From Arylamines

Another possibility for ring closure to annulated 1,3-diazocines employs the thermal decomposition of the diazonium salt derived from arylamine 3.7... 

Ayyangar et al. prepared a number of arylaminomethylenemalonates (255) in 86-96% yields by starting from arylamines, ethyl orthoformate,... 

Fluoroarene formation from arylamines. Also known as the Balz-Schiemann reaction. 

Principally the same, but chemically simpler, sequence was used to prepare arylnitro anion-radicals from arylamines, in high yields. For instance, aqueous sodium nitrite solution was added to a mixture of ascorbic acid and sodium 3,5-dibromo-4-aminobenzenesulfonate in water. After addition of aqueous sodium hydroxide solution, the cation-radical of sodium 3,5-dibromo-4-nitro-benzenesulfonate was formed in the solution. The latter was completely characterized by its ESR spectrum. Double functions of the nitrite and ascorbic acid in the reaction should be underlined. Nitrite takes part in diazotization of the starting amine and trapping of the phenyl a-radical formed after one-electron reduction of the intermediary diazo compound. Ascorbic acid produces acidity to the reaction solution (needed for diazotization) and plays the role of a reductant when the medium becomes alkaline. The method described was proposed for ESR analytical determination of nitrite ions in water solutions (Lagercrantz 1998). 

Aryldiazonium salts, usually obtained from arylamines, undergo replacement of the diazonium group with a variety of nucleophiles to provide advantageous methods for producing aryl halides, cyanides, phenols and arenes by reductive removal of the diazo group. Coupling reaction of aryldiazonium salts with phenols or arylamines give rise to the formation of azo dyes. 

This enzyme [EC 2.3.1.87], also known as serotonin acetyltransferase and serotonin acetylase, catalyzes the reaction of acetyl-CoA and arylalkylamine to generate coenzyme A and A-acetylarylalkylamine. The enzyme exhibits a rather narrow specificity toward other aryl-alkylamines. This enzyme is distinct from arylamine acetyltransferase. 

B. Ganem, Chemtracts Org. Chem. 2, 127 -128 (1989) , Role Reversal in the Cyclocondensation of Cyc-lopentadiene with Heterodienophiles Derived from Arylamines and Aldehydes Synthesis of Novel Te-trahydroquinolincs11. 

Readily accessible aryliminodithiazoles 56 can be converted by LiAlH4 reduction into the rearranged A-aryl-dithiooxamides 112 (Equation 24) <1999S1345>. Although the yields are moderate (35—42%), this reaction provides a convenient two-step synthesis of unsymmetrical rubeanic acid derivatives from arylamines. 

The Sandmeyer procedure for the synthesis of aryl halides from arylamines has been applied, with modification, to the conversion of 5- and 8-aminoquinolines to the iodo and bromo derivative. 8-Aminoquinoline is converted to 8-bromoquinoline in good yield on treatment with /-butyl nitrite in the presence of CuBr in acetonitrile at 60 °C <2003JOC5123> and 5-amino-6-nitroquinoline is converted to the 5-iodo derivative under equally mild conditions using potassium nitrite and copper iodide in DMSO at 60 °C <2005JOC2445>. 

Arenediazonium salts (formed from arylamines) are relatively stable, however, and they serve as intermediates in a variety of important synthetic reactions. These reactions are discussed in Section 19-17. 

Sec. 24.8) from arylamines by reaction with nitrous acid... 

From arylamines, isoamyl nitrite, and metal acetates or nitrates 225). 

Aromatic halides, in which the halogen is attached to the ring, may be prepared by direct electrophilic aromatic substitution or from arylamines via diazonium compounds (see below). 

Heck reactions are compatible with water (see Chapter 3.2.4) [35], which increases the speed of reaction in the presence of quaternary ammonium salts [36 a]. It is not surprising, then, that aqueous solvents (e. g. CH3CN/H2O) and water-soluble catalysts such as Pd(TPPTS)3 where TPPTS = P(C6H4-m-S03Na)3 [35, 67] can be employed successfully (eq. (10)). However, only aryl and vinyl iodides and aromatic diazonium salts (generated in situ from arylamines in aqueous media) are, up to the present, accessible to this method [36 b-h]. 

Cyclizations. A route to substituted naphthalenes by intramolecular cyclization involves attack by a nascent allyl anion to a ketone group. On the other hand, the generation of N-arylindolines from arylamines and o-halostyrenes is a more complex process. Arylamines. The Pd-catalyzed arylation of amines depends critically on l-BuOK. Synthesis of sulfur compounds. a-Sulfenylation under mild conditions is realized... 

Important drug substrates for the SULT enzymes are acetaminophen, minoxidil, and isoproterenol. The SULT enzymes play an important role in the bioactivation of some chemicals through the conjugation of alcohols to form reactive species. This reaction is most notable in the activation of hydroxylamines derived from arylamines.70,71... 

Quinoline synthesis. 2,4-Disubstituted quinolines are synthesized in one operation from arylamines, aldehydes, and 1-alkynes. A mixture of AuCh and CuBr is used to promote the condensation. The effectiveness of AuCh to transform A-propargylarylamines to quinolines at room temperature has been independently verified. ... 

Organic azides. A method for the preparation of aryl azides from arylamines consists of reaction with t-BuONO and MesSiNs in MeCN. ... 

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