2,5,7‐Cyclooctatrien‐1,4‐dion

Oda, Masaji; Kayama, Yasutaka; Miyazaki, Hideo; Kitahara, Yoshio

doi:10.1002/ange.19750871107

Cited by 18 publications

(4 citation statements)

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“…The cyclooctatetraeneoquinones, 9q1,4 and 9q1,2 , are known , and have been studied computationally . They are nonplanar, nonaromatic, and very reactive, especially the 1,2-quinone, which at room temperature quickly isomerizes to the bicyclic valence isomer:…”

Section: Resultsmentioning

confidence: 99%

“…The study of quinones corresponding to less prosaic polyenes made its debut in 1971 with the synthesis of benzocyclobutenedione ( 1 ) and cyclobutenedione ( 7q ), necessarily more arduous and creative, because the “obvious” hydrocarbon precursors, or suitable derivatives, evaded synthesis. Subsequently, quinones of other nonbenzenoid compounds have been examined: the azulenoquinones, the cyclooctatetraenoquinones ( 9q1,4 and 9q1,2 ), − and the pentalene quinones ( 10 , 11 , 12 , 13 ) (Figure ). Again, indirect synthetic methodologies had to be used, as suitably functionalized derivatives of the parent hydrocarbons remain absent.…”

Section: Introductionmentioning

confidence: 99%

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The Quinones of Benzocyclobutadiene: A Computational Study

2009

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The conventional (excluding non-Kekulé, singlet diradical structures) quinones of benzocyclobutadiene were studied computationally. Eight structures were examined, namely (based on the CA names for benzocyclobutenedione), benzocyclobutenedione or bicyclo[4.2.0]octa-1,3,5-triene-7,8-dione, bicyclo[4.2.0]octa-3,5,8-triene-2,7-dione, bicyclo[4.2.0]octa-1,4,6-triene-3,8-dione, bicyclo[4.2.0]octa-1(6),4,7-triene-2,3-dione, bicyclo[4.2.0]octa-1(8), 4,6-triene-2,3-dione, bicyclo[4.2.0]octa-1(6),3,7-triene-2,5-dione, bicyclo[4.2.0]octa-1(8),3,6-triene-2,5-dione, and bicyclo[4.2.0]octa-1,5,7-triene-3,4-dione (the question of resonance or tautomerism for the 2,3-dione pair and the 2,5-dione pair is considered). Using DFT (B3LYP/6-31G*) and ab initio (MP2/6-31G*) methods the geometries of the eight species were optimized, giving similar results for the two methods. The heats of formation of the quinones were calculated, placing them in low-energy (-17 kJ mol(-1), 7,8-dione), medium-energy (79-137 kJ mol(-1), 2,7-, 3,8-, and 3,4-diones), and high-energy (260-275 kJ mol(-1), 2,3- and 2,5-diones) groups. Diels-Alder reactivity as dienophiles with butadiene indicated the 2,7-, 3,8-, and particularly the 3,4-quinone may be relatively unreactive toward dimerization or polymerization and are attractive synthesis goals. Isodesmic ring-opening reactions and NICS calculations showed aromatic/nonaromatic properties to be essentially as expected from the presence of a benzene or cyclobutadiene ring. UV spectra, ionization energy electron affinity, and HOMO/LUMO energies were also calculated.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The Quinones of Benzocyclobutadiene: A Computational Study

2009

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“…The history of the cycloctatetraenoquinones has been briefly reviewed (17). The 1,2-quinone was reported in 1977 (18) and the 1,4-quinone in 1975 (19), but the question of their putative aromaticity was not specifically addressed experimentally, and apparently the only subsequent work on these compounds has been the computational study by Jakins and Lewars (17); this indicated that these quinones are nonplanar and nonaromatic. The quinones of azulene (e.g., the 1,2-quinone 6, Fig.…”

Section: Introductionmentioning

confidence: 99%

Tests for aromaticity applied to the pentalenoquinones A computational study

Delamere¹,

Jakins²,

Lewars³

2001

Can. J. Chem.

