Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000084.xml
Synthesis 2013; 45(17): 2481-2484
DOI: 10.1055/s-0033-1338504
DOI: 10.1055/s-0033-1338504
paper
Study of the Kulinkovich Synthesis of 1-Methylcyclopropanol and Its Conversion into 1-Methylcyclopropyl 4-Nitrophenyl Carbonate
Further Information
Publication History
Received: 20 April 2013
Accepted after revision: 17 June 2013
Publication Date:
26 July 2013 (online)
Abstract
A detailed investigation of the preparation of 1-methylcyclopropanol via the Kulinkovich reaction is presented. Reaction and workup parameters were optimized to provide a reproducible procedure for the synthesis of multigram quantities of 1-methylcyclopropanol. Key improvements were the use of titanium tetra(2-ethyl)hexyloxide as catalyst, reduction in the volume of reaction solvent, addition of the methyl acetate starting material in portions, and azeotropic distillation to remove by-products. The preparation of the 4-nitrophenyl carbonate ester was likewise studied and optimized.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synthesis. Included are the experimental procedure and 1H NMR spectra of the NMR study of the conversion of 1 into 2 mediated by pyridine and triethylamine and notes on the origin of by-products in the Kulinkovich reaction.
- Supporting Information
-
References
- 1a Epple R, Lelais G, Nikulin V, Westscott-Baker L. Patent WO2010/6191 A1, 2010 ; Chem. Abstr. 2010, 152, 144488
- 1b Neelamkavil SF, Boyle CD, Chackalamannil S, Greenlee WJ. Patent WO2010/9195 A1, 2010 ; Chem. Abstr. 2010, 152, 192139
- 2a Kulinkovich OG, Sviridov SV, Vasilevskii DA, Pritytskaya TS. J. Org. Chem. USSR 1989; 25: 2027
- 2b Kulinkovich OG. Synthesis 1991; 234
- 3 Snider EJ, Wright SW. Tetrahedron Lett. 2011; 52: 3171
- 4a DePuy CH, Mahoney LR, Eilers KL. J. Org. Chem. 1961; 26: 3616
- 4b DePuy CH, Dappen GM, Eilers KL, Klein RA. J. Org. Chem. 1964; 29: 2813
- 4c Wasserman HH, Clagett DC. Tetrahedron Lett. 1964; 341
- 5 See refs. 1 and 2.
- 6 See: Azimioara M, Cow C, Epple R, Jiang S, Lelais G, Mutnick D, Wu B. Patent WO2009/105717 A1, 2009 ; Chem. Abstr. 2009, 151, 1042179.
- 7 DuPont ‘Tyzor TOT’; Aldrich 333484, $27.90 (250 mL).
- 8a Wu Y.-D, Yu Z.-X. J. Am. Chem. Soc. 2001; 123: 5777
- 8b John JE, Adetenu AA, John NG. Eur. J. Org. Chem. 2003; 4721
- 9 Similar rapid decomposition was observed upon attempted saponification of the acetate ester of 1.
See, for example:
Other methods have been reported to produce 1; however, these methods appear to have limited preparative value and remain as isolated instances of the preparation of 1, see: