Novel organo phosphorus–selenium heteroatom compounds from selenation of diamines

One‐Pot Approach to Organo‐Phosphorus–Chalcogen Macrocycles Incorporating Double OP(S)SCn or OP(Se)SeCn Scaffolds: A Synthetic and Structural Study

“…The synthesis and characterisation of compounds 37 and 38 have been reported elsewhere. [19,20] Similar to the reactiono fFcLR with disodium 2,2-dibutylpropane-1,3-bis(olate) and a,a'-dibromo-o-xyene,W oollins' reagent reacted with disodium 2,2-dibutylpropane-1,3-bis(olate) and a,a'-dibromo-o-xyene under identical conditions to give seleniuma naloguen ine-membered 40 incorporated with aP À SeÀSeÀPl inkagei n7 7% isolated yield rather than the expected eleven-membered macrocycle 39 as illustrated in Scheme 7. The singlet at d = 67.3 ppm flankedb yt wo sets of 77 Se satellites was observedi nt he 31 PNMR spectrum of 40.T he coupling constantsw ere revealed to be 1 J(P,Se) = 465 Hz and 2 J(P,Se) = 21.5 Hz based on simulation as an AA'Xs ystem (whereXrepresents 77 Se andA A ' are the magnetically inequivalent phosphorus atoms in the isotopomer that gives rise to the satellite resonances);t his confirmed that the solution NMR spectra of 40 are consistentw ith the formation of aP À SeÀSeÀPl inkage with chemically equivalent, but magnetically inequivalent phosphorus environments.…”

“…[15] The geometry around P(1) and P(2) is distortedt etrahedral S(3)-P(1)-S(1) and S(4)-P(2)-S(2): 114.38 (15) [15] Within 3-5,t he PÀSs ingle bond lengths are in the range of 2.087(3) to 2.097(4) a nd P= Sd ouble bonds in the range of 1.929(3) to 1.936(3) a nd are typical for the P(=S)S moiety. [19,20] Scheme7.Synthesis of phosphorus-selenium heterocycle 40. Figure 2.…”

“…The geometry around P(1) andP (2) is considerably closer to tetrahedral [S(3)-P(1)-S(1) andS (4)-P(2)-S(2): 117.66(9)8 and 107.45(9)8 for 10,a nd 113.48 (8)8 and 115.62(9)8 for 11]. In 10 and 11,t he PÀSs ingle bond lengths [2.077(2) to 2.1011 (19) ] and P=S double bonds [1.9217(18) to 1.9291 (19) ] are consistent with the typical values for the P(=S)S moiety. [21,22] Within 26 and 29 (Figure 7a nd Figure 8), the frameworks are highly ridged thirteen-or sixteen-membered macrocycles with two aryl rings on phosphorus atoms andt wo exocyclic sulfur atoms pointing on opposite sides of the newly formed rings, ' suggesting that the two nBu moieties presenti n26 somewhat affect its conformation due to steric effects.…”

“…Single-crystal X-ray structures of 26 (SS isomer;h ydrogen atoms are omitted for clarity). Selected bond lengths [] and angles [8]: S(1)ÀP(1) 2.0731(18), S(3)ÀP(1) 1.9332 (19), P(1)ÀO(1)1.598(4) ;S (1)-P(1)-O(1) 107.27 (14), S(3)-P(1)-O(1)1 15.88 (14),P (1)-S(1)-C(1)102.07 (8), P(1)-O(1)-C(9) 121.3(3). Chem.…”

Organophosphorus‐Selenium Heteroatom Derivatives from Selenation of Primary/Secondary Amines and Haloalkanes/Dihaloalkanes

“…[12][13][14][15][16][17][18][19][20][21][22][23][24][25] We recently have reported the synthesis of a series of ammonium phenylphosphonamidodiselenoates and phenylphosphonamidodiselenoic diamides from the reaction of WR with primary or secondary amines, 26 and the formation of a series of organo phosphorus-selenium heteroatom derivatives from the selenation of alkenyl or arynyl-diamines. 27 As a part of our continuous exploration into the reactivity of WR towards different organic nucleophiles, herein, we report the synthesis of a series of novel Se-alkylphenylphosphonamidodiselenoates and alkane bis(Nalkyl-P-phenylphosphonamidodiselenoate)s via the reaction of WR with primary/secondary amines, followed by the in situ treatment with haloalkanes or dihaloalkanes. We also report two representative X-ray structures.…”