- Dinaphtho[2,1-b:1′,2′- d] thiophenes as high refractive index materials exploiting the potential characteristics of "dynamic thiahelicenes"
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Dinaphtho[2,1-b:1′,2′-d]thiophene (DNT) is one of the "dynamic thiahelicenes"that is obtained as a racemate due to its low energy barrier for enantiomerization. A careful evaluation of both the metastable DNT film and the stable films of DNT/polymethyl methacrylate (PMMA) blends revealed that DNT has an extra-high refractive index of 1.808 at 633 nm, which is rarely achieved in organic small molecules. The fundamental factors responsible for the unusual observation of DNT were explored by comparing the properties of DNT with those of a flat-shaped dibenzothiophene (DBT) both in experiments and DFT calculations, and by analysing them using the Lorentz-Lorenz equation. It became clear that the unique properties of DNT were based on its flexible dynamic thiahelicene structure, leading to metastable film-forming ability, high compatibility with PMMA, and exhibition of an extra-high refractive index caused by dense packing in the amorphous film. Chemical modification of DNT provided new halogen-free vinyl monomers, which could be easily polymerized to form vinyl polymers with high refractive indices of 1.72-1.74, as well as film-forming ability, high thermal stability, and high transparency in the visible region. Thus, we could demonstrate that the DNT structure is a new promising candidate for organic polymeric high refractive index materials.
- Ishikawa, Ken,Kuwata, Shigeki,Mineyama, Kenji,Nambu, Yoko,Nishikubo, Tadatomi,Takata, Toshikazu,Tsurui, Keisuke,Yanagi, Shohan,Yoshitake, Yoko
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supporting information
p. 726 - 733
(2022/01/22)
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- Helicene synthesis by Br?nsted acid-catalyzed cycloaromatization in HFIP [(CF3)2CHOH]
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A facile synthesis of carbo- and heterohelicenes was achieved via tandem cycloaromatization of bisacetal precursors, which were readily prepared through C-C bond formation by Suzuki-Miyaura coupling. This cyclization was efficiently realized by a catalytic amount of trifluoromethanesulfonic acid (TfOH) in a cation-stabilizing solvent, 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP), which readily allowed gram-scale syntheses of higher-order helicenes, double helical helicenes, and heterohelicenes.
- Fujita, Takeshi,Shoji, Noriaki,Yoshikawa, Nao,Ichikawa, Junji
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supporting information
p. 396 - 403
(2021/03/20)
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- Thiolate-Initiated Synthesis of Dibenzothiophenes from 2,2′-Bis(methylthio)-1,1′-Biaryl Derivatives through Cleavage of Two Carbon-Sulfur Bonds
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A catalytic reaction involving the cleavage of two carbon-sulfur bonds in 2,2′-bis(methylthio)-1,1′-biaryl derivatives is reported. This reaction does not require a transition-metal catalyst and is promoted by a thiolate anion. Notably, based on DFT calculations, the product-forming cyclization step is shown to proceed through a concerted nucleophilic aromatic substitution (CS N Ar) mechanism.
- Chatani, Naoto,Kawashima, Yuki,Kodama, Takuya,Masuya, Yoshihiro,Tobisu, Mamoru
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supporting information
p. 1995 - 1999
(2019/10/22)
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- Cyclization of 2-Biphenylthiols to Dibenzothiophenes under PdCl2/DMSO Catalysis
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A palladium-catalyzed synthesis of dibenzothiophenes from 2-biphenylthiols is described. This highly efficient reaction employs a simple PdCl2/DMSO catalytic system, in which PdCl2 is the sole metal catalyst and DMSO functions as an oxidant and solvent. This transformation has broad substrate scope and operational simplicity and proceeds in high yield. The synthetic utility was demonstrated by the facile synthesis of helical dinapthothiophene 3 and an eminent organic semiconductor DBTDT 4. Importantly, highly strained trithiasumanene 5, a buckybowl of considerable synthetic challenge, was observed under this catalytic system.
