The synthesis of substituted adamantanes from dehydroadamantane

Udding, A.C.; Strating, J.; Wynberg, Hans

doi:10.1016/s0040-4039(01)98951-8

Cited by 24 publications

(7 citation statements)

References 15 publications

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“…A mixture of 2-adamantanol (1.2 g), sodium iodide (4.9 g), and hydriodic acid (58%, 13.2 mL) was stirred at 90−100 °C for 48 h. The mixture was cooled and diluted with 200 mL of water, obtaining a white solid after filtration. Recrystallization from acetone−water gave pure 2-iodoadamantane: mp 46−47 °C (lit . mp 46−47 °C) (1.4 g, 81% yield).…”

Section: Methodsmentioning

confidence: 99%

Reactions of 2-Iodo- and 1,2-Dihaloadamantanes with Carbanions in DMSO by the S_RN1 Mechanism

Lukach

Rossi

1999

J. Org. Chem.

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The reaction of 2-iodoadamantane (1) with the potassium enolate of acetophenone (2) did not occur in the dark but succeeded under irradiation or in the presence of FeBr2 to give the substitution product 3 in 62% and 88% yields, respectively. The photostimulated reaction was inhibited by p-dinitrobenzene (p-DNB). There was no reaction of 1 with the anion of nitromethane (4) in the dark or under irradiation. However, 4 reacted with 1 in the presence of acetone enolate ion (entrainment reaction) to yield 88% of the substitution product 2-adamantylnitromethane (5). The photostimulated reaction of 1 with anthrone (6), 2-naphthyl methyl ketone (9), and N-acetylthiomorpholine (11) anions afforded the substitution compounds 7 (37%), 10 (32%), and 12 (20%), respectively. There was no reaction of 1-chloro-2-iodoadamantane (13) with 2 in the dark (2 h), but under irradiation (5 min) it yielded 52% of the monosubstitution product α-(1-chloro-2-adamantyl)acetophenone (14). Under longer irradiation time (3 h), the same yield of 14 (52%) was obtained but the disubstitution product 15 was formed in 45% yield. Product 15 was also formed in the photostimulated reaction of 14 with 2. 2-Chloro-1-iodoadamantane (18) did not react with 2 in the dark (2 h), but the photostimulated reaction yielded the monosubstitution product α-(2-chloro-1-adamantyl)acetophenone (19) in 53% and 15 in 4% yield. Products 14 and 19 are intermediates in the formation of 15 in these reactions. There was a slow dark reaction of 1,2-diiodoadamantane (20) with 4 in the presence of acetone enolate ion to afford the iodomonosubstitution compound 21 (40%) and the disubstitution product 22 (13%). The photostimulated reaction (25 min) gave 21 (48%) and 22 (41%). On the other hand, after 3 h of irradiation, only traces of 21 could be detected (<5%) and the product distribution consisted mainly of 22. The iodomonosubstitution product 21 is an intermediate in these reactions.

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Section: Methodsmentioning

confidence: 99%

Reactions of 2-Iodo- and 1,2-Dihaloadamantanes with Carbanions in DMSO by the S_RN1 Mechanism

Lukach

Rossi

1999

J. Org. Chem.

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“…l-(2-Hydroxyethoxy)norbornane (3, R = OCH2CH2OH) was obtained as a clear oil: rmax (CCI4) 3431, 2957, 2925, 2872, 1452, 1319, 1262, 1179, 1141, 1071, and 891 cm"1; NMR (CDC13) r 6.31 (m, 4, CH2CH2), 7.5 (s, 1, OH) and 7.87 (br s, 1, CH-4); m/e 156.1148 (caled for C9H1602, 156.1150), 127 (39), 113 (34), 95 (25), and 83 (100). 1 -m-and -p-Tolylnorbornane (3, R = m-and p-CH3C6H4) were isolated as a mixture: ¡Wx (neat) 3055, 3025, 2950, 2922, 2873, 1603, 1508, 1486, 1450, 1329, 1300, 802, 773, and 695 cm"1; >H NMR (CDC13) t 2.73 (m, 5, aromatic H) and 7.64 (s, 3, Ar-CH3); m/e 186.1405 (caled for CI4HI8, 186.1408), 186 (45), and 147 (100).…”

Section: Methodsmentioning

confidence: 99%

Photochemistry of alkyl halides. 4. 1-Norbornyl, 1-norbornylmethyl, 1- and 2-adamantyl, and 1-octyl bromides and iodides

