Thiophen 2-iodo-3-methyl

Thiophene, 2-hydroxy-5-methyl-synthesis, 4, 926 Thiophene, iodo-... 

Thiophene, 2-hydroxy-5-methyl-synthesis, 4, 926 Thiophene, iodo-Grignard reagents, 4, 79, 831 photolysis, 4, 832 reactions, 4, 932 with phenyllithium, 4, 831 synthesis, 4, 835, 934 Ullmann coupling reactions, 4, 837 Thiophene, 2-isopropyl-3-methyl-synthesis, 4, 901 Thiophene, mercapto-reactions, 4, 78 stability, 4, 825 synthesis, 4, 80, 835, 930-931 tautomerism, 4, 38, 727 Thiophene, 2-mercapto-5-methylthio-synthesis, 4, 872 Thiophene, 2-methoxy-chloromethylation, 4, 759 Thiophene, 3-methoxy-chloromethylation, 4, 759 Thiophene, 5-methoxy-2,4-dinitro-Meisenheimer complexes, 4, 815 Thiophene, 2-methoxy-5-methyl-Vilsmeier formylation, 4, 759-760 Thiophene, 2-methoxy-3-nitro-reactions, 4, 827 Thiophene, 2-methyl-bromination, 4, 799-800 conformation, 4, 32 HNMR, 4, 730 metallation, 4, 773 synthesis, 4, 885, 887 trifluoroacetylation, 4, 751 Thiophene, 3-methyl-bromination, 4, 799-800 conformation, 4, 32 H NMR, 4, 730 metallation, 4, 60 oxidation, 4, 800... 

Halothiophenes, which are not activated through the presence of —I—M-substituents, undergo substitution smoothly under more forcing conditions with copper salts in pyridine or quinoline. Hence 3-cyanothiophene and 5-methyl-2-cyanothiophene have been obtained from the corresponding bromo compounds. 2-Bromothiophene reacts readily with aliphatic cuprous mercaptides in quinoline at 200°C to give thioethers in high yields. The use of the copper-catalyzed Williamson synthesis of alkoxythiophenes from iodo- or bromo-thiophenes and alcoholate has been mentioned before. The reaction of 2-bromothiophene with acetanilide in nitrobenzene in... 

To a solution of 2-iodo-5-(4-fluorophenylmethyl)thiophene (5.30 g, 16.6 mmol), in anhydrous DMF (5.0 ml) was added (R)-N-hydroxy-N-(3-butyn-2-yl)urea (2.12 g, 16.6 mmol), triphenylphosphine (84.0 mg, 0.32 mmol), bis(acetonitrile)palladium(II) chloride (40.0 mg, 0.16 mmol), copper(I) iodide (16.0 mg, 0.08 mmol), and diethylamine (5.6 ml). The mixture was stirred under nitrogen at room temperature for 22 h and concentrated in vacuum at 32°C. The residue was subjected to chromatography on silica eluting with 2-7% MeOH in CH2CI2, crystallization from ethyl acetate-hexane and trituration in CH2CI2 to afford (R)-N- 3-[5-(4-fluorophenylmethyl)thien-2-yl]-l-methyl-2-propynylVN-hydroxyurea as a cream-colored solid 0.94 g (18%), melting point 135°-136°C, (dec). 

The Hiyama couplings of heterocycles are still being developed to their full potential. Nevertheless, several heteroaryl halides have been cross-coupled with aryl or heteroaryl silicon reagents [52]. For example, in the presence of catalytic tt-allylpalladium chloride dimer and two equivalents of KF, the cross-coupling of ethyl(2-thienyl)difluorosilane (53) and methyl 3-iodo-2-thiophenecarboxylate led to bis-thiophene 54 under relatively forcing conditions [53]. 

AG(E)508> of -l,2-bis(tri-/i-butylstannyl)ethylene with a 2-iodo-3-substituted thiophene affords monomer (147) <93SM1188>. When 2,5-diiodothiophene derivatives are used, the polymer (148) is obtained directly <93MI 212-12, 93SM1255>. Thiophene-2,5-dicarbaldehyde can also be subjected to benzoin condensation conditions to afford (149) after methylation with dimethylsulfate <93MI 212-13>. 

The first example of alkylthiophene bromination was also demonstrated at that time. Methylthiophene which was obtained from coal tar as a mixture with toluene was reacted with bromine, and dibromo(methyl)thiophene separated from toluene. Its further bromination led to the synthesis of fully substituted tribromo(methyl) thiophene. 2-Iodo-5-methylthiophene was obtained by the same iodination procedure as iodothiophene. Deiodination with sodium allowed for the isolation of pure methylthiophene [80]. 

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