Thiocyanates triphenylphosphine

Keywords Alcohols and thiols, ammonium thiocyanate, triphenylphosphine (PPh3), diethyla-zodicarboxylate (DEAD), acetonitrile, room temperature, thiocyanates... 

The addition of morpholine to 2,3-dihydrofuran in the presence of palladium(II) thiocyanate-bis(triphenylphosphine) yields 2-(morpholin-4-yl)tetrahydrofuran (276)303. Irradiation of mixtures of 2-(2-methylpropenyl)phenol (277) and alkylamines yields adducts, e.g. 278 with isopropylamine304. 

The reaction of chloromethyl aryl ethers with nucleophilic reagents has been described by Barber et al Thus, by reaction with thiourea, potassium thiocyanate, or sodium cyanide, there arc obtained aryloxyalkylisothiouronium salts, aryloxyalkyl thiocyanates, and aryloxyalkylacetonitriles, respectively. The reaction of chloromethyl aryl ethers with butyllithium leads to an aryloxycarbene which on reaction with olefins gives aryloxy-cyclopropanes. The ethers react with triphenylphosphine and a base to give phcnoxymethylene ylides which arc useful in con-... 

Some other common ligands are pyridine (py), ethylenediamine (en), cyanide ion (CN ), thiocyanate ion (SCN, acetylacetonate (acac), sahcy-laldehyde (sal), triphenylphosphine (PPhs) and various trihalophosphines. Ethylenediame and acetylacetonate are examples of two common bidentate hgands. 

SNC, Thiocyanate, gold complex, 26 90 SOOsPC56H45, Osmium, carbonyl(thio-carbonyl)tris(triphenylphosphine)-, 26 187... 

The most common reactions involving nucleophiles and porphyrin systems take place on the metalloporphyrin 77-cation radical (i.e. the one-electron oxidized species) rather than on the metalloporphyrin itself. One-electron oxidation can be accomplished electrochemi-cally (Section 3.07.2.4.6) or by using oxidants such as iodine, bromine, ammoniumyl salts, etc. Once formed, the 77-cation radicals (61) react with a variety of nucleophiles such as nitrite, pyridine, imidazole, cyanide, triphenylphosphine, thiocyanate, acetate, trifluoroace-tate and azide, to give the correspondingly substituted porphyrins (62) after simple acid catalyzed demetallation (79JA5953). The species produced by two-electron oxidations of metalloporphyrins (77-dications) are also potent electrophiles and react with nucleophiles to yield similar products. 

Several amines such as anilines, pyridine, etc., were perfluoroalkylated affording the corresponding ammonium or pyridinium salts [26-28], Other substrates which underwent perfluoroalkylation included triphenylphosphine [26], sodium nitrite [29], potassium thiocyanate [29] and potassium selenocyanate [29]. 

Oxazabicyclohexanes (e.g., 106) can be deoxygenated readily under mild conditions to afford the corresponding pyrrolines (e.g., 107). Deoxygenation reagents include thiourea, triphenylphosphine sulfide, potassium thiocyanate, potassium ethylxanthate, and potassium selenocyanate. The 6-tliia-l-azabicyclo[3.1.0]hexanes 135 liave been suggested as possible intermediates in some of these reactions. 

HALOVINYL KETONES Triphenylphosphine-Carbon tetrachloride. HETEROCYCLES Carbon suboxide. Diethyl isocyanomethylphosphonate. Ethoxy-carbonyl iso thiocyanate. Propargyltriphenylphosphonium bromide. Selenium. HOMOALLYLIC ALCOHOLS ff-2-Methylallylnickel bromide. 2-Methyl-2-thia-zoline. 

Triphenylphosphine sulphide, (CgH5)3PS.i—Triphenylphosphine in carbon disulphide solution combines directly with sulphur to yield the sulphide, and thiocyanic acid or thiocyanogen also gives some sulphide when it reacts with the phosphine. The sulphide crystallises from alcohol in long, brilliant needles, M.pt. 150° to 151° C., readily soluble in alcohol, benzene, chloroform or carbon disulphide, insoluble in water or ether. 

Triphenylphosphine-Thiocyanogen. The reagent is prepared by addition of Brg to lead thiocyanate suspended in CHaCU (0°) the solution of thiocyanogen is decanted and stirred with triphenylphosphine at —40". 

SNC, Thiocyanate, gold complex, 26 90 SNOjCtHs, 1,2-Benzisothiazol-3(2//)-one 1,1-dioxide, chromium and vanadium complex, 27 307, 309 SOOsPCm,H45, Osmium, carbonyl(thiocar-bonyl)tris(triphenylphosphine)-,... 

Adamantanesulfinyl cyanide and triphenylphosphine stirred 5 hrs. at room temp, in benzene -> 1-adamantyl thiocyanate. Y 87%. F. e. s. A. Boerma-Markerink et al., Synth. Commun. 5, 147 (1975). 

The type of analysis discussed in the preceding paragraph with particular respect to c/ iron(ii) complexes has also been attempted for c/ palladium(ii) and gold(iii) substitutions. In the case of the reactions of [Pd(fo)L], where Hgfo is the formazan (5) and L=ammonia or pyridine, with thiocyanate, thiourea, or triphenylphosphine, a kinetic-thermodynamic analysis shows Gibbs free... 

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