Amino thioethers

Ranucci, F.. and Bignotti, F., New basic multifunctional polymers. VIII. Poly(amino-thioether-ketone)s, Chim. Ind., 72,799, 1990,... 

This reaction is analogous to 10-7. It may be acid (including Lewis acids ), base, or alumina catalyzed, occur with electrolysis, and may occur by either an SnI or 8 2 mechanism. Catalysts, such as [Rh(CO)2Cl]2, TiCla (OTf), Fe(C104)3, Cu(BF4)2 m H2O, or BiCla, have been used. (3-Cyclodextrin has been used to promote the reaction with phenoxides in aqueous media. Many of the p-hydroxy ethers produced in this way are valuable solvents, for example, diethylene glycol and Cellosolve. Reaction with thiols leads to hydroxy thioethers. The reaction of alcohols with aziridines leads to p-amino ethers, and reaction with thiols gives p-amino thioethers. " It has been shown that ringopening of aziridines by phenols is promoted by tributylphosphine. ... 

AMINO-THIOETHERS aryl halides + active methylene 13-14... 

There is one report of using 7V-(l,l-dimethylethyl)benzene-sulfenamide to convert an alkene to the amino thioether (eq 11). The sulfenamide reacts with the alkene in dichloromethane in the presence of trifluoromethanesulfonic acid at —23 °C. If a nitrile is used as the solvent instead of dichloromethane, the amidino thioether is obtained in good yield (eq 12). 

The Hf(OTf)4-catalyzed conversion of hemiaminal to a-amino thioether in the synthesis of lemonomycinone amide has been reported (eq 5). ... 

An equimolar mixture of 2-aminopropanol, thiophenol, and acetic acid in benzene refluxed 6-14 hrs. with azeotropic removal of the resulting water -> N-(l-phenylthio-2-propyl) acetamide. Y 80%.—The corresponding 2-amino-thioethers can be obtained by refluxing in coned. HGl. F. e. and limitations s. H. L. Wehrmeister, J. Org. Ghem. 28, 2589 (1963). 

Phthalocyanine sulfonic acids, which can be used as direct cotton dyes (1), are obtained by heating the metal phthalocyanines in oleum. One to four sulfo groups can be introduced in the 4-position by varying concentration, temperature, and reaction time (103). Sulfonyl chlorides, which are important intermediates, can be prepared from chlorosulfonic acid and phthalocyanines (104). The positions of the sulfonyl chloride groups are the same as those of the sulfonic acids (103). Other derivatives, eg, chlormethylphthalocyanines (105—107), / /f-butyl (108—111), amino (112), ethers (109,110,113—116), thioethers (117,118), carboxyl acids (119—122), esters (123), cyanides (112,124—127), and nitrocompounds (126), can be synthesized. 

In aqueous solutions at pH 7, there is little evidence of complex formation between [MesSnflV)] and Gly. Potentiometric determination of the formation constants for L-Cys, DL-Ala, and L-His with the same cation indicates that L-Cys binds more strongly than other two amino acids (pKi ca. 10,6, or 5, respectively). Equilibrium and spectroscopic studies on L-Cys and its derivatives (S-methyl-cystein (S-Me-Cys), N-Ac-Cys) and the [Et2Sn(IV)] system showed that these ligands coordinate the metal ion via carboxylic O and the thiolic 5 donor atoms in acidic media. In the case of S-Me-Cys, the formation of a protonated complex MLH was also detected, due to the stabilizing effect of additional thioether coordination. ... 

Thiols, thioethers and sulfoxides [37-39] e.g. sulfur-containing amino acids... 

A variety of cleavage conditions have been reported for the release of amines from a solid support. Triazene linker 52 prepared from Merrifield resin in three steps was used for the solid-phase synthesis of aliphatic amines (Scheme 22) [61]. The triazenes were stable to basic conditions and the amino products were released in high yields upon treatment with mild acids. Alternatively, base labile linker 53 synthesized from a-bromo-p-toluic acid in two steps was used to anchor amino functions (Scheme 23) [62]. Cleavage was accomplished by oxidation of the thioether to the sulfone with m-chloroperbenzoic acid followed by 13-elimination with a 10% solution of NH4OH in 2,2,2-trifluoroethanol. A linker based on l-(4,4 -dimethyl-2,6-dioxocyclohexylidene)ethyl (Dde) primary amine protecting group was developed for attaching amino functions (Scheme 24) [65]. Linker 54 was stable to both acidic and basic conditions and the final products were cleaved from the resin by treatment with hydrazine or transamination with ra-propylamine. 

In addition to the backbone donor system the amino acid residues can contain a variety of donor centers (679E). The most important of these are the imidazole N atoms of His, the S atom of Cys, and to some extent the, 3-carboxylate O atom of Asp. Other side chain donors like the O atoms of Ser and phenolic O atoms of Tyr or amino N atoms of Lys are of minor importance for coordination of Ni11 ions. Also, thioether S-donors of Met play only a minor role in the interactions with Ni11 ions.1730... 

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