Phosphines dimethylformamide

PAN is, however, only slightly soluble in the reaction medium. Therefore, to verify the hypothesis, a homogeneous system was used methacrylonitrile/triethyl-phosphine/dimethylformamide, which is polymerized in accordance with the same... 

Bromine Ammonia, carbides, dimethylformamide, fluorine, ozone, oleflns, reducing materials including many metals, phosphine, silver azide... 

Amphiphilic resin supported ruthenium(II) complexes similar to those displayed in structure 1 were employed as recyclable catalysts for dimethylformamide production from supercritical C02 itself [96]. Tertiary phosphines were attached to crosslinked polystyrene-poly(ethyleneglycol) graft copolymers (PS-PEG resin) with amino groups to form an immobilized chelating phosphine. In this case recycling was not particularly effective as catalytic activity declined with each subsequent cycle, probably due to oxidation of the phosphines and metal leaching. 

The selective activation of the primary hydroxyl group in methyl a-D-glucopyranoside by reaction with carbon tetrachloride and tris(dimethylamino)phosphine in A/.N-dimethylformamide at —40° has been reported.381 An alkoxytris(dimethylamino)phosphonium... 

Addition of diphenylphosphine or phenylphosphine to methyl 1-cyclohexanecarboxylate under base catalysis yielded 186 and 187 [164] (Figure 17). The Pd-catalyzed Heck reaction of substituted olefins with (p-bromophenyl)diphenylphosphine oxide in dimethylformamide afforded substituted phosphine oxides which could be reduced with trichlorosilane to yiled the corresponding carboxylatedphosphines - 188, too, was prepared this way [165],... 

The palladium-catalyzed coupling of aiyl and vinyl halides to organotin compounds, known as Stille coupling, is one of the most important catalytic methods of carbon-carbon bond formation. The reaction is generally conducted in polar organic solvents, such as dimethylformamide, with tertiary phosphine complexes of palladium, although phosphine-free complexes or simple Pd-salts are also frequently used as catalysts [8]. 

Tributyl amine, palladium acetate, triphenyl phosphine from Fluka AG and N,N-dimethylformamide and formic acid from Farmitalia Carlo Erba Chemicals were used without further purification. 

The complexes are soluble in aromatic solvents and in THF. The tri-p-tolyl-phosphine complex has limited solubility in ether, and the tri-phenyl phosphine complex is insoluble in diethyl ether. Both complexes are insoluble in hexane and related solvents and decompose in chlorinated solvents. Limited solubility is achieved inA jV-dimethylformamide, but moderate decomposition occurs. 

The reaction of halogenotriphenylphosphonium halides (triphenyl-phosphine dihalides) with alcohols is a useful method for the synthesis of alkyl halides (see Section II,2b p. 239). It has been found88 that (alkoxymethylene)dimethyliminium halides are formed in the reactions of these reagents with alcohols in N,N-dimethylformamide a possible mechanism is shown. Hydrolysis of the (alkoxymethylene)-dimethyliminium halide intermediate affords a formic ester, whereas... 

Dimethylformamide (99.8%), mthenium chloride hydrate (RUCI3 XH2O, 35 0% Ru), hydrogen chloride (4 M solution in 1,4-dioxane), and triphenyl-phosphine (99%) are purchased from Aldrich and used as received. DMF is conveniently dried with activated 4-A molecular sieves. As RUCI3 XH2O is a hygroscopic salt, it should be handled only briefly under ambient conditions. 

All presently known phosphamethin-cyanines were prepared according to our original procedure (1964) in which two quaternary salts of a heterocyclic base (e. g. 4) are condensed with tris-hydroxymethyl-phosphine 5 in the presence of a proton-abstracting base The preparation ofbis-[N-ethyl-benzothiazole(2)]-phosphamethin-cyanine-tetrafluoroborate 6 illustrates the synthetic sequence. A mixture of 2 moles of N-ethyl-2-chlorobenzothiazolium-tetrafluoroborate 4 and 1 mole of tris-hydroxymethyl-phosphine 5 in dimethylformamide is slowly reacted with ethyl-di-isopropylamine or pyridine at 0 °C. Addition of water immediately affords the crystalline cyanine dye 6 in ca. 45% yield ... 

