One-Pot Method for Synthesis of N -Phosphorylated Mono- and Diimidates
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One-Pot Method for Synthesis of N-Phosphorylated Mono- and Diimidates V. E. Shishkina, Y. V. Popova, O. V. Anishchenkoa,*, M. A. Shevchenkoa, S. M. Ledeneva, and N. A. Sokolova a Volgograd
State Technical University, Volgograd, 400131 Russia *e-mail: [email protected]
Received March 23, 2020; revised March 23, 2020; accepted April 1, 2020
Abstract—An effective one-pot method was developed for the preparation of organophosphorus derivatives of imidic acids based on the reaction of mono- and diimidates hydrochlorides with dialkyl chlorophosphates in the presence of triethylamine without isolation of free imidates. Keywords: imidate hydrochloride, N-phosphorylated acetimidates, N-phosphorylated malonodiimidates, phosphorylation, dialkyl chlorophosphates
DOI: 10.1134/S1070363220090285 In chemistry, an important place is occupied by organophosphorus compounds, among which phosphoruscontaining derivatives of imidic acids, amines and amides are of particular interest [1, 2]. C-Phosphorylated imidates [3–5] are biologically active substances. Among them, compounds with high insecticidal, acaricidal, fungicidal, herbicidal and growth-regulating activity were found [6]. In addition, due to the high reactivity, phosphorylated imidates can be used to obtain new types of organophosphorus compounds [7, 8]. In order to obtain new derivatives of imidic acids, we performed the N-phosphorylation reaction of ethyl (2-cyano)acetimidates hydrochlorides with diethyl malonodiimidates. The Pinner reaction between malonodinitrile, ethyl alcohol and hydrogen chloride can be used to obtain mono- and diimidate hydrochlorides (Scheme 1). It was found that the transformation of nitrile groups into imide ones occurs stepwise. At a ratio malonodinitrile : alcohol : hydrogen chloride = 1 : 1 : 2, it is possible to selectively obtain ethyl (2-cyano)acetimidate hydrochloride 1 with a yield of 97%, and diethyl malonodiimidate hydrochloride 2 is formed in 97% yield
when using 1 : 2 : 4 ratio of the reagents (Scheme 1). The Pinner reaction was carried out in anhydrous dioxane with hydrogen chloride bubbling through a mixture of dinitrile and alcohol at a temperature of 0±5° C. After saturation with hydrogen chloride in both the first and second cases, the reaction mixture was kept for 15–24 h. The obtained hydrochlorides are crystalline substances that can be stored for a long time in the cold with protection from air moisture. A widely used method for the preparation of N-substituted imidates is a two-stage process, when the free imidate is first isolated, and then the substitution at the imino group is carried out. According to this method, free imidates were quantitatively isolated from hydrochlorides with triethylamine in dioxane medium according to the method [9]. The rуaction of free imidates with phosphorylating agents was carried out in dioxane in the presence of triethylamine as an acceptor of hydrogen chloride. The reactions proceeded rapidly even at room temperature. To complete the process, heating to 40°C for 2–3 h i
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