S dithiolates

DIBENZOYL-1,3-DITHIOLE-1-THIONE (Benzenecarbothioic acid, S.SXS-thioxo-l.S-dithiole. S diy1) ester)... 

C3S2 s s — — — l,2-Dithiolane-4-carboxylic acid 3-phenyl-l,2-dithiolylium iodide 4-methyl-1,2-dithiole-3-thione ... 

Alkylisothiazolium salts (61) undergo N—S bond cleavage when treated with hydrogen sulfide or thiophenol to form acyclic products (62), but 2-aryl compounds give 1,2-dithioles (63 or 64 Scheme 9) (75SST(3)54l, 77SST(4)339). 

Benzene-1,2-dithiol [17534-15-5] M 142.2, m 24-25 , 27-28 , b 110-112 , pKEst(i) -6.0, p K s,(2) 9.4. Likely impurities are the oxidation products, the disulfides which could be polymeric. Dissolve in aq NaOH until the soln is alkaline. Extract with Et20 and discard the extract. Acidify with cold HCl (diluted 1 1 by vol with H2O) to Congo Red paper under N2 and extract three times with Et20. Dry the Et20 with Na2S04, filter, evaporate and distil residue under reduced press in an atmosphere of N2. The distillate solidifies on cooling. [UV J Chem Soc 3076 7 955 J Am Chem Soc 81 4939 7957 Org Synth Coll Vol V 419 1973.]... 

One decade later, the parent compounds 21 were synthesized (78BCJ1427). For example, the reaction of 2-methylthio-l,3-dithiolium iodide with pyrrole gave 2-(2-pyrrolyl)-l,3-dithiolium iodide in a 92% yield, which on treatment with DBU gave 5-aza-l,4-dithiafulvalene 21 (R = H, Z = S, no Ph at dithiole-ring) as thermally stable orange crystals. Using the same type of reaction, the benzoderivatives of type 24 could be isolated (78BCJ1427). 

Diphenylcarbazide as adsorption indicator, 358 as colorimetric reagent, 687 Diphenylthiocarbazone see Dithizone Direct reading emission spectrometer 775 Dispensers (liquid) 84 Displacement titrations 278 borate ion with a strong acid, 278 carbonate ion with a strong acid, 278 choice of indicators for, 279, 280 Dissociation (ionisation) constant 23, 31 calculations involving, 34 D. of for a complex ion, (v) 602 for an indicator, (s) 718 of polyprotic acids, 33 values for acids and bases in water, (T) 832 true or thermodynamic, 23 Distribution coefficient 162, 195 and per cent extraction, 165 Distribution ratio 162 Dithiol 693, 695, 697 Dithizone 171, 178... 

Bidentate dithiolate ligands afford complexes like Au(S2CNR2) (R = Et, Pr, Bu) and Au(S2PR2) (R = Pr), which have dimeric structures based on 8-membered rings with linear S—Au—S coordination and short Au-Au distances. These in turn are associated into chains (Figure 4.16) (Au-Au c. 3.0-3.4 A) [99],... 

The Au-S bond length at 2.30 A is very similar to that in the gold(III) analogue (2.299-2.312 A) and other gold(III) complexes like Au(toluene-3,4-dithiolate) (2.31 A) suggesting substantial covalent character in the bond. 

Platinum blue formation, 2,265 Platinum complexes, S, 351-500 acetylacetone reactions, 2,380 acetylides reactions, 5,402 alcohols, 5,465 alkene-1,2-dithiolates optica] recording systems, 6,126 alkenes, 5,403 bonding, 5,403... 

The photochemical behavior of a number of substituted derivatives of thiochroman-4-one 1-oxides has been examined by Still and coworkers192-194. These authors also report that rearrangement to cyclic sulfenates, with subsequent reaction by homolysis of the S—O bond, appears to be a particularly favorable process. For example, ultraviolet irradiation of a solution of 8-methylthiochroman-4-one 1-oxide (133) in benzene for 24h afforded a single crystalline product which was assigned the disulfide structure 134 (equation 54). More recently, Kobayashi and Mutai195 have also suggested a sulfoxide-sulfenate rearrangement for the photochemical conversion of 2,5-diphenyl-l,4-dithiin 1-oxide (135) to the 1,3-dithiole derivatives 136 and 137 (equation 55). 

Die Methode ist besonders zur Herstellung vicinaler, sekundarer Dithiole geeig-net, die auf andere Weise schwer zuganglich sind (s.a. Tab. 29, S. 342). 

Geminale Dithiole reagieren mit Lithiumalanat (mit Natriumboranat s.Lit.5) unter Bildung von Thiolen6 ... 

Fused 1,4-dithiins are formed when the 1,8-diketones derived from dithiols and a-bromoketones are treated with Lawesson s reagent (LR) <96TL2821>. 

Condensation of dicesium 2-thioxo-l,3-dithiole-4,5-diselenolate with fo/s-alkylating polythioethers under high dilution conditions afforded the TTF-containing macrocycles possessing soft donor sites and 12-, 15-, and 18-membered rings <%JCS(P1)1995>. 

The cycloaddition of alkynes with the tributylphosphine-carbondisulfide adduct 131 results in the in situ formation of the ylides 132 which react with aldehydes to give the novel 2-arylidene or 2-alkylidene-l,3-dithioles 133 (Scheme 36) [132]. Concerning ylides C-substituted by sulfur we can also mention a publication on the behavior of various keto-stabilized ylides towards acyclic and cyclic a s-disulfides allowing the synthesis of substituted thiazoles, thiols, and dithiols [133]. 

Answer Various sequences of C-S disconnections would no doubt all lead to good syntheses. Disconnect ion (4a) has the advantage of giving a symmetrical dithiol (5) and available (p T 53) chloroacetyIchloride. 

Mo3S7(dithiolate)3] 3 PPh3 [Mo3S4(dithiolate)3] -1- 3 S=PPh3... 

The structure of [Mo3S4(dmit)3] (dmit=l,3-dithiole-2-thione-4,5-dithiolate) represents one of the rare examples of M3S4 clusters where each metal atom appears as pentacoordinate instead of its more common type-I structure octahedral environment [39]. Complexes [M3Q4(dmit)3] (M = Mo, W Q = S, Se) degrade in air with an almost quantitative yield and afford a series of M(V) dimers of formula [M202(//-Q)2(dmit)2] where the oxygen atoms are in a syn configuration. 

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