- Macrocyclic Oligothiophene with Stereogenic [2.2]Paracyclophane Scaffolds: Chiroptical Properties from π-Transannular Interactions
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The enantiomers of a new cyclic oligothiophene, bridged by two pseudo-ortho[2.2]paracyclophanes, were synthesized as a new class of the chiral π-conjugated system. Single-crystal X-ray diffraction analysis revealed a twisted structure for these oligothiophenes induced by a torsion of the cyclophane moieties. The embedding oligothiophenes into the inherent planar chirality provided a significant enhancement in circular dichroism (CD) spectra thanks to the large magnetic/electric transition dipole moments. In the dicationic state, an intramolecular π dimer was formed due to the strong interactions of the oligothiophenes. We further recorded unprecedented wide ranges of CD spectra in 250–1800 nm region. The transitions are reasonably described by the exciton coupling of the oligothiophenes.
- Hasegawa, Masashi,Kobayakawa, Kosuke,Matsuzawa, Hideyo,Nishinaga, Tohru,Hirose, Takashi,Sako, Katsuya,Mazaki, Yasuhiro
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- Deprotonative C-H silylation of functionalized arenes and heteroarenes using trifluoromethyltrialkylsilane with fluoride
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A highly selective C-H silylation reaction of functionalized arenes and heteroarenes was developed using Ruppert-Prakash reagent (TMSCF3) activated by alkali metal fluoride. TMSCF3 is considered to play dual roles as a precursor of a mild base and also as a silicon electrophile. The silylation is compatible with sensitive functional groups such as halogen and nitro groups.
- Sasaki, Midori,Kondo, Yoshinori
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- Deprotonative Silylation of Aromatic C-H Bonds Mediated by a Combination of Trifluoromethyltrialkylsilane and Fluoride
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A method for the deprotonative silylation of aromatic C-H bonds has been developed using trifluoromethyltrimethylsilane (CF3SiMe3, Ruppert-Prakash reagent) and a catalytic amount of fluoride. In this reaction, CF3SiMe3 is considered to act as a base and a silicon electrophile. This process is highly tolerant to various functional groups on heteroarenes and benzenes. Furthermore, this method can be applied to the synthesis of trimethylsilyl group-containing analogs of TAC-101, which is a bioactive synthetic retinoid with selective affinity for retinoic acid receptor α (RAR-α) binding. We also report further transformations of the silylated products into useful derivatives.
- Nozawa-Kumada, Kanako,Osawa, Sayuri,Sasaki, Midori,Chataigner, Isabelle,Shigeno, Masanori,Kondo, Yoshinori
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p. 9487 - 9496
(2017/09/23)
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- COUPLED HETEROARYL COMPOUNDS VIA REARRANGEMENT OF HALOGENATED HETEROAROMATICS FOLLOWED BY OXIDATIVE COUPLING (HETEROARYLENE SPACER MOIETY)
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The inventions disclosed and described herein relate to new and efficient generic methods for making a wide variety of compounds having HAr - Z - Har tricyclic cores, wherein HAr is an optionally substituted five or six membered heteroaryl ring, and Hal is a halogen, and Z is a bridging radical, such as S, Sc, NR5, C(O), C(O)C(O), Si(R5)2, SO, S02, PR5, BR5, C(R5)2 or P(O)Rs and both HAr are covalently bound to one another. The synthetic methods employ a "Base-Catalyzed Halogen Dance" reaction to prepare a metallated compound comprising a five or six membered heteroaryl ring comprising a halogen atom, and then oxidatively coupling the reactive intermediate compound. The compounds of Formula (II) and/or oligomer or polymers comprising repeat units having Formula (II) can be useful for making semi-conducting materials, and/or electronic devices comprising those materials. Acyl compounds can be prepared. Heteroarylene substituents can be used. The core tricyclic core can be coupled to itself. The Z group also can be strong electron-withdrawing groups such as C=C(CN)2 or [C=C(CN)212. Organic electronic devices can be made including field-effect transistors. Formula (II).
