Sodium aryloxides

Hartwig et al. demonstrated that the same combination of iridium precursor and phosphoramidite LI also catalyzes allylic etherifications (Scheme 9) [68]. Lithium and sodium aryloxides were shown to react with cinnamyl and hex-2-enyl carbonates to form the branched allylic ethers in high yield, with high branched-to-linear... 

The poly(aryloxythionylphosphazenes) 24 and poly(aminothionylphospha-zenes) 25 show no noticeable change after storage in air for several years. However, in solution, polymer 24 rapidly decomposes in the presence of strong bases such as NaOH or excess sodium aryloxide at elevated temperatures. These reactions are presumably initiated by nucleophilic attack at the sulfur(VI) center. 

NP(OC6H3Bu 2-2,6) 2 have been reported for reactions of (NPCl2)3 with corresponding sodium aryloxides. The formation of bicyclic compounds has been explained by a metal-halogen exchange mechanism. ... 

Sodium trimethylsilanolate has been reported as a convenient synthon for a hydroxy group in the ipso substitutions of fluoride in aromatic compounds. The S vAr displacement of the fluoride by the nucleophilic trimethylsilanolate leads to the silyl ether, which is immediately desilylated by the liberated fluoride ion yielding the sodium aryloxide salts. Acidification of these salts affords the hydroxylated product. For instance, 1,4-difluoroanthracene gives 1-hydroxy-4-fiuoroanthracene in 90% yield by treatment with sodium trimethylsilanolate. 

The reactions of A-chloroalkylphosphazenes with hydroxylamine hydrochloride to give (73) proceed in a similar manner. Derivatives of (73) were obtained by reactions with arylamines, with sodium aryloxides, and with acetic (or formic) acid. The latter is noteworthy in that the proton of the hydroxy-group in (74) does not migrate to nitrogen. 

Several aryloxymethylphosphonates have been prepared in low to moderate yields by the reaction of a variety of sodium aryloxides with diethyl iodornethylphosphonate. The first step is a dealkylation, and the second is the nucleophilic substitution of the iodine atom (Scheme 3.55). ... 

Better yields of aryloxymethylphosphonic acids (65-90%) are obtained from a reaction between the disodium salt of chloromethylphosphonic acid and the corresponding sodium aryloxides. However, dilithium or disodium salts of iodomethylphosphonic acid are reported not to react with sodium phenoxide in HMPA, even at 100°C.3 5... 

Chloroquinoxaline undergoes facile nucleophilic displacement reactions with amines and aryloxides to give the corresponding 2-substituted quinoxalines. With diamines, besides the 2-amino derivatives, bis(quinoxalinyl)alkylenediamines are produced. When 2-chloro-quinoxaline is treated with a sodium aryloxide in an excess of the corresponding phenol, a mixture of the expected 2-aryloxyquinoxaline and the corresponding benzofuro[2,3-6]quinoxaline (144) is obtained. 2-Aryloxyquinoxalines are readily cyclized with polyphosphoric acid to benzofuro[2,3-6]quinoxalines. 2-Arylfuro[2,3-h]quinoxalines (146) result from cyclization of 2-phenacyl-3-quinoxalinones (145). ... 

Chloroquinoxalines are converted into 2-phenoxyquinoxalines by treatment with phenol in which potassium hydroxide has been dissol-ved. " - When 2-chloroquinoxaline is heated with a sodium aryloxide in... 

Cross-coupling reactions leading to the formation of C-X (X = heteroatom) bonds catalyzed by Pd(dba)2 have been reported. Aniline derivatives have been prepared via reaction of amine nucleophiles with aryl halides in the presence of Pd(dba)2 and phosphines, especially P( Bu)3. Likewise, diaryl and aryl alkyl ethers are produced from aryl halides (Cl, Br, I) and sodium aryloxides and alkoxides under similar conditions. Conditions effective for the coupling of aryl chlorides with amines, boronic acids, and ketone enolates using an easily prepared phosphine chloride as a ligand have recently been uncovered (eq 22). The preparation of aryl siloxanes and allyl boronates via Pd(dba)2-catalyzed C-Si and C-B coupling have been reported as well. 

The derivatisation of both 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol and its 3,5-di-tert-butyl congener as mono- and dimeric lithium and sodium aryloxides has afforded structures in which the metal ions are supported by weak interactions with the 4-methylphenoxide ring. Moreover, evidence for interactions between sodium or potassium ions and aromatic n-systems has recently formed the basis of a review article. ... 

---