Synthesis and enol determinations of 2,2-disubstituted 6-cyanocyclohexanones

Kulp, Stuart S.; Schmoyer, Ronald W.; Freeze, David E.; Buzas, Jerome

doi:10.1021/jo00892a016

Cited by 6 publications

(6 citation statements)

References 7 publications

(14 reference statements)

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“…Ibid. 1979, 87, 416. (6) Depicted is the anti isomer in which the epoxide oxygen atom and the benzylic hydroxyl group are on opposite faces of the ring; the syn isomer has these substituents on the same face of the molecule. Current evidence implicates the anti isomers as the principal active metabolites formed in cells.…”

Section: Resultsmentioning

confidence: 99%

“…Dehydration of 6 with p-tosic acid in refluxing benzene for 1 h gave 7 (98%): mp 167-169 °C (lit. * 23 mp 168-169 °C); NMR (CDCI3) 2.28-2.67 (m, 2, Hn), 3.00 (d, 2, Jw " = 8 Hz, H10), 5.92-6.25 (m, 1, Hr>), 6.62 (d, 1, J1213 = 10 Hz', Hla), 7.41-7.73 (m, 4, ,, ), 8.17 (s, 1, Hu), 8.25 (s, 1,' H9), 8.40-8.80 (m, 4, ^,ß)• Method C. A solution of 4 (500 mg, 1.9 mmol) in benzene (150 mL) was heated with DDQ (410 mg) at reflux for 10 min. NMR analysis of the crude product isolated by conventional workup showed the presence of 4 (83%), 7 (8%), and 1 (8%).…”

Section: Resultsmentioning

confidence: 99%

“…Workup in the usual manner4b,5b afforded the crude product which was purified by chromatography on Florisil. Elution with benzene gave frarcs-10,ll-bis(benzoyloxy)-10,ll,12,13-tetrahydro-l (9) as a white solid (7.98 g, 80%); mp 180-181 °C; NMR (CDCla) 2.26-2.66 (m, 2, H12), 3.07-3.46 (m, 2, H13), 5.50-5.86 (m, 1, Hn), 6.73 (d, 1, J10,n = 5.5 Hz, H10), 7.0-8.65 (m, 20, aromatic). trans-10,1 l-Bis(benzoyloxy )-10,l l-dihydrodibenz[a, c]anthracene (2b).…”

Section: Resultsmentioning

confidence: 99%

“…The resulting solution was stirred at 0 °C overnight and worked up conventionally. Chromatography on Florisil eluted with benzene furnished 2b (1.02 g, 34%) as a colorless solid: mp 183-184 °C; NMR (CDCla) 5.99 (dd, 1, 1 ), 6.21 (dd, 1, H12), 6.80 (d, 1, H10), 6.98 (d, 1, Hla), 7.15-8.80 (m, 20, aromatic), J101I = 6 Hz, Ju,12 = 4 Hz, J12,13 = 10 Hz. DDQ Method.…”

Section: Resultsmentioning

confidence: 99%

“…To a solution of 2b (1.1 g, 2.1 mmol) in THF (35 mL) was added a solution of NaOCH3 (232 mg, 4.3 mmol) in methanol (20 mL) and the resulting solution stirred at 60 °C for 20 min. Conventional workup gave 2a (567 mg, 86%) as a white solid: mp 210-212 °C dec; NMR (Me2SO-d6) 4.36 (ddd, 1, Hn), 4.80 (d, 1, H10), 6.03 (dd, 1, H12), 6.70 (dd, 1, H13), 7.55-7.88 (m, 4, H236i7), 7.42-7.86 (m, 6), ^4 539 44, t/10,11 = 9-5 Hz, Jn.u = 2 Hz, J"12|13 = 10 Hz, t/11,13 = 2 Hz.…”

Section: Resultsmentioning

confidence: 99%

See 4 more Smart Citations

Synthesis of oxidized metabolites of dibenz[a,c]anthracene

Harvey¹,

Fu²

1980

J. Org. Chem.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 3 more Smart Citations

Synthesis of oxidized metabolites of dibenz[a,c]anthracene

Harvey¹,

Fu²

1980

J. Org. Chem.

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Keto–enol equilibrium constants

