1-Aryl-3,3-dialkyltriazenes: A Convenient Synthesis from Dry Arenediazonium o-Benzenedisulfonimides - A High Yield Break Down to the Starting Dry Salts and Efficient Conversions to Aryl Iodides, Bromides and Chlorides

Abstract

This research comprises three parts. The first part regards the synthesis of 1-aryl-3,3-dialkyltriazenes 3 by reaction of dry arenediazonium o-benzenedisulfonimides 1, also coming from weakly basic aromatic amines with dimethylamine or diethylamine in aqueous solution at 0-5 °C. Yields were usually greater than 90% and there was the possibility of recovering the o-benzenedisulfonimide (5), which could be reused to prepare the salts 1. In the second part it was demonstrated that there is the possibility of reconverting the triazenes 3 into the starting stable dry salts 1 by using 5 as acid. The reactions were carried out in glacial acetic acid at 50-55 °C and normally afforded salts 1 in yields of around 90-99%. The third part concerns the setting up of two procedures for the conversion of 3 to aryl iodides 9, bromides 10 and chlorides 11. Procedure A used the corresponding aqueous hydrogen halides in acetonitrile at r.t. or 60 °C, sometimes in the presence of aqueous HBF₄, sometimes Cu powder (25 examples, yields 65%-88%). Procedure B usually used anhydrous methanesulfonic acid and tetraalkylammonium halides in anhydrous acetonitrile at temperatures varying from r.t. to 80 °C, sometimes in the presence of Cu (16 examples, yields 65-88%).

Key words

stable dry arenediazonium salts - triazenes - retro reactions - radical reactions - aryl halides

References

• General references:
• 1a Zollinger H. Diazo Chemistry I   VCH; Weinheim: 1994.  Chap 13. p.385-404  
• 1b Engel E. In Houben-Weyl   4th ed., Vol. 16a, Part 2:  Klamann D. Thieme-Verlag; Stuttgart: 1990.  p.1182-1226  
• 1c Hertel H. In Ulmann’s Encyclopedia of Industrial Chemistry   5th ed., Vol. A8:  Gerhartz W. VCH; Weinheim: 1987.  p.513-514  
• 1d Saunders KH. Allen RLM. Aromatic Diazo Compounds   3rd ed.:  Edward Arnold; London: 1985.  Chap. 7. p.368-423  
• 2 Barbero M. Degani I. Diulgheroff N. Dughera S. Fochi R. Synthesis  2001,  585 ; and references cited therein
• General references:
• 3a Zollinger H. Diazo Chemistry I   VCH; Weinheimer: 1994.  p.20-24  
• 3b Engel E. In Houben-Weyl   4th ed., Vol. 16a, Part 2:  Klamann D. Thieme-Verlag; Stuttgart: 1990.  p.1063-1065  
• 3c Saunders KH. Allen R. L. M. Aromatic Diazo Compounds   Edward Arnold; London: 1985.  3rd Chap.1. p.14-19  
• 3d Schank R. In The Chemistry of Functional Group: The Chemistry of Diazonium and Diazo Groups   Patai S., Part 2:  Wiley; New York: 1978.  Chap.14. p.648 
• 3e Putterer R. In Houben-Weyl   4th ed., Vol. 10/3, Part 3:  Stroh R. Thieme-Verlag; Stuttgart: 1965.  p.22-29  
• 3f Sandin RB. Cairns TL. Organic Syntheses   Coll. Vol. II:  Wiley; New York: 1943.  p.604-605  
• 4a Barbero M. Crisma M. Degani I. Fochi R. Perracino P. Synthesis  1998,  1171 
• 4b Barbero M, Degani I, Fochi R, and Perracino P. inventors;  PCT/EP98/01145. 
• 5 Lazny R. Poplawski J. Kobberling J. Enders D. Brase S. Synlett  1999,  1304 ; and references cited therein
• 6 Gross ML. Blank DH. Welch WM. J. Org. Chem.  1993,  58:  2104 
• 7 Patrick TB. Willaredt RP. DeGonia DJ. J. Org. Chem.  1985,  50:  2232 
• 8a Foster NI. Synthesis  1980,  572 
• 8b Ku H. Barrio JR. J. Org. Chem.  1981,  46:  5239 
• 8c Satyamurthy N. Barrio JR. J. Org. Chem.  1983,  48:  4394 
• 8d Moore JS. Weinstein EJ. Wu Z. Tetrahedron Lett.  1991,  32:  2465 
• 8e Wu Z. Moore JS. Tetrahedron Lett.  1994,  35:  5539 
• 9 Barrio JR. Satyamurthy N. Ku H. Phelps ME. J. Chem. Soc. Chem. Commun.  1983,  443 
• 10 Satyamurthy N. Barrio JR. Schmidt DG. Kammerer C. Bida GT. Phelps ME. J. Org. Chem.  1990,  55:  4560 ; and references cited therein
• 11 Galli C. Chem. Rev.  1988,  88:  756 ; and references cited therein
• 12 Abramovitch RA. Gadallah FF. J. Chem. Soc. B  1968,  497 
• 13 Blaschette A. Jones PG. Hamann T. Naveke M. Schomburg D. Cammenga HK. Steppuhn I. Z. Anorg. Allg. Chem.  1993,  619:  912 
• 14 Barbero M. Degani I. Fochi R. Regondi V. Gazz. Chim. Ital.  1986,  116:  165 
• 15 Hendrickson JB. Okano S. Bloom RK. J. Org. Chem.  1969,  34:  3434 
• 16a Barbero M. Degani I. Diulgheroff N. Dughera S. Fochi R. Migliaccio M. J. Org. Chem.  2000,  65:  5600 
• 16b Barbero M. Degani I. Dughera S. Fochi R. J. Org. Chem.  1999,  64:  3448 
• 17 Akhtar MH. McDaniel RS. Fieser M. Oehlschlager AC. Tetrahedron  1968,  24:  3899 
• 18 Wassmundt FW. Kiesman WF. J. Org. Chem.  1995,  60:  1713 
• 19 Arotsky J. Darby AC. Hamilton JBA. J. Chem. Soc., Perkin Trans II  1973,  595 
• 20 Bolton R. Moore C. Sandall JPB. J. Chem. Soc., Perkin Trans II  1982,  1593 
• 21 Bolton R. Sandall JPB. J. Chem. Soc., Perkin Trans II  1977,  278 
• 22 Hodgson HH. Mahadevan AP. J. Chem. Soc.  1947,  173 
• 23 Schoutissen HAJ. J. Am. Chem. Soc.  1933,  55:  4531 
• 24 Andrievskii AM. Gorelik MV. Avidon SV. Al"tman ES. Russ. J. Org. Chem.  1993,  29:  1519 
• 25 Dictionary of Organic Compounds on CD-ROM   Version 9.1:  Chapman & Hall/CRC; London: 2001.