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Criteria for aromaticity and antiaromaticity were applied to the four pentalenoquinones, 1,2-, 1,5-, 1,4-, and 1,6-pentalenoquinone, i.e., bicyclo[3.3.0]octa-4,6,8-triene-2,3-dione (7a), bicyclo[3.3.0]octa-3,5,8-triene-2,7-dione (7b), bicyclo[3.3.0]octa-1(5),3,7-triene-2,6-dione (7c), and bicyclo[3.3.0]octa-1(5),3,6-triene-2,8-dione (7d). Geometry optimizations and frequency calculations were done with the pBP/DN* DFT method as implemented in Spartan, and single-point HF/3-21G calculations to obtain Löwdin bond orders (Spartan), as well as HF/6-31G* NICS calculations (Gaussian 98) were also carried out. Geometries and bond orders, chemical hardness, and NICS values gave no definite indication of aromatic or antiaromatic character. However, homodesmotic ring-opening reactions to give acyclic analogues indicated that 7a and 7b are nonaromatic (resonance energies -11 and 5 kJ mol -1 ) while 7c and 7d are antiaromatic (resonance energies -83 and -54 kJ mol -1 ). The resonance energies were obtained with the aid of an estimate of the strain energy of the molecules 7 (86 kJ mol -1 ) by a novel extrapolation procedure on hydropentalenes. Calculated pBP/DN* activation energies for Diels-Alder reactions with ethyne and ethene placed 7a and 7b in an "unreactive" class similar to 1,3-butadiene and fulvene, and 7c and 7d in a "reactive" class, similar to cyclopentadienone.Résumé : On a appliqué les critères d'aromaticité et d'antiaromaticité aux quatre 1,2-, 1,5-, 1,4-et 1,6pentalénoquinones, soit les bicyclo[3.. On a effectué les optimisations de la géométrie et les calculs de fréquences à l'aide de la méthode « pBP/DN* DFT » telle qu'implémentée dans Spartan; on a aussi effectué des calculs ponctuels HF/3-21G pour obtenir les ordres de liaison de Löwdin (Spartan) ainsi que des calculs « NICS » au niveau HF/6-31G* (Gaussian 98). Les géométries et les ordres de liaison, la dureté chimique et les valeurs « NICS » ne donnent aucune indication concernant le caractère aromatique ou antiaromatique des composés. Toutefois, des réactions d'ouverture de cycle homodesmotiques conduisant à la formation d'analogues acycliques indiquent que les composés 7a et 7b ne sont pas aromatiques (énergies de résonance de -11 et 5 kJ mol -1 ) alors que les composés 7c et 7d sont antiaromatiques (énergies de résonance de -83 et -54 kJ mol -1 ). Les énergies de résonance ont été obtenues à l'aide d'une évaluation de l'énergie de tension des molécules 7 (86 kJ mol -1 ) par le biais d'une nouvelle méthode extrapolation appliquée aux hydropentalènes. Les énergies d'activation calculées par la méthode pBP/DN* pour les réactions de Diels-Alder avec l'éthyne et l'éthène suggèrent que les composés 7a et 7b font partie de la classe de composés non réactifs, comme le buta-1,3-diène et le fulvène alors que les composés 7c et 7d font partie de la classe des composés réactifs, semblables à la cyclopentadiénone. Scheme 3. Selected C-C bond lengths (Å) and (parentheses)Löwdin bond orders of transition states and products from Diels-Alder reactions of 7a-7b, with ...

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“…~~~' ?These quinones can be considered as being related to the corresponding parent hydrocarbons in the same way that benzoquinone is related to benzene. A variety of different temperatures has been used for the addition of the apparently unstable compound dichloroketene to olefins using dichloroacetyl chloride-triethylamine (from -10 "C for 5 min to refluxing in toluene for 24 h).19v20 The addition reaction of dichloroketene to acenaphthylene (4) was repeated more than fifty times under different conditions to optimize the reaction conditions. The yield was raised to 10% by the simultaneous addition of dichloroacetyl chloride and triethylamine at constant equimolar rates during a 12 h period to a stirred solution of acenaphthylene (4) in dry hexane at room temperature.…”

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confidence: 99%

Synthesis and properties of cyclohepta[de]naphthalene-7,8-dione, o-pleiadienequinone

Tsunetsugu¹,

Kanda²,

Takahashi³

et al. 1984

J. Chem. Soc., Perkin Trans. 1

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Cyclohepta [de] naphthalene-7,8-dione, o-pleiadienequinone (2), was synthesized by hydrolysis of the acenaphthylene-dichloroketene adduct (5); chloro( hydroxy) ketone (6) was the precursor. Compound (2) afforded the triacetate (16) by a Thiele-Winter-type reaction and a phenalene compound (19) by alkaline hydrolysis. Spectral data suggest that the dione (2) has contributions from such canonical forms as 2,3-(2a) and/or 4,5benzotropolonate (2b) structures. The polarographic €+ value of the dione (2) is -0.23 V at pH 5.28 which is between that of 1,2-naphthoquinone and anthraquinone.Non-benzenoid quinones can be classified into three categories; diones with peripheral conjugation, diones without peripheral but with cross-conjugation, and fulvalenediones.? Although many non-benzenoid quinones belonging to the first category ([4n + 21 or [4n]annulenediones) have been reported, not many quinones belonging to the second or third categories are known. Belonging to the first category$ are cyclobutene-1,2-dione,' cyclo-octadecatetraenetetrayne-1,6-and -1,lOdione,2 1,6:8,13-propanediylidene[ 14]annulene-2,3-and -2,5d i ~n e , ~ 2,5,7-cyclo-octa-2,5,7-triene-1,4-4 and -1,2-dione,' 2,3,6,7-dibenzobicyclo[6.2.O]deca-2,6,8-trien-4-yne-9,l0-dione and 2,3:6,7-di benzo bicyclo [6.2.0]deca-2,4,6,8( 1)-tetraene-9, lOdione,6 8,9,4dione,,S-di0ne,~ azulene-1,2diones,' azulene-1,5-and -1,7-dione,' and acepleiadylene-5,6and 5,8-dione; ' ' belonging to the second are acenaphthenequinone (1) and cyclohepta[de]naphthalene-7,s-(2) and -7,lO-dione (3); l 3 belonging to the third are sesquifulvalene-7,10-dione,14 heptatriafulvalene-3,4-,'' and -1,2-dione,16 and heptafulvalene-3,4-dione.

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2,5,7‐Cyclooctatrien‐1,4‐dion

Cited by 18 publications

References 7 publications

The Quinones of Benzocyclobutadiene: A Computational Study

The Quinones of Benzocyclobutadiene: A Computational Study

Tests for aromaticity applied to the pentalenoquinones A computational study

Synthesis and properties of cyclohepta[de]naphthalene-7,8-dione, o-pleiadienequinone

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2,5,7‐Cyclooctatrien‐1,4‐dion

Cited by 18 publications

References 7 publications

The Quinones of Benzocyclobutadiene: A Computational Study

The Quinones of Benzocyclobutadiene: A Computational Study

Tests for aromaticity applied to the pentalenoquinones  A computational study

Synthesis and properties of cyclohepta[de]naphthalene-7,8-dione, o-pleiadienequinone

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Tests for aromaticity applied to the pentalenoquinones A computational study