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Page/Page column 40; 41
(2013/03/26)
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- COUPLED HETEROARYL COMPOUNDS VIA REARRANGEMENT OF HALOGENATED HETEROAROMATICS FOLLOWED BY OXIDATIVE COUPLING (ACYL MOIETIES)
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The inventions disclosed and described herein relate to new and efficient generic methods for making a wide variety of compounds having HAr - Z - Har tricyclic cores, wherein HAr is an optionally substituted five or six membered heteroaryl ring, and Hal is a halogen, and Z is a bridging radical, such as S, Se, NR5, C(O), C(O)C(O), Si(R5)2, SO, SO2, PR5, BR5, C(R5)2 or P(O)R5 and both HAr are covalently bound to one another. The synthetic methods employ a "Base-Catalyzed Halogen Dance" reaction to prepare a metallated compound comprising a five or six membered heteroaryl ring comprising a halogen atom, and then oxidatively coupling the reactive intermediate compound. The compounds of Formula (II) and/or oligomer or polymers comprising repeat units having Formula (II) can be useful for making semi-conducting materials, and/or electronic devices comprising those materials. Acyl compounds can be prepared. Heteroarylene substituents can be used. The tricyclic core can be coupled to itself. The Z group also can be strong electron-withdrawing groups such as C=C(CN)2 or [C=C(CN)2]2. Organic electronic devices can be made including field-effect transistors.
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Page/Page column 40; 41
(2013/03/26)
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- COUPLED HETEROARYL COMPOUNDS VIA REARRANGEMENT OF HALOGENATED HETEROAROMATICS FOLLOWED BY OXIDATIVE COUPLING (ELECTRON WITHDRAWING GROUPS)
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The inventions disclosed and described herein relate to new and efficient generic methods for making a wide variety of compounds having HAr - Z - Har tricyclic cores, wherein HAr is an optionally substituted five or six membered heteroaryl ring, and Hal is a halogen, and Z is a bridging radical, such as S, Sc, NR5, C(O), C(O)C(O), Si(R5)2, SO, SO2, PR5, BR5, C(R5)2 or P(O)R5 and both HAr are covalently bound to one another. The synthetic methods employ a "Base-Catalyzed Halogen Dance" reaction to prepare a metallated compound comprising a five or six membered heteroaryl ring comprising a halogen atom, and then oxidatively coupling the reactive intermediate compound. The compounds of Formula (II) and/or oligomer or polymers comprising repeat units having Formula (II) can be useful for making semi-conducting materials, and/or electronic devices comprising those materials. Acyl compounds can be prepared. Heteroarylene substituents can be used. The core tricyclic core can be coupled to itself. The Z group also can be strong electron-withdrawing groups such as C=C(CN)2 or [C=C(CN)2]2. Organic electronic devices can be made including field-effect transistors. Formula (II).
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(2013/03/26)
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- COUPLED HETEROARYL COMPOUNDS VIA REARRANGEMENT OF HALOGENATED HETEROAROMATICS FOLLOWED BY OXIDATIVE COUPLING (COUPLED TRICYCLIC CORE COMPOUNDS)
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The inventions disclosed and described herein relate to new and efficient generic methods for making a wide variety of compounds having HAr - Z - Har tricyclic cores (II) from intermediates (I), wherein HAr is an optionally substituted five or six membered heteroaryl ring, and Hal is a halogen, and Z is a bridging radical, such as S, Sc, NRS, C(O), C(O)C(O), Si(R5)2, SO, S02, PRS, BRS, C(R5)2 or P(O)R5 and both HAr are covalently bound to one another. The synthetic methods employ a "Base-Catalyzed Halogen Dance" reaction to prepare a metallated compound comprising a five or six membered heteroaryl ring comprising a halogen atom, and then oxidatively coupling the reactive intermediate compound. The compounds of Formula (II) and/or oligomer or polymers comprising repeat units having Formula (IT) can be useful for making semi-conducting materials, and/or electronic devices comprising those materials. Acyl compounds can be prepared. Heteroary- lene substituents can be used. The core tricyclic core can be coupled to itself. The Z group also can be strong electron-withdrawing groups such as C=C(CN)2 or [C=C(CN)2]2. Organic electronic devices can be made including field-effect transistors. (Formula I, II)
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Page/Page column 38; 39
(2013/03/26)
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- Synthesis and photovoltaic properties of functional dendritic oligothiophenes
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Novel p-type and low bandgap functional dendritic oligothiophenes bearing hole-transporting carbazole as peripheral substituents and an electron-withdrawing dicyanovinyl core group, namely, DCT(n)-DCN, where n = 1 or 2 for solution-processable photovoltaic (PV) applications have been synthesized. With electron-donating carbazole surface-functionalized moieties conjugated with dicyanovinyl core group, the optical bandgap of these functional dendritic oligothiophene thin-films greatly reduces to 1.74 eV with a strong spectral broadening and a high ionization potential at ~5.5 eV as determined by UV photoelectron spectroscopy. The bulk heterojunction PV cells fabricated from these dendrimers blended with PC71BM as an acceptor showed a power conversion efficiency up to 1.64% with an open circuit voltage of (V oc) = 0.93 V in the annealed device. We have demonstrated that the desirable molecular and PV properties of dendritic oligothiophenes can be obtained/tuned by the incorporation of functional group(s) onto peripheral of the dendron and into the core. In addition, these functional dendritic oligothiophenes show superior functional properties even at low dendritic generation as compared to the unsubstituted higher generation dendritic oligothiophenes as a p-type, low-bandgap semiconductor for solution-processable bulk heterojunction PV cells.
