A Convenient Synthesis of 2-Substituted 3-Hydroxy- and 3-Amino-Thiophens from Derivatives of 2-Chloroacrylic Acid

Huddleston, P. R.; Barker, J. M.

doi:10.1080/00397917908064186

Cited by 52 publications

(12 citation statements)

References 2 publications

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“…HSCH 2 COONa + HCl −→ HSCH 2 COOH + NaCl (5) Therefore, manufacture of thioglycolic acid is associated with the production of aqueous salt waste, so problems of waste disposal have to be resolved in each plant. Where thioglycolic acid is manufactured mainly as an intermediate for conversion to higher alkyl esters, the alcohol of the ester can be used as solvent to extract thioglycolic acid.…”

Section: Manufacturing Processing and Storagementioning

confidence: 99%

Thioglycolic Acid

Labat

2000

Kirk-Othmer Encyclopedia of Chemical Technology

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Thioglycolic acid and its derivatives as well as various other mercaptocarboxylic acids have become widespread. Both the mercapto and carboxylic functions in thioglycolic acid are chemically active, as is the methylene group in esters under alkaline conditions. The most important reactions involve the thio disulfide interchange reactions with cystine units in hair protein, keratin, which property is applied in cosmetology for hair waving, and the formation of esters to give tin stabilizers for poly(vinyl chloride). For esters, the ability to build N and S heterocycles promises prospective development in fine chemistry. Other mercaptocarboxylic acids have experienced interesting developments, mainly as polymer modifiers and polymer stabilizers. Thioglycolic acid is manufactured from the inexpensive starting materials chloroacetic acid and alkali sulfhydrates. Thioglycolic acid is degraded by self‐esterification but is stable at low temperatures. All processes which produce thioglycolic acid are characterized by salt formation.

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Section: Manufacturing Processing and Storagementioning

confidence: 99%

Thioglycolic Acid

Labat

2000

Kirk-Othmer Encyclopedia of Chemical Technology

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“…The melting point of matc is about 63-64 • C [14]. Thus, it is in the solid state at room temperature, which favors the determination of the crystal structure.…”

Section: Introductionmentioning

confidence: 99%

Crystal Structure and Computational Study on Methyl-3-Aminothiophene-2-Carboxylate

et al. 2020

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Methyl-3-aminothiophene-2-carboxylate (matc) is a key intermediate in organic synthesis, medicine, dyes, and pesticides. Single crystal X-ray diffraction analysis reveals that matc crystallizes in the monoclinic crystal system P21/c space group. Three matc molecules in the symmetric unit are crystallographically different and further linked through the N–H⋯O and N–H⋯N hydrogen bond interactions along with weak C–H⋯S and C–H⋯Cg interactions, which is verified by the three-dimensional Hirshfeld surface, two-dimensional fingerprint plot, and reduced density gradient (RDG) analysis. The interaction energies within crystal packing are visualized through dispersion, electrostatic, and total energies using three-dimensional energy-framework analyses. The dispersion energy dominates in crystal packing. To better understand the properties of matc, electrostatic potential (ESP) and frontier molecular orbitals (FMO) were also calculated and discussed. Experimental and calculation results suggested that amino and carboxyl groups can participate in various inter- and intra-interactions.

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“…Thus, a new synthetic route to BTfOR was designed as described in Scheme , which enables successful synthesis of the brominated and stannylated monomers. Methyl 3‐hydroxythiophene‐2‐carboxylate ( 1 ) was prepared according to the reported procedure in literatures, then followed by bromination to afford methyl 4‐bromo‐3‐hydroxythiophene‐2‐carboxylate ( 2 ) . The etherification of compound 2 was readily realized in the presence of 1‐bromododecane and potassium carbonate to give methyl 4‐bromo‐3‐(dodecyloxy)thiophene‐2‐carboxylate ( 3 ).…”

Section: Resultsmentioning

confidence: 99%

“…5 and 5′ positions of BTOR were first protected using trimethylsilyl groups and the compound was directly subjected to a typical fluorination method (Scheme S1, Supporting Information). [43][44][45] The etherification of compound 2 was readily realized in the presence of 1-bromododecane and potassium carbonate to give methyl 4-bromo-3-(dodecyloxy)thiophene-2-carboxylate (3). Thus, a new synthetic route to BTfOR was designed as described in Scheme 1, which enables successful synthesis of the brominated and stannylated monomers.…”

Section: Materials Synthesismentioning

confidence: 99%

Fluorinated Head‐to‐Head Dialkoxybithiophene: A New Electron‐Donating Building Block for High‐Performance Polymer Semiconductors

Huang

Guo

Uddin

et al. 2017

Adv Elect Materials

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New building blocks with good solubility and optimized optoelectrical property are critical for materials development in organic electronics. Herein, a new head‐to‐head linkage containing a donor unit, 4,4′‐difluoro‐3,3′‐dialkoxy‐2,2′‐bithiophene (BTfOR), is synthesized. The dialkoxy chains afford good materials solubility and also planar backbone via noncovalent (thienyl)S⋯(alkoxy)O interactions. Compared to the reported 3,3′‐dialkoxy‐2,2′‐bithiophene (BTOR), F addition leads to BTfOR with lower‐lying frontier molecular orbitals and can further promote polymer packing via additional F⋯S or F⋯H interactions. BTfOR can be readily stannylated to afford tin monomer with high purity and excellent reactivity toward Stille polymerization. As a proof of concept for materials design, BTfOR‐based homopolymer (PBTfOR) is synthesized, showing high molecular weight and strong aggregation. Moreover, the HOMO (−4.98 eV) of PBTfOR is greatly lower than that (−4.54 eV) of nonfluorinated counterpart PBTOR, which is attributed to the addition of F atoms. When incorporated into thin‐film transistors, PBTfOR exhibits a remarkable hole mobility of 0.57 cm2 V−1 s−1, showing an exceptional example of high‐mobility head‐to‐head polythiophene. This study demonstrates that introduction of F atoms can lead to BTfOR with optimized physicochemical properties, and the new BTfOR should find promising use for constructing donor–acceptor copolymers for high‐performance electronic devices.

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A Convenient Synthesis of 2-Substituted 3-Hydroxy- and 3-Amino-Thiophens from Derivatives of 2-Chloroacrylic Acid

Cited by 52 publications

References 2 publications

Thioglycolic Acid

Thioglycolic Acid

Crystal Structure and Computational Study on Methyl-3-Aminothiophene-2-Carboxylate

Fluorinated Head‐to‐Head Dialkoxybithiophene: A New Electron‐Donating Building Block for High‐Performance Polymer Semiconductors

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