- Zhang, Tao,Deng, Guigang,Li, Hanjie,Liu, Bingxin,Tan, Qitao,Xu, Bin
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p. 5439 - 5443
(2018/09/13)
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- METHOD FOR PRODUCING HETEROCYCLIC COMPOUNDS
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PROBLEM TO BE SOLVED: To provide heterocyclic compounds in high yield and by simple compositions. SOLUTION: The method for producing heterocyclic compounds comprises: a step of heating a raw material solution containing a solvent having a raw material substrate dissolved; and a step of cooling the raw material solution after the heating step where, in the heating step, the state of the solvent is a subcritical fluid or a supercritical fluid. The term supercritical fluid refers to a state of a metrial under the a temperature and pressure of the critical point or more. The term subcritical fluid refers to a liquid under high temperature and high pressure below the critical point. SELECTED DRAWING: Figure 1 COPYRIGHT: (C)2017,JPOandINPIT
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Paragraph 0051
(2017/10/05)
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- Photodeoxygenation of dinaphthothiophene, benzophenanthrothiophene, and benzonaphthothiophene: S-oxides
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Photoinduced deoxygenation of dibenzothiophene S-oxide (DBTO) has been suggested to release atomic oxygen [O(3P)]. To expand the conditions and applications where O(3P) could be used, generation of O(3P) at longer wavelengths was desirable. The sulfoxides benzo[b]naphtho-[1,2,d]thiophene S-oxide, benzo[b]naphtho[2,1,d]thiophene S-oxide, benzo[b]phenanthro[9,10-d]thiophene S-oxide, dinaphtho[2,1-b:1′,2′-d]thiophene S-oxide, and dinaphtho[1,2-b:2′,1′-d]thiophene S-oxide all absorb light at longer wavelengths than DBTO. To determine if these sulfoxides could be used to generate O(3P), quantum yield studies, product studies, and computational analysis were performed. Quantum yields for the deoxygenation were up to 3 times larger for these sulfoxides compared to DBTO. However, oxidation of the solvent by these sulfoxides resulted in different ratios of oxidized products compared to DBTO, which suggested a change in deoxygenation mechanism. Density functional calculations revealed a much larger singlet-triplet gap for the larger sulfoxides compared to DBTO. This led to the conclusion that the examined sulfoxides could undergo deoxygenation by two different mechanisms.
- Zheng,Baumann,Chintala,Galloway,Slaughter,McCulla
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p. 791 - 800
(2016/07/06)
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- Palladium-Assisted "Aromatic Metamorphosis" of Dibenzothiophenes into Triphenylenes
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Abstract Two new palladium-catalyzed reactions of aromatic sulfur compounds enabled the conversion of dibenzothiophenes into triphenylenes in four steps. This transformation of one aromatic framework into another consists of 1) 4-chlorobutylation of the dibenzothiophene to form the corresponding sulfonium salt, 2) palladium-catalyzed arylative ring opening of the sulfonium salt with a sodium tetraarylborate, 3) an intramolecular SN2 reaction to form a teraryl sulfonium salt, and 4) palladium-catalyzed intramolecular C-S/C-H coupling through electrophilic palladation. Symmetrical as well as unsymmetrical triphenylenes of interest were synthesized in a tailor-made fashion in satisfactory overall yields. A change of heart: The invention of two palladium-catalyzed arylation reactions of organosulfur compounds enabled the transformation of dibenzothiophenes into triphenylenes and thus a fundamental change in the core aromatic structure (see scheme). Both symmetrical and unsymmetrical triphenylenes were synthesized in a tailor-made fashion in satisfactory overall yield.
- Vasu, Dhananjayan,Yorimitsu, Hideki,Osuka, Atsuhiro
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supporting information
p. 7162 - 7166
(2015/06/08)
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- An efficient synthesis of dinaphthothiophene derivatives
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A short and efficient synthesis of dinaphthothiophene and its derivatives was achieved by employing oxidative photocyclization of the corresponding dinaphthyl sulfides as a key step.
- Sadorn, Karoon,Sinananwanich, Warapon,Areephong, Jetsuda,Nerungsi, Chakkrapan,Wongma, Chalayut,Pakawatchai, Chaveng,Thongpanchang, Tienthong
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p. 4519 - 4521
(2008/09/21)
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- Asymmetric synthesis of axially chiral biaryls by nickel-catalyzed Grignard cross-coupling of dibenzothiophenes
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Catalytic asymmetric Grignard cross-coupling of 1,9-disubstituted dibenzothiophenes (6a-c) and dinaphthothiophene (6d) with aryl- and alkyl-Grignard reagents (7) proceeded with high enantioselectivity (up to 95% ee) in the presence of a nickel catalyst (3-6 mol %) coordinated with 2-diphenylphosphino-1,1′-binaphthyl (H-MOP) or oxazoline-phosphine ligand (i-Pr-phox) in THF to give 2-mercapto-2′-substituted-1,1′-biphenyls (8a-c) and 2-mercapto-2′-substituted-1,1′-binaphthyls (8d) in high yields. The mercapto group in the axially chiral cross-coupling products was converted into several functional groups by way of the methylsulfinyl group. The rate of flipping in dinaphthothiophene was measured by variable-temperature 31P NMR analysis of methyl-phenylphosphinyldinaphthothiophene derivative (21).