Toullec

1990

PATAI'S Chemistry of Functional Groups

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3,7‐Dicyan‐2,6‐dimethoxy‐1,5‐dimethylsemibullvalen

1988

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Michael-Addition vonMethylmalonsiiuredimethylester an Acrylnitril f i r t mit 92% Ausbeute zum Diesternitril 4a, das quantitativ zur Monosiiure 4b hydrolysiert wird. D e m Kolbe-Elektrolyse ergibt mit 21% Ausbeute ein (1:l)-Gemisch der diastereomeren Bis(esternitri1e) meso-und rue-5. Bei der DieckmannKondensation dieses Gemischs mit Kalium-tert-butylat erhglt man aus meso-5 mit 54% Ausbeute das monocyclische u-Cyanketon 6% aus rac-5 mit 68% Ausbeute das bicyclische Bis(&cyan-enol) 7c. (relativ zu der des 3,7-Dicyansemibullvalens la) um 17 kJmol-' entspricht.Semibullvalene sind unter anderem interessant fur den Vergleich molekularer Eigenschaften in Losung und im festen Zustand. So zeigt das unsubstituierte Semibullvalen extrern schnelle entartete Cope-Umlagerung in Losung2). Auch in einer bestimmten festen Phase lagert sich Semibullvalen urn, doch ist die Cope-Umlagerung nicht mehr entartet. In einer zweiten festen Phase ist sie schlieBlich ,,eingefroren"').Fur die isomeren Dicyan-l,5-dimethylsemibullvalene 1 a4) und 2a5) gibt es keinen Zusammenhang zwischen der Geschwindigkeit ihrer Cope-Umlagerung in Losung und den durch Rontgenstrukturbestimmung ermittelten Atomabstanden C(2) -C(8) und C(4)..C(6). Zwei Bromatome an den Enden der Allylsysteme des 3,7-Dicyansemibullvalens 1 a verzogern stark die entartete Cope-Umlagerung. So lagert sich das 2,4-Dibromsemibullvalen 1 b 6000ma1, das 2,6-Dibromsemibullvalen l c 1300mal (bei 200 K) langsamer um als die nicht bromierte Verbindung 1 a. Die Atomabstande C(2)-C(8) und C(4)...C(6) in Einkristallen von 1 a und b sind verschieden, bei 1 c jedoch scheinbar gleich groB. Dieses existiert somit hochst wahrscheinlich in einem plastisch-kristallinen festen Zustand 6, mit statistischer Orientierungsfehlordnung beziiglich der pseudo-zweizahligen Achse senk- Michael reaction of dimethyl methylmalonate and acrylonitrile affords a 92% yield of the diesternitrile 4a, which is quantitatively hydrolysed to give the monoacid 4b. When subjected to Kolbe electrolysis, 4b produced a 1 : 1 mixture (21 % yield) of the diastereomeric bis(esternitri1es) mso-and rac-5. In the Dieckmann condensation of this mixture with potassium tert-butoxide, meso-5 furnishes 54% of the monocyclic a-cyanoketone 6a while ruc-5 affords 68% of the bicyclic bis(fkyanoeno1) 7c. The products of the condensation exist predomlnantly in these tautomeric forms (68 and 7% respectively) and are separated on the basis of their diflrerent acidity. Diazomethane methylates 7c to provide the bis(&cyanoenolether) 10 (79% yield), which is brominated by Nbromosuccinimide to yield the bis(bromo-P-cyanoenolether) 11 (51 % yield). Zinc/copper reagent debrominates 11 to afford the title compound Id (49% yield). The rate constants of the degene- Man kommt daher mit wenigen Schritten aus.

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Synthesis and enol determinations of 2,2-disubstituted 6-cyanocyclohexanones

Cited by 6 publications

References 7 publications

Synthesis of oxidized metabolites of dibenz[a,c]anthracene

Synthesis of oxidized metabolites of dibenz[a,c]anthracene

Keto–enol equilibrium constants

3,7‐Dicyan‐2,6‐dimethoxy‐1,5‐dimethylsemibullvalen

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