Citation: LI Hui-Xue, WANG Xiao-Feng, LI Zhi-Feng, ZHU Yuan-Cheng. Photolysis Reaction of 2-Phenylbenzo[d]oxazole[J]. Acta Physico-Chimica Sinica, ;2012, 28(05): 1094-1100. doi: 10.3866/PKU.WHXB201203062 shu

Photolysis Reaction of 2-Phenylbenzo[d]oxazole

1.
Key Laboratory for New Molecule Design and Function of Gansu Education Department, College of Life Science and Chemistry, Tianshui Normal University, Tianshui 741001, Gansu Province, P. R. China

Received Date: 6 January 2012
Available Online: 6 March 2012
Fund Project: 天水师范学院中青年教师科研基金资助项目(TSA1116). (TSA1116)

The temperature-resilient, high tensile-strength fiber poly[p-phenylene benzobisoxazole] (PBO) is light-unstable and it degrades under ultraviolet radiation. In this paper we study the photolytic mechanism of the PBO monomer, 2-phenylbenzo[d]oxazole (PO). Following absorption of a photon and excitation into the first excited state (S₁), the molecule overcomes an energy barrier of 25.59 kJ·mol^-1 to enter the transition state; the oxazole ring is then opened and both benzene rings form a dihedral angle of about 90° to obtain the product, which under es further addition reaction with water. Calculations reveal that ring-opening is easily achieved in the potential surface of S₁. However, the pathway through which the oxazole ring opens in the ground state remains obscure. The topological properties of these compounds are in od agreement with the expected bond orders and the photolytic mechanism.
- Theoretical study,
- Photolysis reaction,
- 2-Phenylbenzo[d]oxazole
1. [1]
  (1) Fu, Q.; Zhang, H.; Song, B.; Liu, X.; Zhuang, Q.; Han, Z. J. Appl. Polym. Sci. 2011, 121, 1734.
2. [2]
  (2) Hu, X.D.; Jenkins, S. E.; Min, B. G.; Polk, M. B.; Kumar, S. Macromol. Mater. Eng. 2003, 288, 823.
3. [3]
  (3) Jiang, J. M.; Zhu, H. J.; Li, G.; Jin, J. H.; Yang, S. L. J. Appl. Polym. Sci. 2008, 109, 3133.
4. [4]
  (4) Li, J.; Chen, X.; Li, X.; Cao, H.; Yu, H.; Huang, Y. Polym. Int. 2006, 55, 456.
5. [5]
  (5) Li, X.; Huang, Y.; Cao, H.; Liu, L. J. Appl. Polym. Sci. 2007, 105, 893.
6. [6]
  (6) Lin, H.; Zhuang, Q.; Cheng, J.; Liu, Z.; Han, Z. J. Appl. Polym. Sci. 2007, 103, 3675.
7. [7]
  (7) So, Y.H. Polym. Int. 2006, 55, 127.
8. [8]
  (8) Wang, L.; Meng, Y. Z.; Wang, S. J.; Hay, A. S. J. Polym. Sci. Part A: Polym. Chem. 2004, 42, 1779.
9. [9]
  (9) Jin, J.; Yang, S.; Li, G.; Zhu, H.; Jiang, J. Preparing Ultraviolet-Resistant PBO Fiber Comprises Heating 4,6 Bi-Aminoresorcinol Hydrochloride, Terephthalic Acid, Phosphorus Pentoxide and Polyphosphoric Acid to Dissolve And Adding Nanometer Titanium Dioxide and Polyphosphoric Acid. CN Patent 101215732-A, 2008
10. [10]
  (10) Qian, J.; Zhang, Y.; Li, X.; Zhuang, Q.; Zhang, P.; Yin, X. High-Pressure Spinning for Preparing Polybenzoxazole (Pbo) Fiber Comprises Adding Polyphosphoric Acid, Phosphorus Pentoxide, 4,6-Aminoresorcinol Hydrochloride, and Terephthalic Acid into Prepolymerization Kettle and Polymerizing. CN Patent 101824662-A, 2010.
11. [11]