- Zhang, Weifeng,Ng, Ging Meng,Tam, Hoi Lam,Wong, Man Shing,Zhu, Furong
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experimental part
p. 1865 - 1873
(2012/02/04)
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- Benzobis(silolothiophene)-based low bandgap polymers for efficient polymer solar cells
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Two new low bandgap copolymers that contain a thiophene-phenylene-thiophene fused ring in which the linked carbon atoms are replaced by silicon atoms were designed and synthesized. A facile synthetic method was developed to synthesize the benzobis(silolothiophene) donor unit in high yield. 2-Bromothiophene was lithiated by LDA and subsequently quenched with trimethylsilyl chloride, yielding colorless oil. Further lithiation of 2 with LDA and then reaction with 2-isopropoxy-4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolane afforded 3 in 52% yields. After lithiation of 5 by n-BuLi, cyclization with dichlorodialkylsilane was performed to get the disilole 6 in 76% yields. Low band gap polymers PBSTBT and PBSTDTBT were obtained though a Stille reaction between monomer and 4,7-dibromo-2,1,3-benzothiadiazole or 4,7-bis(2-bromo-5-thienyl)-2,1,3- benzothiadiazole, using Pd(PPh3)4 as catalyst in toluene. The AFM images of the blended films containing both polymer and PC 71BM showed rather smooth morphology with small phase segregation.
- Wang, Jie-Yu,Hau, Steven K.,Yip, Hin-Lap,Davies, Joshua A.,Chen, Kung-Shih,Zhang, Yong,Sun, Ying,Jen, Alex K.-Y.
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scheme or table
p. 765 - 767
(2012/02/02)
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- METHOD OF MAKING COUPLED HETEROARYL COMPOUNDS VIA REARRANGEMENT OF HALOGENATED HETEROAROMATICS FOLLOWED BY OXIDATIVE COUPLING
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The inventions disclosed and described herein relate to new and efficient generic methods for making a wide variety of compounds having Formulas (I) and (II) as shown below (Formulas (I) and (II)) wherein HAr is an optionally substituted five or six membered heteroaryl ring, and Hal is a halogen, and Y is a bridging radical, such as S, Se, NR5 C(O), C(O)C(O),Si(R5)2, SO, SO2, PR5, BR5, C(R5)2 or P(O)R5. The synthetic methods employ a "Base-Catalyzed Halogen Dance" reaction to prepare a metallated compound comprising a five or six membered heteroaryl ring comprising a halogen atom, and then oxidatively coupling the reactive intermediate compound. The compounds of Formula (II) and/or oligomer or polymers comprising repeat units having Formula (II) can be useful for making semi-conducting materials, and/or electronic devices comprising those materials.
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(2011/09/15)
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- Base-catalyzed halogen dance reaction and oxidative coupling sequence as a convenient method for the preparation of dihalo-bisheteroarenes
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Figure presented A one-pot preparation of the 2,2′-dibromo-1, 1′-bisheteroarenes 3a-d from bromo-heteroarenes utilizing the sequence of the base-catalyzed halogen dance (BCHD) reaction and CuCl2-promoted oxidative coupling of the in situ formed α-lithio-β-halo-heteroarenes 2a-d provides a convenient access to precursors for the preparation of tricyclic heteroaromatic cores. The structures of 3a,b,d, 6, and 9 were confirmed by single-crystal X-ray analysis, and dibromides 3a and 3b were used for the preparation of dithieno-[2,3-b:3′,2′-d]-pyrrole 10a and its selenophene analogue 10b, respectively.
- Getmanenko, Yulia A.,Tongwa, Paul,Timofeeva, Tatiana V.,Marder, Seth R.
