Mercaptides alkylation

Halogenoplatinous mercaptide-alkyl sulphide complexes, H. M. Fitch, U.S. patent 3,022,177, 1962. 

Cost bilizers. In most cases the alkyl tin stabilizets ate particularly efficient heat stabilizers for PVC without the addition of costabilizers. Many of the traditional coadditives, such as antioxidants, epoxy compounds, and phosphites, used with the mixed metal stabilizer systems, afford only minimal benefits when used with the alkyl tin mercaptides. Mercaptans are quite effective costabilizets for some of the alkyl tin mercaptides, particularly those based on mercaptoethyl ester technology (23). Combinations of mercaptan and alkyl tin mercaptide ate currendy the most efficient stabilizers for PVC extmsion processes. The level of tin metal in the stabilizer composition can be reduced by up to 50% while maintaining equivalent performance. Figure 2 shows the two-roU mill performance of some methyl tin stabilizers in a PVC pipe formulation as a function of the tin content and the mercaptide groups at 200°C. 

The various lubricants formulated into PVC to improve the processing can also enhance the performance of the stabilizet. In pigmented apphcations, calcium soaps, eg, calcium stearate, ate commonly used as internal lubricants to promote PVC fusion and reduce melt viscosity. This additive is also a powerfiil costabilizer for the alkyl tin mercaptide stabilizers at use levels of 0.2 to 0.7 phr. Calcium stearate can significantly improve the eady color and increase the long-term stabiUty at low levels however, as the concentration increases, significant yellowing begins to occur. 

Pt(CO)2Cl2] is used to deposit thin films of metallic platinum on surfaces. Concentiated organic solutions of poorly defined platinum complexes of alkyl mercaptides or sulforesinates are used to coat ceramics and glass. 

Sulfur is reactive ia many forms. Mercaptides are alkylated to thioethers, and thioethers react further to give sulfonium salts, R2S" CH20S0 2-Suitable thiones also alkylate. Thioachdone (34) and thiourea (35) are examples the first gives the alkylmetcaptoacridine and the second gives the isothiourea. 

Mercaptides are unchallenged as the ligand of choice for the other entities bonded to the tin, but carboxylates can also be used. Whereas a variety of mercaptans are used, the thioglycolic acid derivatives remain the largest single mercaptan. Dibutyltin bis(isooctyl thioglycolate) [25168-24-5] and butyltin tris(isooctyl thioglycolate) [25852-70A] are two common examples. These materials are produced by the reaction of the appropriate alkyl tin chloride or oxide, and the mercaptan. 

Triorganotin fluorides can be prepared by the use of new fluorinating systems. 18-Crown-6 or dibenzo-24-crown-8 can act as solid-liquid phase transfer catalysts for CsF. Trialkyltin mercaptides can be fluorodestannylated by CsF in the presence of crown ethers or alkyl bromides358 ... 

The interaction of alkyl halides with mercaptans or alkaline mercaptides prodnces thioalkyl derivatives. This is a typical nncleophilic substitution reaction, and one cannot tell by the nature of products whether or not it proceeds through the ion-radical stage. However, the version of the reaction between 5-bromo-5-nitro-l,3-dioxan and sodium ethylmercaptide can be explained only by the intermediate stage involving electron transfer. As found (Zorin et al. 1983), this reaction in DMSO leads to diethyldisulfide (yield 95%), sodium bromide (quantitative yield), and 5,5 -bis(5-nitro-l,3-dioxanyl) (yield 90%). UV irradiation markedly accelerates this reaction, whereas benzene nitro derivatives decelerate it. The result obtained shows that the process begins with the formation of ethylthiyl radicals and anion-radical of the substrate. Ethylthiyl radicals dimerize (diethyldisulfide is obtained), and anion-radicals of the substrate decompose monomolecularly to give 5-nitro-l,3-dioxa-5-cyclohexyl radicals. The latter radicals recombine and form the final dioxanyl (Scheme 4.4). 

Sulfur is reactive in many forms. Mercaptides are alkylated to thioethers, and thioethers react further to give sulfonium salts, R3S+CH3OSOx. 

Reaction of Coordinated Mercaptide Group with Alkyl Halides... 

Analytical data on the soluble products isolated from chloroform are in excellent agreement with the composition 1 Ni+2 1 monoalkylated ligand 1 I or Br. The magnetic moment of this methylated complex was found to be 1.89 Bohr magnetons per nickel (II). The molar conductivities of the methylated and benzylated complexes in methanol at 25° C. are 75.4 and 68.4 ohm-1, respectively. These values approximate those expected for uni-univalent electrolytes in this solvent. The formulation of these alkylated compounds as dimeric electrolytes (structure VII) does not appear to be totally consistent with their physical properties. One or both halide ions may be bound to the metal ion. These results lead to the easily understood generalization that terminal sulfur atoms alkylate more readily than bridged mercaptide groups. 

