Separation and Infrared Analysis of Products from the Nitration of <i>alpha</i>-Olefins.

Morgan, Harry.; Sherwood, R. M.; Washall, T. A.

doi:10.1021/ac60240a017

Cited by 4 publications

(3 citation statements)

References 3 publications

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“…When 3 was completely decomposed in the presence of deuterium oxide at 75°, the nitro olefin isolated (11) (CH3)2C=CHN02 11 contained 25% deuterium at the 1 position. However, when unlabeled 11 was subjected to reaction conditions, 33% deuterium was incorporated into the molecule.…”

Section: = Fci U1 [Pyridine]mentioning

confidence: 99%

Base-induced decomposition of .beta.-nitroalkyl nitrates

Cummings¹,

Kreuz²

1972

J. Org. Chem.

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The elimination of nitric acid from /3-nitroalkyl nitrates proceeds via an Elcb type of mechanism when the nitro and nitrate groups are attached to primary and secondary carbon atoms, respectively. Where the nitrate function is on a tertiary carbon, it has not been unequivocally shown that an E2 mechanism is operative, although the evidence points in that direction. Previous interpretation of the relative rate differences ascribed to 1,2-dinitrooctadecane, l-nitro-2-octadecyl nitrate, and l-nitro-2-octadecyl nitrite as differences in leaving group abilities may require reconsideration. Most likely these eliminations depend both on the leaving group abilities and on the acidity of the nitromethylene protons.

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Section: = Fci U1 [Pyridine]mentioning

confidence: 99%

Base-induced decomposition of .beta.-nitroalkyl nitrates

Cummings¹,

Kreuz²

1972

J. Org. Chem.

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“…4.68 (CH2N02), or the absorptions at 7.85 [C(CH3)=CHN02] to the absorption at 6 4.82 (CH2N02) in the crude product after the olefin was removed under vacuum. 6 1-Nitro-l-decene typified 1-nitro 1-olefins in exhibiting two intense absorptions in the ir at 6.55 and 7.3 µ. The structure displayed below gives the proton assignments as determined by nuclear magnetic resonance.…”

mentioning

confidence: 99%

“…Hence, 4 must be formed directly in the reaction medium. When acylation was performed using the nitrile, the initial intermediate is probably 6 which is much less acidic than 4 and the latter is not produced until the reaction is quenched. It is, therefore, concluded that acylations of oxazine carbanions are more efficiently performed using nitriles as the acylating agent.…”

mentioning

confidence: 99%

Thermal decompositions of .beta.-nitroalkyl nitrates in olefinic solvents

Larkin¹,

Cummings²,

Kreuz³

1974

J. Org. Chem.

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Experimental Section5a -Ketoalkyloxazines 5. General Acylation Procedure. A solution of 9 (0.02 mol) in 30 ml of tetrahydrofutan was cooled to -78°in Dry Ice-acetone and treated with 0.021 mol (1.6 M) of nbutyllithium (hexane). The system was under a nitrogen atmosphere throughout -the addition. The anion 1 appeared within 1 hr as a yellow suspension and the ester or nitrile (0.21 mole) was added all at once. The reaction was allowed, while stirring, to warm to room temperature (8-15 hr) and then poured into water and acidified (1 N hydrochloric acid). The aqueous acid solution was extracted with ether-pentane (1:1) and the extracts were discarded. The aqueous solution was neutralized with 5% sodium bicarbonate and extracted with ether, dried (NaaSCL), and concentrated. The residue was recrystallized from petroleum ether to afford pure 5 (see Table I for physical constants).

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Nitration of 1‐dodecene with nitric acid

et al. 1976

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A refluxing, heterogeneous mixture of l‐dodecene with aqueous 30% nitric acid leads to a mixture of closely related nitroproducts in greater than 90 % yield within 3 h. Similarly various types of readily available olefins easily undergo nitration with nitric acid. The nitration of l‐dodecene with nitric acid is initiated by nitrous acid, exhibits free‐radical character and is believed to proceed through the agency of nitrogen dioxide although the manner of its propagation is not fully clear. However, a rate‐determining oxidation step apparently determines both the variation of nitration time with change in olefin structure and also the temperature dependence of the rate of nitroproduct formation. Emulsifying agents increase the nitration rate and the slow addition of sufficient nitrous acid obviates the reaction's temperature dependence.

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Separation and Infrared Analysis of Products from the Nitration of alpha-Olefins.

Cited by 4 publications

References 3 publications

Base-induced decomposition of .beta.-nitroalkyl nitrates

Base-induced decomposition of .beta.-nitroalkyl nitrates

Thermal decompositions of .beta.-nitroalkyl nitrates in olefinic solvents

Nitration of 1‐dodecene with nitric acid

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