Chloro- phenylphosphine

The trinuclear gold(I) complexes [(AuX)3( j,-triphos)] (triphos = bis(2-diphenylphos-phinoethyl)phenylphosphine X = Cl, Br, I, CgFs ), where X = Br and I , were reported to emit at room temperature with emission energies significantly red-shifted from that ofthe free phosphine ligand (2477 cm for Br with Agx 350 nm 4482 cm for I with Aex 385 nm) [41]. The chloro, pentafluorophenyl, and l,3,5-tris(trifluor-omethyl)phenyl derivatives do not emit, even at Aex <300 nm. The emission properties... 

Maier, L., Herbicidally Active 2-Nitro-5-(2 -chloro-4 -trifluoromethylphe-noxy)phenylphosphinic Acid Derivatives, U.S. Patent 4,343,108, 1984. 

A further illustration has appeared28 of the reactivity of simple a-keto-alkyldi-phenylphosphine oxides (31) towards addition reactions, as outlined in Scheme 5. In the same paper, alkylation of chloro(di-t-butyl)phosphine (32) by alkyl benzoates is described 28 see Chapter 3 for details. A similar acylation reaction of tetramethyl-diphosphine disulphide (33) has been described, although the acetylphosphine sulphide (34) was not isolated.29... 

The bioreduction of carbonyl compounds with reductases has been exploited for many years, especially in the case of ketones, with baker s yeast Saccharomyces cerevisiae) being the most popular biocatalyst [45]. For instance, yeast treatment of 3-chloropropiophenone affords the expected (lS)-3-chloro-l-phenylpropan-l-ol, which was treated with trifluorocresol in tertrahydrofuran in the presence of tri-phenylphosphine and diethyl azodicarboxylate at room temperature to give (3R)-l-chloro-3-phenyl-3-[4-(trifluoromethyl)phenoxy]propane and the later reaction with methylamine leads to (R)-fluoxetine that is an important serotonin uptake inhibitor (Scheme 10.19) [46]. 

Benzylchlorobis(triphenylphosphine)-, trans- Palladium, benzylchlorobis-(triphenylphosphine)-, trans- Palladium, chloro(phenylmethyl)bis(tri-phenylphosphine)-, (SP-4-3)- (22784-59-4), 67, 86 ( )-Benzyl 2,3-epoxypropyl ether Oxirane, [(phenylmethoxy)methyl]- ... 

Bis(3-diphenylphosphinopropyl)phenylphosphine (99) forms chloro, bromo and iodo rhodium(I) complexes (equations 253 and 254). The bromo complex can be obtained by addition of a large excess of LiBr to [RhCl(cod)]2 prior to addition of the neutral ligand.1051 The iodo complex has also been prepared from [RhI(CgH12)]2.1051,1052 The halo complexes (100) have been shown to be square planar by X-ray crystallography.1051... 

QNPPtSe2C23H25, Platinum(II), chloro-(A, iV-diethyIdiseIenocarbamato)(tri-phenylphosphine)-, 21 10 C1N3P2C,2H3o, 1,3,2,2 4 -Cyclodiphospha-zane... 

PCIRuC.wH24. Ruthenium(II), chloro(T -hexamethylbenzene)hydrido(tri-phenylphosphine)-, 26 181 PCIiCiiHn, Phosphonous dichloride, (2,4,6-tri-tm-butylphenyl)-, 27 236 PCIjSiiCioHjT, Phosphonous dichloride, (tris(trimethylsilyl)methyl]-, 27 239 PCoC Hjo, Cobalt, (-ri -cyclopentadienyl)-(n -1, l -( 1,2-ethynediyl)bisbenzene]-(triphenylphosphine)-, 26 192 PCoCjiHm, Cobalt, (ii -cyclopentadienyl)-(2,3-dimethyl-1,4-diphenyl-l, 3-butadiene- 1,4-diy l)(tripheny Iphosphine)-, 26 195... 

RuCIPCji,H)4, Ruthenium(II), chloro(Ti -hexamethylbenzene)hydrido(tri-phenylphosphine)-, 26 181 RuCljC , Ruthenium(II), (V-b cy-clo 2.2.1 ]hepta-2,5-diene)dichloro-, 26 250... 

Reactions with Alkyl Halides.— The in situ generation and reaction of chlorodi-phenylphosphine (2) with a-chloro-ethers gives good yields of a-alkoxyalkylphosphine oxides (20). The phosphine (2) is made from phosphorus trichloride and benzene, and the sequence looks like a very convenient one-pot procedure - the dangers of certain chloro-ethers aside ... 

Mercaptoalkyl)phenylphosphines, e.g. (9) and (10), may be prepared by treatment of chloro-thiols or episulphides with sodium phenylphosphide. The S—H is more acidic than the P—H in these compounds. 

Chloro-(/7-cyanophenyl)phenylphosphine 349 Dichloro(phenyl)phosphine (60 g) is added to a slurry of i -cyanobenzenediazonium tetrafluoroborate (72 g) and copper(i) bromide (2.4 g) in dry isopropyl acetate (300 ml). After about 20 min a violent reaction sets in which is moderated by external cooling so that the temperature remains between 20° and 40°. When gas evolution ceases, aluminum turnings (8 g) are added and the mixture is stirred for 2 h at 40-50°. Then the liquid is decanted from unused aluminum, and phosphorus oxychloride (51 g) is added to decompose the aluminum chloride complex. Distillation then affords a forerun (5 g), followed by the main fraction (39 g, 47%) between 15870.7 mm and 195°/ 3.1 mm (owing to unavoidable decomposition the pressure does not remain constant during the distillation). Further distillation gives a product boiling at 16270.2 mm. 

With (—)-tabersonine (28) as the starting material and m-chloro-perbenzoic acid as the oxidizing agent followed by reaction with tri-phenylphosphine in acid, the corresponding 14,15-dehydro compounds,... 

ClPjRhC54H45, Rhodium(l), chlorotris(tri-phenylphosphine)-, 28 77 ClP4RhS2C4jH54, Rhodium, chloro[[2-[(diphenylphosino)methyl]-2-methyl-... 

ClPjRhCjjHjo, Rhodium(I), chloro(Ti -f rfl/i /ro-tetraphosphorus)bis(tri-phenylphosphine)-, 27 222 ClRhC (H2g, Rhodium(I), chlorobis(cyclo-octene)-, 28 90... 

The formation of the stable adduct with the Lewis acid BF3 established the enhanced basicity of the Rh(I) in Rh(TTP) over that of the previously known Rh(l)-phosphine complexes. Although [Ir(PPh3)-(CO)Cl] adds BF3, the rhodium analog does not (17). A stronger Lewis acid, e.g. BBrs or BCI3, is required for an observable interaction with [Rh(PPh3)(CO)Cl] (18). Indeed, the only other Rh(I) complex known to form a stable BF3 adduct is chloro-bis(3-diphenylphosphino-propyl)phenylphosphine rhodium(I) (19). The enhanced nucleophilicity of the rhodium in [Rh(TTP)] is considered as evidence of the poor TT-acceptor qualities of the sulfur atoms in the thioether ligand as compared with those of the phosphorus atoms in their similar complexes. 

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