Triphenylphosphine, in preparation

Triphenylphosphine, in preparation of dichloromethylenetriphenyl-phosphorane, 46, 33 reaction with N,N-dimethylamino-benzaldehyde to yield /9,0-di-chloro-p-dimethylaminostyrene, 46,33... 

Nickel salts form coordination compounds with many ligands. Dibromobis(tri- -butylphosphine)nickel(Il) [15242-92-9], [( -C4H2)3P]2NiBr2, dicyanoammineaquanickel(11), Ni(NH3)(H20)(CN)2, and bromonitrosobis(triphenylphosphine)nickel(Il) [14586-72-2], are complexes used for syntheses in preparative organonickel chemistry. 

However, when the chlorine atoms are more dispersed through a polychlorofluorocarbon, both chlorine and fluorine may be removed by zinc. In these cases, triphenylphosphine in dioxane can be used to prepare dechlonnated products in high purity and good yield [6S](equations 36 and 37)... 

The quaternary phosphonium salt is prepared by refluxing for 12 hours or longer a mixture of 4.5 g of benzyl chloride and 13 g of triphenylphosphine in 70 ml of xylene. On cooling to approx. 60°, colorless crystals of benzyltriphenylphosphonium chloride can be filtered off, washed with xylene (approx. 50 ml) and dried. The yield is virtually quantitative, mp 310-311°. 

Triphenylmethylphosphonium bromide A pressure bottle is charged with a solution of 55 g (0.21 mole) of triphenylphosphine in 45 ml of dry benzene and cooled in an ice-salt bath. A commercially available ampoule of methyl bromide is cooled below 0° (ice-salt bath), opened, and 28 g (0.29 mole, approx. 16.2 ml) is added to the bottle in one portion. The pressure bottle is tightly stoppered, brought to room temperature, and allowed to stand for 2 days. After this time, the bottle is opened and the product is collected by suction filtration, the transfer being effected with hot benzene as needed. The yield of triphenylphosphonium bromide is about 74 g (99%), mp 232-233°. This material should be thoroughly dried (vacuum oven at 100°) before use in preparing the ylide. 

Various l-alkyl-4-(benzotriazol-l-yl)-l,2,3,4-tetrahydroquinolines have been prepared by condensation of V-alkylaniline with two equivalents of an aldehyde and one equivalent of benzotriazole <95JOC(60)7631>. Quinolones 66 were simply prepared in good yield by heating a mixture of the appropriate vinylogous amide 65 and NaHCOj in the presence of a catalytic amount of palladium(II) acetate and triphenylphosphine in DMF under a carbon monoxide atmosphere <96CC2253>. 

A unique preparation of 2,3 5,6-di-O-isopropylidene-a-D-mannofuran-osyl fluoride (45) utilizing the Mitsunobu reaction [diethyl azodicarboxy-late (DEAD)-triphenylphosphine in the presence of EtjO BFi ii this case] has been reported (see Table 1). 

Geranyl chloride can be prepared from geraniol by the careful use of triphenylphosphine in carbon tetrachloride. Tris(dimethylamino)phosphine reacts with carbon tetrachloride to form the complex (42) which can be used to form the enol esters (43) from acid anhydrides. Similarly, aldehydes form the alkenes (44), and esters or amides of trichloroacetic acid are converted to glycidic esters. ... 

Highly stabilized phosphorus ylides are prepared from acetylenic esters, a carbon-based nucleophile, and triphenylphosphine in aqueous media.40 In acetone-water (2 1) solvent, the reaction proceeds via the conjugate addition of triphenylphosphine to dialkyl acetylenedicarboxy-lates the resulting vinyl triphenylphosphonium salts undergo Michael addition reaction with a carbon-nucleophile to give the corresponding highly stabilized phosphorus ylides. 

This burgundy-red compound can be easily prepared by reacting RhCl3-3H20 with triphenylphosphine in refluxing ethanol. In this reaction, rhodium(III) is reduced to the rhodium(I) complex RhCl(PPh3)3, whilst the phosphine is oxidized to phosphine oxide according to Eq. (3). 

This method can also be utilized as a general method for the preparation of olefins with terminal difluoromethylene groups from aldehydes.8 Also, by the substitution of tributylphosphine for triphenylphosphine in this procedure, ketones other than those containing an a-perfluoroalkyl group can be converted to terminal difluoromethylene compounds.9... 

The Pd-catalyzed electro-cleavage of the C—O bond of allyl aryl ether proceeds smoothly in a DMF-Bu4NBp4-(Mg)-(Stainless Steel) system, giving depro-tected products in 73 99% yield [437]. The sp-sp intermolecular coupling reaction with the Pd water-soluble catalyst prepared in situ from Pd(II) acetate and sul-fonated triphenylphosphine in an MeCN-H2O system yields diynes in 45 65% yields [438]. Similarly, the sp -sp coupling of 2-iodophenols or 2-iodoanilines and terminal alkynes followed by intramolecular cyclization gives indol and furan... 

Vicinal diazides 85a-c, prepared by the action of sodium azide on the corresponding 3,4-dichloromaleimide, react with triphenylphosphine in refluxing dichloromethane to give 2-amino-l,2,3-triazole derivatives 86a-c (Scheme 9). The stable di-Staudinger side products 87a-c are also produced from the reaction <2005JCX385>. 

The other complex is one that we prepared with this obscure ligand in the cobalt system, also with triphenylphosphine in the pole position. 

The second synthesis of 654 and 655 makes use350,351 of the Wittig reaction. The (methylthio)methyl ether 656 is converted into the chloromethyl ether 657, which reacts with triphenylphosphine to yield a crystalline phosphonium salt (658). Reaction of 658 with phenyllithium gives a phosphorane, treatment of which with acryl-aldehyde leads to ethers 654 and 655 in —50% yield. Pure trtms-diene 654 was obtained352 in a reversed way consisting in preparation of a sugar ether acrylaldehyde (660) by replacement of the p-tolylsulfonyl group in 659, followed by reaction of 660 with methylenetriphenyl-phosphorane. 

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