Ethere from phenols

The reaction gives poor yields of ethers with secondary and tertiary alcohols dehydration to form the corresponding olefin is a more favorable reaction. The reaction fails for the production of diaryl ethers from phenols. 

The mem-dichlorobenzene complex reacts with protected 0-aryltyrosines to give aryl ethers. Both chlorine atoms can be sequentially substituted to give symmetrical or disymmetrical triaryl diethers (Scheme XVI). The building up of such diaryl ethers from phenolic compounds which have amino groups in their side chains... 

Xu, W. Mohan, R. Morrissey, M. M. Polymer-Supported Bases in Combinatorial Chemistry Synthesis of Aryl Ethers from Phenols and Alkyl Halides and Aryl Halides, Tetrahedron Lett. 1997, 38, 7337. 

Xu W, Mohan R, Morrissey MM, Polymer supported bases in combinatorial chemistry synthesis of aryl ethers from phenols and alkyl halides and aryl halides, Tetrahedron Lett., 38 7337-7340, 1997. 

The reactions between i-dinitrobenzene or 1,3,5-trinitrobenzene, aryl halides, and copper(I) oxide in quinoline 17-19, 21) provide a simple synthesis of nitrobiphenyls uncontaminated by symmetrical biphenyls. These couplings may be related to the Ullmann reaction, the decarboxylative coupling of benzoic acids with aryl halides, and the preparation of ethers from phenols 165). Although no intermediates... 

Vttmann diaryl ether synthesis. This copper(I) derivative is recommended as the condensing reagent in the Ullmann synthesis of diaryl ethers from phenols and bromoarenes in refluxing pyridine (equation I). 

Utilization of this principle for the synthesis of the target tree-like (dendritic) macromolecule is shown in Scheme 4.31. The basic reaction chosen was again very simple, namely the formation of benzyl ethers from phenols and benzylic halides. It was found that the coupling of benzylic bromide 91 with 2 equivalents of 3,5-dihydroxybenzyl alcohol 92 could be carried out without affecting the... 

Cyanoethyl ethers from phenols and vinyl cyanide... 

Ethylene derivatives from amines Ethers from phenols... 

Diaryl ethers. This electron-rich and bulky / iV-ligand (1) facilitates the Pd-catalyzed synthesis of diaryl ethers from phenols and aryl halides. 

Show how you could synthesize allyl phenyl ether from phenol and allyl bromide. STRATEGY AND ANSWER Use a Williamson ether synthesis (Section 21.6A). 

Sodium hydride I cuprous bromide Diaryl ethers from phenols and ar. halides Ullmann reaction... 

As noted in the introduction to this section, UUmann also reported the formation of biaryl ethers from phenol and phenyl bromide in the presence of copper and a base. This UUmann ether synthesis has been used extensively to prepare biaryl ethers. " However, the original reaction conditions involved high temperatures (150-200 C), neat phenol or highly polar aprotic solvents, and stoichiometric amounts of copper complexes. The yields for the reactions of unactivated aryl halides were often low. Conditions with catalytic amounts of copper at lower temperatures with broader scope have now been developed. 

Show how to synthesize allyl phenyl ether and 2-butenyl phenyl ether from phenol and appropriate alkenyl halides. 

Preparation.— Two procedures for the production of ethers from alky] halides have been mentioned earlier in this Report. From a study of fluoride salts on alumina as reagents for the alkylation of phenols and alcohols, potassium or caesium fluoride on alumina, in acetonitrile or 1,2-dimethoxyethane as the solvent, has been found to be the best combination for general use. A recently reported one-pot synthesis of phenyl ethers from phenol acetates involves their treatment, in solution in acetone, first with potassium carbonate and then with an alkyl halide. Another interesting new procedure for the alkylation of phenols utilizes the gas-liquid phase-transfer catalysis technique that was discussed above. In this case a phenol (or a thiophenol) and an alkyl halide, both gaseous, are passed through a bed of solid K2CO3 (or NaHCOs) at 170°C in the presence of a PEG e,g. Carbowax 6000) as the catalyst. ... 

---