Alkylation thiophene derivatives

In field-effect transistors based on the thin films of poly(3-alkyl)thiophene derivatives, high field-effect mobility has been observed because of the formation of crystal-like grains [116]. The mobility depends strongly upon the crystallinity of the thin films. Introduction of liquid crystallinity into conjugated polymers is expected to be effective for enhancing microscopic crystallization of conjugated polymers to increase their carrier mobilities. It can also cause anisotropy in various physical properties if macroscopic molecular alignment is achieved. 

Table 2. Antifungal activity of alkyl-thiophene derivatives. O...

A report has described a route to multiply alkylated thiophene derivatives from electrochemically derived diarylcarbenium ions (Scheme 46). Using the cation-pool technique - in which the cationic intermediate is generated in high concentration and pooled - the carbocation (228) alkylates thiophene, providing up to 58% of the trialkylated product (229) and 24% of the dialkylated product (230). 

Thiophene [110-02-1] and a number of its derivatives are significant in fine chemical industries as intermediates to many products for pharmaceutical, agrochemical, dyestuffs, and electronic appHcations. This article concentrates on the industrial, commercial, and economic aspects of the production and apphcations of thiophene and thiophene derivatives and details the main synthetic schemes to the parent ring system and simple alkyl and aryl derivatives. Functionalization of the ring and the synthesis of some functional derivatives that result, not from the parent ring system, but by direct ring cyclization reactions are also considered. Many good reviews on the chemistry of thiophene and thiophene derivatives are available (1 7). 

The thenyl cyanides are of great importance for the preparation of thiophene derivatives. Because of the acidifying effects of both the thienyl and of the cyano groups, carbanions are easily obtained through the reaction with sodamide or sodium ethoxide, which can be alkylated with halides, carbethoxylated with ethyl carbonate, or acylated by Claisen condensation with ethyl... 

An important special case of RSR reduction is desulfurization of thiophene derivatives. This proceeds with concomitant reduction of the double bonds. Many compounds have been made by alkylation of thiophene, followed by reduction ... 

Dialkyl esters of 1,3,4-hexatrienephosphonic acid react with alkyl(phenyl)sul-phenyl halides, to form mixture of 2,5-dihydro-l,2-oxaphosphole-2-oxide derivatives and thiophene derivatives (Scheme 69) [147-149]. 

Shimizu and co-workers reported that thermal decomposition of A4-thiabenzenes ylides afforded both thienofuran and thiophene derivatives in addition to the expected alkyl-rearranged products. A plausible mechanism was proposed with a [3.1.0] bicyclic sulfonium salt 9 as the key reactive intermediate <2001J(P1)2269>. Warren and co-workers, in their study of stereospecific phenysulfanyl migrations, found that [l,4]-sulfanyl participation could compete with the usual [l,2]-sulfanyl participation <1999SL1211>. Rearrangement of alcohol 18 with TsCl in pyridine gave an inseparable mixture of isomeric chlorides, 19 and 20, in a ratio of 52 48, as shown in Equation (3). 

The oxidation of thiophene and its derivatives with H202 was studied using a Ti-Beta molecular sieve. The oxidation product is very dependent from the aromaticity of model compounds. The thiophene oxidation product was mostly sulfates and the benzothiophene oxidation product was benzothiophene sulfone. Oxidation of mono and di-alkyl thiophenes also produced sulfates and sulfones. The diffusivity and aromaticity of the relevant sulfur compounds, intermediates and stable product, as well as the proposed new mechanism of oxidation will be discussed. This proposed new reaction pathway is different from current literature, which reports the formation of sulfones as a stable oxidation product. 

A recent report indicates that thiophenes (not benzothiophenes) may be formed from alkyl phenyl ketones by treatment with a slight excess of thionyl chloride in the cold.58 Propiophenone, for example, yields 3,4-dibenzoyl-thiophene (47). Adipic acid and related carboxylic acids yield thiophene derivatives upon treatment with thionyl chloride in the presence of pyridine.59... 

Challenger and Harrison found both thienothiophene 1 and its isomer 2 in the products of the reaction between acetylene and sulfur. To identify these compounds, Challenger et developed syntheses of unsubstituted and 2-alkyl-substituted thieno[3,2-f>]thiophene (2) from thiophene derivatives. Cyclization of (3-thienylthio)acetic acid in the presence of sulfuric acid gave 2,3-dihydrothieno[3,2-6]thiophen-3-one (22) (R = H) in 14% yield reducing the latter with lithium aluminum hydride resulted in thienothiophene (2) formation in 80% yield [Eq. (9)]. Similarly 2-methyl- and 2-ethyl-2,3-dihydrothieno[3,2-/>]thiophen-3-one were obtained from a-(3-thienylthio)propionic and a-(3-tWenylthio)-butyric acids in 30% and 27% yields, respectively their reduction yielded 2-methyl (32%) and 2-ethylthieno[3,2-6]thiophenes (52%). The parent acids were prepared from 3-mercaptothiophene. ... 

The authors of this review have developed a straightforward procedure for the synthesis of unsubstituted and alkyl-substituted thieno-thiophenes 1, 2, and 3 the method involves intramolecular condensation of ortho-bifunctional thiophene derivatives. Vilsmeier formylation of an alkyl (5-ethyl-2-thienylthio)acetate (53) furnishes the (5-ethyl-3-formyl-. 2-thienylthio)acetate (54) which when heated with alcoholic sodium... 

Though it has long been known that the more highly condensed thiophene structures, such as dibenzothiophene and especially their alkyl-substituted derivatives, have low HDS reactivity (21, 25-29), it is only recently that study in this area has intensified. Researchers throughout the world are now actively seeking understanding of the fundamental causes of low reactivity and attempting to find means to circumvent the problems (29-33). 

As one proceeds to more condensed thiophene derivatives (such as diben-zothiophene), the effects of alkyl substitution become much more signifi-... 

A new synthetic route to alkyl-substituted quinones has relied on the photochemical reaction of 2,3-dichloro-l,4-naphthoquinone with a thiophene derivative (77CL851). Irradiation of a benzene solution of the quinone and thiophene by a high pressure mercury lamp gave photoadduct (295) in 56% yield. Desulfurization of this compound over Raney nickel (W-7) gave the 2-butyl-1,4-naphthoquinone derivative (296 Scheme 62). Alkyl-substituted quinones such as coenzyme Q and vitamin K, compounds of important biological activity, could possibly be prepared through such methodology. 

Alkylation. Thiophenes can be alkylated in the 2-position using alkyl halides, alcohols, and olefins. Choice of catalyst is important the weaker Friedel-Crafts catalysts, eg, ZnCl2 and SnCl4, are preferred. It is often preferable to use the more readily accomplished acylation reactions of thiophene to give the required alkyl derivatives on reduction. Alternatively, metalation or Grignard reactions, on halothiophenes or halomethylthiophenes, can be utilized. 

Thiophenes are desulfurized to give products with a C4 carbon chain (see eqs. 13.60 and 13.63), and hence the desulfurization of thiophene derivatives has been applied for syntheses of compounds with longer alkyl chains, in particular, for long-chain compounds, which are not easily obtainable by conventional synthetic methods. Examples are shown in eqs. 13.87-13.90. 

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