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Synthesis and Crystal Structure of Diethyl Tosyloxybenzylphosphonate

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Abstract

Diethyl tosyloxybenzylphosphonate was synthesized by the reaction of hydroxybenzylphosphonate with p-toluenesulfonyl chloride characterized by NMR spectroscopy, elemental analyses and X-ray single-crystal diffraction. The possessing parameters: m.f. C18H23O6PS, monoclinic, P2(1)/n, a = 8.1087(9) Å, b = 20.215(2) Å, c = 12.5201(12)Å, α= 90°, β= 98.7380(10)°, γ= 90°, V = 2028.5(4) Å3, Z = 4, Mr = 398.39, Dc = 1.305 g/cm3, μ = 0.268 mm-1, F(000) = 840, T = 298(2) K, R1 = 0.0462, wR2 = 0.1076 for 3579 observed reflections with I >2σ;(I).

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... Besides carboxylic chlorides, anhydrides and acids, sulfonic acid derivatives may also function as the acylating agents. By analogy with the reaction of α-hydroxyphosphonates (1B) with carboxylic chlorides, the acylation was also attempted with sulfonyl chlorides [95][96][97]. Methanesulfonyl chloride (Scheme 14, Route "a") [96] and p-toluenesulfonyl chloride (Scheme 14, Route "b") [97] worked well as sulfonylating agents in the presence of triethylamine. of the article emphasize the need for mild reaction conditions (25 °C, 0.5-3.5 h), as heating of the reaction mixture resulted in the formation of a by-product through the trimerization of the starting isothiocyanate. The α-thiocarbamoyl-oxyphosphonates 30 obtained in this way expressed plant growth regulating activity. ...
... By analogy with the reaction of α-hydroxyphosphonates (1B) with carboxylic chlorides, the acylation was also attempted with sulfonyl chlorides [95][96][97]. Methanesulfonyl chloride (Scheme 14, Route "a") [96] and p-toluenesulfonyl chloride (Scheme 14, Route "b") [97] worked well as sulfonylating agents in the presence of triethylamine. of the article emphasize the need for mild reaction conditions (25 °C, 0.5-3.5 h), as heating of the reaction mixture resulted in the formation of a by-product through the trimerization of the starting isothiocyanate. The α-thiocarbamoyl-oxyphosphonates 30 obtained in this way expressed plant growth regulating activity. ...
... Besides carboxylic chlorides, anhydrides and acids, sulfonic acid derivatives may also function as the acylating agents. By analogy with the reaction of αhydroxyphosphonates (1B) with carboxylic chlorides, the acylation was also attempted with sulfonyl chlorides [95][96][97]. Methanesulfonyl chloride (Scheme 14, Route "a") [96] and p-toluenesulfonyl chloride (Scheme 14, Route "b") [97] worked well as sulfonylating agents in the presence of triethylamine. ...
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... Beyond their potential bioactivity, the α-hydroxyphosphonates may be important intermediates in a series of syntheses [1]. The most important reactions are alkylations [1], acylations [12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27], phosphorylations [28], substitutions [1], rearrangements [1], and dealkylations [1]. As regards acylations, a series of α-(aryloxyacetoxy)-alkylphosphonate derivatives [12][13][14][15] was prepared mainly by acylation of different α-hydroxyphosphonates with α-hydroxyphosphonates with carboxylic acid chlorides, including aryloxy-butyryloxy or -valeroxy [16] and heterocyclic derivatives [17,18]. ...
... Obviously, this is an elegant way of acylation. It is noteworthy that a tosyloxybenzylphosphonate was also described [27]. The phosphorylation of α-hydroxyphosphonates [28] was elaborated by us. ...
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