Kropp¹,

Poindexter²,

Pienta³

et al. 1976

J. Am. Chem. Soc.

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“…[42] Previous brominations of 33 with Br 2 under radical (photobromination) and ionic conditions exclusively gave the ring-opened diastereomeric dibromides a,e-and e,e-34 in a ratio of 1.4 to 2. [43] With carbon tetrabromide under PTC conditions (Scheme 4), only small amounts (< 10 %) of dibromides 34 were formed, and 7-bromo-2,4-dehydroadamantane (35) was isolated in 54 % yield. Thus, the PTC bromination protocol is especially valuable for C-H substitutions of strained hydrocarbons.…”

Section: Full Papermentioning

confidence: 99%

Preparation and Reactivity of [D_3d]‐Octahedrane: The Most Stable (CH)₁₂ Hydrocarbon

Meijere

Lee

Кузнецов

et al. 2005

Chemistry A European J

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The synthesis of the (CH)12 hydrocarbon [D(3d)]-octahedrane (heptacyclo[6.4.0.0(2,4).0(3,7).0(5,12).0(6,10).0(9,11)]dodecane) 1 and its selective functionalization retaining the hydrocarbon cage is described. The B3LYP/6-311+G* strain energy of 1 is 83.7 kcal mol(-1) (4.7 kcal mol(-1) per C-C bond) which is significantly higher than that of the structurally related (CH)16 [D(4d)]-decahedrane 2 (75.4 kcal mol(-1); 3.1 kcal mol(-1) per C-C bond) and (CH)20 [I(h)]-dodecahedrane 3 (51.5 kcal mol(-1); 1.7 kcal mol(-1) per C-C bond); the heats of formation for 1-3 computed according to homodesmotic equations are 52, 35, and 4 kcal mol(-1). Catalytic hydrogenation of 1 leads to consecutive opening of the two cyclopropane rings to give C2-bisseco-octahedrane (pentacyclo[6.4.0.0(2,6).0(3,11).0(4,9)]dodecane) 16 as the major product. Although 1 is highly strained, its carbon skeleton is kinetically quite stable: Upon heating, 1 does not decompose until above 180 degrees C. The B3LYP/6-31G* barriers for the S(R)2 attack of the tBuO. and Br3C. radicals on a carbon atom of one of the cyclopropane fragments (Delta(298) = 27-28 kcal mol(-1)) are higher than those for hydrogen atom abstraction. The latter barriers are virtually identical for the abstraction from the C1-H and C2-H positions with the tBuO. radical (DeltaG(298) = 17.4 and 17.9 kcal mol(-1), respectively), but significantly different for the reaction at these positions with the Br3C. radical (DeltaG(298) = 18.8 and 21.0 kcal mol(-1)). These computational results agree well with experiments, in which the chlorination of 1 with tert-butyl hypochlorite gave a mixture of 1- and 2-chlorooctahedranes (ratio 3:2). The bromination with carbon tetrabromide under phase-transfer catalytic (PTC) conditions (nBu4NBr/NaOH) selectively gave 1-bromooctahedrane in 43 % isolated yield. For comparison, the PTC bromination was also applied to 2,4-dehydroadamantane yielding 54 % 7-bromo-2,4-dehydroadamantane.

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The synthesis of substituted adamantanes from dehydroadamantane

Cited by 24 publications

References 15 publications

Reactions of 2-Iodo- and 1,2-Dihaloadamantanes with Carbanions in DMSO by the S_RN1 Mechanism

Reactions of 2-Iodo- and 1,2-Dihaloadamantanes with Carbanions in DMSO by the S_RN1 Mechanism

Photochemistry of alkyl halides. 4. 1-Norbornyl, 1-norbornylmethyl, 1- and 2-adamantyl, and 1-octyl bromides and iodides

Preparation and Reactivity of [D_3d]‐Octahedrane: The Most Stable (CH)₁₂ Hydrocarbon

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The synthesis of substituted adamantanes from dehydroadamantane

Cited by 24 publications

References 15 publications

Reactions of 2-Iodo- and 1,2-Dihaloadamantanes with Carbanions in DMSO by the SRN1 Mechanism

Reactions of 2-Iodo- and 1,2-Dihaloadamantanes with Carbanions in DMSO by the SRN1 Mechanism

Photochemistry of alkyl halides. 4. 1-Norbornyl, 1-norbornylmethyl, 1- and 2-adamantyl, and 1-octyl bromides and iodides

Preparation and Reactivity of [D3d]‐Octahedrane: The Most Stable (CH)12 Hydrocarbon

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Reactions of 2-Iodo- and 1,2-Dihaloadamantanes with Carbanions in DMSO by the S_RN1 Mechanism

Reactions of 2-Iodo- and 1,2-Dihaloadamantanes with Carbanions in DMSO by the S_RN1 Mechanism

Preparation and Reactivity of [D_3d]‐Octahedrane: The Most Stable (CH)₁₂ Hydrocarbon