Download PDF
Synlett 2007(14): 2205-2208  
DOI: 10.1055/s-2007-985573
LETTER
© Georg Thieme Verlag Stuttgart · New York

Gas-Phase Pyrolysis in Organic Synthesis: Rapid Green Synthesis of 4-Quinolinones

Nouria A. Al-Awadi*a, Ismail Abdelshafy Abdelhamida, Ismail Abdelshafy Abdelhamidb, Alya M. Al-Etaibib, Mohamed Hilmy Elngadia
a Chemistry Department, Faculty of Science, Kuwait University, PO Box 5969, Safat 13060, Kuwait
e-Mail: nouria@kuc01.kuniv.edu.kw;
b Natural Science Department, College of Health Sciences, Public Authority for Applied Education and Training, Kuwait
Further Information

Publication History

Received 16 May 2007
Publication Date:
13 August 2007 (online)

    Permissions and Reprints All articles of this category

Abstract

Gas-phase pyrolysis of aminomethylene Meldrum’s acid derivatives gave quinolinones and/or amines depending on the ­nature of arylamino moiety. Effect of substituent on reaction rate and nature of pyrolysis products supports the suggested intramolecular nucleophilic substitution reaction via initially formed keteneamine intermediate.

Key words

Meldrum’s acid - pyrolysis - 4-quinolinones

    References and Notes

  • 1 Hiari YM. Khanfar MA. Qaisi AM. Abu Shuheil MY. El-Abadelah MM. Boese R. Heterocycles  2006,  68:  1163 
    Google Scholar
  • 2 Mann J. Crabbe MJC. Bacteria and Antibacterial Agents   Biochemical & Medicinal Chemistry Series, Oxford University Press; USA: 1996.  p.64 
    Google Scholar
  • 3 Heindel ND. Brodof TA. Kogelschatz JE. J. Heterocycl. Chem.  1966,  3:  222 
    Google Scholar
  • 4a Lauer WM. Kaslow CE. Org. Synth., Coll. Vol. III   Wiley and Sons; New York: 1955.  p.580 
    Google Scholar
  • 4b Reynolds GA. Hauser CR. Org. Synth., Coll. Vol. III   Wiley and Sons; New York: 1955.  p.593 
    Google Scholar
  • 5 Price CC. Roberts RM. Org. Synth., Coll. Vol. III   Wiley and Sons; New York: 1955.  p.272 
    Google Scholar
  • 6 Chen B. Huang X. Wang J. Synthesis  1987,  482 
    Article in Thieme ConnectGoogle Scholar
  • 7 Joule JA. Mills K. Heterocyclic Chemistry   4th ed.:  Blackwell Publishers; London: 2000.  p.133 
    Google Scholar
  • 8 Al-Awadi H. Ibrahim MR. Dib HH. Al-Awadi NA. Ibrahim AI. Tetrahedron  2005,  61:  10507 
    CrossrefGoogle Scholar
  • 9 Al-Awadi NA. George BJ. Dib HH. Ibrahim MR. Ibrahim YA. El-Dusouqui OM. Tetrahedron  2005,  61:  8257 
    CrossrefGoogle Scholar
  • 10 Al-Awadi NA. Elnagdi MH. Ibrahim YA. Kaul K. Kumar A. Tetrahedron  2001,  57:  1609 
    CrossrefGoogle Scholar
  • 11 Hickson CL. Keith EM. Martin JC. McNab H. Monahan LC. Walkinshaw MD. J. Chem. Soc., Perkin Trans. 1  1986,  1465 
    CrossrefGoogle Scholar
  • 17 Smith MB. March J. March’s Advanced Organic Chemistry: Reaction Mechanisms and Structure   5th ed.:  J. Wiley and Sons, Inc.; New York: 2001.  p.68 
    Google Scholar
  • 19 Huang X. Liu Z. J. Org. Chem.  2002,  67:  6731 
    CrossrefGoogle Scholar
  • 20 Tois J. Vahermo M. Koskinen A. Tetrahedron Lett.  2005,  46:  735 
    CrossrefGoogle Scholar
  • 21 Huang X. Liu Z. Tetrahedron Lett.  2001,  42:  7655 
    CrossrefGoogle Scholar
  • 22 Griera R. Armengol M. Reyes A. Alvarez M. Palomer A. Cabre F. Pascual J. Garcia ML. Mauleon D. Eur. J. Med. Chem.  1997,  547 
    CrossrefGoogle Scholar
  • 23 Hirano J. Hamase K. Zaitsu K. Tetrahedron  2006,  62:  10065 
    CrossrefGoogle Scholar
  • 24 For 5-OMe: Cassis R. Tapia R. Valderrama J. Synth. Commun.  1995,  15:  125 
    Google Scholar
  • 25 Ruchelman AL. Kerrigan JE. Li T.-K. Zhou N. Liu A. Liu LF. LaVoie EJ. Bioorg. Med. Chem.  2004,  12:  3731 
    CrossrefGoogle Scholar
  • 26 Reimlinger H. Peiren MA. Merenyi R. Chem. Ber.  1972,  105:  794 
    CrossrefGoogle Scholar
  • 27 Czuba WC. Kowalski P. Grzegozek M. Pol. J. Chem.  1980,  54:  1573 
    Google Scholar
12

Static Pyrolysis of 8-j
The substrate (0.2 g) was introduced in the Pyrex reaction tube (12 cm length and 1.5 cm internal diameter). The tube was sealed under vacuum (0.02 m bar) and placed in the pyrolyzer for 900 s at 300 °C. The content of the tube was then separated by preparative high-performance liquid chromatography (HPLC) and was analyzed by 1H NMR, 13C NMR, IR and GC-MS. Relative and percent yields were determined from NMR.

