ChemInform Abstract: SYNTHESIS AND CERTAIN PROPERTIES OF PHOSPHORYLATED FORMALS

Abstract

Es wird eine allgemeine präparative Methode zur Herstellung phosphorylierter Formale mit drei‐ und fünffach koordiniertem Phosphor vorgestellt, die in der Reaktion von Estern und anderen P(III)‐Säurederivaten mit Orthoameisensäureestern besteht.

Synthesis of new functionalized mono‐ and diphosphonic acids with five‐membered aza‐heterocycles moieties

“…13 C NMR (100 MHz, CDCl 3 ), δ , ppm: 0.67 (s, 2 Me 3 Si), 14.85 (s, 2Me), 63.97 and 64.08 (both s, 2 CH 2 O), and 98.97 (d, 1 J PC =216.0 Hz, C 1 ). 31 P NMR (162 MHz, CDCl 3 ), δ , ppm: −3.58 (s) (cf ).…”

Chemistry of Phosphorylated Formaldehyde Derivatives. Part I

“…First phosphorylated formaldehyde acetals 13 were obtained by the reaction of hydrophosphinoyl compounds 51 – 53 with orthoformate esters 54 on heating. The reaction with dialkyl phosphites 51 [19,75] is conducted by heating to 182 °C [76,77] or at 60 °C in the presence of BF 3 ·Et 2 O as catalyst (without the catalyst the yields decrease from 69%–90% to 25% [75]). In the case of sec -phosphine oxides—dialkylphosphine oxides 52 [77] and diphenylphosphine oxide 53 [77,78], the reaction proceeds at 100 °C [19,77].…”

“…Compounds 33 can be also prepared by the reaction of trialkyl phosphites 58 with orthoformate esters 54 . It was shown that phosphites 58 do not react directly with 54 even on heating [19]. However, as in the case of dialkyl phosphites 51 , orthoformates 54 react with trialkyl phosphites 58 and their analogs (AlkO) 2 POX 59 , where X = Me 3 Si, (AlkO) 2 P, (AlkO 2 )P(O) on heating in the presence of catalytic amounts of boron trifluoride etherate BF 3 ·Et 2 O [19].…”

“…It was shown that phosphites 58 do not react directly with 54 even on heating [19]. However, as in the case of dialkyl phosphites 51 , orthoformates 54 react with trialkyl phosphites 58 and their analogs (AlkO) 2 POX 59 , where X = Me 3 Si, (AlkO) 2 P, (AlkO 2 )P(O) on heating in the presence of catalytic amounts of boron trifluoride etherate BF 3 ·Et 2 O [19]. The reaction of 58 with orthoformate esters 54 is also possible in the presence of phosphorus trichloride (PCl 3 , 60 ) or diethoxychloromethane (EtO) 2 C(H)Cl [80,81] (Scheme 9).…”

“…However, many authors showed that formylphosphinoyl compounds are also stable in the form of formylphosphonic acid ( 12 ) [12,14,15], its disodium salt [15], aldehyde group derivatives such as acetals 13 [18,19,20] and structurally related compounds. These compounds are thioacetals 14 [21,22,23], aminonitriles 15 [24,25,26], diphosphinoyl ( N,N -dialkylaminomethyl)methanes 16 [27,28,29], chloro(or bromo)aminals 17 [30,31,32,33,34], mixed S,O-thioacetals 18 [35,36,37], aminals 19 [30,38], aminoacetals 20 [31,32,38,39], aminothioacetals 21 [32], chloroacetals 22 [40,41], chloro- (or bromo-) thioacetals 23 [40,42,43], α-chlorosulfinyl derivatives 24 [44,45], α-alkoxynitriles 25 [46,47,48], α-thionitriles 26 [46], α-dihalo derivatives 27 [49,50,51], α-alkoxydiphosphoryl compounds 28 [41], α-mercaptodiphosphoryl compounds 29 [40,52,53], α-alkoxysilyl derivatives 30 [54], α-aminosilyl derivatives 31 [29,55], or α-mercaptosilyl derivatives 32 [56] (Figure 2):…”