon atoms to form nitro-oxy-peroxy radicals in the presence of oxygen apparently the NO3 adds preferentially to position 1 (Fig. 12). 3-methyl-4-nitroxy-2-butenal was found as the main product in these experiments. The nitro-oxy-peroxy radicals can react with NO2, in the presence of O2, to yield thermally unstable nitroxy-peroxynitrate compounds. One particularly important feature of the addition of NO3 is the extent to which the initial adduct, which might eliminate NO2 to form an epoxide, is actually converted to the nitro-oxy-peroxy radicals in the atmosphere. 

Rate coefficients have been measured for the reaction of OH radicals with a number of organic ketonitrates (R-C0-CH(0N02)-R) and dinitrates (R-CH(0N02)-CH(0N02)-R) using a relative kinetic method. The compounds investigated included 1,2-propane-, 1,2-butane-, and 2,3-butanediol dinitrate, a-nitro-oxy acetone, l-nitro-oxy-2-butanone, 3-nitro-oxy-2-butanone, 3,4-dinitro-oxy-1-butene and cw-l,4-dinitro-oxy-2-butene (LACTOZ 90). The rate coefficients are listed in Chapter 2, Table la. and this study represented the first determination of the OH rate coefficients for these compounds. 

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