Phosphorylated Aminoacetal in the Synthesis of New Acyclic, Cyclic, and Heterocyclic Polyphenol Structures

Abstract

New phosphorylated aminoacetal has been synthesized by the Kabachnik–Fields reaction; its reactivity has been studied in acid‐catalyzed condensation with linear polyphenols (2‐methylresorcinol, resorcinol, pyrogallol) and the Mannich reaction with macrocyclic polyphenol (calix[4]resorcinol). It has been determined for the first time that acid‐catalyzed reaction of phosphorus‐containing acetal with resorcinol and its derivatives in ethanol in the presence of hydrochloric acid gives new phosphorylated piperazines in addition to the compounds of diarylmethane series. Condensation of macrocyclic polyphenol (calix[4]resorcinol) with formaldehyde and N‐((dihexylphosphoryl)methyl)‐2, 2‐dimethoxyethylamine (the Mannich reaction) has resulted in novel tetrasubstituted calixarene containing aminophosphine oxide and acetal groups on the “upper rim” of molecule.

Synthesis and Aggregation Properties of Salts Based on Aminomethylated Calix[4]resorcinols and 1-Aminoethylidenediphosphonic Acid

“…Elemental analyzes were performed on a Carlo Erba elemental analyzer EA 1108. 4,6,10,12,16,18,22,11,17, 3,7 .1 9,13 .1 15,19 ]octacosa-1(25),3,5,7(28), 9,11,13(27) Purified water (18.2 MΩ cm resistivity at 25 0 C) from Direct-Q 5 UV equipment was used for all solution preparation.…”

“…[2] Earlier, by Mannich reaction of calix [4]resorcinol with formaldehyde and amines, aminomethylated calix [4]resorcinols were obtained. [11,12] The presence of a hydrophobic cavity in these macrocycles along with four strongly basic dialkylaminomethyl groups allows us to construct new supermolecules that can provide, for example, a catalytic action in reactions of phosphonates hydrolysis, [13] and also creates prerequisites for the synthesis of new salt structures with additional centers of coordination. [14] Currently, there is growing interest in obtaining salts of organic molecules based on bisphosphonic acids.…”

Phospha-Mannich reactions of phosphinous acids R 2 P–OH and their derivatives

“…Entry Product Assistant Conditions Yield,% Entry Product Assistant Conditions Yield,% 1 PTSA C6H6, reflux, 3 h 91 [55] 2 PTSA C6H6, reflux, 6 h 93 [56] 3 PTSA C6H6, reflux, 6 h 95 [56,57] 4 PTSA C6H6, reflux, 7 h 93 [57,58] 5 PTSA C6H6, reflux, 4 h 75 [59] 6 PTSA C6H6, reflux, 4 h 68 [59] 7 PTSA C6H6, reflux, 4 h 82 [59] 8 PTSA C6H6, reflux, 7 h 98 [57] 9 PTSA C6H6, reflux, 4 h 81 [59] 10 PTSA C6H6, reflux 64 [60] 11 PTSA C6H6, reflux, 4 h 88 [59] 12 PTSA C6H6, reflux 53 [60] 13 PTSA C6H6, reflux, 6 h 92 [61] 14 W MeCN, 100 °C, 1 h 96 [62,63] 15 PTSA C6H6, reflux 81 [8] 16 PTSA C6H6, reflux 98 [8] 17 W MeCN, 100 °C, 1 h 98 [62][63][64] 18…”

Synthesis of α-Aminophosphonates and Related Derivatives; The Last Decade of the Kabachnik–Fields Reaction

“…New α-aminophosphine oxides and α-aminophosphonates ( 32 / 33 ) were made available by the PTSA-catalyzed reaction of amines containing an acetal group ( 31 ), paraformaldehyde, and >P(O)H reagents ( Scheme 27 and Scheme 28 ) [ 50 , 51 ]. No yields were achieved for the second series of reactions.…”