Abstract
Full Text
N. P. GRECHKIN, R. N. KHAMITOV
ORGANOPHOSPHORUS DERIVATIVES OF AZETIDINE. AZETIDIDES OF PHOSPHORIC ACIDS
(Presented by Academician B. A. Arbuzov, 7 XII 1964)
Organophosphorus derivatives of azetidine have not, up to the present time, been subjected to systematic study. Only one communication has been published in the chemical literature (^1) on the preparation of diethoxyphosphonazetidide.
At the same time, organophosphorus derivatives of azetidine may be of considerable interest from the standpoint of studying their biological
Table 1
Azetidides of phosphoric acids
| Compound formula | B.p., °C/mm Hg | \(n_D^{20}\) | \(d_4^{20}\) | \(MR\), found | \(MR\), calcd. | N, %, found | N, %, calcd. | Yield, % |
|---|---|---|---|---|---|---|---|---|
| \((\mathrm{CH_3O})_2\mathrm{PONC_3H_6}\) | 108–9/11 | 1.4447 | 1.1801 | 37.18 | 37.28 | 8.35 8.46 |
8.48 | 76.5 |
| \((\mathrm{C_2H_5O})_2\mathrm{PONC_3H_6}\) | 109/8 | 1.4410 | 1.0933 | 46.62 | 46.52 | 7.35 7.48 |
7.25 | 85.5 |
| \((\mathrm{iso}\text{-}\mathrm{C_3H_7O})_2\mathrm{PONC_3H_6}\) | 123/15 | 1.4353 | 1.0310 | 55.98 | 55.75 | 6.24 6.21 |
6.33 | 80.5 |
| \((n\text{-}\mathrm{C_3H_7O})_2\mathrm{PONC_3H_6}\) | 133–4/10 | 1.4423 | 1.0469 | 55.90 | 55.75 | 6.53 6.63 |
6.33 | 88.5 |
| \((\mathrm{iso}\text{-}\mathrm{C_4H_9O})_2\mathrm{PONC_3H_6}\) | 143/10 | 1.4404 | 1.0090 | 65.10 | 64.99 | 5.70 5.78 |
5.62 | 86.0 |
| \((n\text{-}\mathrm{C_4H_9O})_2\mathrm{PONC_3H_6}\) | 158–9/10 | 1.4446 | 1.0134 | 65.36 | 64.99 | 5.46 | 5.62 | 86.5 |
| \((\mathrm{iso}\text{-}\mathrm{C_5H_{11}O})_2\mathrm{PONC_3H_6}\) | 164–5/10 | 1.4453 | 0.9956 | 74.07 | 74.23 | 5.01 5.20 |
5.05 | 85.0 |
| \((\mathrm{C_6H_5O})_2\mathrm{PONC_3H_6}\) | 203–4/6 | 1.5548 | 1.2186 | 76.10 | 76.26 | 4.64 4.90 |
4.84 | 83.6 |
| \((\mathrm{C_2H_5O})\mathrm{PO}(\mathrm{NC_3H_6})_2\) | 82–3/1.2 | 1.4746 | 1.1209 | 51.20 | 51.14 | 13.86 13.98 |
13.73 | 73.0 |
| \((n\text{-}\mathrm{C_3H_7O})\mathrm{PO}(\mathrm{NC_3H_6})_2\) | 102–2.5/1.3 | 1.4735 | 1.0936 | 55.98 | 55.76 | 12.80 | 12.84 | 55.0 |
| \((n\text{-}\mathrm{C_4H_9O})\mathrm{PO}(\mathrm{NC_3H_6})_2\) | 103/1.0 | 1.4723 | 1.0720 | 60.63 | 60.37 | 12.01 12.22 |
12.07 | 72.0 |
| \(\mathrm{OP}(\mathrm{NC_3H_6})_3\) | 124/2.5 | crystalline substance, strongly hygroscopic | crystalline substance, strongly hygroscopic | crystalline substance, strongly hygroscopic | crystalline substance, strongly hygroscopic | 19.60 19.80 |
19.56 | 74.0 |
activity. Interest in this field of application of azetidine derivatives has increased considerably, chiefly owing to the successes achieved in recent years in the study of organophosphorus derivatives of ethylenimine (the lower homolog of azetidine) and their practical significance.