13

Flash Vacuum Pyrolysis of 8a-j The sample was volatilized from a tube in a Buchi Kugelrohr oven through a 30 × 2.5 cm horizontal-fused quartz tube and was heated externally by a cabolite Eurotherm tube furnace MTF-12/38A to 600 °C. The products were collected in a U-shaped trap cooled in liquid nitrogen. The whole system was maintained at a pressure of 10-2 Torr by an Edwards Model E2M5 high-capacity rotary oil pump, the pressure being measured by a Pirani gauge situated between the cold trap and pump. Under these condition the contact time in the hot zone was estimated to be 10 ms. Products collected in the U-shaped trap were analyzed by 1H NMR, 13C NMR, IR and GC-MS. Relative and percent yields were determined from NMR.
Compounds 11a,c,d,f-h,j-n, 16, and 17 has been reported earlier and proved to be identical with products obtained here. [19-27]

14

6-Methyl-1 H -quinolin-4-one ( 11b)
Mp 240-242 °C. IR (KBr): 3050 (NH), 1625 (CO) cm-1. LC-MS: m/z (%) = 159 (100) [M+]. 1H NMR (400 MHz, DMSO): δ = 2.39 (s, 3 H, CH3), 6.0 (d, 1 H, J = 7.2 Hz, quinoline-H3), 7.45 (d, 1 H, quinoline-H8), 7.48 (d, 1 H, quinoline-H7), 7.86 (d, 1 H, J = 7.2 Hz, quinoline-H2), 8.31 (s, 1 H, quinoline-H5), 11.72 (br s, 1 H, D2O exchangeable, NH). 13C NMR (DMSO, 100 MHz): δ = 21.55, 109.09, 119.18, 124.70, 125.96, 134.31, 134.57, 138.67, 140.50, 178.48. DEPT 135: δ = 21.55, 109.09, 119.18, 124.70, 125.96, 134.57, 140.50.

15

7-Bromo-1 H -quinolin-4-one ( 11e)
Mp 242-244 °C. LC-MS: m/z = 225 [M + 1]. 1H NMR (400 MHz, DMSO): δ = 6.04 (d, 1 H, H3, J = 7.37 Hz), 7.52 (d, 1 H, J = 8.56 Hz), 7.74 (s, 1 H, H-5), 7.82 (d, 1 H, J = 7.37 Hz, H2), 8 (d, 1 H, J = 8.56 Hz, H6), 11.22 (br, 1 H, NH). 13C NMR (100 MHz, DMSO): δ = 111.5, 120.4, 123.2, 126, 128.4, 132.7, 141, 143.4, 177.4.

16

5-Bromo-1 H -quinolin-4-one ( 11i)
Mp 234-236 °C. IR (KBr): 1645 (CO) cm-1. LC-MS: m/z = 225 [M + 1]. 1H NMR (400 MHz, DMSO): δ = 6.06 (d, 1 H, H3, J = 7.24 Hz), 7.41-7.47 (m, 3 H, ArH), 7.93 (d, 1 H, J = 7.24 Hz, H-2), 11.18 (br, 1 H, NH). 13C NMR (75 MHz, DMSO): δ = 110.3, 119.5, 121.5, 125.6, 127.2, 130.6, 139.3, 142, 177.

18

Pyrazino[1,2- a ]pyrimidin-4-one ( 19) Mp 178-180 °C. IR (KBr): 1692 (CO) cm-1. LC-MS: m/z = 148 [M + 1]. 1H NMR (400 MHz, DMSO): δ = 6.67 (d, 1 H, J = 6.44 Hz, pyrimidine-H), 8.19 (d, 1 H, J = 4.64 Hz, pyrazine-H), 8.41 (d, 1 H, J = 6.44 Hz, pyrimidine-H), 8.73 (d, 1 H, J = 4.64 Hz, pyrazine-H), 9.13 (s, 1 H, pyrazine-H). 13C NMR (75 MHz, DMSO): δ = 109.6, 118.2, 133.0, 145.8, 154.2, 155.9, 156.8. DEPT 135: δ = 109.6, 118.2, 133.0, 154.2, 155.9. Anal. Calcd for C7H5N3O (147.14): C, 57.14; H, 3.43; N, 28.56. Found: C, 57.53; H, 3.62; N, 28.83.