Aminobenzenethiols

Amino-77/-dibenz[/),t/]azepin-7-ones, e.g. 7, prepared either by successive bromination, aminodebromination, and dehydrogenation of 5-tosyl-5A/-dihydro 7>,t/]azepin-7(6//)-ones, or by the oxidation of 6-ethoxy-6,7-dihydro-5//-dibenz 7>,r/]azepincs with lead(IV) acetate followed by aminodemethoxylation, on treatment with a bidentate nucleophile (e.g.. benzene-1,2-diamine or 2-aminobenzenethiol) yield the pentacyclic systems 8 and 9, respectively.27... 

The reaction of diketene with 2-aminobenzenethiol was reported to yield 4-methyl-l,5-benzo-thiazepin-2(3//)-one (1A),52 which exists in tautomeric equilibrium with the hydroxy form IB.53... 

Aminobenzenethiol undergoes a Michael reaction with methyl 5,5-dimethyl-2-oxo-2,5-dihyd-rofuran-3-carboXylate (4) to give the adduct 5, which cyclizes to the tricyclic benzothiazepinone 6 under the influence of triethylamine hydrochloride.426... 

An unexpected cleavage has also been described for the coordinated Schiff base of 2-aminobenzenethiol in alkaline solution. Instead of neutral complexes of the Schiff bases, anionic 1 2 Tc(V) oxo complexes are formed the donor groups are now the thiol and generated amino groups [206]. 

NIR region (see Chapter 9.13), complexes of 1,2-dithiolene (DT) and related ligands have attracted considerable attention for their (largely cubic) NLO properties. The complex (156) (a.k.a. BDN) is a highly photochemically stable, saturable absorber and has hence found extensive applications in laser Q-switching. The cubic NLO properties of (156) have been studied by DFWM148,403-407 and more recently, Z-scan.408 Time-resolved DFWM has been applied to square planar Co, Ni, Cu, or Pt complexes of 1,2-benzenedithiolate (BDT) or 1,2-aminobenzenethiolate ligands by Lindle and co-workers.409,410... 

The most common method for the preparation of 1,2,3-benzothiadiazoles is the diazotization of 2-aminobenzenethiol. This method was discussed and exemplified in CHEC-II(1996). The method has been extended in recent years to include heterocyclic derivatives. The 2-aminothiophene 79 can be converted into the thienothiadiazole 82 on treatment with sodium nitrite in HC1 but in poor yield (16%). The bis(BOC)-protected derivative 80 or the mono(BOC)-protected derivative 81 when reacted under similar conditions afford product 82 in much higher yields (BOC = /-butoxycarbonyl Scheme 9). The increase in yield is explained in terms of hard and soft electrophilic character. The intermediate in the BOC-protected examples has a soft character allowing attack by sulfur to proceed more easily <1999JHC761>. 

Aminobenzenethiol, a297 Aminobenzyl cyanide, a255 1-Aminobutane, b509... 

Both oxidation and fluorodediazoniation with sodium nitrite and hydrogen fluoride/pyridine mixtures have been used advantageously in the synthesis of fluorinated aryl disulfides from aminobenzenethiols.98 In this case, too, the global yield is dependent on the hydrogen fluoride/ pyridine ratio (e.g., fluorodediazoniation yield = 65% with 20 wt % pyridine, 90% with 30 wt % pyridine, 93 % with 40 wt % pyridine and 10 % with 50 wt % pyridine for the formation of 4-fluorobenzenethiol).98... 

When aqueous ethanolic solutions of 2-aminobenzenethiol (abt) and chromium(II) chloride are mixed, the green suspension first formed turns light blue within one hour. The blue product... 

Generally, two strong tt bases are required to stabilize Os(VI), hence its chemistry is dominated by octahedral complexes with the trans-dioxo moiety. However, a complex containing three doubly depro-tonated 2-aminobenzenethiol ligands, [Os(abt)3], has been characterized (24). In addition, a growing number of five-coordinate complexes... 

The condensation of o-aminobenzenethiol with pyridine-2,6-dicarbaldehyde does not form the corresponding Schiff base but a polyheterocyclic compound which behaves as a tridentate ligand towards nickel(II).2365 In contrast the reaction of 2-(2-pyridyl)benzothiazoline with nickel(II) results in the opening of the heterocyclic ring and in the formation of a Schiff base ligand which coordinates to nickel(II) as a mononegative tridentate ligand.2366,2367... 

The buff-coloured bis chelate formed by 2-aminobenzenethiol (334) can be oxidized in alkaline solution to a blue-coloured complex of nickel(II) which contains the ligand in an oxidized form (Scheme 34).2422,2462 Complex (334) reacts with Mel in acetone affording the six-coordinate complex NiL containing the S-methylated ligand.2452... 

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