Sulfur-containing derivatives

Sulfur-containing derivatives are of immense importance in the pyrimidine series, mainly because their diverse reactions make them convenient intermediates. 

Related sulfur-containing derivatives are formed from the reaction of 49 with 2-methyl-2-propanethiol, cyclo-hexanethiol, and 2-propanethiol in toluene at ambient temperature. The resulting tetrameric cyclopentadienyl thiolato complexes [(if-Cp)Mg(/.t3-SR) ]4 (R = Bu, CgFIn, Pr1) are colorless crystalline solids. Treatment of... 

In practice the sulfur-containing derivative is dissolved or suspended in a suitable solvent, treated with a sufficient quantity of Raney nickel, and either left at room temperature or heated under reflux, recovery of the product being effected by concentration of the liquid phase. The following example may be taken as typical.7... 

The number of nitrogen- and sulfur-containing derivatives of acyclic terpenoids that are known to be important fragrance and flavor substances is smaller than in the nonterpenoid aliphatic series discussed in Section 2.1.6. However, a few nitriles are used in rather large amounts in soap perfumes because of their relatively high stability toward alkali. 

Closely related are the syntheses from various sulfur-containing derivatives of 2-pyridylhydrazine by which it is possible to obtain the 3-thiol (or thione) 6180 or 3-methylaminotriazolopyridine (62).88 By use of dithio-carbamates instead of acylhydrazines, the iminoether synthesis gives the tetrahydrotriazolopyridine-3-thiol (or thione) 63.89-92 Cyclization of the amidine 64 gives 3-anilinotriazolopyridine (65).93... 

Research to date focused on isolating insecticidal prototype leads from marine origin has resulted in the report of about 40 active compounds.44 In an attempt to summarize these compounds and their activity margins, they have been categorized into seven classes of chemical structures polyhalogenated monoterpenes, polyhalogenated C15-metabolites, diterpenes, peptides and amino acids, phosphate esters, sulfur-containing derivatives, and macrolides. 

Five-membered rings with two adjacent heteroatoms are most frequently made using a hydroxylamine or hydrazine derivative. However, dipolar cycloadditions are also significant. Methods forming a Z—Z bond are important particularly for sulfur-containing derivatives. 

The synthesis of the heteroarylcarboxylic acid chlorides is fraught with difficulties. When isolated, the acid chlorides are generally unstable and readily produce bisheteroaryl ketones (see Section 3.05.1.2.9). Using standard preparative procedures the increase in the acidity of the reaction medium can cause polymerization, whilst the addition of a base can result in the formation of compounds of the type (403) and (404). Attempts to prepare indole-2 -carboxylic acid chloride using thionyl chloride result in the isolation of sulfur-containing derivatives, which arise from electrophilic attack at the 3-position (64JOC178). 

See also page 47, Section 93 and page 49, Section 9.4, for reduction of sulfur-containing derivatives of alcohols and phenols and page 229, Section 4, for reduction of allylic sulfonates and sulfones with double bond transposition. 

Both sulfide and disulfide are more commonly encountered as bridging ligands in cobalt clusters. There are few systematic syntheses. For example, [Co2(CO)g] reacts at room temperature with CS2 either neat or in the presence of hydrocarbon solvents to form [Co3(S)(CO)c,], [Co6(C)(S)2(CO)12] and at least three other sulfur-containing derivatives in addition to sulfur-free species such as [Co3(CXCO)9].979 Similarly, [Co2(CO)g] with elemental sulfur in hydrocarbon solvent gives [Co3(S)(CO)9], [Co4(S)2(CO)l0], [Co6(S)3(CO)6] and [Co6(S)4(CO) 4],980 with the product distribution dependent on the reaction conditions. Details of several cluster preparations are given in Table 79 and structural data in Table 80. 

Catalytic reduction of acetates (tertiary or allylic) with Ni boride (reaction (e)) may serve as a shortcut option to achieve the transition from oxidation level 1 to oxidation level 0. This pathway eliminates the necessity first to prepare sulfur-containing derivatives. 

Oxiranes are transformed by tris(ethylthio)borane to sulfur-containing derivatives.With selenoboranes, terminal or a,)3-disubstituted epoxides yield 3-hydroxyse enides trisubstituted epoxides give allyl alcohols. 

Phosphoric, phosphinic, and phosphonic acid. Phosphinic acid-based extractants contain the P(0)0H acid functionality as well as two R groups attached to the phosphorus, where R can be hydrogenic, aliphatic, or aromatic. Sulfur containing derivatives are known as monothiophosphinic acids, where the phosphonyl oxygen is replaced with a sulfur, and dithiophosphinic adds, where both oxygens are replaced with sulfur (Figure 88). 

Kato, H., and M. Ohta Studies on organic sulfur compounds III Sulfur-containing derivatives of dicarboxylic acid dihydrazides. J. chem. Soc. Japan, Pure Chem. Sec. 78, 158S (1957) Chem. Abstracts 54, 1502 (i960). 

On comparing the phosphate derivatives with the thio-, generally poly-thiophosphate derivatives, it may be concluded that the effect of derivatives also containing sulfur is always much higher. A possible mode of the fungicidal action is connected with the disturbance of the redox processes of the fungal cells. Moreover, it is assumed that sulfur-containing derivatives also attach the nucleic acids at the site of the phosphate radicals and interfere with their normal functions. 

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