  (11) Zhang, C.; Huang, Y.; Meng, L.; Lu, X.; Huang, S. High Pressure Nitrogen Storage Bottle Made of PBO Fiber and Carbon Fiber Composite Material and Its Preparation Method. CN Patent 1948816-A, 2007.
12. [12]
  (12) Zhang, C. H.; Huang, Y. D.; Zhao, Y. D. Mater. Chem. Phys. 2005, 92, 245.
13. [13]
  (13) Zhang, T.; Hu, D. Y.; Jin, J. H.; Yang, S. L.; Li, G.; Jiang, J. M. Eur. Polym. J. 2009, 45, 302.
14. [14]
  (14) Fukumaru,T.; Fujigaya, T.; Nakashima, N. Polym. Chem. 2012, 3, 369.
15. [15]
  (15) Park, S. J.; Seo, M. K.; Lee, J. R. J. Colloid Interface Sci. 2003, 268, 127.
16. [16]
  (16) Dang T. D. Polym. Mater. Sci. Eng. 1990, 62, 86.
17. [17]
  (17) Takahashi, Y. Macromolecules 2002, 35, 3942.
18. [18]
  (18) Takahashi, Y. Macromolecules 2003, 36, 8652.
19. [19]
  (19) Zhang, T.; Yang, S.L.; Hu, D.Y.; Jin, J.H.; Li, G.; Jiang, J. M. Polym. Bull. 2009, 62, 247.
20. [20]
  (20) Hodges, C. S.; Neville, F.; Konovalov, O.; Hammond, R. B.; Gidalevitz, D.; Hamley, I. W. Langmuir 2006, 22, 8821.
21. [21]
  (21) Kumar, S.; Dang, T. D.; Arnold, F. E.; Bhattacharyya, A. R.; Min, B. G.; Zhang, X.; Vaia, R. A.; Park, C.; Adams, W. W.; Hauge, R. H.; Smalley, R. E.; Ramesh, S.; Willis, P. A. Macromolecules 2002, 35, 9039.
22. [22]
  (22) Ran, S.; Burger, C.; Fang, D.; Zong, X.; Chu, B.; Hsiao, B. S.; Ohta, Y.; Yabuki, K.; Cunniff, P. M. Macromolecules 2002, 35, 9851.
23. [23]
  (23) Ran, S.; Burger, C.; Fang, D.; Zong, X.; Cruz, S.; Chu, B.; Hsiao, B. S.; Bubeck, R. A.; Yabuki, K.; Teramoto, Y.; Martin, D. C.; Johnson, M. A.; Cunniff, P. M. Macromolecules 2001, 35, 433.
24. [24]
  (24) Walsh, P. J.; Hu, X.; Cunniff, P.; Lesser, A. J. J. Appl. Polym. Sci. 2006, 102, 3517.
25. [25]
  (25) Walsh, P. J.; Hu, X.; Cunniff, P.; Lesser, A. J. J. Appl. Polym. Sci. 2006, 102, 3819.
26. [26]
  (26) Chin, J.; Forster, A.; Clerici, C.; Sung, L.; Oudina, M.; Rice, K. Polym. Degrad. Stab. 2007, 92, 1234.
27. [27]
  (27) Jackson, P. F.; Morgan, K. J.; Turner, A. M. J.Chem. Soc. Perkin Trans. 2 1972, 1582.
28. [28]
  (28) Kim, Y. J.; Einsla, B. R.; Tchatchoua, C. N.; McGrath, J. E. High Perform. Polym. 2005, 17, 377.
29. [29]
  (29) So, Y.H.; Zaleski, M. J.; Murlick, C.; Ellaboudy, A. Macromolecules 1996, 29, 2783.
30. [30]
  (30) Zhang, W.; Shen, G.; Zhuang, J.; Zheng, P.; Ran, X. J. Photochem. Photobiol., A 2002, 147 25.
31. [31]
  (31) Martineau, A.; Dejongh, D. C. J. Anal. Appl. Pyrolysis 1983, 5, 39.
32. [32]
  (32) Roos, B. O. Adva. in Chem. Phys. 1987, 399.
33. [33]
  (33) Scalmani, G.; Frisch, M. J.; Mennucci, B.; Tomasi, J.; Cammi, R.; Barone, V. The J.chem.Phys. 2006, 124, 094107.
34. [34]
  (34) Wu, C.; Tretiak, S.; Chernyak, V. Y. Chem. Phys. Lett. 2007, 433, 305.
35. [35]
  (35) Rohatgi-Mukherjee, K. Fundamentals of Photochemistry; Wiley Eastern: New Delhi, 1978.
36. [36]
  (36) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al . Gaussian 09, Revision A.01; Gaussian Inc.: Wallingford, CT, 2009.
37. [37]
  (37) Starikova, Z.; Obodovskaya, A.; Bolotin, B. J. Struct. Chem. 1982, 23, 105.
