Thiophenes Grignard reagents

The synthesis involves the nickel-catalyzed coupling of the mono-Grignard reagent derived from 3-alkyl-2,5-diiodothiophene (82,83). Also in that year, transition-metal hahdes, ie, FeCl, MoCl, and RuCl, were used for the chemical oxidative polymerization of 3-substituted thiophenes (84). Substantial decreases in conductivity were noted when branched side chains were present in the polymer stmcture (85). 

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[6]thiophene, 6-bromo-synthesis, 4, 878, 934 Benzo[6]thiophene, 5-t-buty 1-3-methyl-synthesis, 4, 880... 

Dichlorothiophene has become easily available through chlorination and dehydrochlorination of tetrahydrothiophened Another example of the aromatization of tetrahydrothiophene derivatives is the preparation of 3-substituted thiophenes by the reaction of 3-ketotetrahydrothiophene with Grignard reagents followed by the aromatization of the intermediate dihydrothiophene. Recent gas chromatographic analysis showed, however, that 2,3-dichlorothio-phene is the main product from the dehydrochlorination of tetra-chlorotetrahydrothiophene. 

Grignard reagents has been introduced by Wynberg et for the preparation of 3-substituted thiophenes. 

By reaction of 3-thienyllithium with magnesium bromide, the Grignard reagent, free from entrainment Grignard reagent, was obtained,- which is useful for the preparation of 3-acetothiophene by reaction with acetic anhydride at —70 0 and for the preparation of 3-t-butoxythiophene through reaction with t-butyl perbenzoate. It is the opinion of the present author that most 3-substituted thiophenes are prepared more conveniently from 3-thienyllithium than from 3-thenyl bromide. The latter method, however, is superior if the introduction of the 3-thenyl group is desired. 

As already mentioned, unsubstituted PT is an insoluble and infusible material. Once the polymer is prepared, it is difficult (if not impossible) to further process it as a material for electronic applications. The solubility can be greatly enhanced by the introduction of side chains at position 3 (or at both, 3 and 4). The most widely studied side chains are n-alkyl substituents that can be easily introduced into the thiophene core by reaction of 3-bromothio-phene with alkyl-Grignard reagents [464]. 

Substituted dibenzothiophenes 156 react with Grignard reagents to give products of the thiophene ring cleavage. With a chiral Ni catalyst, axially chiral biaryl compounds 157 can be obtained in high enantioselectivities (equation 93) . ... 

The reactive 3-carbonyl group in compounds of type (279) undergoes aldol condensation with active methylene compounds such reactions of isatin with indoxyl, oxindole (Section 3.3.2.5.4) and with thiophenes (Section 3.3.1.5.7.ii) have already been mentioned. These compounds also react with Grignard reagents and phosphorus halides as expected, e.g. isatin (279 Z = NH) with MeMgBr and PC13 yields (285) and (286), respectively. 

Chloromethylthiophene shows similar reactivity to benzyl chloride, in that it is readily converted into 2-cyanomethylthiophene, thiophene-2-carbaldehyde (by treatment with hexamethylenetetramine) and a Grignard reagent (345). The latter reacts with electrophiles to give 2-methyl-3-substituted thiophenes e.g. 346). 

Although a limited range of Grignard reagents is available, the most widely used group is undoubtedly the lithio group introduced by direct lithiation (see Section 3.3.1.6.2). The ready formation of the lithio derivatives of pyrroles, furans and thiophenes and their benzo-fused derivatives has had a most important impact on the chemistry of these heterocyclic systems. Reaction of the... 

Iodothiophene reacts with magnesium to form a Grignard reagent and is hence useful in the preparation of other thiophene derivatives. 

In this section we discuss the opening of the thiophene ring by Grignard reagents. Nucleophilic ring-opening reactions of cyano- and nitro-thiophenes are relegated to the appropriate sections (3.14.3.3 and 3.14.3.5). 

The reaction of Grignard reagents with thiophene and benzo[6]thiophene in presence of bis(triphenylphosphine)nickel dichloride catalyst results in ring opening with replacement of C—S bonds by C—C bonds (Scheme 38) (79CC637). Thus phenylmagnesium bromide gives 1,4-diphenylbutadiene and phenylstilbene respectively as a 1 1 mixture of stereoisomers. 

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