Halogen displacements

Halogen Displacement. Poly(phenylene oxide)s can also be prepared from 4-halo-2,6-disubstituted phenols by displacement of the halogen to form the ether linkage (48). A trace of an oxidizing agent or free radical initiates the displacement reaction. With 4-bromo-2,6-dimethylphenol, the reaction can be represented as in equation 10 ... 

The halogen displacement polymerization proceeds by a combination of the redistribution steps described for oxidative coupling polymerization and a sequence in which a phenoxide ion couples with a phenoxy radical (eq. 11) and then expels a bromide ion. The resultant phenoxy radical can couple with another phenoxide in a manner that is analogous to equation 11 or it can redistribute with other aryloxy radicals in a process analogous to equations 7 and 8. 

Pyran, 2-halotetrahydro-dipole moments, 3, 628 halogen displacement reactions, 2, 64 C NMR, 3, 587 Pyran, 2-hydroxy-synthesis, 3, 741 Pyran, 3-hydroxy-synthesis, 2, 91... 

When potassium fluoride is combined with a variety of quaternary ammonium salts its reaction rate is accelerated and the overall yields of a vanety of halogen displacements are improved [57, p 112ff. Variables like catalyst type and moisture content of the alkali metal fluoride need to be optimized. In addition, the maximum yield is a function of two parallel reactions direct fluorination and catalyst decomposition due to its low thermal stability in the presence of fluoride ion [5,8, 59, 60] One example is trimethylsilyl fluoride, which can be prepared from the chloride by using either 18-crown-6 (Procedure 3, p 192) or Aliquot 336 in wet chlorobenzene, as illustrated in equation 35 [61],... 

Halogeno compounds have been prepared by direct halogena-tion or by Sandmeyer reaction on 4-aminoisothiazoles. As expected from general considerations, a halogen atom in the 4-position is less reactive than one in the 5-position, but nitriles are obtained in good yield with cuprous cyanide at elevated temperatures. With butyllithium, lithiation occurs exclusively in the 5-position, and no evidence of halogen displacement has been obtained. ... 

Approximate Relative Rates of Halogen Displacement FROM 4-Substituted Halobenzenes and 4-Substituted 2-Nitrohalobenzenes... 

The Ullman reaction has long been known as a method for the synthesis of aromatic ethers by the reaction of a phenol with an aromatic halide in the presence of a copper compound as a catalyst. It is a variation on the nucleophilic substitution reaction since a phenolic salt reacts with the halide. Nonactivated aromatic halides can be used in the synthesis of poly(arylene edier)s, dius providing a way of obtaining structures not available by the conventional nucleophilic route. The ease of halogen displacement was found to be the reverse of that observed for activated nucleophilic substitution reaction, that is, I > Br > Cl F. The polymerizations are conducted in benzophenone with a cuprous chloride-pyridine complex as a catalyst. Bromine compounds are the favored reactants.53,124 127 Poly(arylene ether)s have been prepared by Ullman coupling of bisphenols and... 

A. Preparation.—Halogen displacement reactions have been used to prepare a number of new aminofluorophosphines. Aminodifluorophos-phine (1) has been prepared for the first time, from either bromodifluoro-phosphine or chlorodifluorophosphine, and ammonia. Studies of its n.m.r. spectrum have been made (see Chapter 11). The related NN-difluoroaminodifluorophosphine (2) has been prepared, from difluoroiodo-phosphine, and found to be explosive. Two syntheses of A-alkyl-amino-difluorophosphines have been reported, one of which was complicated by the subsequent formation of the phosphorane (3) and the bis-(A-alkylamino)fluorophosphine (4). 

Sn2 and SN2 Reactions with Halides and Sulfonates. Corey and Posner discovered that lithium dimethylcuprate can replace iodine or bromine by methyl in a wide variety of compounds, including aryl, alkenyl, and alkyl derivatives. This halogen displacement reaction is more general and gives higher yields than displacements with... 

NLO materials (16 and 17) (Fig. 13) have been obtained from polyurethanes by the incorporation of sidechains with boron chromophores.37 The dihydroxy ligand of an azobenzene ligand containing a dimesityl boron acceptor was reacted in a polycondensation fashion with the diisocyanate groups of the polyurethanes to yield the desired polymers. Halogen displacement and transmetallation reactions have been utilized in the development of extended ir-conjugated systems of tri-9-anthrylborane with dendritic structures.38 In one (18) (Fig. 14) of the novel compounds, three identical... 

Amines tend to give more complex results. The compound obtained by treating a 5-halofuran-2-carboxaldehyde with aniline is now thought to have a structure resulting from anil formation, halogen displacement, protropy and protonation. The free base is too unstable to be studied easily but acetylation of the salt provides readily recognizable products.182 A related example is discussed later (Section X,A,2). 

Halogen Displacement Materials and Equipment Round-bottom flask (50 mL)... 

It was observed that in the case of bromo- or iodo-substituted benzyhc tellurides the lithium-Br exchange and/or the halogen displacement by the n-butylhthinm competes with the Te-Li exchange, resulting in lower yields of the desired products. This drawback is avoided by using ether as solvent. 

The polymerization of halophenoxides by copper (II) mediated halide displacement is a mechanistically complicated reaction. Elucidation of the structure of the polymers is essential to an understanding of both the polymerization chemistry and the peculiar physical properties of the polymers. The physical tool which has yielded most information on the polymer structure is nmr. The first conclusion which derives from a study of the spectra of poly(dihalophenyleneoxides) is that regioselectivity in halogen displacement is more likely the source of the polymer properties than branching. A more rigorous confirmation of the polymer structures will depend on a detailed analysis of the spectra of model compounds for the chain segments. 

Halogen displacement in 2,3-dihalogeno-l,4-oxathiins has been exploited. An intramolecular approach with a carboxamide function as nucleophile affords the bicyclic /3-lactam 97 <1999H(50)713>. An intermolecular substitution with sodium A,A-dimethyldithiocarbamate in acetonitrile was also reported to give 98 after HBr elimination <1996S198>. 

Halogen displacement from 2-halo-tetrahydropyrans and -hexahydropyrimidines is extremely easy, being assisted, in the SnI process, by the electron pairs on the heteroatom (equation 124). 3-Halohexahydropyridines can also show accelerated halogen displacement (anchimeric assistance from nitrogen equation 125). Apart from these and other (normal) substitutions, eliminations of H—Hal are also commonly found. 

As is true for other classes of aromatic nucleophilic substitution, the halogen displacement can frequently be catalyzed by copper or copper(I) salts. Using sodium hydride as the base and copper(I) iodide as catalyst, a series of o-bromophenylethylamine derivatives, including both amides and carbamates, have been cyclized. Oxidation to the indole can be effected with manganese dioxide (81JCS(P1)290). 

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