4.4 -diaminodiphenyl oxide

The new method of Yoneda s group132 is also a one-pot diazotization-fluoro-de-diazoniation in a liquid-liquid two-phase mixture of pyridine and hydrogen fluoride. Yields for 25 aromatic amines and diamines are 50-100%, except for 2-and 3-fluorobenzoic acid, the three nitroanilines, 3- and 4-diaminobenzene and 4,4 -diaminodiphenyl-oxide (10-50%). In their 1994 paper the authors demonstrate that, in the same system, the photochemical decomposition gives in many cases significantly higher yields than the thermal reaction. The most spectacular increase in yield was found for the fluorination of 2-fluoroaniline where o-difluorobenzene was obtained photochemically in 80.2% yield, but thermally only in 0.6% ... 

Aminophenyl Ether (4,4-Oxydianiline, 4,4-Diaminodiphenyl Oxide, N-Phenylbenzeneamine)... 

SYNS p-AMINOPHENYL ETHER 4-AMINOPHENYL ETHER BIS(p-AMINOPHENYL)ETHER BIS(4-AMINOPHENYL)ETHER DADPE 4,4 -DIAMINO-BIPHENYLOXIDE DIAMINODIPHENYL ETHER p,p -DIAMINODIPHENYL ETHER 4,4-DIAMINODI-PHENYL ETHER 4,4 -DIAMINODIPHENYL OXIDE 4,4 -DIAMINOPHENYL ETHER NCI-C50146 OXYBIS(4-AMINOBENZENE) p,p -OXYBIS(ANILINE)... 

Another group of polymers with good heat resistance includes certain aryl-alicyclic compounds. They are generated from the polycondensation of 4,4 -diaminodiphenyl oxide with various anhydrides such as tricyclo[4,2,2,0 ]dec-9-ene-3,4,7,8-tetracarboxylic acid anhydride, 9-oxatricyclo[4.2,2,0 ]nonane-3.4,7,8-tetracarboxylic acid anhydride, cyclobutene-1,2,3,4-tetracarboxylic acid anhydride, and bicyclo[2,2,2]octane-23,5,6-tetracarboxylic acid anhydride. Thermal stability of these polymers is affected by the ring stability (strain) regardless the true chemical structure. Pyrolysis at 650° C generates some compounds that are the same in nature and some others that are characteristic for each polymer. The main decomposition paths, as indicated by the main pyrolysis products are shown below for each polymer (Ar = 4,4 -diphenylene oxide) ... 

Thus, the interaction of dioxo- and dithio-bis(naphthalic anhydrides) with 4,4 -diaminodiphenyl oxide, as shown in Scheme 39 [97, 98] resulted in poly-naphthylimides with ether and thioether groups, which were soluble in phenolic solvents. Reactions were carried out in m-cresol at 10% concentration using quinoline or iso-quinoline as catalyst. 

Polynaphthylimides having free carboxylic groups were prepared by the interaction of l,l-bisnaphthyl-4,4, 5,5, 8,8 -hexacarboxylic acid dianhydride with 4,4 -diaminodiphenyl oxide and benzimidazole-containing aromatic diamines [159-161]... 

This polymer showed solubility only in m-cresol and melted without decomposition. In the synthesis of copolymers, m-phenylenediamine or 4,4"-diaminodiphenyl oxide were added (Scheme 1.7). 

When studying the reaction of l,4-bis(l,8-dicarboxynaphthoyl-4)-benzene dianhydride with 4,4"-diaminodiphenyl oxide, it was established that, depending on the viscosity of the... 

On the basis of the observation that the polymers derived from 4,4 -diaminodiphenyl oxide and 4,4 -diaminodiphenylmethane formed friable films, in contrast to a polymer based on 3,3-dimethylbenzidine, Sek and co-workers arrived at a controversial conclusion that the ortho substituents exert a stronger effect on the polymer flexibility than the bridging bonds between the phenylene nuclei [75]. 

With the very active W-6 or W-7 Raney Ni (alkaline), desulfurization occurs before ring fission and /V-mclhylanilinc is the only product, while with less active W-5 and degassed W-7 Raney Ni in the presence of alkali, ring fission takes place to some extent before desulfurization, which may lead to o-aminothiophenol (isolated in its oxidized form, 2,2 -diaminodiphenyl disulfide) and aniline, probably via the formyl derivative as the intermediate as shown in Scheme 13.13.148... 

When both benzene rings are amino-substituted in the ortho positions, phenazines are easily formed in good yield with the elimination of an ortho group. Reaction of 2,2 -diaminodiphenyl-amines 3 with iron(III) chloride in dilute hydrochloric acid affords initially, by a cyclization reaction with concomitant elimination of ammonia, dihydrophenazines which undergo rapid oxidation in air to the corresponding phenazines 4 in almost quantitative yields. 

