Aniline moiety

Aromatic Amines and Phenols. The discovery that sulfaguanidine [57-67-0] was goitrogenic to rats was serendipitous. Many related compounds were then examined, and the aniline moiety was usually present (2,6). Such compounds, as well as resorcinol-like phenols, may act as goitrogens by inhibiting thyroid peroxidases. These are not used clinically. 

The current methodology to determine residues of alachlor, acetochlor, propachlor, and butachlor in crops and animal products was developed over the last two decades by researchers at the Monsanto Company. These herbicides degrade rapidly in plants and animals to numerous metabolites that can be hydrolyzed to common aniline moieties. Little to no parent herbicide is found as intact residue in crops and animal products therefore, the residue methodology focuses on the determination of the common moieties that are derived from the parent herbicides and their metabolites. Initially, gas chromatography (GC) with flame ionization detection, nitrogen-phosphorus... 

Residues of alachlor and acetochlor are determined by similar methods involving extraction, hydrolysis to the common aniline moieties, and separation and quantitation by reversed-phase FIPLC with electrochemical detection. The analytical method for acetochlor is included as a representative method for residue determination of alachlor and acetochlor in plant and animal commodities. Propachlor and butachlor residues, both parent and metabolite, are determined by similar analytical methods involving extraction, hydrolysis to common aniline moieties, and separation and quantitation by capillary GC. The analytical method for propachlor is included as a representative method. The details of the analytical methods for acetochlor and propachlor are presented in Sections 4 and 5, respectively. Confirmation of the residue in a crop or... 

Stepwise addition of the aniline moieties in analogy to Scheme 7 (Route A) allows the preparation of asymmetrically substituted derivatives.55,56 The use of pyridine-3,4-dicarboxylic acid anhydride similarly results in the formation of mixtures of 5- and 6-azaphthalides.57 Quinoline-2,3-dicarbo-xylic anhydride has also been converted into the corresponding azaphthal-ides in a similar manner.58 Pyrazine-2,3-dicarboxylic acid anhydride yields... 

Li s group prepared a series of substituted 2-(hydroxyalkyl)tetrahydroquinohne derivatives 2-619 and 2-620 starting from anilines 2-617 and cyclic enol ethers 2-618 in the presence of catalytic amounts of InCl3 (Scheme 2.141) [322], Good yields of 73-90 % were obtained with an electron-donating or no substituent R at the aniline moiety. 

N substituent chemical shifts (SCS) of a variety of anticonvulsant phenylacetanilides 1 and 2, with a substituent at the para or meta position of the aniline moiety, were analysed by means of DSP (dual substituent parameter) equations33. 

Plant. Degrades to a demethylated intermediate which subsequently is degraded to the aniline moiety (possibly 3-trifluoromethylaniline) (Hartley and Kidd, 1987 Humburg et al, 1989). Duke et al. (1991) reported that fluometuron degrades in plants via the following degradative pathway fluometuron to TV-methyl-A -(3-(trifluoromethyl) phenyl) urea which undergoes demethylation to... 

The antibacterial agent sulfamethoxazole produced chlorinated and nonchlorinated DBFs when reacted with chlorine [91]. A ring-chlorinated product was formed via halogenation of the aniline moiety at sub-stoichiometiic concentrations of chlorine. 3-Amino-5-methylisoxazole, sulfate, and A-chloro-p-benzoquinone imine were formed via rupture of the sulfamethoxazole sulfonamide moiety at stoichiometric excess of chlorine. 

Neighboring groups at the ortho position of the aniline moiety can bring about side reactions that would compete with the photo-Fries rearrangement [100,101], (Some examples are shown in Scheme 39.)... 

Portoghese and coworkers also considered other naltrindole derivatives substituted in position 6 or 7 with aryl, benzyl or aniline moieties to evaluate the effect of flexible aryl groups on selectivity, but obtained non-selective compounds only. This result demonstrates that the conformational flexibility of these aryl groups causes them to reside preferentially in regions of space that are not accepted by the 8 opioid receptor (Portoghese et al., 1994). A more rigid compound however, 7-benzylidene-naltrindole (BNTX) proved to be a potent and highly... 

The monoazo and disazo pigments contain one or more chromophoric groups usually referred to as the azo -fN=N> group. However, it has been shown by x-ray diffraction analysis and nuclear magnetic resonance (nmr) techniques that azo pigments exist in the hydrazone rather than the azo tautomeric form. The hydrazone form, which has three intramolecular hydrogen bonds, renders the molecule planar (with the exception of the aniline moiety) which is a stabilizing influence. 

