A General Procedure to Selectively Prepare N-Alkylanilines by an Unexpected Reaction of (Z)-(tert-Butylsulfanyl)(aryl)diazenes with Alkyllithium Reagents

Margherita Barbero; Iacopo Degani; Stefano Dughera; Rita Fochi

doi:10.1055/s-2003-38082

PAPER

A General Procedure to Selectively Prepare N-Alkylanilines by an Unexpected Reaction of (Z)-(tert-Butylsulfanyl)(aryl)diazenes with Alkyllithium Reagents

Margherita Barbero, Iacopo Degani*, Stefano Dughera*, Rita Fochi
Dip.to di Chimica Generale ed Organica Applicata, Università, C.so M. D"Azeglio 48, 10125 Torino, Italy
e-Mail: iacopo.degani@unito.it;

Abstract

All articles of this category

Abstract

A general procedure has been set up to prepare, selectively, the N-monoalkylanilines 7, reacting (Z)-(tert-butylsulfanyl)(aryl)diazenes 3 with alkyllithium 6 (MeLi, BuLi, s-BuLi, n-C₆H₁₃Li). The reactions were carried out in anhydrous diethyl ether at 0 °C or -78 °C, depending on the reagent 6, and then at room temperature. In optimal conditions the yields of the pure products 7 (uncontaminated by dialkylation products) were from good to excellent: for 38 considered examples, 34 were positive with yields varying between 61% and 91% (average yield 78%). Collateral proofs were carried out to support a hypothesized reaction mechanism.

Key words

N-alkylanilines - amines - diazonium compounds - diazosulfides - allkyllithium

Full Text

References

1 Barbero M. Degani I. Diulgheroff N. Dughera S. Fochi R. Migliaccio M. J. Org. Chem. 2000, 65: 5600

For some examples on the preparation, stability and synthetic applications of (Z)-(tert-butylsulfanyl)(aryl) diazenes, see:

2a van Zwet H. Kooyman EC. Recl. Trav. Chim. Pays-Bas 1967, 86: 993

2b van Beek LKH. van Beek GC. Boven J. Schoot CJ. J. Org. Chem. 1971, 36: 2194

2c Brokken-Zijp J. van de Bogaert H. Tetrahedron 1973, 29: 4169

2d Brokken-Zijp J. van de Bogaert H. Tetrahedron Lett. 1974, 49

2e Petrillo G. Novi M. Dell’Erba C. Tavani C. Berta G. Tetrahedron 1990, 46: 7977 ; and references therein

2f Caposcialli N. Dell’Erba C. Novi M. Petrillo G. Tavani C. Tetrahedron 1998, 54: 3529 ; and references therein

For examples, see:

3a Gross ML. Blank DH. Welch WM. J. Org. Chem. 1993, 58: 2104 ; and references therein

3b Lazny R. Poplawski J. Kobberling J. Enders D. Brase S. Synlett 1999, 1304 ; and references therein

3c Barbero M. Degani I. Diulgheroff N. Dughera S. Fochi R. Synthesis 2001, 2180 ; and references therein

Recent reviews on N-monoalkylation of anilines:

4a Wurziger H. Kontakte (Darmstadt) 1987, 3: 8 ; Chem. Abstr. 1988, 109: 109906

4b Xiaojian Z. Zuwang W. Huagong Jinzhan 1996, 5 ; Chem. Abstr. 1996, 124, 320046

Some recent examples on the N-monoalkylation of anilines:

5a Wimmer P, Buysch HJ, Puppe L, and Froehlich C. inventors; Bayer A.-G., Eur. Pat. 410243. ; Chem. Abstr. 1991, 115, 8274f

5b Pappas PG, and Melville JB. inventors; Amoco Corp. USA, US Pat. 5159115. ; Chem. Abstr. 1993, 118, 41193p

5c Verardo G. Giumanini AG. Strazzolini P. Poiana M. Synthesis 1993, 121

5d Ivanov EI. Polishchuk AA. Zh. Obshch. Khim. 1993, 63: 403

5e Matsuo K. Shichida Y. Nishida H. Nakata S. Okuba M. J. Phys. Org. Chem. 1994, 7: 9

5f Fache F. Valot F. Milenkovic A. Lemaire M. Tetrahedron 1996, 52: 9777 ; and references therein

5g Sreekumar K. Jyothi TM. Talawar MB. Kiran BP. Rao BS. Sugunan S. J. Mol. Catal. A: Chem. 2000, 152: 225 ; and references therein

5h Sreekumar K. Jyothi TM. Govindankutty RC. Rao BS. Sugunan S. React. Kinet. Catal. Lett. 2000, 70: 161 ; and references therein

5i Zhang R. Wu Z. Lin L. Yang H. SEPU 2000, 18: 532 ; Chem. Abstr. 2001, 134, 162664

Some recent examples on the synthesis of N-monoalkylanilines, apart from N-monoalkylation of anilines:

