Diphenyl ether 4-carboxylic acid

Updated Entry replacing P-00890 Diphenyl ether 4-carboxylic acid [2215-77-2]... 

Fig. 4. Synthesis of diphenyl ether carboxylic acid intermediate.

Diphenyl Ether carboxylic Acid See Phenoxybenzoic Acid. 

Mapara and Desai carried out the cyclization of N-(3-substituted phe-nyl)aminomethylenemalonates (757, R1 = H) in a 2 1 mixture of acetic anhydride and concentrated sulfuric acid and in diphenyl ether (54JIC951). Acidic conditions yielded mainly 5-substituted quinoline-3-carboxylates (758, R1 = H), whereas on heating in diphenyl ether, the 7-substituted compounds (759, R1 = H) were the major products. 

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. 

Ammonium laureth sulfate Ammonium nonoxynol-4 sulfate Ammonium nonoxynol-9 sulfate Buteth-3 carboxylic acid Ceteareth-15 Ceteareth-40 Cetyl esters Cocamine oxide Cocodimethylammonium-3-sulfopropylbetaine Cocoyl sarcosine C9-11 pareth-8 Cl 2-13 pareth-5 Cl 2-13 pareth-7 C12-14 pareth-5 Cl 2-15 pareth-5 C12-15 pareth-9 Cl 2-16 pareth-1 Cl 2-16 pareth-2 Cl 2-16 pareth-3 Cl 2-16 pareth-5 C12-16 pareth-6 Cl 2-16 pareth-7 Cl 2-16 pareth-8 Cl2-16 pareth-11 DEA-lauryl sulfate Decyl diphenyl ether disulfonic acid Diethanolaminooleamide DEA Diisotridecyl adipate Dimethicone copolyol Disodium decyl diphenyl ether disulfonate Disodium tallowiminodipropionate Ditridecyl adipate Dodecyl diphenyl ether disulfonic acid Glyceryl isostearate Glycol stearate Isocetyl stearate lsolaureth-3 lsolaureth-6 lsolaureth-10 Isooctyl oleate Isooctyl stearate Isopropylamine dodecylbenzenesulfonate Isostearyl hydroxyethyl imidazoline Isotridecyl stearate Laureth-3... 

A perfect transformation of an a2 + b2b into an ab2 polycondensation was first reported by a team of DSM NV [78, 79], Bis(2hydroxypropyl)amine reacts rapidly and almost quantitatively with the amino group, so that a bis(hydroxyalkyl) carboxylic acid is formed (see Formula 10.5). The polyesterification at higher temperatures yields a poly(ester amide), which was commercialized under the trademark Hybrane. Another example of an in situ formation of an ab2 monomer was described by Shu et al. [80]. The reaction of 1,4-diaminobenzene with the monoanhydride of a diphenyl ether tetracarboxylic acid (see Formula 10.5) produces an amino dicarboxylic acid which upon further polycondensation yields a hb poly(amide imide). Polycondensations of 4,3, 5 -trifluorodiphenylsulfone with commercial diphenols were studied by the Fossum group [81, 82]. The para C-F bond id particular reactive and substitution of one meta-position lowers the reactivity of the last C-F group. Therefore, variation of the reactions conditions allows for systematic variation of the DB. 

Tile same methodology as mentioned for the preparation of (9) was applied for the synthesis of 8-nitro-l,6-naphthyridines. Heating diethyl N- 3-nitropyridin-4-yl)aminomethylenemalonate (12) in diphenyl ether yields ethyl 8-nitro-l,6-naphthyridin-4(lH)-one 3-carboxylate (13) (63JCS4237, 30%) and acid treatment of 4-( y, y-diethoxypropylamino)-5-nitro-2-(/3,/3 -trifluoroethoxy)-pyridine (14) gives in a similar way 8-nitro-5-(/3, /3-triflu-oroethoxy)-l,2-dihydro-l,6-naphthyridine (15, 76%). Subsequent oxidation with chloranil, acid hydrolysis, and methylation with methyl iodide gives 8-nitro-6-methyl-l,6-naphthyridin-5(6H)-one (16,63%) (81JHC941). 

The smooth intramolecular nucleophilic displacement of biphenyl carboxylic acids leading to benzocoumarins (See Section II.A.) inspired also investigation of the behavior of similar diphenyl ether, diphenyl sulfide and A-methyldiphenyl amine derivatives 458 under similar conditions. However, all these attempts to achieve cyclization to tricyclic compounds 459 were unsuccessful, probably due to the unfavorable stereochemistry for the formation of the required seven-mem-bered transition states and also to the presence of the deactivating bridge groups X (Eq. 42) [68JCS(C)1030]. 

The reaction of 3-aminopyrazine-2-carboxylic acid and EMME at 160-I80°C for 2 hr, or in diphenyl ether at 200°C for 2 hr, afforded 2-pyrazinylaminomethylenemalonate in 60% yield (70T3069 71IJC201) (Scheme 13). 

