Reinvestigation of the Vilsmeier-Haack Formylation of Triphenylamine

Synlett

Volumn 1997, Issue 11, 1997, Pages 1275-1276

  Lai, Gaifa ^a   Bu, Xiu R ^a   Santos, Javier ^a   Mintz, Eric A ^a  

^a CLARK ATLANTA UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000198806     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1997-1024     Document Type: Article

References (18)

1. New address: Schering-Plough Research Institute, Chemical Process Development, U-5-A, 1011 Morris Avenue, Union, NJ 07083, USA.
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5. (d) Xu, C.; Wu, B.; Dalton, L. R.; Shi, Y.; Ranon, P. M.; Steier, W. H. Marcromolecules 1991, 24, 5421.
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8. (c) Bu, X. R.; Lai, G.; Ahmed, M.; Rutherford, J.; Mintz, E. A. Polymer Preprint 1996, 37, 254.
9. Wilson, C. D. U.S. Patent 1951, 2,558,285; CA 1952, 46, 1041.
10. Baker, III, T. N.; Doherty, Jr., W. P.; Kelley, W. S.; Newmeyer, W.; Rogers, Jr. J. E.; Spalding, R. E.; Walter. R. I. J. Org. Chem. 1965, 30, 3714.
11. 2: C, 79.71; H, 5.02; N, 4.65. Found: C, 79.63, H, 5.07; N, 4.63.
12. 3 (6.32 mL, 67.12 mmol, 8.2 equiv) when repeating Wilson's procedure.
13. 3 (1.2 ml, 12.87 mmol, 1.05 equiv) dropwise with stirring. The resulting mixture was stirred at 95-100°C under nitrogen for 20 h when TLC analysis showed that no starting material existed. The mixture was then cooled to room temperature, poured into ice-water (150 mL), and neutralized with 4 M NaOH solution. The solid was collected, washed with water, and dried. Purification by column chromatography (silica gel, EtOAc-hexanes, 1:5) afforded monoaldehyde 3 (3.14 g, 94%).
14. 3 (4 ml, 42.91 mmol, 10.5 equiv) dropwise with stirring. The resulting mixture was stirred at 95-100 °C under nitrogen for 6 h, followed by similar workup. Purification by column chromatography (silica gel, EtOAc-hexanes, 1:4) afforded dialdehyde 4 (875 mg, 71%) along with 3 (33 mg, 3%).
15. (a) Simchen, G. In Houben-Weyl, 4th ed., Thieme: Stuttgart, 1983, Vol. E3, pp 36-85.
16. (b) Downie, I. M.; Earle, M. J.; Heaney, H.; Shuhaibar, K. F. Tetrahedron 1993, 49, 4015.
17. 3: C, 76.58; H, 4.59; N, 4.25. Found: C. 76.69. H, 4.65; N, 4.28.
18. Financial support of this research by NASA is greatly appreciated.