7-substituted 4-thio

Carbon disulphide reacts additively with primary and secondary aliphatic amines to form alkylammonium salts of alkyldithiocarbamic acids. The products obtained with dimethylamine, diethylamine and piperidine, also certain derivatives of these products, are manufactured on a large scale for use as accelerators in the vulcanisation of rubber. With aromatic amines the disulphide reacts with elimination of hydrogen sulphide and formation of substituted thio-ureas, e.g. thiocarbanilide. 

One other novel approach to DHPMs has been described by Shutalev et al. and is outlined in Scheme 4.6 [135], This synthesis is based on the condensation of readily available a-tosyl-substituted (thio)ureas 16 with the (in situ prepared) eno-lates of acetoacetates or 1,3-dicarbonyl compounds. The resulting hexahydropyri-midines 17 need not be isolated and can be converted directly into DHPMs 14. This method works particularly well for aliphatic aldehydes and thioureas and produces high overall yields of the desired target compounds. 

Periphepherally octaalkylthiosubstituted derivatives may be synthesized from thio substituted phthalonitrile (V in Scheme2 [13]). The latter is obtained from the commercially available 4,5-dichlorophthalonitrile (IV, Scheme 2). Peripherally or nonperipherally tetra substituted MPc complexes may be synthesized from mono-substituted thio phthalonitrile (VII, Scheme 3) which in turn is obtained from commercially available 4-nitrophthalonitrile (VI, Scheme 3) or 3-nitrophthalonitrile [ 14]. 

Table 45 One-bond C-H coupling constants corresponding to carbons 3, 4, and 5 in thiophene and 2-substituted thio- ...

NPCl2)n reacts with 1-hexanethiol to give the fully substituted thio polymer utilizing 4-picoline as base in thf solutions. Only degradation products are obtained when the reaction is carried out with sodium hexanethiolate as... 

Spectra of some azido substituted thio-ethers and amines see Lieber and Rao. ... 

In DMF the two substituted thio derivatives of pyrmidine, 97b and 97c, were found to dimerize upon reduction in the absence as well as in the presence of acid [275]. For 97b, however, the coulometric w-value was close to 0.5 in the absence of proton donors, indicating that the V-proton in 97b is sufficiently acidic to protonate either the radical anion or the dimer dianion, thereby leaving half of the substrate on the unreducible anionic form. In the presence of stoichiometric amounts of HCIO4, the reduction takes place via the preprotonated substrate as for 97a [275]. The rate constant for dimerization of 97c (in the absence of acid) was found to be close to that for 97a [275]. 

Methods for the direct conversion of 1,6-anhydropyranoses to thioglycosides have been described using either substituted thio(trimethyl)silanes or ethanethiol in the presence of Lewis acid [42,43] the resulting thioglycosides are furnished with a free primary hydroxyl group that is available for further reaction (O Scheme 14). 

TL3799). It is to be noted that this reaction is impractical with 5-diazo-6-(N,N-disubstituted amino)- and 6-(substituted thio)dihydrouracils owing to a 1,2-shift of the functional group in the intermediate car bene, which results in 5-substituted derivatives. 

Base catalysed reaction of 3-chloro-6-nitroaniline (106a) and 3-chloro-6-ni-troacetanilide (106b) with thiophenol and propanethiol gives 3-substituted thio-6-ni-... 

The 4-substituted Thio-Ibo derivatives 83a-g (Scheme 20) were prepared with similar chemistry from the corresponding 4-substituted 3-benzyloxy-isothiazoles 76, 77 and 78 synthesised as outhned in Scheme 19. The use... 

Substituted 1,2-dithiolanyl radicals are formed by intramolecular cyclization of thiyl radicals generated by photochemically induced sulphur-hydrogen bond homolysis in 1-substituted thio-3-... 

The kinetics of the reactions of various substituted thio phenols with liquid sulfur have been investigated, and intermediates of the general form RS H and HS H have been identified. The studies suggest that the reaction is usually free radical involving an initiation period in which a steady state concentration of sulfur radical species is established, The reaction appears to be second order in mercaptan and third order in sulfur. These findings have been interpreted using a complex sulfur radical species involving several Sg molecules. 

TABLE 8. O-SUBSTrrUTED OXY- AND S-SUBSTITUTED THIO- OR SULFONYL-1,2.3-TRI AZOLES... 

Ch. 10 S-Substituted Thio-, Sulfinyl-, or Suffonyl- 1,2, 4-thiazoles, 3,3 -Dithiobis[l,2,4]triazoles, and 1,2,4-Triazolesulfonic Acids and Iheir Functional Derivatives Ch. 11 Mono-, Di-, and Trihalo-1,2,4-triazoles... 

Ch. 8 0-Substituted Oxy- and S-Substituted Thio- or Sulfonyl-1,2,3 Triazoles Ch. 9 Halo-1,2,3-Triazoles... 

Figure 5.31 Nitration of diaikyi substituted thio-urea.

Fig. 4.24 Oxidation of a eyelopropyl-substituted thio- cyclopropyl ring-opening reaction is too slow to compete ether occurs without opening of the cyclopropyl ring, be- with oxygen transfer to the sulfur cause either a sulfur radical cation is not formed or the...

Flotation results of Cu, Mo, and Fe ores using these two N-substituted thio-carbamides, butyl xanthate and thiambutosine, are shown in Figs. 1.2 and 1.3. 

Sulfides, disulfides, and polysulfides (also called thioethers) are the characterizing components of the alliaceous vegetables (e.g., onion, garlic, leek), although the more subtle attributes of these profiles are contributed by substituted thio compounds. 

Mori and co-workers have proposed antioxidant substituted tri-azine compounds, which act as combined vulcanizing agents and antioxidant systems which resist the leeching action of fluids during immersion, particularly in sour gasoline. Another method involving the use of thiophenols and amine-substituted thio compounds has been described by Weinstein where the attachment is achieved during or after the polymerization process. 

The reaction of rhodium vinylidene metal complexes 3 with sulfur, selenium and tellurium affords complexes of metal substituted thio-, seleno- and telluroketenes 4. ... 

The effect of S and Se substitution in the ketene series is also shown in Fig. 46. The trend is the same as in the carbonyls but the double bond is shorter in the ketenes, due to the partial triple bond character in the C=C=X moiety. It is unfortunate that more data are not available for substituted thio- and selenoketenes to extend the observed trends. 

Isocyanates and thioisocycanates equally harbor cumulated double bonds. As they combine virtually quantitatively with all kinds of organic lithium, sodium, or potassium compounds, they were much appreciated as trapping reagents in the early history of polar organometallic chemistry. Moreover, the products derived from iV-phenyl, yV-naphthyl, or A/-rer/-butyl substituted (thio)isocyanates crystallize extremely well. 

The reaction of l,2-dithiole-3-thiones with enamines gave substituted thio-pyranthiones such as (12). Another synthesis of (12) employed the reaction of 1,2-dithiolium salts with CNCHgCSNHg. Various syntheses of substituted thiopyranylidenes (18) have been reported and their photoisomerization about the exocyclic double bond has been studied. The thermal isomerization of... 

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