Chemistry

N. I. Rizpolozhenskii, L. V. Boiko, M. A. Zvereva

Synthesis of Glycidyl Esters of Phosphorus Acids

(Presented by Academician B. A. Arbuzov, 6 XII 1963)

In 1952 B. A. Arbuzov and B. P. Lugovkin \((^1)\) obtained 2,3-epoxypropyldiethyl phosphinate by the rearrangement of triethyl phosphite with epihydrin. Information on the synthesis and study of the properties of glycidyl esters of phosphorus acids is absent from the periodical chemical literature, with the exception of several patent reports \((^2)\).

However, the published patents give almost no data on the physicochemical properties of these esters. Therefore it seemed to us that the synthesis and study of the properties of glycidyl esters of phosphorus acids is of definite theoretical as well as practical interest. This work was carried out, and its results are reported below. Thus, by the interaction of glycidol with mono- and dichloroanhydrides of esters of trivalent phosphorus acids and in the presence of triethylamine in an ether medium, the corresponding glycidylalkyl esters of phosphorus acids were obtained; the constants and formulas of these esters are presented in Table 1.

Table 1

General formula

\[ (\mathrm{RO})(\mathrm{R'O})\mathrm{POCH}_2\mathrm{CHCH}_2 \quad \begin{matrix} & \\ & \!\!\!\!\diagdown\!\!\diagup \\ & \mathrm{O} \end{matrix} \]

The esters obtained, containing a trivalent phosphorus atom, can, first, add sulfur with the formation of the corresponding glycidylalkyl esters of thiophosphorus acids according to the reaction:

\[ (\mathrm{RO})(\mathrm{R'O})\mathrm{POCH}_2\mathrm{CHCH}_2 + \mathrm{S} \rightarrow (\mathrm{RO})(\mathrm{R'O})\mathrm{P(S)OCH}_2\mathrm{CHCH}_2 . \]

\[ \begin{matrix} \quad\diagdown\!\!\diagup & & \quad\diagdown\!\!\diagup \\ \mathrm{O} & & \mathrm{O} \end{matrix} \]

The constants of the thioesters are presented in Table 2.

Secondly, these esters can be oxidized. Thus, for example, upon oxidation with \(\mathrm{N_2O_4}\), glycidylalkyl esters of phosphoric and phosphonic ...

Table 2

General formula
\[ (\mathrm{RO})(\mathrm{R'O})\mathrm{P(S)OCH_2CHCH_2} \]
\[ \begin{array}{c} \ \ \diagup\!\!\!\diagdown\\[-0.6em] \mathrm{O} \end{array} \]

* Compounds 5 and 7 were distilled on a molecular distillation apparatus; Table 2 gives the temperature of the apparatus spiral.

Table 3

General formula
\[ (\mathrm{RO})(\mathrm{R'O})\mathrm{P(O)OCH_2CHCH_2} \]
\[ \begin{array}{c} \ \ \diagup\!\!\!\diagdown\\[-0.6em] \mathrm{O} \end{array} \]

* Compound 6 was oxidized with oxygen at 125—130°.

acids. The oxidation reaction of the esters proceeds according to the scheme:

\[ (\mathrm{RO})(\mathrm{R'O})\mathrm{POCH_2CHCH_2}+\mathrm{N_2O_4} \rightarrow (\mathrm{RO})(\mathrm{R'O})\mathrm{P(O)OCH_2CHCH_2}. \]
\[ \begin{array}{cc} \ \ \diagup\!\!\!\diagdown & \ \ \diagup\!\!\!\diagdown\\[-0.6em] \mathrm{O} & \mathrm{O} \end{array} \]

The constants of the compounds obtained in this way are presented in Table 3.

Glycidyl esters of alkylphosphonic and alkylphosphinic acids can also be obtained by the direct interaction of glycidol with the corresponding acid chlorides of phosphorus acids in the presence of Et₃N or C₅H₅N in an ether medium. The constants of the esters obtained by this method are presented in Table 4.

Table 4

General formula
\[ (\mathrm{RO})(\mathrm{R'O})\mathrm{P(O)OCH_2CHCH_2} \]
\[ \qquad\qquad\quad \begin{matrix} & \mathrm{O} \\[-0.5em] \diagup & \diagdown \end{matrix} \]

The glycidyl esters of phosphorus acids obtained are being studied by us as possible monomers for the preparation of phosphorus-containing epoxy resins; the biological activity of these esters is also being studied.

Chemical Institute named after A. E. Arbuzov
Kazan Branch of the Academy of Sciences of the USSR

Received
2 XII 1963

REFERENCES

1. B. A. Arbuzov, V. P. Lugovkin, ZhOKh, 22, 1193 (1952).
2. A. S. Muller, C. W. Schroeder, E. C. Shokal, U. S. Pat. 2 826 592; Chem. Abstr., 52, 12895 (1958); C. W. Smith, G. B. Payne, E. C. Shokal, U. S. Pat. 2 856 362; Chem. Abstr., 53, 2686 (1959).