Oxychloride complexes

Aluminum chloride-phosphorus oxychloride complex, 31, 88 Amberlite IR-4B resin, 32, 13 Amidation, of isocyanic acid with bromo-aniline and other aromatic amines, 31,8... 

R = CHO) by the action of the dimethylformamide-phosphorus oxychloride complex, and 0-(p-nitrophenyl)hydroxylamine and ethyl benzoylacetate yield, inter alia, the benzofuran (77 R = COaEt). Sodium salts of 2-hydroxyben-zofuran-esters, e.g. (78), are produced by the action of dimethyl chloromalonate on hydroquinones. ... 

A kinetic study of the nitrosation, at C-3, of the indolizine (764) and of its nitration, which occurs at C-4, has been presented.The reaction of diethyl azodicarboxylate with 2-methylindolizine yields a mixture of the mono-adduct (765 R = H) and the di-adduct [765 R = N(C02Et)NHC02Et]. "" The novel zwitterion (767 Ar = P-CIC6H4) is formed by the action of chlorobenzene-p-sulphonyl azide on the cyclohexenoindolizine (766). A stable carbo-selenaldehyde (768) has been obtained by treatment of 2,7-dimethylindolizine with the dimethylformamide-phosphorus oxychloride complex followed by sodium hydrogen selenide. ... 

Although Vilsmeier and Haack in 1927 were the first who recognized the general applicability of this method, Dimroth and Zoeppritz in 1902 had obtained dihydroxybenzaldehyde from resorcinol, formanilide, and phosphorus oxychloride. The modern mechanistic interpretation of this reaction was advanced by Arnold and Sorm Jutz and Bosshard and Zollinger (, 43 example, when a suitable substrate, such as N,N-dimethylaniline, is treated with the phosphorus oxychloride complex of a N,N-disubstituted formamide, the intermediate iminium chloride... 

It is not necessary to use phosphorus oxychloride complexes of formamides, because Roh and Kochendorfer in 1937 demonstrated that the iminium chlorides themselves react similarly and Bosshard and Zollinger have shown that comparable yields can be obtained using chlorodimethylformiminium chloride as the reagent. However, in the synthesis of diarylketones good yields are only obtained when the phosphorus oxychloride complex of the corresponding arylcarboxylic acid amide has been used The synthesis of ketones from carboxylic acid amides, phosphorus oxychloride and suitable substrates predates the aldehyde synthesis by approximately 40 years but it is of only limited usefulness because side reactions are very often encountered... 

In general, one can conclude that the phosphorus oxychloride complex is the most useful reagent, but often the carbonyl chloride complex and/or the iminium chloride reacts-equally well. A comparative study with regard to the use of N,N-dimethylformamides versus N-alkyl-N-arylformamides in the synthesis of alkylmercaptobenzaldehydes has been conducted by Dallacker and Eschelbach These authors found that maximum yields at 50°C are obtained when the phosphorus oxychloride complex of N-4-methoxyphenyl-N-methylformanilide is used. 

This reductive deammination [43] can be attributed to the more complex functionality of the carbon surface, which besides various types of oxygen-containing groups, contains pi bonds and pyridine-N-oxide groups [44] that give rise to the oxidation-reduction reaction wherein the metal complex is reduced and the carbon surface is oxidized. Carbon has also been shown to reduce Pt+ chloride and oxychloride complexes to Pt+ at acidic conditions, where in the same pH range the Pf is completely stable over alumina [45, 46]. 

Shi, M. Cui, S. Yin, W. Highly efficient catalytic nitration of phenolic compounds by nitric acid with a recoverable and reusable Zr or Hf oxychloride complex and KSE. Eur. J. Org. Chem. 2005,... 

An example of the cationic polymerization initiated by a chaige transfer complex is the reaction of Yamada, which can be illustrated by the polymerization of isobutylene with vanadium oxychloride complex with naphthalene in the heptane environment. The resulting complex decays with the formation of radical ions, which then react with isobutylene according to the following reactions ... 

---