Water-Soluble Phosphines. 17.¹Novel Water-Soluble Secondary and Tertiary Phosphines with Disulfonated 1,1‘-Biphenyl Backbones and Dibenzophosphole Moieties

Abstract

Reaction of 2,2'-difluoro-1,1'-biphenyl with chlorosulfonic acid and subsequent hydrolysis followed by neutralization with potassium or sodium hydroxide affords disodium or dipotassium 5,5'-disulfonato-2,2'-difluoro-1,1'-biphenyl (1a, 1b). On treatment of 1b with diphenyl- or phenylphosphine in the superbasic medium DMSO/KOH, phosphine ligand 2 or 3 with a disulfonated 1,1'-biphenyl backbone or a dibenzophosphole moiety is formed. The structure of the oxide of 5-phenyldibenzophosphole 3, which crystallizes as 4.2.5H(2)O in the monoclinic space group P2(1)/n with a = 13.799(3) A, b = 19.246(4) A, c = 17.764(4) A, beta = 105.63(3) degrees, and Z = 4, has been determined by X-ray analysis. Nucleophilic phosphination of 1a with NaPH(2) in liquid ammonia yields the sodium phosphide 5a which on protonation gives the water-soluble 5H-dibenzophosphole 5. Reaction of 1b with PH(3) in the superbasic medium DMSO/KOtBu affords 5b in addition to the oxidation product 6a. On oxidation of 5a or 5b with H(2)O(2), the sodium or potassium salts of the sulfonated phosphinic acids 6a or 6b, respectively, are formed. Alkylation of the sodium dibenzophospholide 5a with 2,2'-bis(chloromethyl)-1,1'-biphenyl or 1,4-di-O-p-toluenesulfonyl-2,3-O-isopropylidene-D-threitol yields the chiral water-soluble bidentate phosphine ligands 8 and 9, respectively.

Comparative Study of Novel Phosphordiamidite and Phosphite Ligands Used in Alkene Hydroformylation; Synthesis, Characterization, Metalation, and Catalytic Evaluation

“…The stretching frequencies of the symmetrical stretching band of the carbonyl of the complexes of the L1 (2029 cm –1 ) and L3 (2024 cm –1 ) are quite similar, which is interesting because one might expect the π‐accepting abilities of these ligands to be different . The values of these stretching frequencies are similar to those of phosphines {for example the comparative value for cis ‐[Mo(CO) 4 (PPh 3 ) 2 ] is 2023 cm –1 } vs. those of phosphites cis ‐[Mo(CO) 4 {P(OPh 3 )} 2 ] is 2046 cm –1 …”

Phosphines and Related Tervalent Phosphorus Systems

“…375 Very many new phosphines have been prepared utilising the reactivity of functional groups in the ortho-or para-positions to phosphorus in an arylphosphine. Thus, e.g., the spiro-phosphino-oxazine (160) has been obtained by the reaction of ortho-diphenylphosphinobenzonitrile with a spiro-aminoalcohol, 376 new chiral arylphosphino-phosphito ligands have been prepared from the reactions of chiral ortho-phosphinophenols with chlorophosphites, 377 and treatment of o-(diphenylphosphino)benzyl chloride with various 1-substituted imidazoles has given a series of phosphino-imidazolium salts (161), potential precursors of nucleophilic carbene ligands. 378 However, most reports of this nature centre on the reactions of phosphinoarylaldehydes, -carboxylic acids, and -amines.…”

“…160 A new water-soluble arene-sulfonated 2,2 0 -bis (diphenylphosphino)biphenyl and other diphosphines involving a sulfonated dibenzophosphole system have also been described. 161 Metallophosphide routes have been applied to the preparation of a wide range of di-, tri-and tetra-phosphines bearing additional donor or other reactive functional groups. Findeis and Gade have described the synthesis of a series of di-and triphosphines bearing alkenyl, alkynyl 162,163 and hydroxyalkyl groups, 164 e.g., (82), these acting as linkers for the synthesis of phosphino-functional dendrimers and related catalyst systems.…”

Recent studies of the synthesis, functionalization, optoelectronic properties and applications of dibenzophospholes

“…Stelzer, Sheldrick et al obtained 5-phenyl-2,2 0 -bis(sulfonato)-5H-dibenzophosphole dipotassium salt 11 by reaction of primary phenylphosphine with 5,5 0 -bis(sulfonato)-2,2 0 -diuoro-1,1 0 -biphenyl dipotassium salt 10 in superbasic medium DMSO/KOH in 60% yield (Scheme 3). 26 This research group also obtained the P-unsubstituted dibenzophosphole 14 by reaction of 5,5 0 -bis(sulfonato)-2,2 0 -diuoro-1,1 0 -biphenyl disodium salt 12 with NaPH 2 in liquid ammonia. In this reaction, the trisodium salt 13 was formed rst, which upon acidication with aqueous HCl under aerobic conditions gave the dibenzophosphole disalt 14 accompanied by its dimer 15 (Scheme 4).…”

“…In this reaction, the trisodium salt 13 was formed rst, which upon acidication with aqueous HCl under aerobic conditions gave the dibenzophosphole disalt 14 accompanied by its dimer 15 (Scheme 4). 26 Various bridged dibenzophospholes 17-21 have been obtained by a radical phosphanylation. An example of this approach is the reaction of tetrabromobiphenyls 16 (R ¼ H, Ph) with (Me 3 Sn) 2 PPh in benzene or triuoromethylbenzene, in the presence of V-40 (1,1 0 -azobis(cyclohexane-1-carbonitrile)) as a radical initiator followed by a subsequent oxidation of the corresponding intermediate with H 2 O 2 .…”