Raychaudhuri and Basu investigated the formation of side products in the large-scale cyclization of diethyl /V-(3-chlorophenyl)aminomethy-lenemalonate (250) in diphenyl ether (70J1C25). As side products, 7-chloro-1-ethyl-l,4-dihydro-4-oxoquinoline-3-carboxylic acid (551), 7-chloro-4-ethoxyquinoline (552), and 7-chloro-l-ethyl-4(l//)-quinoline (553) could be isolated. These were probably formed from the primarily cyclized product, ethyl 7-chloro-4-hydroxyquinoline-3-carboxylate. The quantities of the side products depended on the reaction temperature during the cyclization, the duration of heating, and the purity of the starting N-(3-chlorophenyl)aminomethylenemalonate (250). 

The cyclization of /V-(6-methyl-2-pyridyl)aminomethylenemalonate (1001, R = Me, R1 = H), labeled on one of the carboxyl groups with l4C, gave labeled 1,8-naphthyridine (1003, R = Me, R1 = H) in boiling diphenyl ether and labeled pyrido[l,2-a]pyrimidine (1002, R = Me, R1 = H) in a mixture of phosphoryl chloride and polyphosphoric acid in 77% and 85% yields, respectively (73MI2 75MI2). 

Regioselective cyclization of /V-(4-benzoyl-5-benzimidazolyl)amino-methylenemalonates (969, R = H, Me) was observed. When the cyclization was carried out in polyphosphoric acid, then 4-phenylimidazo-[4,5-/]quinoline-5-carboxylates (970) were obtained, while the thermal cyclization in diphenyl ether at 200°C, or the cyclization in a mixture of phosphoryl chloride and polyphosphoric acid afforded 4-benzoyl-8-hydroxyimidazo[5,4-g]quinoline-7-carboxylates (971) (89KFZ692). 

Heating diethyl (l-isoquinolylamino)methylenemalonates in diphenyl ether gave ethyl 4-oxo-4//-pyrimido[2,l-a]isoquinoline-3-carboxylates (97) (78USP4127720). Cyclization of diethyl[(4-amino-l-isoquinolyl)amino] methylenemalonate in a mixture of acetic anhydride and pyridine in methylene chloride at ambient temperature afforded ethyl 7-acetylamino-4-oxo-4//-pyrimido[2,l-a]isoquinoline-3-carboxylate [84JAP(K)84/172472]. The 7-nitro derivative was prepared similarly. Cyclization of diethyl [(7-methoxy-3-methyl-l-isoquinolyl)amino]methylenemalonate in polyphos-phoric acid at 130°C for 6 h gave 10-methoxy-6-methyl-4//-pyrimido[2,l-a]isoquinolin-4-one in 29% yield [94IJC(B)795]. 

Arene(tricarbonyl)chromium complexes, 19 Nickel boride, 197 to trans-alkenes Chromium(II) sulfate, 84 of anhydrides to lactones Tetrachlorotris[bis(l,4-diphenyl-phosphine)butane]diruthenium, 288 of aromatic rings Palladium catalysts, 230 Raney nickel, 265 Sodium borohydride-1,3-Dicyano-benzene, 279 of aryl halides to arenes Palladium on carbon, 230 of benzyl ethers to alcohols Palladium catalysts, 230 of carboxylic acids to aldehydes Vilsmeier reagent, 341 of epoxides to alcohols Samarium(II) iodide, 270 Sodium hydride-Sodium /-amyloxide-Nickel(II) chloride, 281 Sodium hydride-Sodium /-amyloxide-Zinc chloride, 281 of esters to alcohols Sodium borohydride, 278 of imines and related compounds Arene(tricarbonyl)chromium complexes, 19... 

The best catalyst precursors are Ru(methallyl)2( l,4-bis(diphenylphosphino)bu-tane) (A) and Ru(methallyl)2(dppe) (B), where dppe is l,2-bis(diphenyl-phosphino)ethane, the choice of the appropriate complex depending on the steric demand of both the alkyne and the carboxylic acid. A large variety of carboxylic acids and alkynes have been used, including AT-protected amino acids, a-hydroxy acids and functionalized alkynes such as enynes and propargylic ethers (Table 1) [20,21]. 

Ptsi Fe49 Pt(acac)2, Fe(CO)5 diphenyl ether, hexadecyl amine 1-adamantane- carboxylic acid 260 6 87... 

Phenazine-1,6-dicarboxylic acid (1) is a precursor for microbiological transformation to phenazine-6-carboxylic acid. " - Decarboxylation of phenazine-l,6-dicarboxylic acid (1) in refluxing diphenyl ether affords a mixture of phenazine (2 yield 33%) and phenazine-l-car-boxylic acid (3 yield 25% mp 242-243... 

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