5-Butyl-2- thiophene, synthesis

Friedel-Crafts alkylation of 2,5-dimethylthiophene with f-butyl chloride and A1C13 gave only the mono-r-butylated product (49) and none of the expected di-f-butylated thiophene (50). In order to facilitate di-r-butylation at positions 3 and 4, the substituents at 2 and 5 were tied back in the thiophenophane (51). This on alkylation gave, unexpectedly, the rearranged mono-f-butyl derivatives (52 30%) and (53 57%), and the di-f-butyl derivative (54 12%). The structures of the products were proved by NMR, Raney nickel desulfurization and independent synthesis (75T2551). One other such isomerization under Friedel-Crafts conditions had been previously reported (65JOC1058) 2,5-di-f-butylthiophene isomerizing to 2,4-di-f-butylthiophene. 

Chloro-2,3-diethyl-2-cyclobutenone (611) undergoes a palladium-catalyzed cross-coupling with 2-(tri- -butyl)stannyl-5-trimethylsilylthiophene (612) to give the intermediate compound (614) (Equation (110)). Without isolation, (614) is converted to the benzothiophene (613) on thermolysis at 100°C followed by acetylation. Although this procedure seems not to be generally applicable to benzo[6]thiophene synthesis, it provides a general synthesis of dibenzothiophenes, and thus a series... 

Benzo[i]thiophene, 6-/-butyl-3-methyl-synthesis, 4, 880 Benzo[6]thiophene, 2-chloro-... 

Thiophene, bromotetrahydromethyl-pyrolysis, 3, 902 Thiophene, 5-t-butyl-2-methyl-dealkylation, 4, 800 Thiophene, chloro-polymerization, 4, 758 reaction with n-butyllithium, 4, 831 synthesis, 4, 835, 882, 933 Thiophene, 2-chloromercurio-reactions... 

Thiophene, 3,5-di-t-butyl-2-methyl-sulfonation, 4, 764 Thiophene, 2,4-dicarboxy-synthesis, 4, 870 Thiophene, 2,3-dichloro-synthesis, 4, 933 Thiophene, 2,5-dichloro-synthesis, 4, 933 Thiophene, 3,4-dichloro-... 

The first synthesis of the parent compound of the benzo[4,5]thieno[2,3-f]pyrrole ring system 387 <2003T1477> and its derivatives was accomplished using the same synthetic sequence (Scheme 42). Starting with 2-methyl-benzo[ ]thiophene-3-carbaldehyde 388, an intermediate 389 was obtained. Treatment of bromo compound 389 with sodium azide in ethanol led to the stable triazoline 390. 1,3-Dipolar cycloreversion of 390 was induced by a catalytic amount of />-TsOH to give the parent 2//-benzo[4,5]thieno[2,3-c]pyrrole 387. Alternatively, direct treatment of bromo compound 389 with excess ammonia furnished 387 in one step. Compound 387 was treated with di-/-butyl dicarbonate and 4-dimethylaminopyridine (DMAP) to give iV-BOC derivative 391. Reaction of 389 with... 

SYNTHESIS OF (45)-[(i -l,5-CYCLOOCTADIENE)- 4-ferf-BUTYL-2-(3-DIPHENYLPHOSPHINO-THIOPHENE-2-YL)-4, 5-DIHYDROOXAZOLE IRIDIUM(I)]-TETRAKIS[3, 5-BIS(TRIFLUOROMETHYL)PHENYL]BORATE... 

Alkanes and cycloalkanes. Obviously a variety of acyclic and cyclic hydrocarbon structures can be synthesized from the appropriate alkyl- or aryl-thiophenes (Scheme 46). The reaction is especially useful for the construction of macrocycles (Scheme 47). One of the most interesting applications of this reaction is in the synthesis of the chiral hydrocarbon butylethylmethylpropylmethane (210) (80JOC2754). The chiral acid (209) was the precursor, in which the thiophene was the potential n-butyl group. Raney nickel desulfurization, followed by standard manipulations to convert the acetic acid unit into an ethyl group, gave the hydrocarbon (210) (Scheme 48) this had [a]578 = -0.198°. It was established that... 

Tetrahydrobenzo[6]thiophen-4-one (103) may be prepared from y-(2-thienyl)butyric acid by cyclization with phosphoric acid854 or by Friedel-Crafts cyclization of the corresponding acid chloride.194, 355.358 j s 5-methyl,357 2-ethyl,194 2-isopropyl,358 2- and 3-tert-butyl,359 2,3-dimethyl,360 2-ethyl-3-methyl,360 and 2-bromo 354 derivatives and diethyl 4,5,6,7-tetrahydrobenzo[6]thiophene-4,5-di-carboxylate861 may be prepared similarly. 4,5,6,7-Tetrahydrobenzo-[6]thiophen-7-one (104)357 362,863 and its 5- and 6-methyl 357 and 2-chloro 362 derivatives are obtained from the appropriately substituted y-(3-thienyl)butyric acid, A recent patent 364 describes the vapor phase cyclization of y-(2-thienyl)butyric acid to 103. Ketones (103 and 104) are useful intermediates for the synthesis of 4- and 7-substituted benzo[6]thiophenes, respectively their reactions are discussed in Section VI, B, 4. 

Benzo[6]thiophene, 2-(aryloxymethyl)-3-chloromethyl-synthesis, 4, 872 Benzo[6]thiophene, 2-arylthio-synthesis, 4, 931 Benzo[6]thiophene, 2-bromo-reaction with potassamide, 4, 829-830 synthesis, 4, 934 Benzo[6]thiophene, 3-bromo-Grignard reagents, 4, 831 reactions, 4, 830 synthesis, 4, 934 Benzo[6]thiophene, 4-bromo-synthesis, 4, 878, 934 Benzo[6]thiophene, 5-bromo-electrophilic substitution, 4, 797 Benzo[f>]thiophene, 6-bromo-synthesis, 4, 878, 934 Benzo[f>]thiophene, 5-f-butyl-3-methyl-synthesis, 4, 880... 

Fig. 19. Synthesis of l-butyl-3-(2-thiophen-2-yl-ethyl)urea (41) and l-(3-isopr0PoX propyl)-3-phenethylthiourea (43).

The stable did -azulcnyl)thieno[3,2-9]thiophene-2,5-diyl spacers 78a and 78b were prepared by hydride abstraction of the corresponding 2,5-bis[bis(methyl and 3,6-di-tert-butyl-l-azulenyl)methyl]thieno[3,2-9]thiophenes 77a and 77b, the synthesis of which was established by the reaction of 1-methyl- and 1,6-di-t-butylazulcncs 75a and 75b with thicno 3,2-9 thiophene-2,5-dicarbaldehyde 76 (Scheme 11). The dications 76 showed high stability with large pA"R+ values. The electrochemical behavior of 78 was examined by cyclic voltammetry (CV). Chemical reduction of 78 with Zn powder in acetonitrile afforded 79 as deep-colored crystals, which exhibited rather high... 

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