Phenols diaryl ethers

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. 

ULLMANN GOLDBERG Aromatic substitution Cu catalyzed substitution of aromatic halides in the synthesis of disryls, diaiyl ethers, diaryl amines, phenols... 

Sjwyer and coworkers have developed an efficient alternative UUmann synthesis of diaryl ethers, diaryl thioethers, and diarylamines using the SnAt reaction. Phenol, thiophenol, or aniline reacts v/ith an appropriate aryl halide, In the presence of KF-aliunina and 18-crovm-6 In acetonitrile or DMSO to give the corresponding diaryl ether or diaryl thio ether as shovm In Eqs. 9.6 and 9.7. ... 

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... 

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). 

Intramolecular anodic coupling of diaryl amides is a synthetically interesting reaction that may be applied to the synthesis of alkaloidal structures [210]. However, this aryl coupling is initiated by the oxidation of an aromatic ring (aryl ether or phenol) and not by oxidation of the nitrogen. Therefore, it is not discussed further in this chapter. 

The total synthesis of the lichen diphenyl ether epiphorellic acid 1 was achieved in the laboratory of J.A. Elix using the Smiles rearrangement as the key step. The diaryl phenolic ester substrate was heated in dry DMSO in the presence of potassium carbonate, which brought about the rearrangement. The resulting carboxylic acid was converted to the methyl ester with diazomethane and was debenzylated under catalytic hydrogenation conditions. 

Arylbismuth 671, 673 Arylboronic acid 671, 673 Arylbutenes, formation of 613 Aryl-2-cyclohexenones 653 Aryl ethers—see also AUyl aryl ethers. Diaryl ethers. Phenyl ethers, Propargyl aryl ethers formation from calixarenes 1387 Aryl haUdes, as phenol precursors 396, 397 Ai-Arylhydroxylamines, isomerization of 801-805 oxidation of 419 3-Arylindoles, synthesis of 1236 Aryl ketones, oxidation of 424, 425 Aryloxylium cations 179 Asatone, synthesis of 1178, 1179 Ash, from incineration of municipal waste, phenoUc compounds in 938 Aspersitin, synthesis of 1327, 1328 Aspirin 10, 11... 

Substitution of aromatic halides or recrystes in the synthesis of diaryls, diaryl ethers, diaryl amines, phenols etc catalyzed by Cu and other catalysts... 

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

Cyclic imines. Alkynylamincs c> Diaryl ethers. The phenol-ar>l (MeCN)4CuPF6. 

Cyclic imines. Alkynylamines cyclize under the influence of (MeCN)4CuPF(,. Diaryl ethers. The phenol-aryl halide coupling is promoted by CS2CO3 and (MeCN)4CuPF(,. 

A high yield synthesis of diaryl ethers involves nucleophilic attack by phenoxide on arynes generated from iodobenzenes. The arynic nature was established with substituted iodobenzenes ( -MePhI and phenol, for example, gave 35% m-tolyl phenyl ether as well as 25% of t -tolyl phenyl ether). Diaryl sulfides were similarly prepared from thiophenols and iodoarenes. 

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

Ullman reaction The synthesis of diaryls by the condensation of aromatic halides with themselves or other aromatic halides, with the concomitant removal of halogens by a metal, e.g. copper powder thus bromobenzene gives diphenyl. The reaction may be extended to the preparation of diaryl ethers and diaryl thio-ethers by coupling a metal phenolate with an aryl halide. 

DicblorobenzotnfIuoride. This compound is produced by chlorination of 4-chloroben2otrifluoride and exhibits sufficient activation to undergo nucleophilic displacement with phenols to form diaryl ether herbicides, eg, acifluorofen sodium [62476-59-9]. 

S Ar reacdons also provide an important strategy for the preparadon of various kinds of diaryl ethers -Dinitrobenzene reacts v/ith even sterically hindered phenols to give the corresponding diaryl ethers fEq 9 3 ... 

In Figure 13.2, the intensity of the ion at m/z 170 represents a molecular ion of an aromatic compound. The characteristic losses from the molecular ion (M - 1, M - 28, and M - 29) suggest an aromatic aldehyde, phenol, or aryl ether. The molecular formula of Ci2H 0O is suggested by the molecular ion at m/z 170, which can be either a biphenyl ether or a phenylphenol. The simplest test to confirm the structure is to prepare a TMS derivative, even though m/z 11 strongly indicates the diaryl ether. 