By the action of azetidine on dialkylphosphoric acid chlorohydrides, the synthesis of a series of azetidides of dialkylphosphoric acids was carried out.
\[ (\mathrm{RO})_2\mathrm{POCl} + 2\mathrm{HNC_3H_6} \rightarrow (\mathrm{RO})_2\mathrm{P(O)NC_3H_6} + \mathrm{C_3H_6NH}\cdot\mathrm{HCl} \]
By an analogous reaction, diazetidides of alkylphosphoric acids and triazetidide of phosphoric acid were obtained.
The properties of the compounds obtained by us are given in Table 1.
Using the reactivity of the azetidine ring, we have begun a study of certain transformations of azetidides of dialkylphosphoric acids. Thus, by the action of chlorine on diethoxyphosphonazetidide, N-chloro-, N-γ-chloropropylamide of diethylphosphoric acid was obtained.
\[ (\mathrm{C_2H_5O})_2\mathrm{P(O)N} \begin{matrix} \ \ \mathrm{CH_2}\\[-2pt] \diagup \ \ \diagdown\\[-2pt] \mathrm{CH_2}\ \ \mathrm{CH_2} \end{matrix} + \mathrm{Cl_2} \to (\mathrm{C_2H_5O})_2\mathrm{P(O)N} \begin{matrix} \diagup \mathrm{CH_2CH_2CH_2Cl}\\[-2pt] \diagdown \mathrm{Cl} \end{matrix} \]
Toward a number of chemical agents possessing labile hydrogen (amines, thiophenol, etc.), the azetidine ring in its organophosphorus derivatives proved to be considerably more stable than the aziridine ring.
Experimental Part
1. Preparation of azetidides of phosphorous acids. All azetidides of dialkylphosphorous, alkylphosphonous, and phosphoric acids were obtained under identical conditions. Example: preparation of ethylphosphonic acid diazetidide.
To a solution, cooled to \((-)\ 5\text{–}0^\circ\), of 12.4 g of azetidine in 60 ml of benzene, a solution of 8.9 g of ethylphosphonous acid dichloroanhydride in 50 ml of benzene is slowly added dropwise with vigorous stirring. The reaction mixture is then stirred for 2 hours at room temperature and for about 1 hour at reflux temperature. The precipitate is then filtered off, and the filtrate, after removal of the solvent, is distilled twice. The bath temperature must not exceed \(200^\circ\), since above this temperature polymerization of the product occurs in the distillation flask. This gives 8.1 g of product with b.p. \(82\text{–}83^\circ/1.2\) mm.
2. Addition of chlorine to diethylphosphoric acid azetidide (2). To a solution of 4.85 g of the amide in 40 ml of carbon tetrachloride, a solution of 1.8 g of chlorine in the same amount of solvent was added. The temperature was maintained at \(0^\circ\). After the reagents had been combined, the whole was left overnight. The next day the solvent was removed under vacuum, and the residue was distilled twice. Obtained: 4.64 g (70% of theory) of a thick oily substance with b.p. \(124\text{–}5^\circ/2\) mm, \(n_D^{20}\ 1.4565;\ d_4^{20}\ 1.2174;\ MR\) found 59.00; calculated 58.45.
\[ \mathrm{C_7H_{16}O_3PNCl_2}. \quad \begin{aligned} &\text{Found \%: } \mathrm{Cl}\ 26.60;\ 26.46\\ &\text{Calculated \%: } \mathrm{Cl}\ 26.89 \end{aligned} \]
On standing for a long time it crystallizes in the form of needles.
A. E. Arbuzov Chemical Institute
Academy of Sciences of the USSR
Received
1 XII 1964
References Cited
\(^{1}\) N. P. Grechkin, Izv. AN SSSR, OKhN, 1962, No. 8, 1495.
\(^{2}\) N. P. Grechkin, Izv. AN SSSR, OKhN, 1957, No. 9, 1053.