Aminoenone (87), when heated with phosphoryl chloride, cyclizes to 2-(trif uoro-methyl)quinoline, rather than the expected 4-isomer.126 A series of crossover experiments using different perfluoroalkyl and aniline moieties suggest an amine exchange process. A 1,3-diaminoallyl cation (88), i.e. a vinylogous formidinimn salt, is proposed to act as turntable in the process. 

Fig. 4.69. Reaction scheme for the formation of DNS derivatives of carbamate and urea herbicides (example, Linuron). 1 = Hydrolysis 2 dansylation of the aniline moiety.

For HPLC analysis the hexane extract containing the aniline moieties of the herbicides is evaporated to dryness. The residue is dissolved in 1 ml of acetone and then treated with 0.2 ml of DNS-C1 in acetone (0.1%) and with ca. 1 mg of solid sodium carbonate. 

A series Pd-catalyzed annulation reactions have been developed by the reaction of o-heterosubstituted iodoarenes 68 and 69 with 1,2-, 1,3- and 1,4-dienes. In the reaction of o-iodoaniline with 1,3-cyclohexadiene (70), the 7i-allyl intermediate 71 reacts with the aniline moiety to give 72 [32, 33]. Carboannulation of the malonate derivative 73 with the 1,3-diene 74 gives 75 in high yield [33a]. 

The similarities in the influences of the different parameters in the two subseries suggested that the optimum compound for development should still contain the p-Cl-aniline moiety, so that diflubenzuron was ultimately selected as the final benzoylphenyl urea derivative to be developed as a new selective insecticide. 

Catalytic hydrogenation of the nitro group of 21 with Raney nickel under hydrogen atmosphere followed by catalyst removal and recrystallization from methanol-water then furnished aniline 22 and set the stage for the ultimate installation of costly biphenyl-2-carbonyl chloride. Selective acylation of the aniline moiety of 22 was readily achieved by treatment with biphenyl-2-carbonyl chloride in a refluxing mixture of pyridine and acetonitrile. Subsequent addition of a solution of hydrogen chloride in ethyl acetate to the cooled reaction mixture resulted in the precipitation of conivaptan HCl (1), which was isolated in 74% yield. 

Fisons PLC (UK) also had an early interest in the PPI area. Apparently, by having an early understanding of the chemical mechanism for the acid rearrangement reaction, they devised two novel ideas (a) to exchange the pyridine in omeprazole for an N-alkyl- and N,N-dialkyl-substituted aniline moiety and (b) to exchange the methylene as a connecting chain for a phenylene unit. At least one compound of this latter type, FPL 65372 [28] was quite active in early human testing, but no compound of this type ever reached the market (Fig. 2.14). 

Compared to the preceding statements, the addition of the lithium enolate of menthyl acetate to p-substituted phenylaldimines is of significant value, since it furnishes /3-amino acids in good yields and with diastereomeric ratios up to 94%. Using 1.2 equivalent of LDA to generate the enolate led to unparalleled diastereoselectivities when increasing the Hammett p constant values of the 4-substituents of the aniline moieties. Alternatively, in the case of a methoxy substituent, a spectacular d.r. enhancement has been obtained when using 3 equivalents of LDA, probably as a consequence of the formation of a more selective new binary LDA-enolate complex (Scheme 114)562. 

By reaction of secondary V-arylketoenamines in the aminocyclopentenone series and quinones, the cyclopent[Z ]indole skeleton and dibenzo[6,d]cyclopent[/]azepines are accessible. The reaction involves an oxidative cyclization of the Michael adduct by attack of either the nucleophilic nitrogen atom or of the aromatic o-position of the aniline moiety on the quinone317 (equation 235). 

The aminopyrazole derivative (31) is indicated72 by H NMR and infrared spectroscopies to have two intramolecular hydrogen bonds the first with the nitro group on the aniline moiety, and the second with the C=0 group of the ester on the pyrazole ring, as depicted in the structure 31. 

The N—H N hydrogen bond is responsible for the formation of the complexes between aniline and aliphatic amines (ammonia, methylamine, dimethylamine and tri-methylamine) which act as proton acceptors. Infrared photodissociation spectra and DFT calculation indicate208 that the clusters [aniline/ammonia]+ and [aniline/methylamine]+ have a non proton transferred (without the proton donation from the aniline moiety to the amine molecule) structure, while the complexes [aniline/dimethylamine]+, [aniline/ trimethylamine]+ possess a proton transferred structure. Reasonably, the proton transfer increases on increasing the proton affinity of the amine used as solvent. 

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