Easy and general access to α,α-difluoromethylene phosphonothioic acids. A new class of compounds

Tetrahedron Letters

Volumn 37, Issue 13, 1996, Pages 2229-2232

  Piettre, Serge R ^a   Raboisson, Pierre ^a  

^a SANOFI   (France)

Author keywords

[No Author keywords available]

Indexed keywords

ALPHA,ALPHA DIFLUOROMETHYLENE PHOSPHONOTHIOIC ACID DERIVATIVE; PHOSPHONIC ACID DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; DRUG SYNTHESIS; NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS;

EID: 0029878638     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)00238-9     Document Type: Article

References (33)

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24. 31P-NMR spectroscopy) apparently resulting from a scrambling at the phosphorus center.
25. 31P-NMR spectroscopy.
26. Gross, V.; Halazy, S. unpublished results.
27. This contrasts with diethyl α-lithio-α,α-difluoromethylenephosphonate 5a, stable only at -78°C.
28. 2): 10: H-C (9:1); 12a: H-A (98:2); 12b: H-A (98:2); 12c: H-C (8:2); 12d: H-C (8:2); 12e: H-C (85:15); 12 g: H-A (98:2).
29. β,β-Disubstituted-α,α-difluoromethylenephosphonates and -phosphonothioates can be prepared conveniently through the addition reaction between phosphonyl or thiopnosphonyl radicals and difluoroolefins; see Piettre, S. R., following paper.
30. The major product is the tetrabenzyl 6-bromo-1,1-difluoropentyl-1-phosphonothioate 12e (56%); also isolated as a by-product is tetrabenzyl 1,1,6,6-tetrafluorphexyl-1,6-bisphosphonothioate (20%).
31. 4) are as follows: 15a: H-C (8:2); 76.3 ppm. 15b: H-A (9:1); 75.7 ppm. 15c: H-C (6:4); 74.6 ppm. 16: H-C (8:2); 71.0 ppm. 17: H-C (8:2); 71.0-74.0 ppm. 18: H-A (8:2); 4.3 and 73.9 ppm. 19: H-A (8:2); 16.5-18.6 and 71.0-73.9 ppm.
32. The analogous phenyl difluoromethyl sulfone is a known compound, reported to be stable; see Sabol, J. S.; McCarthy, J. R. Tetrahedron Lett. 1992, 33, 3101.
33. 31P-NMR spectroscopy, mass spectrometry, infra-red spectroscopy and combustion data) in accordance with the structures depicted in the paper.