Die Reaktion von dreiwertigen Phosphorchloriden mit Orthoestern und deren Thioanaloga. Darstellung von C‐phosphorylierten Formaldehydacetalen

Abstract

Bd. 712 Reaktion von 2-Chlor-1.3.2-benzodioxaphosphol~1) (11) mit Orrhoameisensaureirimethylester: 87.3 g (0.5 Mol) 11 wurden in 60 Min. zu 53 g (0.5 Mol) HC(OCH3J3 unter Kiihlung getropft. Nach 3.5 Stdn. bei 100-140" ergab Destillation bei 80-85" (12 Torr) 77.3 g (91 %) gaschromatographisch reines 2-Methoxy-I.3.2-benzodioxaphosphol~~) (8). n b = 1.52 15. C7H703P (170.2) Ber. C49.4 H 4.1 P 18.2 Gef. C49.0 H 4.1 P 17.9 Reaktion rnit Orthoessigsauretriathylester'3) : Analog ergaben 34.9 g (0.2 Mol) 11, in 30 Min. zu 32.4 g (0.2 Mol) Ester getropft, nach 6 Stdn. bei 150" 30.9 g (84%) gaschromatographisch reines 2-Athoxy-1.3.2-benzodioxaphosphol~2) (10). ng = 1.5 170, Sdp.20 101 -105". C8H903P (184.2) Ber. C 52.2 H 5.0 P 16.8 Gef. C 51.8 H 5.3 P 17.1 Reaktion mit Orthoameisensauretributylester: Analog ergaben 46.4 g Ester, in 30 Min. zu 34.9 g 11 getropft, nach 3 Stdn. bei 150-180" 24.5 g (58%) gaschromatographisch reines 2- Buryloxy-1.3.2-benzodioxaphosphol~2) (9). n'," = 1.5068, Sdp.8 98 -100".

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

“…MeCN, 100 °C, 0.5 h 92 [6,7] 26 -MeCN, reflux, 3 h 86 [13] PTSA C6H6, reflux 85 [8] 28 -MeCN, reflux, 3 h 70 [2] 29 PTSA C6H6, reflux 80 [8] 30 -MeCN, reflux, 3 h 60 [2,14] 31 -C7H8, reflux, 1 h 30 [15] 32 -C7H8, reflux, 1 h 50 [15] 33 -C7H8, reflux, 1 h 85 [15] 34 -C7H8, reflux, 1 h 73 [15] 35 -C7H8, reflux, 1 h 84 [15] 36 PTSA C7H8, reflux, 24 h 57 [16] 37 PTSA C7H8, reflux, 72 h 65 [16] 38 PTSA C7H8, reflux, 96 h 24 [16] 39 PTSA C7H8, reflux, 24 h 69 [16] 40 PTSA C7H8, reflux, 72 h 72 [16] 41 PTSA C7H8, reflux, 8 h 27 [16] 42 90, [17,18] 91, [15] 99 [19][20][21] 2 A 94 [15] 3 A [17] 4 A 74 [15] 5 A 63 [22] 6 A [23] 7 A 76 [24] 8 A 72 [25] 9 A [24] 10 A 64 [24] 11 A 71 [24] 12 A [25] 13 A 86 [26] 14 A 91 [26] 15 A [26] 16 A 45 [27] 17 A 47, [27] 55 [25] 18 A [25] 19 A 43 [27] 20 A 60 [27] 21 A …”

Chemistry of Phosphorylated Formaldehyde Derivatives. Part I

“…The most general method of synthesis of phosphorylated formaldehyde acetals 13 is the reaction of phosphorus trichloride derivatives 60 with orthoformate esters 54 . Excess of 54 reacts on heating with 60 [79,81,83,84,85] and mono- and dialkyl AlkPCl 2 63 , Alk 2 PCl 64 , alkoxy (AlkO)PCl 2 65 , (AlkO) 2 PCl 66 , and phenyl PhPCl 2 67 , Ph 2 PCl 68 [80,84,86,87,88,89] derivatives of 60 (Scheme 11), to form symmetrical and unsymmetrical acetals 33 , 49 , 50 and 69 , 70 , respectively. It was noted that the reaction of 2-chloro-1,2,3-dioxaphospholanes 71 with 54 leads to the opening of the dioxaphospholane ring to form ethyl (β-chloroethyl) ([1,3]-dioxolan-2-yl)phosphonates 72 [90].…”