Abstract
A variety of substituted aryl amines were transformed into aryl azides using t-BuONO and moist NaN3 in t-BuOH in good to excellent yields. Smooth transformation was observed with anilines, having electron withdrawing and donating groups. Both acid- and base-sensitive groups survived the reaction conditions.
Key words
amines - azides - anilines - diazo compounds - sodium azide
References
1
Scriven EFV.
Turnbull K.
Chem. Rev.
1988,
88:
297
2a
Rostovsev VV.
Green LG.
Fokin VV.
Sharpless KB.
Angew. Chem. Int. Ed.
2002,
41:
2596
2b
Wang Q.
Chan TR.
Hilgraf R.
Fokin VV.
Sharpless KB.
Fin MG.
J. Am. Chem. Soc.
2003,
125:
3192
2c
Tornoe CW.
Christensen C.
Meldal M.
J. Org. Chem.
2002,
67:
3057
3a
Biffin MEC.
Miller J.
Paul DB. In The Chemistry of the Azido Groups
Patai S.
Interscience;
London/ New York:
1971.
p.147-176
3b
The Chemistry of Functional Groups, The Chemistry of Halides, Pseudo Halides and Azides
Suppl. D:
Patai S.
Rappoport Z.
Wiley;
Chichester UK:
1983.
Part 1, 2.
3c
Hassner A. In Houben-Weyl, Organische Stickstoffverbindungen
Vol. E16q:
Klamann D.
Thieme;
Stuttgart/ New York:
1990.
Part I/2.
p.1234
4a
Fischer W.
Anselme J.-P.
J. Am. Chem. Soc.
1967,
89:
5284
4b
Nakajima M.
Anselme J.-P.
Tetrahedron Lett.
1976,
4421
5
Smith PAS.
Rowe CD.
Bruner LB.
J. Org. Chem.
1969,
34:
3430
6
Liu Q.
Tor Y.
Org. Lett.
2003,
5:
2571
7
Zhu W.
Ma D.
Chem. Commun.
2004,
888
8 Diazotization of aryl amines in the presence of alkyl nitrite has been discussed in: Frieman F.
Chlebowski JF.
J. Org. Chem.
1968,
33:
1633
9 GC analysis showed the presence of ca. 40% t-BuOH in t-BuONO. This reagent could be stored in the refrigerator (4 °C) for one week. However, t-BuONO stored more than a week was not as effective and larger excess of reagent was needed for completion of the reaction. The amount of t-BuONO was calculated on the basis of 60% purity.
Rate enhancement of a reaction by addition of minute quantities of H2O has been observed before:
10a
Liotta CL.
Burgess EM.
Ray CC.
Black ED.
Fair BE.
Phase Transfer Catalysis New Chemistry Catalysts and Applications
Starks CM. ACS Symposium Series 326;American Chemical Society;
Washington DC:
1987.
p.15
10b
Liotta CL.
Burgess EM.
Ray CC.
Black ED.
Fair BE.
Prepr. - Am. Chem. Soc., Div. Pet. Chem.
1985,
30:
367
Similar was the observation by Chandrasekaran’s group in heterogeneous permanganate oxidation of olefins in presence of small quantities of t-BuOH and H2O:
10c
Baskaran S.
Das J.
Chandrasekaran S.
J. Org. Chem.
1989,
54:
5182
11 Isoamyl nitrite was purchased from Aldrich Chemical.
12 2-Aminobenzoxazole did not undergo transformation to corresponding azide under the reaction conditions.
13a
Brickner SJ.
Hutchinson DK.
Barbachyn MR.
Manninen PR.
Ulanowicz DA.
Garmon SA.
Grega KC.
Hendges SK.
Toops DS.
Ford CW.
Zurenko GE.
J. Med. Chem.
1996,
39:
673
13b
Genin MJ.
Allwine DA.
Anderson DJ.
Barbachyn MR.
Emmert DE.
Garmon SA.
Graber DR.
Grega KC.
Hester JB.
Hutchinson DK.
Morris J.
Reischer RJ.
Ford CW.
Zurenko GE.
Hamel JC.
Schaadt RD.
Stapert D.
Yagi BH.
J. Med. Chem.
2000,
43:
953
14
Leffler JE.
Temple RD.
J. Am. Chem. Soc.
1967,
89:
5235
15
Di Nunno L.
Scilimati A.
Tetrahedron
1986,
42:
3913
16
Kita Y.
Tohma H.
Hatanaka K.
Takada T.
Fujita S.
Mitoh S.
Sakurai H.
Oka S.
J. Am. Chem. Soc.
1994,
116:
3684
17
Dyall LK.
Kemp JE.
Aust. J. Chem.
1967,
20:
1395
18
Takabatake T.
Miyazawa T.
Hasegawa M.
J. Heterocycl. Chem.
1996,
33:
1057
19
Hagedorn M.
Sauers RR.
Eichholz A.
J. Org. Chem.
1978,
43:
2070