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Volumn 637, Issue 1-3, 2003, Pages 91-100

Structure of substituted o-benzynes and their cycloaddition to ketene dialkyl acetals

Author keywords

Arynes; Cycloaddition; Density functional calculations; LUMO energies

Indexed keywords

2 BENZYNE DERIVATIVE; ACETAL DERIVATIVE; ALKYL GROUP; BENZENE DERIVATIVE; KETENE DERIVATIVE; RADICAL; UNCLASSIFIED DRUG;

EID: 0141673219     PISSN: 01661280     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0166-1280(03)00412-3     Document Type: Article
Times cited : (22)

References (80)
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    • note
    • Likewise, according to the ref. 11, the DFT calculations agree best with the experimental results.
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    • note
    • In the cases of 22e, 22g, 22h and 22r, the 2Pz orbital contribution is not equal to zero and was considered. This result is explained by the non-planearity of the aromatic ring (dihedral angle C(6)-C(1) -C(2) -C-3)(°), 22e: 0.49; 22g: 0.09; 22h: 0.7; 22r: 0.26).
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    • note
    • 13C coupling constants with those of model compounds suggested a cumulenic character for o-benzyne, see ref. 12b.
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    • note
    • -1 (Becke3LYP/ 6-311 + G(d,p)).
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    • note
    • +,).
  • 53
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    • note
    • The structures of substituted benzenes calculated at the B3LYP/6-311G(d,p) level are in good agreement with experiment.
  • 54
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    • and the references cited therein
    • For the energy of the 1,2-didehydrogenation of benzene, MP2/6-311G(d,p), QCISD/6-311G(d,p), CCSD(T)/6-311G(d,p) and BLYP/6-311G* calculations produce the values of 86.1, 91.2, 86.8 and 82.8kcal/mol, respectively, see: ref. 14c. The previously CCSD(T)/6-31G* reaction energy was of 91.00kcal/mol, see ref. 141; and at MP2/6-31G*//MP2/6-31G* level, 95.2 kcal/mol, see: ref. 14j. The experimental estimate value is 86.6(3.0 kcal/mol (at T = 298 K), see:P.G. Wenthold, R.R. Squires, J. Am. Chem. Soc. 116 (1994) 6401-6412. and the references cited therein.
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    • note
    • Much to our surprise, all attempts of cycloaddition conducted on 4-bromonitrobenzene and 4-bromobenzonitrile with 2-methylene-1,3-dioxepane failed to give the corresponding benzocyclobutanone dialkyl ketals. The starting material was recovered in each cases.
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    • Similarly, studies concerning the [2s + 2a] cycloaddition of acetylene to ethylene to give cyclobutene led to an high transition state (75 kcal/mol), see:B.A. Hess Jr., L.J. Schaad, D.N. Reinhoudt, Int. J. Quant. Chem. 29 (1986) 345-350.
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  • 78
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    • note
    • 2 = 0.38.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.