The susceptibility of the mercaptide groups in these Schiff base complexes to ligand reaction was evaluated by treating these compounds with methyl iodide and benzyl bromide in chloroform solution. The pure compounds isolated from these reaction mixtures were of the composition NiL.2RX, where L represents the tetradendate Schiff base and RX represents the alkyl halide added. These reactions proceed smoothly and the stoichiometry of the products implies that both sufur atoms are reactive. The products are monomeric in dichloroethane. They exhibit magnetic moments consistent with octahedral structures, and they behave as di-univalent electrolytes in coordinating, polar solvents. 

The kinetics of the carbon disulfide elimination reaction were studied using PMR and visible spectroscopy (16). This spontaneous reaction was found to be first order in the M(RSXant)2 complexes (M = Ni, R = Et, r-Bu, Bz M = Pd, R =/ -Bu), both in the disappearance of the starting material and in the formation of the mercaptide-bridged species in CHC13 and THF. The pseudo-first-order kinetics observed in CS2 are attributed to an equilibrium between the M(RSXant)2 complexes and this solvent. Rate constants for the reaction are of the order of 10 3 to 10"1 min"1 depending on solvent, temperature, alkyl... 

In 1959, the coordinated mercaptide ion in the gold(III) complex (4) was found to undergo rapid alkylation with methyl iodide and ethyl bromide (e.g. equation 3).9 The reaction has since been used to great effect particularly in nickel(II) (3-mercaptoamine complexes.10,11 It has been demonstrated by kinetic studies that alkylation occurs without dissociation of the sulfur atom from nickel. The binuclear nickel complex (5) underwent stepwise alkylation with methyl iodide, benzyl bromide and substituted benzyl chlorides in second order reactions (equation 4). Bridging sulfur atoms were unreactive, as would be expected. Relative rate data were consistent with SN2 attack of sulfur at the saturated carbon atoms of the alkyl halide. The mononuclear complex (6) yielded octahedral complexes on alkylation (equation 5), but the reaction was complicated by the independent reversible formation of the trinuclear complex (7). Further reactions of this type have been used to form new chelate rings (see Section 7.4.3.1). 

O-Allyl-5-alkyl dithiocarbonates react with Pd° catalysts to provide a ir-allyl complex with a thiocar-bonate serving as counterion. Under the reaction conditions the carbonate expels free methyl meicaptide, generating COS. Attack of the mercaptide was shown to occur exclusively via ligand addition (equation 195).221... 

Formation of a symmetrical sulphide (a) (e.g. dipropyl sulphide, Expt 5.204), is conveniently effected by boiling an alkyl halide (the source of carbocations) with sodium sulphide in ethanolic solution. Mixed sulphides (b) are prepared by alkylation of a thiolate salt (a mercaptide) with an alkyl halide (cf. Williamson s ether synthesis, Section 5.6.2, p. 583). In the case of an alkyl aryl sulphide (R-S Ar) where the aromatic ring contains activating nitro groups (see Section 6.5.3, p. 900), the aryl halide is used with the alkyl thiolate salt. The alternative alkylation of a substituted thiophenol is described in Section 8.3.4, p. 1160. The former procedure is illustrated by the preparation of isobutyl 2,4-dinitrophenyl sulphide (Expt 5.205) from l-chloro-2,4-dinitrobenzene and 2-methylpropane-1-thiol. 

The unique feature of the alkyllithium compounds that makes them useful as diene initiators is their character as exceedingly powerful bases yet they are soluble in organic solvents and quite thermally stable. Alkyllithium compounds are sufficiently basic to add to hydrocarbon monomers. However, lithium salts of stabilized anions, such as acetylide and fluorenyl anions, are too weakly basic to add to such double bonds. Similarly, alkoxides and mercaptides fail to react with hydrocarbon monomers, but lithium alkyl amides react analogously to alkyllithium compounds. 

Organotin compounds are widely used as stabilisers for PVC. They are usually stabilised with R2SnX2 compounds, where R is the alkyl, and X is oxygen, ester, mercaptide, acetyl and other groups. 

As shown in the second step of Figure 2 orange cobalt-bleomycin A2 was demethylated with a mercaptide and then alkylated at the terminal sulfur atom with a bifunctional chelating agent (4,18). 

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