38. [38]
  (38) Wiberg, K. Tetrahedron 1968, 24, 1083.
39. [39]
  (39) Sosa, G. L.; Peruchena, N. M.; Contreras, R. H.; Castro, E. A. J. Mol. Struct. -Theochem. 2002, 577, 219.
40. [40]
  (40) Li, Z. F.; Zhu, Y. C.; Zuo, G. F.; Tang, H. A.; Li, H. Y. Acta Phys. -Chim. Sin. 2010, 26, 429. [李志锋, 朱元成, 左国防, 唐慧安, 李红玉. 物理化学学报, 2010, 26, 429.]
41. [41]
  (41) Yuan, K.; Liu, Y. Z.; Zhu, Y. C.; Zhang, J. Acta Phys. -Chim. Sin. 2008, 24, 2065. [袁焜, 刘艳芝, 朱元成张继. 物理化学学报, 2008, 24, 2065.]
1. [1]
  Baitong Wei , Jinxin Guo , Xigong Liu , Rongxiu Zhu , Lei Liu . Theoretical Study on the Structure, Stability of Hydrocarbon Free Radicals and Selectivity of Alkane Chlorination Reaction. University Chemistry, 2025, 40(3): 402-407. doi: 10.12461/PKU.DXHX202406003
2. [2]
  Yanglin Jiang , Mingqing Chen , Min Liang , Yige Yao , Yan Zhang , Peng Wang , Jianping Zhang . Experimental and Theoretical Investigations of Solvent Polarity Effect on ESIPT Mechanism in 4′-N,N-diethylamino-3-hydroxybenzoflavone. Acta Physico-Chimica Sinica, 2025, 41(2): 100012-. doi: 10.3866/PKU.WHXB202309027
3. [3]
  Xuyang Wang , Jiapei Zhang , Lirui Zhao , Xiaowen Xu , Guizheng Zou , Bin Zhang . Theoretical Study on the Structure and Stability of Copper-Ammonia Coordination Ions. University Chemistry, 2024, 39(3): 384-389. doi: 10.3866/PKU.DXHX202309065
4. [4]
  Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
5. [5]
  Tingbo Wang , Yao Luo , Bingyan Hu , Ruiyuan Liu , Jing Miao , Huizhe Lu . Quantitative Computational Study on the Claisen Rearrangement Reaction of Allyl Phenyl Ethers: An Introduction to a Computational Chemistry Experiment. University Chemistry, 2024, 39(11): 278-285. doi: 10.12461/PKU.DXHX202403082
6. [6]
  Fei Xie , Chengcheng Yuan , Haiyan Tan , Alireza Z. Moshfegh , Bicheng Zhu , Jiaguo Yu . d带中心调控过渡金属单原子负载COF吸附O₂的理论计算研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2407013-. doi: 10.3866/PKU.WHXB202407013
7. [7]
  Danqing Wu , Jiajun Liu , Tianyu Li , Dazhen Xu , Zhiwei Miao . Research Progress on the Simultaneous Construction of C—O and C—X Bonds via 1,2-Difunctionalization of Olefins through Radical Pathways. University Chemistry, 2024, 39(11): 146-157. doi: 10.12461/PKU.DXHX202403087
8. [8]
  Caixia Lin , Zhaojiang Shi , Yi Yu , Jianfeng Yan , Keyin Ye , Yaofeng Yuan . Ideological and Political Design for the Electrochemical Synthesis of Benzoxathiazine Dioxide Experiment. University Chemistry, 2024, 39(2): 61-66. doi: 10.3866/PKU.DXHX202309005
9. [9]
  Xueting Cao , Shuangshuang Cha , Ming Gong . 电催化反应中的界面双电层：理论、表征与应用. Acta Physico-Chimica Sinica, 2025, 41(5): 100041-. doi: 10.1016/j.actphy.2024.100041
10. [10]
  Shiyan Cheng , Yonghong Ruan , Lei Gong , Yumei Lin . Research Advances in Friedel-Crafts Alkylation Reaction. University Chemistry, 2024, 39(10): 408-415. doi: 10.12461/PKU.DXHX202403024
11. [11]
