1,4-Dithiins thiophenes

Dithiin, 2,4-dimethyl-2,4,6-triphenyl-thiophene synthesis from, 4, 903... 

Tile preparation of beiizo-l,2-dithiete (264) had been claimed by oxidation of 1,2-benzenedithiol (25JIC318). However, later work has shown that the reaction product was probably a polymeric mixture (61JOC4782). Subsequently, compound 265 was irradiated to give a mixture of CO, sulfur, and dithiin and thiophene derivatives, which could, at least in part, be explained by the formation of 266 (72JHC707). Results of the thermolysis of 267 were also rationalized in terms of the intermediacy of o-dithiobenzo-quinone (the tautomer of 264) (78JOC2084). 

Kobayashi and Mutai75 have recently reported an interesting rearrangement of the 1,4-dithiin sulfone (53) to the thiophenes (54) and (55) (equation 12). While 54 presumably arises as a result of simple photoextrusion, the rearranged thiophene (55) is postulated to arise via the valence isomer (56), followed by cyclization to the thiophene, concomitant with, or preceded by, loss of S02. Some support for the intermediacy of the thioketone (56) was revealed by the isolation of the pyrrole (57), when the photolysis was conducted in n-butylamine. Compound 57 presumably arises by cyclization of the iV-butylimine analog of 56 initially formed. 

In the synthesis of l,3-dithiole-2-thione derivatives as intermediates for electropolymerization precursors, the bicyclic 462 was found to be inert to normal cyclization conditions <1999JOC6418>. This is believed to be due to steric hindrance, from the boat conformation of the dithiin ring. Cyclization was achieved, albeit in only moderate yields, by heating with P2S3 to give the thiophene 463a or HBr/AcOH for the furan 463b (Equation 125). 

Tetracyanoethylene (TCNE)175,176 reacts with thiobenzophenones to yield 2,3-dihydrothiophene, thiophene, and 1,2-dithiin derivatives, thus depending on temperature. Okuma suggested a mechanism176 for the formation of 2,3-dihydrothiophenes through [2+2] and [4+2] sequential cycloadditions. 

A thiophene ring can also be produced from two methylene groups. Here 2,5-dicarbethoxy-3,4-dicyanomethylthiophene 19 reacted with sulfur mono-chloride to give tetrasubstituted thieno[3,4-c]thiophene 20 in moderate yield (2002JCX72453). A mechanism for the thiophene 20 formation was proposed and 1,2-dithiine derivative 21 was likely to be an intermediate (Scheme 10) because sulfur monochloride gave higher yields of 20 than SCl2. At the next step (21 20), sulfur monochloride apparently acted as an oxidant. 

Krespan and McKusick have studied the addition reaction of dithietenes to various oleflnes and acetylenes. Thus, the reaction of 3,4-bis(trifluoromethyl)-l,2-dithiete (378) with DMAD gives a dithiin derivative (379), which loses sulfur on heating to give 2,5-dicarbomethoxy-4,5-bis(trifluoromethyl)thiophene (380) [Eq. (57)]. 

The spectroscopic data of a number of 1,2-dithiin derivatives (Scheme 13) are summarized in Table 2. Comparison of the H NMR spectroscopic data of the dithiins 51 with those of the corresponding thiophenes shows that both the a- and ft- protons are significantly shielded in 51, reflecting the presence of the ring current effect in the thiophenes <2000JA5052>. 

Conversion of dithiins to thiophenes by thermal or photochemical sulfur loss... 

To study the photochemistry of the dithiins 51b (Scheme 13) in solution, the compounds were irradiated with visible light at —60 to —75 °C to afford the thiiranes 118 in excellent yields which were characterized by H and NMR spectroscopy. Upon warming or further exposure to light, the thiiranes 118 afforded the thiophenes 119 (Scheme 29) <2000MI159, 1996JA4719>. 

A facile [4+l]-type synthetic route to thiophenes from dienol silyl ethers and elemental sulfur has been published however, the intermediate 1,2-dithiin derivatives were not isolated <2006T537>. 

Finally, an unorthodox pathway to the dithiin systems has been reported Tetracyanoethylene 214 combines with two molecules of thiobenzophenone in refluxing benzene to give the tetrasubstituted 1,2-dithiins 215. However, these were obtained only in addition to the corresponding thiophenes 216 as the main reaction products (Scheme 59) <1985TL1849, 1997LA1677>. 

Thieno[3,4-3]thiophenes 500 were prepared from thiophen-3-yl-substituted [l,3]dithiol-2-ones 496 in good yields <2003JOG7115>. The photochemical irradiation of 496 leads to thieno[3,4-f]dithiines 497 via a unique ring cleavage reaction and subsequent reductive treatment of dithiines 497 proceeds to give 2,3-dihydrothieno[3,4-/ ]thiophenes 498 and 499. Heating of 499 in the presence of further iodomethane leads to the formation of the thieno[3,4-/ ]-thiophenes 500 (Scheme 63). 

Reaction of various aldehydes with hydrogen sulfide leads to substituted thiophenes, dihydrothiophenes, dithiolanes and trithiolane, as well as to six-membered ring thiopyran derivatives and dithiins. Ledl (33) obtained 2,4-dimethylthiophene (1, R Me) as a product of the reaction of propionaldehyde with hydrogen sulfide in the presence of ammonia. Sultan (29) reported the formation of 2,4-diethylthiophene (1, R - Et), 2,4-dibutyl-thiophene (1, R - Bu), and their dehydro derivatives from the reaction of ammonium sulfide with butyraldehyde and caproaldehyde (hexanal), respectively. The mechanism suggested for their formation is depicted in Scheme 1. Space limitations do not allow us to discuss the mechanism here in detail (for additional information, see ref. 29). 

Related reactions include preparations of furans from pyrylium cations (Section 3.2.1.6.3.v). 1,4-Dithiins (56JA850) and 1,2-dithiins (67AG(E)698) readily lose sulfur on heating, yielding the corresponding thiophene (191 — 192 193 — 194). 

Several heterocyclic sulfur compounds have been shown to function as C2S sources in this type of thiophene synthesis. Thus 2,5-diphenyl- 1,4-dithiin 1,1-dioxide (255a) condenses... 

A [5 - 2 + 2 + 1] fragmentation followed by cyclization forming a new five-membered ring was observed by FVP studies of 2-propenyl-l,3-dithiolan 1,1-dioxide (79) (95H1967). The reaction mixture consists of four products thiophene (26%), 2,5-dihydrothiophene (80,34%), 4-methyl-2-propenyI-4//-l,3-dithiine (20%), and 2,6-dimethyl-2//,6//-l,5-dithiocine (20%). The last two compounds are formed by [4 + 2] or [4 + 4] dimerization of the intermediate 2-butenethial. Formation of 80 involves a 1,5-H shift of the as-butenethial, followed by cyclization. 

---