2,3,5,6,7,8‐Hexakis(methylene)bicyclo[2.2.2]octane

Pilet, Olivier; Vogel, Pierre

doi:10.1002/anie.198010031

Cited by 12 publications

(2 citation statements)

References 15 publications

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“…(±)-2-Alkyl-l0-undecenoic Acids (3). The preparation of 2-ethyl-and 2-n-propylundecenoic acids followed the general procedure of Pfeffer and Silbert.7 The 2-ethylated acid 3a was obtained in 95.2% yield (<5% unalkylated) from 10-undecenoic acid: bp 125-227 °C (0.01 mm).9 The 2-n-propylated acid 3b was obtained in 98.5% yield (<5% unalkylated): bp 116-120 °C (0.005 mm); IR 1705 (C=0), 990,910 cm"1 (CH=CH2); NMR 0.88 (t, 3 H, CH3CH2), 2.05 (m, 2 H, CH2C=), 2.36 (m, 1 H, CHC02H), 4.95 and 5.80 (m, 3 H, CH=CH2); CIMS of methyl ester, m/e 241 (P + 1).…”

Section: Methodsmentioning

confidence: 99%

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Syntheses of the stereoisomers of the sex pheromones of the southern corn rootworm and lesser tea tortrix

Sonnet¹

1982

J. Org. Chem.

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NMR -0.26 (Si(CH3)3, X), -0.20 (Si(CH3)3, XVIII), 0.54-2.38 (ring protons), 4.47 (>CHOH, XVIII), 5.95 (>C=CCH), XVIII).3-Methyl-5-(trimethylsilyl)cyclohexan-l-one was obtained in low yield by faithful repetition in all particulars of the reported procedure,1 and on one occasion none of the desired product was obtained. Still1 did not silylate 5-methylcyclohex-2-en-l-one (with (CH^gSiLi), but he did report no conjugate addition to isophorone.The reasons for these differences have not been established, but the (CHg)gSiLiCu1 reagent appears to have certain advantages.8 3-Methyl-5-(trimethylsilyl)cyclohexan-l-one (XI and XII) was distilled (92 °C (8 mmHg)).

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Section: Methodsmentioning

confidence: 99%

“…Syntheses of Diastereomerically Pure Amides 4. The carboxylic acids, 3 (1 equiv) were converted to acid halides with SOCl2 (1.2 equiv) and DMF (0.12 equiv) in anhydrous Et20.16a…”

Section: Methodsmentioning

confidence: 99%

Syntheses of the stereoisomers of the sex pheromones of the southern corn rootworm and lesser tea tortrix

Sonnet¹

1982

J. Org. Chem.

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Synthesis of Fluorinated Dienes by Palladium‐Catalyzed Coupling Reactions

Akkerman

Kickbusch

Lentz

2008

Chemistry An Asian Journal

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The synthesis of partly fluorinated 1,3- and 1,4-dienes by palladium-catalyzed coupling makes these compounds available on the laboratory scale. Several catalyst systems were tested to maximize the yields and minimize the by-products. The molecular structures of 1,1,2,4,4-pentafluorobutadiene, chloro(N,N'-tetramethylethylenediamine)(trifluorovinyl)zinc, PCy(2)R, and P(O)Cy(2)R (Cy=cyclohexyl, R=2-(1-naphthyl)phenyl) were elucidated by X-ray crystallography.

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Synthesis and Diels‐Alder Reactivity of 2,3,5,6‐Tetramethylidenenorbornane

Pilet

Vogel

1981

Helvetica Chimica Acta

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Pd‐catalyzed double carbomethoxylation of the Diels‐Alder adduct of cyclo‐pentadiene and maleic anhydride yielded the methyl norbornane‐2,3‐endo‐5, 6‐exo‐tetracarboxylate (4) which was transformed in three steps into 2,3,5,6‐tetramethyl‐idenenorbornane (1). The cycloaddition of tetracyanoethylene (TCNE) to 1 giving the corresponding monoadduct 7 was 364 times faster (toluene, 25°) than the addition of TCNE to 7 yielding the bis‐adduct 9. Similar reactivity trends were observed for the additions of TCNE to the less reactive 2,3,5,6‐tetramethylidene‐7‐oxanorbornane (2). The following second order rate constants (toluene, 25°) and activation parameters were obtained for: 1 + TCNE → 7: k1 = (255 + 5) 10−4 mol−1 · s−1, ΔH≠ = (12.2 ± 0.5) kcal/mol, ΔS≠ = (−24.8 ± 1.6) eu.; 7 + TCNE → 9, k2 = (0.7 ± 0.02) 10−4 mol−1 · s−1, ΔH≠ = (14.1 ± 1.0) kcal/mol, ΔS≠ = ( −30 ± 3.5) eu.; 2 + TCNE → 8: k1 = (1.5 ± 0.03) 10−4 mol−1 · s−1, ΔH≠ = (14.8 ± 0.7) kcal/mol, ΔS≠ = (−26.4 ± 2.3) eu.; 8 + TCNE → 10; k2 = (0.004 ± 0.0002) 10−4 mol−1 · s−1, ΔH≠ = (17 ± 1.5) kcal/mol, ΔS≠ = (−30 ± 4) eu. The possible origins of the relatively large rate ratios k1/k2 are discussed briefly.

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2,3,5,6,7,8‐Hexakis(methylene)bicyclo[2.2.2]octane

Abstract: The first permethylenated bicyclic, the title compound (1), was synthesized in several steps from (2). Compound (1) forms colorless crystals. The hedgehog‐shaped molecule suggests the name “hericenes” (Latin name for hedgehog = hericeus) for such polycyclics.

Cited by 12 publications

References 15 publications

Syntheses of the stereoisomers of the sex pheromones of the southern corn rootworm and lesser tea tortrix

Syntheses of the stereoisomers of the sex pheromones of the southern corn rootworm and lesser tea tortrix

Synthesis of Fluorinated Dienes by Palladium‐Catalyzed Coupling Reactions

Synthesis and Diels‐Alder Reactivity of 2,3,5,6‐Tetramethylidenenorbornane

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