Reactions of Dimethyl Benzoylphosphonate

Shahak, Israël; Peretz, J.

doi:10.1002/ijch.197100006

Cited by 6 publications

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“…α-Hydroxyphosphonate esters have been obtained previously by the Abramov and Pudovik reactions which consist of adding phosphites to carbonyl compounds or by the reduction of acylphosphonate diesters using various reducing agents. Thus dialkyl acylphosphonates have been reduced to α-hydroxyphosphonates by sodium borohydride, , aluminum isopropoxide, activated zinc in acetic acid,7a diborane in tetrahydrofuran, and by lithium triethylborodeuteride …”

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confidence: 99%

Direct Approach to α-Hydroxyphosphonic and α,ω-Dihydroxyalkane-α,ω-bisphosphonic Acids by the Reduction of (Bis)acylphosphonic Acids

Chen

Breuer

1998

J. Org. Chem.

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Acylphosphonic and bisacylphosphonic acid sodium salts were directly reduced by sodium borohydride to the corresponding hydroxyphosphonates and dihydroxyalkanebisphosphonates. The solution conformation of the (bis)hydroxyphosphonic acid sodium salts, elucidated from the homonuclear and heteronuclear coupling constants of the proton adjacent to the hydroxy and the phosphonic groups, was identical with the solid-state conformation as determined for 1-hydroxy-2-phenylethylphosphonic acid, a representative compound, by X-ray crystallography.In previous papers it was reported from our laboratory that R,R′-difunctionalized long-chain bisphosphonates such as bisacylphosphonates 1 1 and R,R′-bishydroxyiminophosphonates 2 2 are biologically active in calciumrelated disorders such as hydroxyapatite formation and dissolution. This is in contrast to alkane-R,ω-bisphosphonates which are devoid of any activity. 3 To elucidate the roles of the functional groups in R positions for biological activity, we have undertaken a systematic study of synthesizing variously difunctionalized longchain bisphosphonates. This paper describes the development of a practical method for the synthesis of R,ωdihydroxyalkane-R,ω-bisphosphonic acids 3 which are also suitable for the synthesis of simple R-hydroxyphosphonic acids 5.R-Hydroxyphosphonate esters have been obtained previously by the Abramov and Pudovik reactions which consist of adding phosphites to carbonyl compounds 4 or by the reduction of acylphosphonate diesters using various reducing agents. Thus dialkyl acylphosphonates have been reduced to R-hydroxyphosphonates by sodium borohydride, 5,6 aluminum isopropoxide, 7 activated zinc in acetic acid, 7a diborane in tetrahydrofuran, 8 and by lithium triethylborodeuteride. 9 Attempted synthesis of R,ω-dihydroxyalkane-R,ω-bisphosphonic acids 3 by reduction of tetramethyl bisacylphosphonates to the corresponding dihydroxyalkanebisphosphonate tetramethyl esters, followed by bromotrimethylsilane-induced demethylation to the corresponding bisphosphonic acids, gave rise in our hands to impure products which were difficult to purify because of their highly polar nature.We considered that since both acylphosphonic and R-hydroxyphosphonic acids, as well as their salts, are far more stable than the esters 10 (R-hydroxyphosphonate diesters fragment easily to the corresponding carbonyl compound by eliminating dialkyl hydrogen phosphonate 7 ), direct reduction of bisacylphosphonic acids might lead to the desired R-hydroxy and R,R′-dihydroxyalkane-R,ω-bisphosphonic acids more efficiently.

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confidence: 99%

Direct Approach to α-Hydroxyphosphonic and α,ω-Dihydroxyalkane-α,ω-bisphosphonic Acids by the Reduction of (Bis)acylphosphonic Acids

Chen

Breuer

1998

J. Org. Chem.

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Acylphosphonates and their Derivatives

Breuer

2009

Patai's Chemistry of Functional Groups

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(2,3‐Epoxy‐4‐oxoalkyl)phosphonsäure‐ester als Synthone für Thiazole

1988

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34-38.Bei der klassischen Hantzsch-Synthese von Thiazolen werden a-Halogencarbonylverbindungen in einem Substitutions-KondensationsprozeD mit Thioharnstoffen bzw.Thioamiden umgesetzt I). Sie wurde auch mehrfach zur Synthese von Phosphonsaureestern rnit Thiazolylsubstituenten herangezogen ". Analoge Cyclisierungsreaktionen von a$-Epoxyketonen 1 sollten unter Beteiligung des Oxiran-Sauerstoffs als Abgangsgruppe nach dem gleichen Reaktionsprinzip zu Thiazolen 2 mit einem 1-Hydroxyalkylrest a n C-5 fiihren (Schema 1). Einige aus der Literatur bekannte Beispiele3' sowie eigene U n t e r s~c h u n g e n~) zeigten jedoch, daD die zunachst gebildeten Cyclisierungsprodukte 2 in starker Abhingigkeit von Substrat und Reaktionsbedingungen oft in uniibersichtlicher Weise weiterreagieren, so daB neben 2 u. a.5) auch die Dehydratisierungsprodukte 4 und/oder die durch Abspaltung einer Carbonylkomponente gebildeten, a n C-5 unsubstituierten Thiazole 5 isoliert werden. Im Gegensatz dazu reagieren (1,2-Epoxy-3-oxoalkyl)phosphon- den Thioamiden 10 und 11 gezeigt, daD dieser offenkundige Einfluf3 eines Dialkoxyphosphoryl-Substituenten auf dieChem.

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Reactions of Dimethyl Benzoylphosphonate

Cited by 6 publications

References 20 publications

Direct Approach to α-Hydroxyphosphonic and α,ω-Dihydroxyalkane-α,ω-bisphosphonic Acids by the Reduction of (Bis)acylphosphonic Acids

Direct Approach to α-Hydroxyphosphonic and α,ω-Dihydroxyalkane-α,ω-bisphosphonic Acids by the Reduction of (Bis)acylphosphonic Acids

Acylphosphonates and their Derivatives

(2,3‐Epoxy‐4‐oxoalkyl)phosphonsäure‐ester als Synthone für Thiazole

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