Volume 4, Issue 5 pp. 503-510

Dedicated Article

Full Access

Phosphonic systems. Part 12. Fragmentation-rearrangement of dialkyl 2-acyloxyalkylphosphonates^†^‡

Connie P. de Jongh,

Connie P. de Jongh

Centre for Heteroatom Chemistry, Department of Chemistry, University of Pretoria, Pretoria 0002, South Africa

Search for more papers by this author

Tomasz A. Modro,

Corresponding Author

Tomasz A. Modro

Centre for Heteroatom Chemistry, Department of Chemistry, University of Pretoria, Pretoria 0002, South Africa

Centre for Heteroatom Chemistry, Department of Chemistry, University of Pretoria, Pretoria 0002, South AfricaSearch for more papers by this author

Agnes M. Modro,

Agnes M. Modro

Centre for Heteroatom Chemistry, Department of Chemistry, University of Pretoria, Pretoria 0002, South Africa

Search for more papers by this author

Connie P. de Jongh,

Connie P. de Jongh

Centre for Heteroatom Chemistry, Department of Chemistry, University of Pretoria, Pretoria 0002, South Africa

Search for more papers by this author

Tomasz A. Modro,

Corresponding Author

Tomasz A. Modro

Centre for Heteroatom Chemistry, Department of Chemistry, University of Pretoria, Pretoria 0002, South Africa

Centre for Heteroatom Chemistry, Department of Chemistry, University of Pretoria, Pretoria 0002, South AfricaSearch for more papers by this author

Agnes M. Modro,

Agnes M. Modro

Centre for Heteroatom Chemistry, Department of Chemistry, University of Pretoria, Pretoria 0002, South Africa

Search for more papers by this author

First published: October 1993

https://doi.org/10.1002/hc.520040516

Citations: 4

^†

Dedicated to Prof. Antonino Fava on the occasion of his seventieth birthday.

^‡

Part 11 of this series: E. L. Muller, T. A. Modro, Bull. Soc. Chim. France, in press.

About

PDF

Tools

Share a link

Email
Wechat
Bluesky

Abstract

Dialkyl esters of 2-acyloxyalkylphosphonic acids, RCH(OAc)CH₂PO₃R′₂, undergo thermolytic fragmentation to an alkene RCHCH₂, a new ester AcOR′, and an alkyl metaphosphate R′OPO₂. The reaction represents a new type of a process in which a metaphosphate species is generated from a neutral precursor and involves alkyl group (R′) migration as a prerequisite for the reaction. Mechanistic studies indicate that the reaction involves interaction between the phosphoryl group and the electrophilic center of the Ac group, followed by the intramolecular dealkylation of the POR′ function and the subsequent fragmentation of the intermediate.

