Amino arylation

Ketones C=0 continued) o-Amino-aryl or o-hydroxy-aryl ketones 1655-1635 Low because of intramolecular H bonding. 

The wide variety of ketomethylene and amino ketone monomers that could be synthesized, and the abiUty of the quinoline-forming reaction to generate high molar mass polymers under relatively mild conditions, allow the synthesis of a series of polyquinolines with a wide stmctural variety. Thus polyquinolines with a range of chain stiffness from a semirigid chain to rod-like macromolecules have been synthesized. Polyquinolines are most often prepared by solution polymerization of bis(i9-amino aryl ketone) and bis (ketomethylene) monomers, where R = H or C H, in y -cresol with di-y -cresyl phosphate at 135—140°C for a period of 24—48 h (92). 

Amino(aryl)carbene complexes prefer cyclopentannulation over benzannulation. Amino(alkenyl)carbene complexes may react in a benzannulation reaction. 

The superior donor properties of amino groups over alkoxy substituents causes a higher electron density at the metal centre resulting in an increased M-CO bond strength in aminocarbene complexes. Therefore, the primary decarbo-nylation step requires harsher conditions moreover, the CO insertion generating the ketene intermediate cannot compete successfully with a direct electro-cyclisation of the alkyne insertion product, as shown in Scheme 9 for the formation of indenes. Due to that experience amino(aryl)carbene complexes are prone to undergo cyclopentannulation. If, however, the donor capacity of the aminocarbene ligand is reduced by N-acylation, benzannulation becomes feasible [22]. 

Der. 134f.( 258-261, 366ff., 479 182, 488, 523 2-AthyI-1-[l-dimethylamino-propyI-(2)]- 259 2-Athyl-l-phenyl- 258 2-AIkyl-1,2-diphenyl- 259 2-Alkyliden-l-acyl- 261 (Amino-aryl)- 489 2-(3-Amino-propyl)-l-benzoyI-... 

Testing the limits of carbene stabilization by substituents, Bertrand and coworkers reported the synthesis and analysis of (amino)(aryl)carbenes where only one substituent can contribute to the stability of the carbene center. Carbene 30 was designed to have the amino substituent as a jr-donor and the 2,6-bis(trifluoromethyl)... 

Xu, B. and Huang, K., 1995. Role of a-amino aryl phosphorated organic depressant in flotation of high nickel matte. Nonferrous Metals, 1(47) 21-23 (in Chinese)... 

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). 

Several unique synthetic strategies for bidentate(amino)(oxy)- and (amino)(aryl) carbenes have been described (Scheme 10). For the former, the reaction of the amino(phosphino)carbene with an ort/io-quinone leads to the transient formation of a zwitterionic species featuring both a phosphonio nucleofuge and an aryloxide nucleophile that allow for a subsequent intramolecular substitution process. The... 

Auch Amino-acetonitril selbst (Rl = H) bzw. 2-Amino-alkansaure-nitrile sowie Amino-aryl-acetonitrile (R1 = Alkyl, Aryl) konnen eingesetzt werden196,197. 

Die cyclischen N-(2-Amino-aryl)-dicarbonsaure-imide kondensieren in einer Aza-Wittig-Reak-tion mit Dibrom-triphenyl-phosphoran83 oder Dibrom-trimethoxy-phosphoran60 zu polycy-clischen Benzimidazolen z.B.83 ... 

Vielfach lassen sich auch (Nitro-aryl)-l,2,4-oxadiazole mit Natriumsulfld in waCrigem 1,4-Dioxan bei 80° in oft guter Ausbeute zu (Amino-aryl)-l,2,4-oxadiazolen reduzieren277 z.B. ... 

Zur Synthese von 2-(Amino-aryl)-l, 3,4-oxadiazolen ist deshalb der Weg fiber die Cycli-sierung von (Nitro-aroyl)-hydrazinen mit Orthocarbonsaure-triestern und die anschlieBende Reduktion der Nitro-Gruppe zu beschreiten286. Auch bei phenolischen Substituenten ist eine partielle Kondensation der Hydroxy-Gruppe mit dem Orthocarbonsaure-triester moglich, wenn durch Nitro-Gruppen deren Reaktivitat erhoht wird, wie es ftir 4-Nitro-salicylsaure-hydrazid zutrifft286. 

