Science China Chemistry

, Volume 55, Issue 3, pp 359–367 | Cite as

Photodissociation of acryloyl chloride in the gas phase

  • ChunFan Yang
  • WeiQiang Wu
  • KunHui Liu
  • Huan Wang
  • HongMei Su


The 193 nm photodissociation dynamics of CH2CHCOCl in the gas phase has been examined with the technique of time-resolved Fourier transform infrared emission (TR-FTIR) spectroscopy. Vibrationally excited photofragments of CO (ν ⩽ 5), HCl (ν ⩽ 6), and C2H2 were observed and two photodissociation channels, the C-Cl fission channel and the HCl elimination channel have been identified. The vibrational and rotational state distributions of the photofragments CO and HCl have been acquired by analyzing their fully rotationally resolved νν−1 rovibrational progressions in the emission spectra, from which it has been firmly established that the mechanism involves production of HCl via the four-center molecular elimination of CH2CHCOCl after its internal conversion from the S1 state to the S0 state. In addition to the dominant C-Cl bond fission along the excited S1 state, the S1→S0 internal conversion has also been found to play an important role in the gas phase photolysis of CH2CHCOCl as manifested by the considerable yield of HCl.


TR-FTIR photodissociation vibrational and rotational state distribution four-center elimination internal conversion 