6a MiĘoviĘ IV. IvanoviĘ MD. Piantak DM. BojiĘ V. Synthesis 1991, 1043

6b Guram AS. Rennels RA. Buchwald SL. Angew. Chem., Int. Ed. Engl. 1995, 34: 1348

6c Wolfe JP. Buchwald SL. J. Org. Chem. 1996, 61: 1133

6d Louie J. Driver MS. Hamann BC. Hartwig JF. J. Org. Chem. 1997, 62: 1268

6e Wolfe JP. Buchwald SL. J. Org. Chem. 1997, 62: 6066

6f Bernardi P. Dembech P. Fabbri G. Ricci A. Seconi G. J. Org. Chem. 1999, 64: 641 ; and references therein

6g Beletskaya IP. Bessmertnykh AG. Guilard R. Synlett 1999, 1459

6h Bae JW. Cho YJ. Lee SH. Yoon C.-OM. Yoon CM. Chem. Commun. 2000, 1857

6i Wolfe JP. Buchwald SL. J. Org. Chem. 2000, 65: 1144 ; and references therein

6j Periasamy MM. Natarajan Jayakumart K. Bharathi P. J. Org. Chem. 2000, 65: 3548

6k Bae JW. Cho YJ. Lee SW. Yoon C.-OM. Yoon CM. Chem. Commun. 2000, 1857

7 Blaschette A. Jones PG. Hamann T. Naveke M. Schomburg D. Cammenga HK. Steppuhn I. Z. Anorg. Allg. Chem. 1993, 619: 912

8 Barbero M. Degani I. Fochi R. Regondi V. Gazz. Chim. Ital. 1986, 116: 165

9 Hendrickson JB. Okano S. Bloom RK. J. Org. Chem. 1969, 34: 3434

10a Barbero M, Degani I, Fochi R, and Perracino P. inventors; National Research Council of Italy, PCT/EP9801145. ; Chem. Abstr. 1998, 129, 24494

10b Barbero M. Crisma M. Degani I. Fochi R. Perracino P. Synthesis 1998, 1171

10c Barbero M. Degani I. Dughera S. Fochi R. Perracino P. Synthesis 1999, 90

11 Dell’Erba C. Novi M. Petrillo G. Tavani C. Tetrahedron 1992, 48: 325

12 Dictionary of Organic Compounds on CD-ROM Version 10.1: Chapman & Hall Electronic Publishing Division; London: 2002.

13 Barluenga J. Fanãnãs FJ. Villamaña J. Yus M. J. Org. Chem. 1982, 47: 1560

14 Reilly J. Hickinbottom WJ. J. Chem. Soc. 1918, 113: 974

15 Watanabe Y. Tsuji Y. Ige H. Ohsugi Y. Ohta T. J. Org. Chem. 1984, 49: 3359

16 Kenyon J. Phillips H. Pittman VP. J. Chem. Soc. 1935, 1072

17 Emerson WS. Robb WD. J. Am. Chem. Soc. 1939, 61: 3145

18 Berthell MIH, and Wilde BE. inventors; Monsanto Chem. Ltd., US 3114730. ; Chem. Abstr. 1964, 61, 5885

19 Wilde BE, and Wilde MIH. inventors; Monsanto Chem. Ltd., US 3114729. ; Chem. Abstr. 1964, 61, 3283

20 Brown RA. Fernando SIS. Roberts RMG. J. Chem. Soc., Perkin Trans 1 1994, 197

21 Berthelot J. Guette C. Desbène P.-L. Basselier J.-J. Can. J. Chem. 1987, 67: 2061

22 Kakimoto S. Tone I. J. Med. Chem. 1965, 8: 867

23 Zablocki JA. Rico JG. Garland RB. Rogers TE. Williams K. Schretzman LA. Rao SA. Bovy PR. Tjoeng FS. Lindmark RJ. Toth MV. Zupec M E. McMackins DE. Adams SP. Miyano M . Markos CS. Milton N. Paulson S. Herin M. Jacqmin P. Nocholson NS. Panzer-Knodle SG. Haas NF. Page JD. Szalony JA. Taite BB. Salyers AK. King LW. Campion JG. Feign LP. J. Med. Chem. 1995, 38: 2378

24 Jones P. Villeneuve GB. Fei C. DeMarte J. Haggarty AJ. Nwe KT. Martin DA. Lebuis A.-M. Finkelstein JM. Gour-Salin BJ. Chan TH. Leyland-Jones BR. J. Med. Chem. 1998, 41: 3062

25 Surrey AR. Hammer HF. J. Am. Chem. Soc. 1944, 66: 2127

26 Yin CC. Deeming AJ. J. Organometal. Chem. 1978, 144: 351

27 Reid DJ. Lynch DFJ. J. Am. Chem. Soc. 1936, 58: 1430

28 Ito A. Ono Y. Tanaka K. J. Org. Chem. 1999, 64: 8236