1-Nitrobutane

Primary nitroparaffins react with two moles of formaldehyde and two moles of amines to yield 2-nitro-l,3-propanediamines. With excess formaldehyde, Mannich bases from primary nitroparaffins and primary amines can react further to give nitro-substituted cycHc derivatives, such as tetrahydro-l,3-oxa2iaes or hexahydropyrimidines (38,39). Pyrolysis of salts of Mannich bases, particularly of the boron trifluoride complex (40), yields nitro olefins by loss of the amine moiety. Closely related to the Mannich reaction is the formation of sodium 2-nitrobutane-1-sulfonate [76794-27-9] by warming 1-nitropropane with formaldehyde and sodium sulfite (41). 

C3H7F 1-FLUORO- -282.862 2.6769E-01 2.8109E-05 -200.29 166 C4H9N02 2-NITROBUTANE -166.954 5.2869E-01 3.0809E-05 -6.23... 

Accordingly, cyclic nitronates can be a useful synthetic equivalent of functionalized nitrile oxides, while reaction examples are quite limited. Thus, 2-isoxazoline N-oxide and 5,6-dihydro-4H-l,2-oxazine N-oxide, as five- and six-membered cyclic nitronates, were generated in-situ by dehydroiodination of 3-iodo-l-nitropropane and 4-iodo-l-nitrobutane with triethylamine and trapped with monosubstituted alkenes to give 5-substituted 3-(2-hydroxyethyl)isoxazolines and 2-phenylperhydro-l,2-oxazino[2,3-fe]isoxazole, respectively (Scheme 7.26) [72b]. Upon treatment with a catalytic amount of trifluoroacetic acid, the perhydro-l,2-oxazino[2,3-fe]isoxazole was quantitatively converted into the corresponding 2-isoxazoline. Since a method for catalyzed enantioselective nitrone cycloadditions was established and cyclic nitronates should behave like cyclic nitrones in reactivity, there would be a good chance to attain catalyzed enantioselective formation of 2-isoxazolines via nitronate cycloadditions. 

Giacomelli et al. constructed 3-propylisoxazole-5-yl-methanol via a [3-1-2] cycioaddition (Fig. 15) [158]. Nitrobutane was converted to nitrile oxide in the presence of 4-(4,6-dimethoxy [1,3,5]triazin-2-yl)-4-methylmorpholinium chloride (DMTMM) and catalytic 4-dimethylaminopyridine (DMAP). Trityl chloride resin-bound propargyl alcohol was employed as the dipolarophile to trap the nitrile oxide, forming the cyclo adduct isoxazole ring under unusually mild conditions (i.e., microwave irradiation at 80 °C for five times 1 min). Disappearance of the starting material was monitored by FT-IR. 

Fig. 15 Microwave-assisted isoxazole synthesis via on resin [3-1-2] cycioaddition. Reagents and conditions a 1-nitrobutane, DMTMM, DMAP, MeCN, THE, MW 80 °C, 5 min, open vessel b TEA CH2CI2 (5 95), rt, 20 min...

Hydroxy-3,5-dinitrobenzene arsonic acid 1-Nitrobutane (iii) Ammonium nitrate... 

Nitrobutane 1-Nitro-3-butene (i) Reactive vinyl monomers... 

Effects of chain length and substitution. Comparing the stabiiity of alkyl nitrates or aliphatic nitrated derivatives, in spite of instability to the extent of making it hazardous to handle them, stability increases rapidly with the number of alkyl groups. So nitroethanes, especially nitropropanes and nitrobutanes, are commonly used industrial raw materials. 

The f-nitrobutane employed was prepared by the procedure of Kornblum, Clutter, and Jones.2 This method is essentially the same as that previously reported in Organic Syntheses ... 

FIGURE 1.23. Variations of the transfer coefficient with the electrode potential derived from convolutive cyclic voltammetry of the following systems with double layer correction, t-nitrobutane in acetonitrile ( ), r-nitrobutane in DMF ( ), nitrodurene in acetonitrile + 2%H20 (a), nitrodurene in acetonitrile ( ), nitromesitylene in acetonitrile (y). Data from reference 64 and references therein. 

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