Phosphines carbonyl sulfides

Numerous diamines and aromatic dianhydrides have been investigated. WhoUy aromatic Pis have been stmctiirally modified by incorporating various functional groups, such as ether, carbonyl, sulfide, sulfone, methylene, isopropjlidene, perfluoroisopropyUdene, bipyridyls, sdoxane, methyl phosphine oxide, or various combinations of these, into the polymer backbone to achieve improved properties. The chemistry and apphcations of Pis have been described in several review articles (4). 

Aliphatic iodine derivatives, 14 376 Aliphatic ketones, 14 563, 571, 581-585 reactions of, 16 331-332 Aliphatic monothiopolyesters, 23 739 Aliphatic nitration, 12 187 Aliphatic peroxyacids, 13 464 Aliphatic peroxycarboxylic acids, 18 463 Aliphatic phosphines, 19 60 Aliphatic polyamides (PA), 10 207-210 19 713, 739. See also Aromatic polyamides PA entries producers of, 10 210 properties of, 10 208, 209t Aliphatic polycarbonates, 24 703 preparation of, 19 798 Aliphatic polyketones (PK), 10 197 costs of, 10 222 properties of, 10 198t Aliphatic poly(monosulfide)s, 23 702-704 Aliphatic polyphosphonate dyes, 9 480 Aliphatic poly(polysulfide)s, 23 711 Aliphatic polysulfides, 23 734 Aliphatic polysulfoxides, 23 733 miscibility of, 23 735 Aliphatic polyurea preparation, carbonyl sulfide in, 23 625... 

The mass spectrum of Fe2(CO)9, long assumed to be completely involatile, shows a parent ion, but the base peak is Fe2(CO) J, with a structure retaining the three bridging carbonyl groups [Fe(CO)3Fe]+ (70). Similar bridged ions containing iron have been postulated in the spectra of some phosphine and sulfide complexes (Section VI). 

Fluoroalkyl(aryl)iodonium salts are the most stable and practically important class of alkyl(aryl)iodonium derivatives. The application of such salts as electrophilic fiuoroalkylating reagents was reviewed in 1996 by Umemoto [1017]. Perfluoroalkyl(phenyl)iodonium trifiates (FITS reagents) 764 are efficient perfluoroalky-lating reagents toward various nucleophiUe substrates, sueh as arenes, carbanions, alkynes, alkenes, carbonyl compounds, amines, phosphines and sulfides [1017]. Scheme 3.300 shows several representative examples of electrophilic perfluoroalkylations using FITS reagents. 

In general, peroxomonosulfates have fewer uses in organic chemistry than peroxodisulfates. However, the triple salt is used for oxidizing ketones (qv) to dioxiranes (7) (71,72), which in turn are useful oxidants in organic chemistry. Acetone in water is oxidized by triple salt to dimethyldioxirane, which in turn oxidizes alkenes to epoxides, polycycHc aromatic hydrocarbons to oxides and diones, amines to nitro compounds, sulfides to sulfoxides, phosphines to phosphine oxides, and alkanes to alcohols or carbonyl compounds. 

Cyclododecene may be prepared from 1,5,9-cyclododecatriene by the catalytic reduction with Raney nickel and hydrogen diluted with nitrogen, with nickel sulfide on alumina, with cobalt, iron, or nickel in the presence of thiophene, with palladium on charcoal, with palladimn chloride in the presence of water, with palladium on barium sulfate, with cobalt acetate in the presence of cobalt carbonyl, and with cobalt carbonyl and tri- -butyl phosphine. It may also be obtained from the triene by reduction with lithium and ethylamine, by disproportionation, - by epoxidation followed by isomerization to a ketone and WoliT-Kishner reduction, and from cyclododecanone by the reaction of its hydrazone with sodium hydride. ... 

The ionization and oxidation (peak) potentials [53] of metal carbonyls listed in Table 3 establish their mild donicity despite their (formally) neutral oxidation state. However, partial replacement of carbonyls by stronger donor ligands (such as phosphine, sulfide, etc.) effects an incremental increase in their reducing properties [54], Such a fine-tuning of the oxidation potentials of structurally similar organometallic donors is ideal for studies of the correlation between rate constants and the electron-transfer driving force (see Section 2.5). 

In addition, manganese oxide oxidizes benzylic methyl or methylene to carbonyl [814] and cleaves the carbon bonds of vicinal diols [577, 522]. It converts amines into imines [577, 525] tertiary amines into secondary amines [572], formamides [526, 527, 525], or ketones aromatic primary amines [575, 525] and hydrazo compounds [525] into azo compounds hy-droxylamines into nitroso [576] or nitro compounds [525] hydrazones into diazo compounds [520] phosphines into phosphine oxides [575] thiols into disulfides [576] and sulfides into sulfoxides [541]. 

Dimethyl sulfoxide (DMSO), (CH3)2SO, is a versatile reagent for the oxidation of alcohols to carbonyl compounds under gentle conditions. In addition to the previously mentioned dehydrogenations, it is capable of other oxidations acetylenes to a-diketones [997], alkyl halides to aldehydes 998, 999], tosyl esters to aldehydes [1000], methylene groups adjacent to carbonyl groups to carbonyls [1001, 1002], a-halocarbonyl compounds to u-dicarbonyl compounds [1003,1004,1005], aldehydes to acids [1006], and phosphine sulfides and selenides to phosphine oxides [1007]. 

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