Halodecarboxylation of α,β-acetylenic and α,β-ethylenic acids

Tetrahedron Letters

Volumn 40, Issue 8, 1999, Pages 1495-1498

  Homsi, Fadi ^a   Rousseau, Gérard ^a  

^a UNIVERSITÉ PARIS SUD   (France)

Author keywords

Alkenyl halides; Alkynyl halides; Carboxylic acids; Hundsdiecker reaction

Indexed keywords

ACETYLENE DERIVATIVE; ACRYLIC ACID DERIVATIVE; ALPHA,BETA ACETYLENIC ACID DERIVATIVE; ALPHA,BETA ETHYLENIC ACID DERIVATIVE; BROMINE; ETHYLENE DERIVATIVE; IODINE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL MODIFICATION; CHEMICAL REACTION; CYCLIZATION; DECARBOXYLATION; SYNTHESIS;

EID: 0033582791     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)00021-0     Document Type: Article

References (17)

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6. 1(1.13 g, 2.2 mmol). After stirring the reaction mixture 30 min at rt, the solvent was removed under vacuum and the residue purified by chromatography over silica gel (hexanes/ether: 95/5).
7. 13C NMR δ 14.95; 20.6; 21.3; 29.5; 32.7; 38.6; 80.3.
8. Homsi, F.; Rousseau G. J. Org. Chem. 1999, in press
9. Lavallée, J. F.; Spino, C.; Ruel, R.; Hogan, K.T.; Deslongchamps, P. Can. J. Chem. 1992, 70, 1406-1426.
10. 1H NMR. E-isomer: δ 1.55-1.70 (m, 2H), 2.00-2.10 (m, 2H), 2.38-2.47 (t, J = 7.5 Hz, 2H), 3.57 (s, 3H), 4.85 (s, 1H), 4.95-5.15 (m, 1H). Z-isomer: δ 1.65-1.80 (m, 2H), 2.00-2.15 (m, 2H), 2.70-2.75 (t, J = 7.5 Hz, 2H), 3.20 (s, 3H), 4.95-5.15 (m, 3H), 5.70-5.92 (m, 1H).
11. Large scale preparation of (E)-β-bromostyrene: A 250 mL three-necked round-bottomed flask containing a stirring bar is equipped with a nitrogen inlet, a thermometer and a condenser. The flask is charged with 10 g of trans-cinnamic acid (0.07 mol), 140 mL of toluene, 0.4 g of 2,6-di-tert-butyl-4-methylphenol and 40 g of bis(2,4,6-trimethylpyridine)bromine(I)hexafluorophosphate (0.086 mol). The solution is heated at 65°C for 1 h and formation of a white precipitate is observed. After cooling at 25°C, 100 mL of ether are added and the organic phase is washed with 4×100 mL of 1N HCl, 100 mL of saturated sodium chloride solution and dried over sodium sulphate. The organic phase is concentrated under vacuum and 1 g of 2,6-di-tert-butyl-4-methylphenol is added. The mixture is distilled under high vacuum to give (E)-bromostyrene (8.5 g - 9 g, 66-70%, E-Z: 99.5-0.5) as a light yellow liquid: bp 50°C under 0.1 mmHg.
12. Sheldon, R.A.; Kochi, J.K. Org. React. (NY) 1972, 19, 279. Crich, D. in "Comprehensive Organicsynthesis", ed. Trost, B.M. and Fleming, I. Pergamon Press 1991, vol. 7, p. 717.
13. Sheldon, R.A.; Kochi, J.K. Org. React. (NY) 1972, 19, 279. Crich, D. in "Comprehensive Organic Synthesis", ed. Trost, B.M. and Fleming, I. Pergamon Press 1991, vol. 7, p. 717.
14. See for example: Sliwa, H.; Maitte, P. Bull. Soc. Chim. Fr. 1962, 369-374.
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