Diaminodiphenyl disulfide, when treated with peroxysulfuric acid, is oxidized to o-aniiinesulfonic acid in 80% yield (equation 588) [187. ... 

Adenosine triphosphate, when oxidized to its dialdehyde with periodate and condensed with Sepharose-adipic (or sebacic) acid hydrazide, has been used to isolate poly(A) polymerase, and also myosin and its fragments from different sources. A poly(A)-linked resin has been prepared by condensing 4,4 -diaminodiphenyl-methane with periodate-oxidized starch, reducing the resulting Schiff bases with borohydride, diazotizing, and then coupling with the polynucleotide. The resulting material may be used to isolate poly(U) sequences. 

As almost all foreign compounds are distributed via the bloodstream, the components of the blood are exposed at least initially to significant concentrations of toxic compounds. Damage to and destruction of the blood cells results in a variety of sequelae such as a reduced ability to carry oxygen to the tissues if red blood cells are destroyed. Aromatic amines such as aniline and the drug dapsone (4,4-diaminodiphenyl sulphone) are metabolized to hydroxylamines, and in the latter case the metabolite is concentrated in red blood cells. Also, nitro compounds such as nitrobenzene, which can be reduced to hydroxylamines, are similarly toxic to red blood cells. These hydroxylamines are often unstable and can be further oxidized to reactive products, in the presence of oxygen in the... 

DIAMINODIPHENYL or p-DIAMINODIPHENYL (92-87-5) Combustible solid. Reacts violently with strong oxidizers. Contact with red fuming nitric acid may cause fire. Incompatible with aldehydes, nonoxidizing mineral acids, cellulose nitrate (of high surface area), sulfuric acid, organic anhydrides, isocyanates, nitrates. Oxidizes in air and light crystals become dark. 

Starting from 4,4 -diaminodiphenyl ether oxide and various dianhydrides of oxyarylene-and thioarylene-bisfnaphthalic acids), PNI of the general formula shown in Figure 1.16 were synthesised [21,70]. The polycondensation reaction proceeded under homogeneous conditions in m-cresol using quinoline or isoquinoline as the catalysts. PNI formed solutions in w-cresol up to a concentration of 15%. 

The most important representative of cyclic iodonium salts, the dibenziodolium or diphenyleneiodonium (DPI) cation 238, known in the form of iodide, chloride, hydrosulfate, hexafluorophosphate, or tetrafluoroborate salts, can be obtained by three different procedures (A, B and C) summarized in Scheme 2.71. Method A, originally developed by Mascarelli and Benati in 1909 [355], uses 2,2 -diaminodiphenyl (235) as the starting material, which upon diazotization with sodium nitrite in a hydrochloric acid solution followed by potassium iodide addition, gives DPI 238 as iodide salt. A similar reaction starting from 2-amino-2 -iododiphenyl 236 affords DPI as hexafluorophosphate or tetrafluoroborate in excellent yields (Method B) [356]. The third method involves the peracetic oxidation of 2-iodobiphenyl (237) to an iodine(III) intermediate that then cyclizes in acidic solution (Method C) [357]. More recently, these methods were used to prepare the tritium labeled DPI and of its 4-nitro derivative [358]. 

Ammonium molybdophosphate on filter paper 2,4 -Diaminodiphenyl hydrochloride in HCI 8-Quinolinol (oxide) soln in ethanol... 

Synthesis chemical oxidation of aniline and 4,4 -diaminodiphenyl sulfone mixture by K2S2O8 in acid media [724] or by electropolymerization [725]. 

The object of the study was a micro-heteropneous polyurethane urea (PUU) based on the prepolymer SKU-PFL-100 (M 1.4 x 10 ), synthesized by the interaction of oli-gotetramethylene oxide diol (M 1 x 10 ) with a double excess of 2,4-toluene diisocyanate. MOCA (aromatic diamine 3,3 -dichloro-4,4 -diaminodiphenyl methane) was used to cme SKU-PFL-100. The NCO/NH2 ratio was 1.2 for this reaction. Piepolymer was degassed at 50 + 10 °C before the reaction. Reaction mixture was stirred for 3 minutes at 50 + 1 °C and a residnal pressure of 1-2 kPa after injection of melted aromatic diamine. Cnring period was 3 days at 80 2 °C. Cured samples were further stored at the room temperature for at least 30 days. 

The few properties listed in this table illustrate the main advantage of these aromatic polyimides, namely an outstanding thermostability combined with low sensitivity to oxidation. These properties come close to the limits of soluble organic polymers. Probably the most widely used representative of this class of polyimides is poly(4,4 -diaminodiphenyl ether pyrromellitimide), which was... 

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