Place in another flask Pd(dba)2 (86 mg, 0.15 mmol), tris(2-furyl)phosphine (70 mg, 0.3 mol), and dry dimethylformamide (5 mL). Stir the mixture until the dark solution turns clear. 

Among the procedures tried were thionyl chloride and pyridine, phosphorus pentachlo-ride, triphenyiphosphine dibromide in N, N-dimethylformamide, triphenylphosphine and carbon tetrachloride, tris(dimethylamino)phosphine and bromine, o-phenylenephosphoro-chloridite and bromine, tris(dimethylamino)phosphine and carbon tetrachloride, and tri-n-octylphosphine and carbon tetrachloride. 

The reaction between dialkynyl(organo)phosphine oxides and disodium telluride in dimethylformamide/water produced 2,6-dialky l-4-organo-4-oxo-4//-1,4-telluraphos-phorins2. 

As an example we describe here the synthesis of the l//-l,2,4-diazaphosphole 22 that, on account of its easy accessibility and as parent compound of the class, is of general interest. The synthesis proceeds through condensation of the cation 21. The reaction of 21 with hydrazine involves cleavage of an ammonium salt to furnish the phosphole 23.46 The cation 21 is obtained via a methanaminium chloride—generated as an intermediate from N, A-dimethylformamide and oxalyl chloride—by condensation with tris(trimethylsilyl)phosphine. 

To the crude product from Step 1 (6.96 g) dissolved in 30 ml triethylamine and 6 ml dimethylformamide at ambient temperature was added 3 ml trimethylsilylacetylene, Cul (150 mg) and bis(triphenyl-phosphine)palladium(II)chloride (300 mg). The mixture was heated 1 hour to 50-60°C, an additional 0.3 ml trimethylsilylacetylene added, and heating continued 30 minutes. The cooled mixture was diluted with 250 ml water, extracted with 250 ml diethyl ether, separated, dried, and concentrated. The material was purified by chromatography on silica gel using CH2Cl2/hexane, 1 1, re-crystallized from diethyl ether/hexane, and the product isolated, mp = 181-182°C. H-NMR, MS, and elemental analysis data supplied. 

P-lactams Aceto(carbonyl)cyclopenta-dienyl-(triphenylphosphine)iron. Benzene-sulfenyl chloride. Chlorodicarbonylrho-dium(I) dimer. 2-Chloro-l-methylpyridin-ium iodide. Dimethylformamide-Thionyl chloride. Ketene bis(trimethylsilyl)-ketals.p-Tolylsulfinylacetic acid. Triphenyl-phosphine-Diethyl azodicarboxylate. Zinc. 

Complexes of uranyl chloride with a variety of oxygen donor ligands continue to be reported, notably with phosphine oxides (55), pyridine N-oxides (27), N,IV-dimethylformamide (7J), acetamide (15), and with the N,IV,IV, IV -tetramethyldicarboxylic acid amides (14), the last being mainly polymeric compounds. A few similar complexes of uranyl bromide (54) and iodide (71) are also known. 

Preparation.- Trialkyl or triaryl phosphites and trithiophosphites (55) can be obtained in 50-90% yields from white phosphorus, carbon tetrachloride, triethylamine, and the appropriate alcohol, phenol, or thiol in a polar aprotic solvent such as dimethylformamide. A series of racemic phenylbis(dialkylamino)phosphines (56) have been prepared in a one-pot synthesis as shown the bulk of the dicyclohexyl-amino group prevents substitution of the second chlorine atom, and the products (56) are claimed to be stable to air and moisture. In a one-pot synthesis tris(diethylamino)-phosphine has been treated successively with three different alcohols to give a 89% yield of the thiophosphate (57) after oxidation with sulphur. ... 

Warren and co-workers reported that DBU did not influence the formation of olefin from eryi/jro-(2-hydroxyl-l-methyl-2-phenylethyl)diphenyl-phosphine oxide (215) in dimethylformamide (84JCS(P 1)243). 

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