Process development for a herbicide intermediate via catalytic carboxylation of an aromatic diazonium compound

Organic Process Research and Development

Volumn 7, Issue 3, 2003, Pages 429-431

  Siegrist, Urs ^a   Rapold, Thomas ^b   Blaser, Hans Ulrich ^a  

^a SOLVIAS AG   (Switzerland)

^b SYNGENTA CROP PROTECTION AG   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

2 SULFO 4 METHOXYBENZOIC ACID; AROMATIC COMPOUND; DIAZONIUM COMPOUND; HERBICIDE; PALLADIUM; SULFONIC ACID DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CARBONYLATION; CARBOXYLATION; CATALYSIS; CHEMICAL REACTION; FEASIBILITY STUDY; REACTION OPTIMIZATION;

EID: 0038722872     PISSN: 10836160     EISSN: None     Source Type: Journal    
DOI: 10.1021/op025621m     Document Type: Article

References (10)

1. 1H NMR (DMSO, 250 MHz) 3.94 ppm (s, 3H), 7.16 ppm (m, 1H), 7.47 ppm (m, 1H), 7.93 ppm (m, 1H).
2. Trost, B. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 259.
3. Heck, R. F. Palladium Reagents in Organic Synthesis; Academic Press: London, 1985.
4. Kikukawa, K.; Kono, K.; Nagira, K.; Wada, F.; Matsuda, T. Tetrahedron Lett. 1980, 21, 2877. Kikukawa, K.; Nagira, K.; Wada, F.; Matsuda, T. J. Org. Chem. 1980, 45, 2365. Kikukawa, K.; Kono, K.; Nagira, K.; Wada, F.; Matsuda, T. J. Org. Chem. 1981, 46, 4413.
5. Kikukawa, K.; Kono, K.; Nagira, K.; Wada, F.; Matsuda, T. Tetrahedron Lett. 1980, 21, 2877. Kikukawa, K.; Nagira, K.; Wada, F.; Matsuda, T. J. Org. Chem. 1980, 45, 2365. Kikukawa, K.; Kono, K.; Nagira, K.; Wada, F.; Matsuda, T. J. Org. Chem. 1981, 46, 4413.
6. Kikukawa, K.; Kono, K.; Nagira, K.; Wada, F.; Matsuda, T. Tetrahedron Lett. 1980, 21, 2877. Kikukawa, K.; Nagira, K.; Wada, F.; Matsuda, T. J. Org. Chem. 1980, 45, 2365. Kikukawa, K.; Kono, K.; Nagira, K.; Wada, F.; Matsuda, T. J. Org. Chem. 1981, 46, 4413.
7. For a recent overview, see: Beller, M. In Applied Homogeneous Catalysis by Organometallic Complexes, 2nd ed.; Cornils, B., Herrmann, W. A., Eds.; Wiley-VCH: Weinheim, 2002; p 145.
8. Experimental procedure for the diazotization: 48 g of 2-amino-4-methoxy-sulfonic acid were suspended in 100 mL of water and 100 mL of 37% hydrochloric acid and cooled to 10°C. Sodium nitrite (10.4 g, dissolved in 10 mL water) was added within 2 h under stirring, and the reaction mass was stirred for an additional 1 h; 5.6 g of sulfamic acid was then added. The precipitated product was filtered and washed with 20 mL of 2 N HCl, methanol, and diethyl ether, respectively. The light yellow crystals were dried at rt; yield: 98%.
9. For a precedent, see: Baumeister, P.; Meyer, W.; Oertle, K.; Seifert, G.; Siegrist, U.; Steiner, H. Chimia 1997, 51, 144.
10. 2 (0.83 g dissolved in 17 g of acetonitrile) was added and the reactor immediately pressurized to 8 bar CO. The reaction mixture was heated to 60°C; after 30 min the autoclave was vented to 3 bar and the pressure increased again to 8 bar with CO; this cycle was repeated five times. After 3 h the pressure was completely released. After evaporation the light-brown 2-sulfo-4-methoxybenzoic acid was dried at 60°C: yield 97%.