Amine-thiophenolates

Ni11 complexes of various amine/thiophenolate ligands have been investigated (for Ni complexes of ortho-aminothiophenol see Section 6.3.4.9.2(iv)). Thiophenolate is expected to exhibit decreased bridging tendency compared to aliphatic thiolates, but complexes (466) and (467) still consist of two pseudo-octahedral NiL fragments bridged via thiolate donors. In contrast to the parent complex (466), the thiolate and thioether donors in (467) coordinate cis to the Ni center... 

BlNUCLEATING AzA-ThIOETHEES 40c-40p AND AMINE-THIOPHENOLATES H2L24-H2L31... 

It is well-established that the molecular and electronic structures of metal complexes of azamacrocycles are greatly affected upon N-alkylation (197). This is mainly due to two factors (a) the decrease of the ligand field strength and (b) the increase in the steric requirements upon going from a secondary to a tertiary amine donor function (251). To examine whether the properties of the dinuclear amine-thiophenolate complexes are affected by the N-alkyl substituents, analogous complexes of the... 

To this scheme most of the reactions of quinone conform, and all those which are of most importance, e.g. the addition of HC1, HCN, amines, thiophenol, thiosulphuric acid, acid chlorides, and add anhydrides. 

Compounds that are classified as antioxidants (such as alkylphenols, aromatic amines, thiophenols, and imines) generally exhibit moderately high reactivity toward organic peroxy radicals (ROO ). A plausible reaction sequence for the formation of ROO is given in Figure 12.3b. 

Dilute sodium hydroxide solution. Carboxylic acids (RCOOH), sulphonic acids (RSO3H), phenols (ArOH), thiophenols (ArSH), mer-captans (RSH), imides (RCONHCOR), aryl sulphonamides (AxSOjNHj), arylsulphonyl derivatives of primary amines (AxSOjNHR), oximes (RCH=NOH), primary and secondary nitro compounds (RCH=NOOH and RjC=NOOH-oci forms), and some enols (e.g., of 1 3-diketones... 

A solid-liquid phase-transfer technique is used to synthesize aryl difluoro-methyl sulfides and selenides thiophenols dissolved in an aromatic solvent are treated with solid sodium hydroxide in the presence of a catalytic amount of tris(3,6-dioxaheptyl)amine (TDA1) [49] This condensation proceeds by a carbene mechanism (equation 44)... 

The catalytic effect of protons has been noted on many occasions (cf. Section II,D,2,c) and autocatalysis frequently occurs when the nucleophile is not a strong base. Acid catalysis of reactions with water, alcohols, mercaptans, amines, or halide ions has been observed for halogeno derivatives of pyridine, pyrimidine (92), s-triazine (93), quinoline, and phthalazine as well as for many other ring systems and leaving groups. An interesting displacement is that of a 4-oxo group in the reaction of quinolines with thiophenols, which is made possible by the acid catalysis. 

Auch Alkohole und Phenole, Thiole und Thiophenole, sowic prim, und sek. Amine reagieren unter Wasser-stoffentwicklung. 

When thionyl chloride is used, diaryl sulfoxides are usually the main products. Unsymmetrical diaryl sulfides can be obtained by treatment of an aromatic compound with an aryl sulfenyl chloride (ArSCl) in the presence of a trace amount of iron powder.Aromatic amines and phenols can be alkylthiolated (giving mostly ortho product) by treatment with an alkyl disulfide and a Lewis acid catalyst. With certain substrates (primary amines with a chloro group, or a group not replaceable by chloro, in the para position), treatment with S2CI2 and NaOH gives thiophenolate salts ... 

Radical cyclization is compatible with the presence of other functional groups. Treatment of XCH2CON(R)-C(R )=CH2 derivatives (X = Cl, Br, 1) with Ph3SnH and AIBN led to formation of a lactam via radical cyclization. " Cyclization of N-iodoethyl-5-vinyl-2-pyrrolidinone led to the corresponding bicyclic lactam, " and there are other examples of radical cyclization with molecules containing a lactam unit " or an amide unit. Radical cyclization occurs with enamines as well. Photochemical irradiation of A,A-dialIyl acrylamide leads to formation of a lactam ring, and in this case thiophenol was added to generate the phenylthio derivative. Phenylseleno N-allylamines lead to cyclic amines. co-Iodo acrylate esters cyclize to form lactones. " ... 

Allyl p-tolyl sulphoxide 535 reacts with sodium methoxide in methanol by initial prototropic isomerization and subsequent addition of methanol to give 536 (equation 333). Protic solvents are photochemically incorporated by the open chain olefinic bond of trans methyl )S-styryl sulphoxide 537 in a Markovnikov regiospecificity (equation 334). Mercaptanes and thiophenols add to vinyl sulphoxides in a similar manner (compare also Reference 604 and Section IV.B.3) to give fi-alkylthio(arylthio)ethyl sulphoxides 538 (equation 335). Addition of deuteriated thio-phenol (PhSD) to optically active p-tolyl vinyl sulphoxide is accompanied by a low asymmetric a-induction not exceeding 10% (equation 336) . Addition of amines to vinyl sulphoxides proceeds in the same way giving )S-aminoethyl sulphoxides in good to quantitative yields depending on the substituents at the vinyl moiety When optically active p-tolyl vinyl sulphoxides are used in this reaction, diastereoisomeric mixtures are always formed and asymmetric induction at the p- and a-carbon atoms is 80 20 (R = H, R = Me) and 1.8 1 (R = Me, R = H), respectively (equation 337) ... 

A-Protected amines were assembled on solid-phase via sulfonamide-based handle 58 (Scheme 27) [67]. Tertiary sulfonamides were generated upon reaction with allylic, benzylic and primary alcohols under Mitsu-nobu conditions. Secondary amines were released from the support using mild nucleophilic conditions such as treatment with thiophenol and potassium carbonate. 

A versatile approach for the solid-phase synthesis of aminopyr-idazines used the anchoring of 3,6-dichloropyridazine to resin-bound thiophenol 59 (Scheme 28) [68]. Treatment with nucleophilic amines released the aminopyridazine products from the solid support without further oxidation. 

The relative rates of reaction of the silene Me2Si=C(SiMe3)2 with a series of amines, alcohols, phenols, thiophenols, dienes, and alkenes were obtained174 and are reported in Table VIII Section IV.C. 

It is synthesized by reaction of the diazonium salt from amine 1 with potassium ethyl xanthate, followed by alkaline hydrolysis to afford thiophenol 2. 

Corrosion inhibition is primarily associated with acidizing. Buffered hydrofluoric acid compositions have been shown to be less corrosive (147). Corrosion inhibitors are designed to reduce the rate of reaction of fluid with metal surfaces, generally by forming films on the surfaces. Acetylenic alcohols and amines are frequently components of corrosion inhibitor blends. Other compounds that have been used include nitrogen heterocyclics, substituted thioureas, thiophenols, and alpha-aminoalkyl thioethers (148). 

In a related and more recent study by the same group, syntheses of various solid-supported acylating agents for microwave-mediated transformations of amines, alcohols, phenols, and thiophenols have been presented [129]. In a microwave-mediated... 

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