Aminodiphenyl ethers

Other functional groups may be present during reduction. Aromatic amino ethers are prepared by the same general procedures described above, e.g., 772-aminoanisole (80%) and 2-aminodiphenyl ether (94%). The reduction of o-nitrobenzaldehyde to the sensitive o-aminobenzaldehyde is successfully accomplished by the action of ferrous sulfate and ammonia (75%). m-Dimethylaminobenzaldehyde is formed by reduction of the nitro acetal in aqueous solution with sodium sulfide followed by methyla-tion (74% over-all) or by catalytic reduction of m-nitrobenzaldehyde in... 

When the method described in Section III.l is a Iied to either 2-aminodiphenyl ether (53.10, X - O) or thio ether (53.10, X = S), a new oxazepine or thiazepine ring is formed. 

Dinitrodiphenyl ether (94) was electrolytically reduced in a single wave with an uptake of eight electrons per molecule, giving rise to the bishydroxylamino intermediate (95), which underwent an intramolecular disproportionation. The resulting 2-nitroso-2 -aminodiphenyl ether (%) underwent a chemical follow-up reaction leading to dibenzo[/>/)-l,4,5-oxadiazepine (97) and phenazine (98) via two steps as shown in Scheme 16 <83CCC379>. 

The effectiveness of the antimicrobial activity can be enhanced by combining zinc citrate with triclosan [22-24]. Triclosan, or 2,4,4 -trichloro-2-hydroxy diphenyl ether, is an aromatic, trichlorinated synthetic componnd. It can be obtained by reaction of 2,4-dichlorophenol with 2,5-dichloronitrobenzene in the presence of alkali and reduction of the 2,4,4 -trichloro-2 -nitrodiphenyl ether into 2,4,4 -trichloro-2 -aminodiphenyl ether. This is diazotized with sodium nitrite with excess sulfnric acid. After hydrolization, 2,4,4 -trichloro-2 -hydroxydiphenyl ether is extracted with xylene and purified [20-25]. 

Dichloroallyl mercaptan, see Diallate 2,4 -Dichloro-4 -aminodiphenyl ether, see Nitrofen Dichloroaniline, see Iprodione... 

Photolytic. The UV photolysis (7, = 300 nm) of bifenox in various solvents was studied by Ruzo et al. (1980). In water, 2,4-dichloro-3 -(carboxymethyl)-4 -hydroxydiphenyl ether and 2,4-di-chloro-3 -(carboxymethyl)-4 -aminodiphenyl ether were identifled. In cyclohexane, 2,4-dichloro-4 -nitrodiphenyl ether and methyl formate were the major products. In methanol, a dichloro-methoxy phenol was identified. Photodegradation occurred via reductive dechlorination, de-carboxymethylation, nitro group reduction, and cleavage of the ether linkage (Ruzo et al., 1980). 

CASRN 1836-75-5 molecular formula C13H7F3N2O5 FW 284.10 Chemical/Physical. When nitrofen as an aqueous suspension was irradiated using UV light (A. = 300 nm), 2,4 -dichloro-4 -aminodiphenyl ether formed as the major products (>80% of total product formation). In addition, 4-nitrophenol and 2,4-dichlorophenol formed as minor products (<10%). In cyclohexanone, the major photooxidation product was aminonitrofen (Ruzo et al., 1980). 

Methyldiphenyl Ether from 4-Methyl-4 -aminodiphenyl Ether. 297... 

A solution of 19.9 g. (0.1 mole) of 4-methyl-4 -aminodiphenyl ether in 50 cc. of concentrated hydrochloric acid, 50 cc. of glacial acetic add, and 200 cc. of water is chilled in ice and diazotized in the usual manner with 7 g. of sodium nitrite dissolved in a little water. A solution of 100 g. of commercial sodium hydroxide in 600 cc. of water is then prepared and placed with 500 g. of ice in a 5-1. flask fitted with a mechanical stirrer. 

Bromo-aryl ether 46 (Scheme 18), on treatment with one equivalent of sodium amide in boiling benzene, underwent rearrangement into 47 in 92% yield. The presence of an N-alkyl substituent on the anihne nitrogen atom was essential for the rearrangement. Flowever, 46 heated with potassium carbonate in dimethylformamide afforded 2-chloro-lO-(3-dimethylaminopropyl)phenoxazine 48 in 90% yield [33]. It was later proved [34] that the cyclization of 46 into 48 involves the rearrangement via 47. Rearrangements of orfho-aminodiphenyl ethers have been reviewed [35]. 

Quinamines having no substituents at the para-position of the aniline ring gave 4-aminodiphenyl ethers 77 as the principal products in almost quantitative yields. The behavior of quinamines 76 and their geometric features as well as the kinetic characteristics of the reaction make this transformation very similar to the well-known benzidine rearrangement (Section III.B.l). Like the latter, the mechanism of the quinamine rearrangement involves a transition state that resembles a sandwich of two rings (jr-complex)129. 

In NMP, 0,85 mol 2-chloro-p-phenylenediamine, and 0.15 mol 4,4 -di-aminodiphenyl ether are dissolved. 0.985 mol 2-chloroterephthaloyl chloride is added. After 2 hours, the polymerization is complete. The mixture is then neutralized with lithium hydroxide. The polymer solution is filtered and cast onto an endless belt. The solvent is evaporated at 160°C. A... 

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