Bis-aminophenolate

A facile synthesis of the bis-fused oxadiazepines 302 by condensation of the bis-aminophenols 301 with ethanedial has been reported by Ochoa and co-workers yields however were only modest [01T55]. 

A-terf-BUTYL ortho - AMIN OPHENOL, ortfio-IMINOQUINONE, AND A ZIRCONIUM(IY) BIS(AMINOPHENOLATE) COMPLEX... 

Bis(benZoxaZol-2-yl) Derivatives. Bis(benzoxazol-2-yl) derivatives (8) (Table 3) aie prepared in most cases by treatment of dicaiboxyhc acid derivatives of the central nucleus, eg, stilbene-4,4Cdicarboxyhc acid, naphthalene-l,4-dicarboxyhc acid, thiophene-2,5-dicarboxyhc acid, etc, with 2 moles of an appropriately substituted o-aminophenol, followed by a ring-closure reaction. These compounds are suitable for the brightening of plastics and synthetic fibers. 

The low condensation of diacyl chloride and bis-orf/zo-aminophenol gave a polyhydroxy amide that was submitted to a thermal dehydration.185 187 The two functions of an aminophenol could be acylated, and the question of chemose-lective acylation has been discussed.188 The problem is not O-acylation versus N-acylation because the N-acylated product is tire more stable isomer, but the question is how to control N-monoacylation versus diacylation that could reduce the molecular weight. It has been shown that the condensation in the presence of inorganic salt (LiCl) in NMP gives selectively the N-monoacylated... 

Substitution of two chlorines in (l,2-benzenedioxy)trichlorophosphorane by N,0 bis(trimethylsilyl)amino acids gives 34 (X = Cl) further substitution of chlorine by phenol gives 34 (X = OPh) (Scheme 22) <1998S855>. The reaction of P(NMe2)3 with 2-aminophenols generates aminophosphoranes 33 (R = H, Buc) (Equation 20) <2000HAC11>. 

Mamyama et al.25 have obtained high-molecular-weight poly(benzoxazole)s by the low-temperature solution polycondensation of A,A 0,0 -tetrais(trimethyl-silyl)-substituted 2,2-bis(3-amino-4-hydroxyphenyl)-l,l,l,3,3,3-hexafluoro-propane (25) with aromatic diacids and subsequent thermal cyclodehydration of the resulting poly(o-hydroxy amide)s in vacuo. In this method, aromatic diamines with low nucleophilicity are activated more positively through the conversion to the /V-silylated diamines, and the nucleophilicity of the fluorine-containing bis(o-aminophenol) can be improved by silylation. 

Aminophenol Bis(2-ethylhexyl)phosphate Silicone/cellulose Citric buffer pH 3.8 12... 

The synthesis of the bis(amino) aryl ether ketimine oligomer was carried out in an analogous fashion to the poly(aryl ether) oligomers described before (Scheme 5) [43]. The ketimine functional 4,4 -bisfluoride was reacted with hyd-roquinone and 3-aminophenol in an NMP/toluene solvent mixture in the presence of potassium carbonate. The characteristics of the oHgomer synthesized are shown in Table 1 (sample le). 

Eichhom and his co-workers have thoroughly studied the kinetics of the formation and hydrolysis of polydentate Schiff bases in the presence of various cations (9, 10, 25). The reactions are complicated by a factor not found in the absence of metal ions, i.e, the formation of metal chelate complexes stabilizes the Schiff bases thermodynamically but this factor is determined by, and varies with, the central metal ion involved. In the case of bis(2-thiophenyl)-ethylenediamine, both copper (II) and nickel(II) catalyze the hydrolytic decomposition via complex formation. The nickel (I I) is the more effective catalyst from the viewpoint of the actual rate constants. However, it requires an activation energy cf 12.5 kcal., while the corresponding reaction in the copper(II) case requires only 11.3 kcal. The values for the entropies of activation were found to be —30.0 e.u. for the nickel(II) system and — 34.7 e.u. for the copper(II) system. Studies of the rate of formation of the Schiff bases and their metal complexes (25) showed that prior coordination of one of the reactants slowed down the rate of formation of the Schiff base when the other reactant was added. Although copper (more than nickel) favored the production of the Schiff bases from the viewpoint of the thermodynamics of the overall reaction, the formation reactions were slower with copper than with nickel. The rate of hydrolysis of Schiff bases with or/Zw-aminophenols is so fast that the corresponding metal complexes cannot be isolated from solutions containing water (4). 

Poly(arylene ether benzoxazole)s were also synthesized from the reaction of bis[(4-hydroxyphenyl)benzoxazole]s and activated aromatic difluoro monomers as shown in Eq. (7) [28,29]. The bis[(4-hydroxyphenyl)benzoxazole]s were readily prepared by condensation of the appropriate bis(o-aminophenol) (e.g. 3,3 -dihydroxy-4,4 -diaminobiphenyl) with phenyl-4-hydroxybenzoate in diphenyl sulfone at 260°C. Under proper conditions, the less expensive 4-hydroxybenzoic acid can be used in place of the phenyl ester to provide high yields of the desired bis[(4-hydroxyphenyl)benzoxazole]s. As presented in Table 9, the hexafluoroisopropylidene (6F) containing polymers were amorphous. These polymers were prepared in DMAc. However, the polymers derived from 6,6 -bis[2-(4-hydroxyphenyl)benzoxazole] were prepared in diphenyl sul-... 

The nitro groups in 3,5-dinitrodiaryl ethers may be readily replaced with the residues of mono-and bis-phenols. The simplest 3,5-dinitrodiaryl ether - 3,5-dinitrodiphenyl ether - was reacted with 4-aminophenol or 4-acetamidophenol with the formation of 3-nitro-5-[4-amino(amido)]-phenoxydiphenyl ether subsequent transformation of this product led to 3-amino-5-(4-aminophenoxy)-diphenyl ether [24] (Scheme 4.9). 

Tsunoda et al. (73BCJ3499) have reported a novel reverse Smiles rearrangement of N,N- bis-(l,3,5-triazinyl)-2-aminophenols (Scheme 25). 2,4,6-Tris(l-aziridinyl)-l,3,5-triazine is rearranged by acid into the tetracyclic compound (40 equation 16) (55JA5922). 

In a closely related publication, carboxylic acids were employed instead of acid chlorides in a microwave-assisted direct synthesis of 2-substituted benzoxazoles [79]. The reactions with 2-aminophenol were performed in a household microwave oven and worked well with aromatic, heteroaromatic, aj/i-unsalurated and arylalkyl carboxylic acids (35-82% yields). Phthalic acid formed only mono-benzoxazoles, while the use of succinic acid led to a mixture of mono- and bis-benzoxazoles. Phthalic and succinic anhydrides could... 

Furthermore, we have extended the high-pressure polycondensation to the synthesis of condensation polymers other than polyimides. A successful example was the high-pressure synthesis of polybenzoxazoles starting from the bis-o-aminophenol (or its hydrochloride) and aliphatic dinitriles (Eq. 8) [35]. The polycondensation readily proceeded under high pressure in a closed reaction vessel with the elimination of the by-product of ammonia (or ammonium chloride). 

The tautomeric equilibrium between phenolic Schiff s bases and 2,3-dihydrobenzoxazoles is discussed in Section 4.18.2.5.2. An authentic 2,3-dihydrobenzoxazole, the 2,2-bis(trifluoromethyl) derivative, is obtained by the action of the dithietane (305) on o-aminophenol (equation 164) (74BCJ785). 

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