Many reactions have been shown to benefit from irradiation with ultrasound (ref. 19). We therefore decided to investigate the effect of ultrasound, different catalysts and the presence of solids on Ullmann diaryl ether synthesis. Indeed, sonication of mixtures of a phenol and a bromoaromatic compound, in the absence of solvent and presence of copper (I) iodide as catalyst and potassium carbonate as base, produces good yields of diaryl ethers at relatively low temperatures (Fig. 10) (ref 20). 

The key structural features of compound 1 are the chiral cis-diaryl benzox-athiin fused ring system, two phenols, and one phenol ether linkage with the pyrrolidinylethanol. Originally, SERM 1 was prepared by medicinal chemists from a key ketone intermediate 5 shown in Scheme 5.1. Compound 5 was prepared in four steps with rather low yield [4a], Among these steps, the high temperature de-methylation step and the use of extremely toxic MOM-C1 were not particularly suitable for scale-up. The ketone 5 was then brominated with PhMe3NBr3 (PTAB) and coupled with thiophenol 7 to produce adduct 8. The key step of the synthesis was the conversion of adduct 8 to cis-diaryl benzoxathiin 9 under the Kursanov-Parne reaction conditions (TFA/Et3SiH). This novel reaction allowed the formation... 

Previously we have shown that phenolic compounds have a remarkable positive effect (4) on the coal liquefaction in the presence of Tetralin, depending strongly on the character of coal as well as on the concentration of phenols. The effect of phenols on the decomposition of diaryl ethers will give a good explanation for the previous results, because aliphatic ether structures of some young coals will be decomposed rapidly at relatively low temperatures and so the rate of coal dissolution will not be affected by the addition of phenols, on the other hand, the polycondensed aromatic ether structures will be decomposed effectively by the addition of phenols in the course of coal liquefaction. 

Reactions of aryl halides with phenoxides or phenols (Equation (30)) and base catalyzed by complexes of these ligands occurred in significantly higher yields than did the same reactions catalyzed by complexes of DPPF or BINAP. For example, a large number of diaryl ethers have... 

The Pd-catalyzed intermolecular C—O bond formation has also been achieved [105-108]. Novel electron-rich bulky phosphine ligands utilized by Buchwald et al. greatly facilitated the Pd-catalyzed diaryl ether formation [109], When 2-(di-tert-butylphosphino)biphenyl (95) was used as the ligand, the reaction of triflate 93 and phenol 94 elaborated diaryl ether 96 in the presence of Pd(OAc)2 and K3PO4. The methodology also worked for electron-poor, neutral and electron-rich aryl halides. 

Patents of Dow Chemicals first described 9,9-diaryl-substituted PF homopolymers 204 and 205 by Yamamoto polymerization of the corresponding 2,7-dibromo monomers [272], although the methods for monomer preparation were not described. For unsubstituted fluorenone, a convenient method for its conversion into 9,9-(4-hydroxyphenyl)-[307-309] and 9,9-(4-alkoxyphenyl)fluorenes [310] was reported previously, which included condensation of fluorenone with phenol or its ethers in acidic conditions (dry HC1 [308,309] or H2SO4 [307,311]) in the presence of (3-mcrcaptopropionic or mercaptoacetic acids. Both polymers 204 and 205 showed similar Mn 21,000 with PDI of 1.48 and 1.75, respectively, and spectral data typical for PF (205 Aabs = 389 (r 50,000 //(mol cm) APL = 417, 439, and 473 mn (THF)) (Chart 2.48). 

Phenols (29) substituted with bromo-and chloro-atoms in the o, o -positions were oxidized to diaryl ethers (30), while the iodo-substituted phenols (29) provided the diaryls (31) as major products (Scheme 11) [68]. 

Phenolic compounds can be condensed forming aryl-aryl and aryl-oxygen-aryl (ether linkages) bonds to yield diaryl and diaryl ether polymers (59). These are in many ways similar to natural humic acids, confirming earlier research by others (60-62) that humic acids are formed from the copolymerization of phenolic compounds with amino acids, peptides, and amino sugars. 

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