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supporting information; experimental part
p. 2136 - 2139
(2010/08/05)
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- Convergent synthetic routes to orthogonally fused conjugated oligomers directed toward molecular scale electronic device applications
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This paper describes the synthetic organic phase of a project directed toward the construction of molecular scale electronic devices. Outlined is a convergent synthetic route to orthogonally fused conjugated organic oligomers. The final systems are to have a potentially conducting chain fused perpendicularly to a second potentially conducting chain via a a bonded network. One of the core segments synthesized is based on a spirobithiophene moiety with a central silicon atom. It is formed by a zirconium-promoted bis(bicyclization) of a tetrapropargylsilane. The second core is a 9,9′-spirobifluorene system. Terminal halide groups provide the linkage points for further extension of the chains via Pd-catalyzed or Pd/Cu-catalyzed cross coupling methods. All four branching arms are affixed to the core in a single operation, thus making the syntheses highly convergent. In the cases of the larger functionalized systems, alkyl substituents on the thiophenes afford soluble materials. In order to prepare the molecules with > 50 A lengths, an iterative divergent/convergent approach had to be utilized for the construction of oligo(thiophene-ethynylene) branching arms. Organopalladium-catalyzed procedures are used extensively for the syntheses of the orthogonally fused compounds.
- Wu, Ruilian,Schumm, Jeffry S.,Pearson, Darren L.,Tour, James M.
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p. 6906 - 6921
(2007/10/03)
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- Halogen Dance Reactions at Thiophenes and Furans: Selective Access to a Variety of New Trisubstituted Derivatives
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LDA-induced halogen migrations and their selective preventions on various bromo substituted thiophenes and furans gave upon reaction with electrophiles access to a large variety of new tri-substituted derivatives.Extension of HD-methodology to 5,5'-dibromo-2,2'-bithiophene enabled for the first time control of selective mono- and double halogen migration.
- Froehlich, J.
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p. 615 - 634
(2007/10/03)
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- NOVEL HALOGENATION OF THIOPHENES WITH BENZENESELENINYL CHLORIDE AND ALUMINUM HALIDE
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In the presence of aluminum halide, benzeneseleninyl chloride is an efficient regioselective halogenating reagent for heterocyclic compounds such as thiophene, 2-methylthiophene, 3-methylthiophene, 2,5-dimethylthiophene, and furan.In the case of pyrrole, no halogenated product was obtained.A plausible reaction mechanism involving a positive halogen intermediate is proposed.
- Kamigata, Nobumasa,Suzuki, Takashi,Yoshida, Masato
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- SYNTHESIS AND CHARACTERIZATION OF ALKYL-, HALO- AND HETEROSUBSTITUTED DERIVATIVES OF THE POTENT PHOTOTOXIN &α-TERTHIENYL
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A number of derivatives of α-terthienyl were prepared including a series of naturally occurring compounds.A description of the syntheses of some new compounds, including 5-iodo, 5,5''-diiodo, 5,5''-diformyl, 5,5''-di-tert butyl, 5-tert-butyl, 5-tert-butoxy, 5-trimethylsilyl, 5-thiomethyl, 5,5''-dithiomethyl and 5-carboxyl-5''-(trimethylsilyl)-2,2':5',2''-terthienyl is also given.An analysis of the 1H NMR data of the derivatives is presented.
- Eachern, Anita Mac,Soucy, Chantal,Leitch, Leonard C.,Arnason, John T.,Morand, Peter
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p. 2403 - 2412
(2007/10/02)
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- THE RATES OF BASE CLEAVAGE OF SUBSTITUTED 2-THIENYLTRIMETHYLSILANES. AB INITIO CALCULATIONS OF THE ACIDITIES OF MONOSUBSTITUTED THIOPHENS
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Rates of cleavage in NaOMe-MeOH at 50 deg C have been determined for the mono-substituted 2-trimethylsilylthiophens X*C4H2S*SiMe3-2 with X = H, 3-NO2, 3-Br, 4-Br-, and 5-NO2, -CN, -COPh, -Me, -OMe and -NMe2, and for one disubstituted compound, 4,5-Br2*C4HS*SiMe3-2.For several compounds the rate and product isotope effects have also been determined.The energies involved in the process X*C4H3S X*C4H2S- for deprotonation at the 2-position have been calculated by an ab initio method (STO-3G), and the results used in analysis of the substituent effects in the cleavage of the XC4H2S*SiMe3-2 compounds.The results are consistent with the view the aryl anions separate in the rate-determining step of the cleavage.The isotope effects are all close to unity, whereas by comparison with results for XC6H4CH2SiMe3 and related species of similar reactivity, values in the region of 10 would be expected for the 3- and 5-NO2 compounds if the product isotope effect for a carbanion R depended only in the pKa of RH.The difference between the thienyl- and benzyl-type anions is attributed to the absence of conjugative delocalization of the charge in the former. Approximate pKa values are derived for the 2-positions of the X*C4H3S compounds.
- Seconi, Giancarlo,Eaborn, Colin,Stamper, John G.
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p. 153 - 168
(2007/10/02)
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