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  1. 1.
    Wortelboer HM, Usta M, Zanden JJ, Bladeren PJ, Rietjens IMCM, Cnubben NHP. Inhibition of multidrug resistance proteins MRP1 and MRP2 by a series of α,β-unsaturated carbonyl compounds. Biochem Pharmacol, 2005, 69: 1879–1890CrossRefGoogle Scholar
  2. 2.
    Billard T. Synthetic applications of β-fluoroalkylated α,β-unsaturated carbonyl compounds. Chem Eur J, 2006, 12: 974–979CrossRefGoogle Scholar
  3. 3.
    Guerin DJ, Miller SJ. Asymmetric azidation-cycloaddition with open-chain peptide-based catalysts: A sequential enantioselective route to triazoles. J Am Chem Soc, 2002, 124: 2134–2136CrossRefGoogle Scholar
  4. 4.
    Brocksom TJ, Coelho F, Depres JP, Greene AE, de Lima MEF, Hamelin O, Hartmann B, Kanazawa AM, Wang YY. First comprehensive bakkane approach: Stereoselective and efficient dichloroketene-based total syntheses of (±)- and (−)-9-acetoxyfukinanolide, (±)- and (+)-bakkenolide A, (−)-bakkenolides III, B, C, H, L, V, and X, (±)- and (−)-homogynolide A, (±)-homogynolide B, and (±)-palmosalide C. J Am Chem Soc, 2002, 124: 15313–15325CrossRefGoogle Scholar
  5. 5.
    Chatani N, Oshita M, Tobisu M, Ishii Y, Murai S. A GaCl3-catalyzed [4+1] cycloaddition of α,β-unsaturated carbonyl compounds and isocyanides leading to unsaturated γ-lactone derivatives. J Am Chem Soc, 2003, 125: 7812–7813CrossRefGoogle Scholar
  6. 6.
    Oshita M, Yamashita K, Tobisu M, Chatani N. Catalytic [4+1] cycloaddition of α,β-unsaturated carbonyl compounds with isocyanides. J Am Chem Soc, 2005, 127: 761–766CrossRefGoogle Scholar
  7. 7.
    Arendt MF, Browning PW, Butler LJ. Emission spectroscopy of the predissociative excited state dynamics of acrolein, acrylic acid, and acryloyl chloride at 199 nm. J Chem Phys, 1995, 103: 5877–5885CrossRefGoogle Scholar
  8. 8.
    Szpunar DE, Miller JL, Butler LJ, Qi F. 193-nm photodissociation of acryloyl chloride to probe the unimolecular dissociation of CH2CHCO radicals and CH2CCO. J Chem Phys, 2004, 120: 4223–4230CrossRefGoogle Scholar
  9. 9.
    Lau KC, Liu Y, Butler LJ. Probing the barrier for CH2CHCO→ CH2CH+CO by the velocity map imaging method. J Chem Phys, 2005, 123: 054322CrossRefGoogle Scholar
  10. 10.
    Pietri N, Monnier M, Aycard J-P. Photolysis of matrix-isolated acryloyl chloride: 1,3 Chlorine migration and further evolutions. J Org Chem, 1998, 63: 2462–2468CrossRefGoogle Scholar
  11. 11.
    Feairheller WR, Katon JE. Vibrational spectra and rotational isomerism in acrylyl (propenoyl) chloride and related α,β-unsaturated acyl halides. J Chem Phys, 1967, 47: 1248–1255CrossRefGoogle Scholar
  12. 12.
    Keirns JJ, Curl RF. Microwave spectrum of acryloyl fluoride. J Chem Phys, 1968, 48: 3773–3778CrossRefGoogle Scholar
  13. 13.
    Durig JR, Church JS, Compton DAC. Low frequency vibrational spectra and internal rotation of 2-chlorobuta-1,3-diene, propenoyl fluoride, and propenoyl chloride. J Chem Phys, 1979, 71: 1175–1182CrossRefGoogle Scholar
  14. 14.
    Hagen K, Hedberg K. Conformational analysis. 8. Propenoyl chloride. An electron-diffraction investigation of the molecular structure, composition, syn-anti energy and entropy differences, and potential hindering internal rotation. J Am Chem Soc, 1984, 106: 6150–6155CrossRefGoogle Scholar
  15. 15.
    Cui GL, Li QS, Zhang F, Fang WH, Yu JG. Combined CASSCF and MR-CI study on photoinduced dissociation and isomerization of acryloyl chloride. J Phys Chem A, 2006, 110: 11839–11846CrossRefGoogle Scholar
  16. 16.
    Xiang TC, Liu KH, Zhao SL, Su HM, Kong FA, Wang BS. Multichannel reaction of C2Cl3 + O2 studied by time-resolved Fourier transform infrared emission spectroscopy. J Phys Chem A, 2007, 111: 9606–9612CrossRefGoogle Scholar
  17. 17.
    Liu KH, Song D, Zhao SL, Wang SF, Yang CF, Su HM. Competitive reaction pathways of C2Cl3 + NO via four-membered ring and bicyclic ring intermediates. Phys Chem Chem Phys, 2011, 13: 1990–2000CrossRefGoogle Scholar
  18. 18.
    Arunan E, Setser DS, Ogilvie JF. Vibration-rotational Einstein coefficients for HF/DF and HCl/DCl. J Chem Phys, 1992, 97: 1734–1741CrossRefGoogle Scholar
  19. 19.
    Coxon JA, Roychowdhury UK. Rotational analysis of the B1Σ+ → X1Σ+ system of H35Cl. Can J Phys, 1985, 63: 1485–1497CrossRefGoogle Scholar
  20. 20.
    Lin S-R, Lin S-C., Lee Y-C, Chou I-C, Chen I-C, Lee Y-P. Three-center versus four-center HCl-elimination in photolysis of vinyl chloride at 193 nm: Bimodal rotational distribution of HCl (ν ⩽7) detected with time-resolved Fourier-transform spectroscopy. J Chem Phys, 2001, 114: 160–168CrossRefGoogle Scholar
  21. 21.
    Wu WQ, Liu KH, Yang CF, Zhao HM, Wang H, Yu YQ, Su HM. Reaction mechanisms of a photo-induced [1,3] sigmatropic rearrangement via a nonadiabatic pathway. J Phys Chem A, 2009, 113: 13892–13900CrossRefGoogle Scholar
  22. 22.
    Chang N-Y, Shen M-Y, Yu C-H. Extended ab initio studies of the vinylidene-acetylene rearrangement. J Chem Phys, 1997, 106: 3237–3242CrossRefGoogle Scholar
  23. 23.
    Parsons BF, Butler LJ, Ruscic B. Theoretical investigation of the transition states leading to HCl elimination in 2-chloropropene. Mol Phys, 2002, 100: 865–874CrossRefGoogle Scholar

Copyright information

© Science China Press and Springer-Verlag Berlin Heidelberg 2011

Authors and Affiliations

  • ChunFan Yang
    • 1
  • WeiQiang Wu
    • 1
  • KunHui Liu
    • 1
  • Huan Wang
    • 1
  • HongMei Su
    • 1
  1. 1.State Key Laboratory of Molecular Reaction Dynamics; Beijing National Laboratory for Molecular Sciences (BNLMS); Institute of ChemistryChinese Academy of SciencesBeijingChina

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