  Tianlong Zhang , Rongling Zhang , Hongsheng Tang , Yan Li , Hua Li . Online Monitoring and Mechanistic Analysis of 3,5-diamino-1,2,4-triazole (DAT) Synthesis via Raman Spectroscopy: A Recommendation for a Comprehensive Instrumental Analysis Experiment. University Chemistry, 2024, 39(6): 303-311. doi: 10.3866/PKU.DXHX202312006
12. [12]
  Xueli Mu , Lingli Han , Tao Liu . Quantum Chemical Calculation Study on the E2 Elimination Reaction of Halohydrocarbon: Designing a Computational Chemistry Experiment. University Chemistry, 2025, 40(3): 68-75. doi: 10.12461/PKU.DXHX202404057
13. [13]
  Yingchun ZHANG , Yiwei SHI , Ruijie YANG , Xin WANG , Zhiguo SONG , Min WANG . Dual ligands manganese complexes based on benzene sulfonic acid and 2, 2′-bipyridine: Structure and catalytic properties and mechanism in Mannich reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1501-1510. doi: 10.11862/CJIC.20240078
14. [14]
  Aili Feng , Xin Lu , Peng Liu , Dongju Zhang . Computational Chemistry Study of Acid-Catalyzed Esterification Reactions between Carboxylic Acids and Alcohols. University Chemistry, 2025, 40(3): 92-99. doi: 10.12461/PKU.DXHX202405072
15. [15]
  Jiajie Li , Xiaocong Ma , Jufang Zheng , Qiang Wan , Xiaoshun Zhou , Yahao Wang . Recent Advances in In-Situ Raman Spectroscopy for Investigating Electrocatalytic Organic Reaction Mechanisms. University Chemistry, 2025, 40(4): 261-276. doi: 10.12461/PKU.DXHX202406117
16. [16]
  Yiying Yang , Dongju Zhang . Elucidating the Concepts of Thermodynamic Control and Kinetic Control in Chemical Reactions through Theoretical Chemistry Calculations: A Computational Chemistry Experiment on the Diels-Alder Reaction. University Chemistry, 2024, 39(3): 327-335. doi: 10.3866/PKU.DXHX202309074
17. [17]
  Ling Fan , Meili Pang , Yeyun Zhang , Yanmei Wang , Zhenfeng Shang . Quantum Chemistry Calculation Research on the Diels-Alder Reaction of Anthracene and Maleic Anhydride: Introduction to a Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 133-139. doi: 10.3866/PKU.DXHX202309024
18. [18]
  Ronghao Zhao , Yifan Liang , Mengyao Shi , Rongxiu Zhu , Dongju Zhang . Investigation into the Mechanism and Migratory Aptitude of Typical Pinacol Rearrangement Reactions: A Research-Oriented Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 305-313. doi: 10.3866/PKU.DXHX202309101
19. [19]
  Xuzhen Wang , Xinkui Wang , Dongxu Tian , Wei Liu . Enhancing the Comprehensive Quality and Innovation Abilities of Graduate Students through a “Student-Centered, Dual Integration and Dual Drive” Teaching Model: A Case Study in the Course of Chemical Reaction Kinetics. University Chemistry, 2024, 39(6): 160-165. doi: 10.3866/PKU.DXHX202401074
20. [20]
  Zhuoyan Lv , Yangming Ding , Leilei Kang , Lin Li , Xiao Yan Liu , Aiqin Wang , Tao Zhang . Light-Enhanced Direct Epoxidation of Propylene by Molecular Oxygen over CuO_x/TiO₂ Catalyst. Acta Physico-Chimica Sinica, 2025, 41(4): 100038-. doi: 10.3866/PKU.WHXB202408015

Get Citation

PDF

XML

Metrics

PDF Downloads(727)
Abstract views(2113)
HTML views(11)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142