Free radical chlorination of norcarane

Boikess, Robert S.; Mackay, M.; Blithe, Diana

doi:10.1016/s0040-4039(01)96451-2

Cited by 9 publications

(6 citation statements)

References 21 publications

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“…These results were confirmed to obtain authentic samples of these materials for GC-MS comparison. The free radical chlorinations of norcarane and spiro[2.5]octane were carried out in accord with a previous study . A competitive chlorination of these two substrates afforded 4-chloromethylcyclohexene and 1-(2-chloroethyl)cyclohexene in relative ratios of 4:1 with respect to the unrearranged chlorides, indicating a 4-fold slower rearrangement rate of the intermediate radical of spiro[2.5]octane. , …”

Section: Resultsmentioning

confidence: 89%

Revisiting the Mechanism of P450 Enzymes with the Radical Clocks Norcarane and Spiro[2,5]octane

et al. 2002

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Norcarane (1) and spiro[2.5]octane (2) yield different product distributions depending on whether they are oxidized via concerted, radical, or cationic mechanisms. For this reason, these two probes were used to investigate the mechanisms of hydrocarbon hydroxylation by two mammalian and two bacterial cytochrome P450 enzymes. Products indicative of a radical intermediate with a lifetime ranging from 16 to 52 ps were detected during the oxidation of norcarane by P450(cam) (CYP101), P450(BM3) (CYP102), CYP2B1, and CYP2E1. Trace amounts of the cation rearrangement product were observed with norcarane for all but CYP2E1, while no cation or radical rearrangement products were observed for spiro[2.5]octane. The results for the oxidation of norcarane with a radical rearrangement rate of 2 x 10(8) s(-1) are consistent with the involvement of a two-state radical rebound mechanism, while for the slower (5 x 10(7) s(-1)) spiro[2,5]oct-4-yl radical rearrangement products were beyond detection. Taken together with earlier data for the hydroxylation of bicyclo[2.1.0]pentane, which also suggested a 50 ps radical lifetime, these three structurally similar and functionally simple substrates show a consistent pattern of rearrangement that supports a radical rebound mechanism for this set of cytochrome P450 enzymes.

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Section: Resultsmentioning

confidence: 89%

Revisiting the Mechanism of P450 Enzymes with the Radical Clocks Norcarane and Spiro[2,5]octane

et al. 2002

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“…Thus, it has only recently been shown that the neophyl rearrangement is much slower than the analogous vinyl migration, 23-o_24 (706,707). The bicyclic radical must be formed reversibly • ώ =xr h -O 25 26 27 since the ring opening of 26 (770) and related radicals (110)(111)(112)(113) yields the primary alkyl preferentially (see also Section V). The bicyclic radical must be formed reversibly • ώ =xr h -O 25 26 27 since the ring opening of 26 (770) and related radicals (110)(111)(112)(113) yields the primary alkyl preferentially (see also Section V).…”

Section: T= ^Ymentioning

confidence: 99%

Free-Radical Rearrangements

Beckwith¹,

Ingold²

1980

Organic Chemistry: A Series of Monographs

114

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“…Caled for C14H12CI2N4: C, 54.72; , 3.90; N, 18.24. Found: C, 54.80; , 4.11; N, 18.24. The other band was assigned as 10 (674 mg, 41%): mp 128-129.5 °C; ir 3485 cm-1 (-OH); NMR 8.13 (1, m, C7-, ), 7.15-7.05 (3, m, aromatic H), 5.75 (1, s, -OH), 1.75 (3, s, 2'-CH3), 1.39 and 1.22 [6, s, 3',3'-(CH3)2]; m/e 324 (M-+, 27.5), 306 ( •+ -H20,17.7), 291 (M-+ -MeOH, 96.5).…”

mentioning

confidence: 99%

“…The ratio was not changed in a NMR sample tube kept for 1 week. (8) The same manner as ref 7 for the estimation. (9) The compound was extremely unstable and lost weight during weighing in preparation for the microanalysis owing to atmospheric hydrolysis to benzylamine hydrochloride.…”

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confidence: 99%

“…We now report on the results obtained for the photolysis of EtOCONs (Hanovia medium-pressure 100-W lamp, room temperature, 6-8 h) in neat cisand irons-bicyclo[4.4.0]decanes (decalins) (1 and 3), cis-bicyclo[4.3.0]nonane (hydrindane) ( 5), ci's-bicyclo[4.1.0]heptane (norcarane) (6), cisand irons -1,2-dimethylcyclohexanes (CDCH and TDCH) (2 and 4), and methylcyclohexane (7). Repeated experiments and careful integration of peak areas gave the results shown in Table I.…”

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confidence: 99%

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