References and Notes

1 F. H. Westheimer, Chem. Rev., 81, 1981, 313.
10.1021/cr00044a001
CAS Web of Science® Google Scholar
2 C. H. Clapp, F. H. Westheimer, J. Am. Chem. Soc., 96, 1974, 6710.
10.1021/ja00828a028
CAS Web of Science® Google Scholar
3 R. Bodalski, L. D. Quin, J. Org. Chem., 56, 1991, 2666 and the references cited therein.
10.1021/jo00008a017
CAS Web of Science® Google Scholar
4 J. Katzhendler, R. Karaman, D. Gibson, E. Breuer, J. Chem. Soc. Perkin Trans., 2, 1989, 589.
10.1039/p29890000589
Web of Science® Google Scholar
5 L. D. Quin, X-P. Wu, E. Breuer, M. Mahajna, Tetrahedron Lett., 31, 1990, 6281.
10.1016/S0040-4039(00)97042-4
CAS Web of Science® Google Scholar
6 S. Cocks, T. A. Modro, Tetrahedron Lett., 26, 1985, 945.
10.1016/S0040-4039(00)61971-8
CAS Web of Science® Google Scholar
7 J. Symes, T. A. Modro, Can. J. Chem., 64, 1986, 1702.
10.1139/v86-280
CAS Web of Science® Google Scholar
8 C. P. de Jongh, T. A. Modro, J. Chem. Soc., Chem. Commun., 1992, 1003.
Google Scholar
9 J. B. Conant, E. L. Jackson, J. Am. Chem. Soc., 46, 1924, 1003 and the preceeding articles of this series;
10.1021/ja01669a025
CAS Google Scholar
J. A. Maynard, J. M. Swan, Aust. J. Chem., 16, 1963, 596.
10.1071/CH9630596
CAS Web of Science® Google Scholar
10 Direct determination of the polymer was difficult because of the solubility problems.
Google Scholar
11 A. M. Modro, T. A. Modro, Org. Prep. Proc. Int., 24, 1992, 57.
10.1080/00304949209356699
CAS Web of Science® Google Scholar
12 D. E. C. Corbridge: Phosphorus. An Outline of its Chemistry, Biochemistry and Technology, 4th Ed., Elsevier, Amsterdam, p. 44 (1990).
Google Scholar
13 As the Referee pointed out, F⁻ ion could also add to the phosphonium intermediate (Scheme 5c). We have found, however, that fluoride ions do not change the rate of the fragmentation.
Google Scholar
14 In the fragmentation which does involve anchimeric assistance, we have found the p-methoxyphenyl substituted substrate to be at least 50 times more reactive than the phenyl derivative [6].
Google Scholar
15 M. D. Gray, D. J. Smith, Tetrahedron Lett., 21, 1980, 859.
10.1016/S0040-4039(00)71526-7
CAS Web of Science® Google Scholar
16 H. Maskill: The Physical Basis of Organic Chemistry, Oxford University Press, Oxford, p. 451 (1985).
Google Scholar
17 C. Reichardt: Solvent Effects in Organic Chemistry, Verlag Chemie, Weinheim, p. 270 (1979).
Google Scholar
18 B. K. Carpenter: Determination of Organic Reaction Mechanisms, Wiley-Interscience, New York, ch. 7.2 (1984).
Google Scholar
19 D. W. Emerson, A. P. Craig, I. W. Potts, J. Org. Chem., 32, 1967, 102.
10.1021/jo01277a026
CAS Web of Science® Google Scholar
20 F. Mathey, P. Savignac, Tetrahedron, 34, 1978, 649.
10.1016/0040-4020(78)88099-5
CAS Web of Science® Google Scholar
21 A. M. M. M. Phillips, M. J. Mphahlele, A. M. Modro, T. A. Modro, A. Zwierzak, Phosphorus, Sulfur, and Silicon, 71, 1992, 165.
10.1080/10426509208034507
CAS Web of Science® Google Scholar
22 G. Berti, J. Chem. Soc., 1954, 1213.
Google Scholar
23 The Merck Index, 11th ed., Merck & Co., Rahway, p. 3657 (1989).
Google Scholar
24 W. C. J. Ross, W. Davis, J. Chem. Soc., 1957, 2420.
Google Scholar
25 C. Stolzer, A. Simon, Chem. Ber., 93, 1960, 1323.
10.1002/cber.19600930613
CAS Web of Science® Google Scholar

Citing Literature

All articles

Phosphonic systems. Part 12. Fragmentation-rearrangement of dialkyl 2-acyloxyalkylphosphonates^†^‡

Abstract

References and Notes

Citing Literature

References

Information

About Wiley Online Library

Help & Support

Opportunities

Connect with Wiley

Phosphonic systems. Part 12. Fragmentation-rearrangement of dialkyl 2-acyloxyalkylphosphonates†‡

Abstract

References and Notes

Citing Literature

References

Related

Information

Phosphonic systems. Part 12. Fragmentation-rearrangement of dialkyl 2-acyloxyalkylphosphonates^†^‡