1H‐1,2,4‐Diazaphospholes via 2‐Phosphaallyl Chlorides

Abstract

experiments we could show that 1 -chloro-2,2-bis(trimethyl-si1yl)-1 -pho~phaethene['~] also undergoes [3 f 2]-cycloaddition with diazoalkanes. 1 also reacts with azides, nitrile imines, and nitrile oxides. Experimental 3d: 1 (1.60 g, 7.00 mmol) was treated with a solution of benzoyldiazomethane (1.00 g, 6.8 mmol) in anhydrous ether (I0 mL) at 0°C under pure nitrogen in a 25 m L flask fitted with a capillary side-arm and stopcock. The solution slowly turned dark brown. After stirring for 3 h at room temperature the solvent was removed and the viscous, dark residue dissolved in chloroform and treated with n-pentane. 3d separated from the solution as a brown powder, which could be purified by distillation from a microdistillation apparatus at torr. 3d distilled off as a bright yellow oil which rapidly crystallized; pale yellow crystals, m.p. 142°C (from ethyl acetatelpentane), yield 0.65 g (35%). Received: July 24, 1984 [Z 937 IE] German version: Angew. Chem. 96 (1984) 899 R = NMe2, does not react. The 1,2,4-diazaphospholes 3 (like azaphospholes in general) are not oxidized by atmospheric oxygen; in contrast to their isomers of the type A -Angew. Chem. Int. Ed. Engl. 23 (1984) No. I1 0 Verlag Chemie CmbH, D-6940 Weinheim. 1984 0570-0833/84/111 1-0903 $ 02.50/0

Paddlewheel 1,2,4-diazaphospholide distibines with the shortest antimony–antimony single bonds

“…18 The 1 H NMR (600 MHz, THF-d 8 , 23°C) spectrum of 4 showed one broad peak, at δ = 1.31 ppm (72 H), for the tBu groups, but only one sharp peak was showed at 1.31 ppm in C 6 D 6 . This peak is shifted down-field relative to the corresponding signal for the free heterocyclic ligands 7, at δ = +65.4 ppm, 17 8, at δ = +66.9, 15 and H[3,5-Cy 2 dp], at δ = +67.3 ppm 16 and to the potassium salts 1, at δ = +50.6 ppm, 14 2, at δ = +46.3, 4 and 3, +47.9 ppm. 4 Only one sharp and intense resonance was observed in the 31 P{ 1 H} NMR (243 MHz, C 6 D 6 , 23°C) spectrum of each product, at δ = +88.62 ppm for 4, +73.09 for 5, and +75.22 ppm for 6.…”

Tris(trimethylsilyl)phosphine

“…Reaction with imidoyl chlorides can give 2-phosphaallylic cations, 33 which can be condensed with hydroxylamine to give 1,2,4-oxazaphospholes 33,34 and 1,2,4diazaphospholes. [33][34][35][36][37] Selected examples are given in eq 12.…”

Electron‐Rich Aromatic 1,3‐Heterophospholes – Recent Syntheses and Impact of High Electron Density at σ2P on the Reactivity

“… Comparison of 31 P NMR chemical shifts of selected CPC‐type heterophospholes and phosphinines ( 1a , b ,16 2a , b ,26a 2c ,25a,25c 4a , 4 N ,11a 5a , 5 Li , 5e 11c 16a , b ,38a 17a , b ,38c 18a , b ,12 24a , b ,46c 26a – c ,1,52 27a , b ,50 28a , b ,51 29a , b 50). …”