C in THF, which cleanly led to the formation of (amino)(aryl)carbene Xllla (Scheme 8.8). ° A NMR signal at 8 = 314.2 ppm leaves no doubt of the formation of Xllla. Carbene Xllla is stable for days in solution at —50 °C but undergoes a C—H insertion reaction at room temperature within a few hours, giving rise to the 4,6-di-ferf-butyl-l,l-dimethyl-3-(methyl-rcrt-butylamino)mdane as the major product. It is interesting to note that this reaction, typical of transient singlet and triplet carbenes, has never been observed for diamino carbenes. This striking difference demonstrates the less perturbed character of carbene Xllla. 

O-acylation, O-sulfanylation, O-triflation/Suzuki coupling followed by N-quaternization (six inputs) and Hofmann elimination to release a 3,042-member library of tertiary amino aryls. One advantage of small-molecule nonoligomeric libraries... 

The styryl dyes also include compounds in which the amino aryl nitrogen atom is part of a carbazole (as in the commercial dye 30) [71], phenoxazine [72], or tet-rahydrobenzoxazine system [73],... 

The cooperative complex of ALB 2 and La(OTf)3.nH20 catalyze direct asymmetric Mannich-type reactions with good selectivity providing /3-amino aryl ketones in good yields and with 31-44 % ee. 

An attempt to generate an amino-aryl carbene 154 from the alkylated phenanthridinium salt 153 (Equation 78) <2006TL531> was unsuccessful due to steric interactions. The actual reaction with a variety of strong, sterically hindered bases/nucleophiles is shown (Equations 79-81). The mesityllithium products proved that a carbene intermediate is not possible. Unlike /-butyl alcohol and hexamethyldisilazane, trimethylbenzene, the conjugate acid of mesityllithium, is not prone to carbene insertion reactions. Electronically this is explained by the planar nature of 153 which serves to lower the lowest unoccupied molecular orbital (LUMO) energy of the iminium moiety. 

R e = alkyl, alkoxy, thioether, ester amino, aryl, halogen etc. 

Amino-alkan- -diphenylester E2, 362 Amino-aryl-methan- E2, 304... 

The ortho-isomer is formed predominantly. However, the para-sulfate is formed in small amounts with certain anilines. The intermediate A formed first in the Boyland-Sims oxidation on rearrangement gives both the ortho- and para-amino aryl sulfates B and C (Scheme 7.31). ... 

Alkylthio-2-nitro-l-phenyl- E21e, 5020 (En - H/SR) 2-(2-Amino-aryl)-l, 1 -dimethoxy-E6b/1, 569 (N02 NH2)... 

The yield of o-amino aryl sulphate is generally 10-40 %. If both ortho positions are blocked then para substitution results. For preparative purposes the sulphate is hydrolysed by acid, as with the Elbs reaction. Behrman studied the oxidation of 2-amino-pyridine, and showed that the kinetics are second -order for the major part of reaction, viz. 

The intermediate X, present in low concentration, is probably an aryl hydro-xylamine-O-sulphonate. The further oxidation products consistmainlyof polymeric humic acid. The stationary-state approximation applied to [X] shows that the ratio of the rate of formation of o-amino aryl sulphate to the rate of formation of other products is k3/k2[S20g ]", in qualitative agreement with the dependence of the yield of o-amino aryl sulphate on peroxodisulphate concentration, and the deviation from first-order kinetics with respect to peroxodisulphate towards the end of a run. 

Consensus on nomenclature had been reached by the 1890s. Aniline was the parent of its derivatives, though sulfonic acids were considered derivatives of benzene, such as aminobenzenesulfonic acid. The prefix amino- was added to naphthalene and its derivatives. Many trivial names came into use, particularly for aminonaphthalenesulfonic acids, found in both academic and industrial research laboratories. Though IUPAC convention now numbers amino aryl compounds according to the parent hydrocarbon, the earlier system of numbering has often been retained, since some names include the positions of substituents at carbon atoms numbered according to the older systems. 

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