Borane - THF: New solutions with improved thermal properties and stability

Organic Process Research and Development

Volumn 11, Issue 2, 2007, Pages 210-214

  Potyen, Mark ^a   Josyula, Kanth V B ^a   Schuck, Mike ^c   Lu, Sean ^b   Gao, Peng ^a   Hewitt, Chris ^a  

^a Sigma Aldrich Co   (United States)

^b Sigma RBI   (United States)

^c Sigma Croup   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 34247244753     PISSN: 10836160     EISSN: None     Source Type: Journal    
DOI: 10.1021/op060203t     Document Type: Article

References (28)

1. (a) Brown, H. C.; Zaidlewicz, M. Organic Synthesis via Boranes; Aldrich Chemical: Milwaukee, 2001 ; Vol. 2, Product Number Z40,095-5.
2. (b) Pelter, A.; Smith, K.; Brown, H. C. Borane Reagents; Academic Press: London, 1988.
3. (c) Yardley, J. P.; Fletcher, H., III;, Russell, P. B. Experientia 1978, 14, 1124.
4. (d) Renn, O.; Meatres, C. F. Bioconjugate Chem. 1992, 3, 563.
5. (e) Follet, M. Chem. Ind. 1986, 123.
6. Zaidlewicz, M.; Brown, H. C. Encyclopedia of Reagents for Organic Synthesis; Paquette, L. A., Ed.; J. Wiley: New York, 1995; Vol. 1, p 638.
7. For a review on amine-boranes, see: Kanth, J. V. B. Aldrichimica Acta 2002, 35, 57.
8. (a) Wirth, H. E.; Massoth, F. E.; Gilbert, D. X. J. Phys. Chem. 1958, 52, 870.
9. (b) Elliott Roth, W. L.; Roedel, G. F.; Boldebuck, E. M. J. Am. Chem. Soc. 1952, 74, 5211.
10. (a) Lane, C. F. Chem. Rev. 1976, 76, 773.
11. (b) Brown, H. C.; Heim, P.; Yoon, N. M. J. Am. Chem. Soc. 1970, 92, 1637.
12. (c) Prasad, A. S, B.; Kanth, J. V. B.; Periasamy, M. Tetrahedron 1992, 48, 4623.
13. (a) When borane gas is passed into anhydrous THF at room temperature, a 5-10°C temperature rise is generally observed. Accordingly, it is always a practice to cool the THF to 10°C (ice water) to control the heat of reaction, to avoid undesired side products. (b) During stability testing, when BTHF solutions were heated without stirring, the decomposition was found to be more rapid than with stirring. This may have been from hot spots that were created where the immersion heating coil contacts the solution.
14. (a) Brown, H. C. U.S. Patent 3,634,277, 1972.
15. 4 (δ -40 ppm).
16. Nettles, S. M.; Matos, K.; Burkhardt, E. R.; Rouda, D. R.; Corella, J. A. J. Org. Chem. 2002, 67, 2970.
17. For requirements and testing details, see: Code of Federal Regulations 49 CFR 173.21 (f), 10-1-03 edition, U.S. Government Printing Office, p 417. A link to this reference can be found at: http://www.access.gpo.gov/nara/cfr/ waisidx_03/49cfr173_03.html. Some experimental details are given in the Supporting Information.
18. 4, using the procedure described in ref 9, resulted in a self-accelerating temperature of 42°C.
19. (b) For an industrial incident involving 2 M THF in a 400-L cylinder, please see Chem. Eng. News, July 1, 2002,
20. and Safety Highlights in Org. Process. Res. Dev. 2003, 7, 1029.
21. (a) Fu, X;, McAllister, T. L.; Thiruvengadam, T. K.; Tann, C-H.; Su, D. Tetrahedron Lett. 2003, 44, 801.
22. (b) Xu, J.; Wei, T.; Zhang, Q. J. Org. Chem. 2003, 68, 10146.
23. Lobben, P. C.; Leung, S. S-W.; Tummala, S. Org. Process Res. Dev. 2004, 8, 1072.
24. For details, please see the Supporting Information
25. (a) See Supporting Information section for details.
26. (b) The hydride estimations were carried out using the procedures described in: Brown, H. C. Organic Syntheses via Boranes; Aldrich Chemical Co., Inc.: Milwaukee, WI, 1997; Vol. 1.
27. Brown, H. C.; Kanth, J. V. B.; Dalvi, P. V.; Zaidlewicz, M. J. Org. Chem. 2000, 65, 4655,
28. For further details about the safe handling of new amine-stabilized BTHF solutions, please see Aldrich Technical Bulletin 218, which can be requested by e-mail (aldrich@sial.com) or can be accessed on the web: http://www. sigmaaldrich.com/aldrich/bulletin/al_techbull_al218.pdf.