Profft, Elmar; Hoffmann, Hubert published the artcile< Thiophene. VIII. Sulfur derivatives of 2,3-dichloro-thiophene>, Synthetic Route of 31166-29-7, the main research area is .
The α-Cl atom of RCH2Cl (I) [R = 2,3-dichlorothien-5-yl] is very loosely held. Thus, 3.4 g. I reacted immediately in the cold with 1.7 g. KSCN in 30 ml. EtOH to give 68.8% RCH2SCN, m. 70° (petr. ether). I (51 g.) and 28 g. NH2CS2NH4 in 100 ml. EtOH gave RCH2SCSNH2 (II), yellowish crystals, m. 130° (petr. ether), almost quant. II warmed with 2N KOH gave 90.7% RCH2SH (III), b14.5136-8°. I (26.6 g.) warmed gently with KSH (from 9.4 g. KOH and H2S) in EtOH gave 56.6% crude III (which resinified on attempted distillation) and 41.4% (RCH2)2S (IV), m. 80-1°. III with Br in Et2O gave 80.5% (RCH2S)2 (V), m. 56°. III (2.5 g.) and 5 ml. H2O2 (Perhydrol) in 50 ml. HOAc at 50° gave 36.4% RCO2H, m. 196-7° (aqueous EtOH), probably via V. IV (2.8 g.) and 0.75 ml. Perhydrol in 25 ml. AcOH, after standing a few days, gave 99.2% (RCH2)2SO, m. 128° (EtOH). Similarly, 2.5 g. IV and 7 ml. Perhydrol gave 95.6% (RCH2)2SO2, m. 186° (EtOH). From I and Na mercaptides in absolute EtOH or from the Na salt of III and alkyl halides, the following RCH2SR’ (VI) were prepared in yields of 71-8% (R’ given): Et, b15 157°; Pr, b15 168°; Bu, b15 179°; Ph, m. 38° (EtOH); p-MeC6H4 (VII), m. 69° (EtOH). VI with a 4-fold excess of H2O2 in AcOH gave quant. the following RCH2SOR’ (R’ and m.p. given): Et, 92°; Pr, 106°; Bu, 82°; Ph, 137°. VII (1.2 g.) and 1 ml. Perhydrol in 10 ml. AcOH gave quant. p-MeC6H4SO2CH2R, m. 175-6° (EtOH). Portionwise addition of ClCH2COOK (from 4.8 g. acid) to an aqueous alc. solution of RCH2SK (from 10 g. III), keeping the temperature below 40°, and acidification, gave 77.5% RCH2SCH2COOH, m. 95° (petr. ether). No pure product could be isolated from the reaction of III with HNO3. I did not react with K3SO3 at room temperature; at a higher temperature (RCH2)2O was formed.
Journal fuer Praktische Chemie (Leipzig) published new progress about 31166-29-7. 31166-29-7 belongs to class chlorides-buliding-blocks, and the molecular formula is C5H2Cl2O2S, Synthetic Route of 31166-29-7.
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Chloride – Wikipedia,
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