Naphthoannelated cycloheptatrienylidene and cycloheptatetraene: generation and properties

Balci, M.; Winchester, William R.; Jones, W. M.

doi:10.1021/jo00147a028

Cited by 19 publications

(11 citation statements)

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“…Jones’ group prepared naphthotropone 436 using published procedures and known intermediates ( Scheme 84 ) [ 228 – 231 ]. The ketone 461 prepared in 11 steps starting from naphthalene ( 17 ) was converted to 462 through ring-opening of cyclopropane with a base followed by oxidation.…”

Section: Reviewmentioning

confidence: 99%

“…Jones’ group also reported the generation and properties of a naphthoannelated cycloheptatrienylidene-cycloheptatetraene intermediate from both the corresponding salt 492 derived from 436 or a mixture of bromocycloheptatrienes 499 and 500 ( Scheme 89 ) [ 228 ]. While thermolysis of salt 492 in cyclohexane or benzene afforded only a mixture of naphthoannelated heptafulvalenes 493 and 494 , thermolysis in the presence of dimethyl fumarate ( 495 ) yielded the expected spirocyclopropane 496 along with trace amounts of the same two dimers.…”

Section: Reviewmentioning

confidence: 99%

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One hundred years of benzotropone chemistry

Daştan

Kılıç

Saraçoğlu

2018

Beilstein J. Org. Chem.

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Section: Reviewmentioning

confidence: 99%

Section: Reviewmentioning

confidence: 99%

One hundred years of benzotropone chemistry

Daştan

Kılıç

Saraçoğlu

2018

Beilstein J. Org. Chem.

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“…In support of our assignment, we note that calculations place 8 as the lowest energy isomer of the six possible isomeric benzocycloheptatrienylidenes and benzocycloheptatetraenes. 21 In addition, dehydrohalogenation of a mixture of 11 and 12 produces 3-methyl-4,5-benzocycloheptatetraene (13), which yields an isolable [2 + 2] dimer. 22 In summary, irradiation of 1-and 2-naphthyldiazomethane produces 4,5-and 2,3-benzobicyclo[4.1.0]hepta-2,4,6-triene, respectively.…”

Section: Scheme Imentioning

confidence: 99%

Benzobicyclo[4.1.0]hepta-2,4,6-trienes

West¹,

Mooring²,

McMahon³

et al. 1986

J. Org. Chem.

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“…In this paper we investigate the C 7 H 6 potential energy surface, in particular that part involving species 1 − 10 , using modern ab initio molecular orbital theory. Previous calculations confined to species 1 − 4 at the INDO, MINDO/3, MNDO, and ab initio (4−31G//STO-3G), or DZ+d SCF/TCSCF 28 levels of theory as well as combined force field-SCF calculations 14 have been reported. With the availability of ever faster computers, it is now feasible to study this relatively large system at a reliable level of theory.…”

Section: Introductionmentioning

confidence: 99%

Interconversions of Phenylcarbene, Cycloheptatetraene, Fulvenallene, and Benzocyclopropene. A Theoretical Study of the C₇H₆ Energy Surface

1996

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Ab initio calculations at the G2(MP2,SVP) and B-LYP/6-311+G(3df,2p)+ZPVE levels have been used to examine the potential energy surface of C(7)H(6). Fulvenallene (6) is the most stable C(7)H(6) isomer considered in this study. 1-Ethynylcyclopentadiene (9A), benzocyclopropene (10), and 1,2,4,6-cycloheptatetraene (4) lie 12, 29, and 49 kJ mol(-)(1), respectively, above 6. Phenylcarbene (1) is calculated is to have a triplet ((3)A") ground state, 16 kJ mol(-)(1) more stable than the singlet state ((1)A'). Interconversion of 1 and 4 is predicted to have a moderate activation barrier, with the involvement of a stable bicyclic intermediate (bicyclo[4.1.0]hepta-2,4,6-triene, 2). However, 2 is found to lie in a shallow potential energy well with a small barrier (8 kJ mol(-)(1)) to rearrangement to 4. At the G2(RMP2,SVP)//QCI level, the (3)A(2) and (3)B(1) triplet states of cycloheptatrienylidene ((3)3) are predicted to lie very close in energy. The singlet "aromatic" cycloheptatrienylidene ((1)3, (1)A(1)) is found to be a transition structure interconverting two chiral cyclic allenes (4) and it lies approximately 25 kJ mol(-)(1) below the triplet states. Bicyclo[3.2.0]hepta-1,3,6-triene (5) is predicted to be a stable equilibrium structure, lying in a significant energy well. Rearrangement of 4 to 5 constitutes the rate-determining step for the rearrangement of phenylcarbene to fulvenallene (6), the ethynylcyclopentadienes (9), and spiro[2.4]heptatriene (7). Rearrangement of 9A to 6, via a 1,4-H shift, requires a large barrier of 325 kJ mol(-)(1). Rearrangement of benzocyclopropene (10) to 6 involves a methylenecyclohexadienylidene intermediate (27) and is associated with an energy barrier of 223 kJ mol(-)(1). The calculated mechanisms and energetics for the interconversions of various C(7)H(6) isomers are in good accord with experimental results to date.

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Naphthoannelated cycloheptatrienylidene and cycloheptatetraene: generation and properties

Cited by 19 publications

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One hundred years of benzotropone chemistry

One hundred years of benzotropone chemistry

Benzobicyclo[4.1.0]hepta-2,4,6-trienes

Interconversions of Phenylcarbene, Cycloheptatetraene, Fulvenallene, and Benzocyclopropene. A Theoretical Study of the C₇H₆ Energy Surface

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Naphthoannelated cycloheptatrienylidene and cycloheptatetraene: generation and properties

Cited by 19 publications

References 0 publications

One hundred years of benzotropone chemistry

One hundred years of benzotropone chemistry

Benzobicyclo[4.1.0]hepta-2,4,6-trienes

Interconversions of Phenylcarbene, Cycloheptatetraene, Fulvenallene, and Benzocyclopropene. A Theoretical Study of the C7H6 Energy Surface

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Interconversions of Phenylcarbene, Cycloheptatetraene, Fulvenallene, and Benzocyclopropene. A Theoretical Study of the C₇H₆ Energy Surface