Photochemical Decomposition of t-Butyl Nitrite

Coe, Clarence S.; Doumani, Thomas F.

doi:10.1021/ja01184a065

Cited by 64 publications

(25 citation statements)

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“…They invoked an intramolecular mechanism: (9) TBN -+ MZK + CHINO in addition to the above scheme, as the major route for the production for nitrosomethane. This had been suggested earlier by Coe and Doumani [8] to account for the production of nitrosomethane by the photolysis of TBN. Kinetic studies by Levy [9] in a static system at 201°C showed that NO had an inhibiting effect on the rate.…”

Section: Introductionmentioning

confidence: 64%

ChemInform Abstract: THE GAS PHASE PYROLYSIS OF ALKYL NITRITES. I. T‐BUTYL NITRITE

Batt¹,

Milne²

1976

Chemischer Informationsdienst

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The rate of decomposition of t-butyl nitrite (TBN) has been studied in a static system over the temperature range of 12O-16O0C. For low concentrations of TBN (lo-" 10-4M), but with a high total pressure of CF4 (-0.9 atm) and small extents of reaction (-I%), the first-order homogeneous rates of acetone (M2K) formation are a direct measure of reaction (l), since k3>> k2 (NO): TBN 2 t-BuO + NO, t-BuO -+ MZK + Me. Addition of large amounts of NO in place of CF4 almost completely suppresses M2K formation.This shows that reaction (1) is the only route for this product. The rate of reaction From. &So1 and A,, k2 is calculated to be 1010.4M-1.~-1, implying that combination of t-BuO and NO occurs once every ten collisions. From an independent observation that k2/k2) = 1.7 =k 0.25 independent of tempera,ture, it is concluded that kt' = 101n~2hf-1~s-1 and k,' = 1015.9-40~2/6 s-l; t -B u O N O z q t-BuO + NO2. This study shows that MeNO arises solely as a re+ of the combination of Me and NO. Since NO is such an excellent radical trap for t-BuO, reaction (2) may be used in a competitive study of the decomposition of t-BuO in order to obtain the first absolute value for k3. Preliminary results show that k3 ( a ) = 1015.7-17.0/e s-,. The pressure dependence of k3 is demonstrated over the range of 10-z-l atm (ISOOC). The thermochemistry for reaction (3) implies that the H g 6(3P1) sensitised decomposition of t-BuOH occurs via reaction (m):I n addition to the products accounted for by the TBN radical split, isobutene is formed as a result of the 6-centre elimination of HONO: TBN 4 isobutene + HONO. The rate of formation of isobutene is given by k7 = 1012.9-33.6/8 s-l. t-BuOH, formed at a rate comparable to that of isobutene-at least in the initial stages-is thought to arise as a result of secondary reactions between TBN and HONO. The apparent discrepancy between this and previous studies is reconciled in terms of the above parallel reactions (1) and (7), such that k + 2k7 = 1014.'-36.2/f3 s-l.

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Section: Introductionmentioning

confidence: 64%

ChemInform Abstract: THE GAS PHASE PYROLYSIS OF ALKYL NITRITES. I. T‐BUTYL NITRITE

Batt¹,

Milne²

1976

Chemischer Informationsdienst

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“…78-80°C (9 mm). 'H NMR 6 (CDCl'): 1.3-1.9 (m, 14H), 3.95 (bd, J = 7 Hz, 2H superimposed over c. 3.9 (m, lH), 5.33 (complex t, primary J = 7 Hz, 1H). Cyclohexyl 3-methyl-2-butenyl ether (9).…”

Section: Cydopentyl 3-methyl-2-butenyl Ether (8)mentioning

confidence: 99%

Detection of C‐nitroso dimer formation by field desorption mass spectrometry

Johnson

Lever

Brent

1983

Org. Mass Spectrom.

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“…was carried out by the photolytic decomposition of i-butyl nitrite at 25°C and at a pressure of 50 mm using a 300 watt mercury vapor lamp (General Electric "Uviarc") as a source of radiation [36]. 122°-122.2°C corr.)…”

Section: Free Radical Nitrosationmentioning

confidence: 99%

C-Nitroso Compounds

1971

Organic Chemistry: A Series of Monographs

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Photochemical Decomposition of t-Butyl Nitrite

Cited by 64 publications

References 1 publication

ChemInform Abstract: THE GAS PHASE PYROLYSIS OF ALKYL NITRITES. I. T‐BUTYL NITRITE

ChemInform Abstract: THE GAS PHASE PYROLYSIS OF ALKYL NITRITES. I. T‐BUTYL NITRITE

Detection of C‐nitroso dimer formation by field desorption mass spectrometry

C-Nitroso Compounds

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