My watch list
my.chemeurope.com  

my.chemeurope.com

With an accout for my.chemeurope.com you can always see everything at a glance – and you can configure your own website and individual newsletter.

  • My watch list
  • My saved searches
  • My saved topics
  • My newsletter
Register free of charge
Login  
eng  
DeutschEnglishFrançaisEspañol

Michaelis-Arbuzov reaction



The Michaelis-Arbuzov reaction is the chemical reaction of a trialkyl phosphite and an alkyl halide to form a phosphonate.

The reaction was discovered by Michaelis in 1898[1], and greatly explored by Aleksandr Arbuzov soon thereafter.[2][3] This reaction is widely used for the synthesis of various phosphonates, phosphinates, and phosphine oxides. Several reviews have been published.[4][5]

Reaction mechanism

The Michaelis-Arbuzov reaction is initiated with the SN2 reaction of the nucleophilic phosphite (1) with the electrophilic alkyl halide (2) to give a phosphonium intermediate (3). Triaryl phosphites, which are unable to perform the second step of the Michaelis-Arbuzov reaction, have been shown to produce stable phosphonium salts.[6] Likewise, aryl and vinyl halides are unreactive towards phosphites.

The displaced halide anion reacts via another SN2 reaction with the phosphonium intermediate to give the desired phosphonate (4) and another alkyl halide (5). When chiral phosphonium intermediates are produces, it has been shown the halide substitution proceeds with inversion of configuration, as expected by a SN2 reaction.[7]

As a general guideline, the reactivity of the organic halide (2) can be listed as follows: (from most reactive to least reactive) 

RCOX > RCH2X > RR'CHX >> RR'R"CX

and 

RI > RBr > RCl

The Michaelis-Arbuzov reaction of α-bromo- and α-chloroketones does not give the expected product. This side reaction is called the Perkow reaction. α-Iodoketones do, in fact, give the expected phosphonate.[8] Other methods of producing β-ketophosphonates have been developed.[9]

References

  1. ^ Michaelis, A.; Kaehne, R.; Ber. 1898, 31, 1048.
  2. ^ Arbuzov, A. E.; J. Russ. Phys. Chem. Soc. 1906, 38, 687.
  3. ^ Arbuzov, A. E.; Chem. Zentr. 1906, II, 1639.
  4. ^ Arbuzov, B. A. Pure Appl. Chem. 1964, 9, 307-353. (Review)
  5. ^ Bhattacharya, A. K.; Thyagarajan, G. Chem. Rev. 1981, 81, 415-430. (doi:10.1021/cr00044a004; Review)
  6. ^ Landuer, S. R.; Rydon, H. N. J. Chem. Soc. 1953, 2224.
  7. ^ Gerrard, W.; Green, W. J. J. Chem. Soc. 1951, 2550.
  8. ^ Jacobsen, H. I.; Griffin, M. J.; Preis, S.; Jensen, E. V. J. Am. Chem. Soc. 1957, 79, 2608.
  9. ^ Nagata, W.; Wakabayashi, T.; Hayase, Y. Organic Syntheses, Coll. Vol. 6, p.448 (1988); Vol. 53, p.44 (1973). (Article)

See also
 
This article is licensed under the GNU Free Documentation License. It uses material from the Wikipedia article "Michaelis-Arbuzov_reaction". A list of authors is available in Wikipedia.
Your browser is not current. Microsoft Internet Explorer 6.0 does not support some functions on Chemie.DE