449. Methylenebisphosphonates and related compounds. Part II. Synthesis from α-keto-phosphonates

Abstract

By J. A. CADE. By the interaction of dialkyl hydrogen phosphites and dialkyl a-ketophosphonates in the presence of a base, tetra-alkyl l-hydroxyalkane-1 : 1bisphosphonates (RO),PO*CR'(OH)*PO(OR"), are formed. Some symmetrical and unsymmetrical alcohols are described.

Phenyl‐, benzyl‐, and unsymmetrical hydroxy‐methylenebisphosphonates as dronic acid ester analogues from α‐oxophosphonates by microwave‐assisted syntheses

“…The yields of 34–52% obtained for products 2a, 2b , and 5 after optimization are comparable with those described in the literature 23,26,31.…”

“…Products 2a and 2b were isolated from the best experiments (entry 2 of Table 1 and entry 2 of Table 2) in yields of 40% and 34%, respectively. Compounds 2a and 2b were described earlier 23,26, but 2a was not characterized. The phosphonate‐phosphates ( 3a and 3b ) were identified on the basis of their 31 P NMR spectra described in the literature 27–29.…”

“…Δ P (CDCl 3 ) 17.3; (M + H) + found = 381.1225 C 15 H 27 O 7 P 2 requires 381.1232. Compound 2a was described, but no spectral data were provided 26.…”

Synthesis of a Phosphonate‐Linked Aminoglycoside–Coenzyme A Bisubstrate and Use in Mechanistic Studies of an Enzyme Involved in Aminoglycoside Resistance

“…As an alternative route, the Michaelis–Arbuzov reaction of trimethylphosphite and diiodomethane was attempted, but proceeded with an extremely low yield due to the decomposition of diiodomethane and the rearrangement of trimethylphosphite to dimethyl methylphosphonate 24–26. To optimize this reaction, various conditions and catalysts were tested.…”

The Synthesis of Dialkyl α-Halogenated Methylphosphonates

“…82 Kinnear-Perren reaction : In the presence of AlBr 3 , the reaction between dibromomethane and phosphorus tribromide gives bromomethylphosphonyl dibromide in 60 % yield. 61 Further treatment of this acid bromide with a sodium alkoxide in alcohol yields the corresponding dialkyl bromomethylphosphonate (ethanol, 49 % ; allyl alcohol, 43 % overall yield). 61 (i-PrO) 3 75,76 ).…”