- Cho, Yong-Hwan,Kina, Asato,Shimada, Toyoshi,Hayashi, Tamio
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p. 3811 - 3823
(2007/10/03)
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- Ethynyl sulfides as participants in cascade cycloaromatizations
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Isomerization of soluble precursor compounds to produce fused-ring systems is an attractive approach for preparing conjugated polymers and oligomers. Cycloaromatization chemistry has previously been explored in this capacity employing reactions based on the Bergman cyclization. Using ethynyl sulfides with a terminal o-diethynylbenzene unit, an alternative strategy is demonstrated that offers selectivity advantages in the kinetically controlled radical cyclizations. The products are acene-fused thiophenes in which the diethynylsulfide acts as a relay for the diradical produced in a Bergman cyclization.
- Lewis, Kevin D.,Rowe, Michael P.,Matzger, Adam J.
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p. 7191 - 7196
(2007/10/03)
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- A parallel colorimetric method for the rapid discovery and optimization of heterogeneous hydrodesulfurization catalysts
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A spectrophotometric based, parallel approach to screen heterogeneous catalysts for hydrodesulfurization has been developed. The method utilizes optical changes resulting from the hydrodesulfurization of 1,1′-binaphthothiophene to 1,1′-binaphthyl to determine catalyst activity. Hydrodesulfurization of 1,1′-binaphthothiophene to 1,1′-binaphthyl results in a loss of conjugation in the binaphthyl ring system. This results in a blue shift of more than 60 nm in the UV-vis spectrum. Since only small amounts of the HDS catalyst and 1,1′-binaphthothiophene are required, a large number of catalysts may be screened simultaneously. The synthesis of the 1,1′-binaphthothiophene and conditions for HDS catalyst screening are described. Copyright
- Staiger, Chad L.,Loy, Douglas A.,Jamison, Gregory M.,Schneider, Duane A.,Cornelius, Christopher J.
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p. 9920 - 9921
(2007/10/03)
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- Synthesis of an octahydro-1,1′-binaphthyl thioether ligand and comparison with unhydrogenated binaphthyl analogues
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Acylation of octahydro-BINOL with Me2NC(=S)Cl, in the presence of NaH, allows the formation of 2-(OH)-2′-(Me2NC(S)O)-1, 1′-C10H20. Subsequent Newman-Kwart rearrangement (275°C, 12 min) proceeds cleanly with a small amount of racemisation (96-97% ee). The equivalent BINOL-derived species undergoes an identical rearrangement (but with higher racemisation, 79-80%) and appreciable amounts of a thiophene by-product are formed. Semi-empirical calculations (PM3) predict a higher racemisation barrier for the octahydro compound and suggest that the Newman-Kwart rearrangement could proceed via a concerted pathway. The H 8-BINOL derived compound can be modified to 2-(OH)-2′-(SBu n)-1,1′-C10H20 and the BINOL species to 2-(OH)-2′-(SBut)-1,1′-C10H12. The former promotes the 1,4-addition of AlMe3 to non-3-en-2-one in 57% ee the latter in 63% ee.
- Albrow, Victoria,Biswas, Kallolmay,Crane, Andrew,Chaplin, Nicholas,Easun, Tim,Gladiali, Serafino,Lygo, Barry,Woodward, Simon
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p. 2813 - 2819
(2007/10/03)
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- Nickel-catalyzed asymmetric Grignard cross-coupling of dinaphthothiophene giving axially chiral 1,1′-binaphthyls
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Asymmetric cross-coupling of dinaphtho[2,1-b:1′,2′-d]thiophene with ArMgBr (Ar = Ph, 4-MeC6H4, 4-MeOC6H4) proceeded withhigh enantioselectivity in THF at 20 °C in the presence of 3 mol % of a nickel catalyst gen
- Shimada, Toyoshi,Cho, Yong-Hwan,Hayashi, Tamio
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p. 13396 - 13397
(2007/10/03)
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- Condensations of thiophene with ketones
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Thiophene reacts with aliphatic ketones in aqueous 75% v/v sulfuric acid to give condensation products containing up to five thiophene units. Ketones bearing phenyl substituents yield mono- and di-styrylthiophenes. All the reactions occur at the C-2 and -5 positions of thiophene. 2,5-Bis(α-phenylstyryl)thiophene undergoes photocyclisation to give a dinaphthothiophene.
- Morrison, Brian J.,Musgrave, Oliver C.
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p. 1944 - 1947
(2007/10/03)
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- BINAPS - An axially chiral P,S-heterodonor ligand for asymmetric catalysis based on binaphthalene backbone
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The chelating P,S-heterodonor ligand 2-diphenylphosphanyl-1,1′-binaphthalene-2′-thiol (11) (BINAPS), which features a chiral axis as the unique stereogenic element, has been prepared in both racemic and enantiopure form through a multistep reaction sequence using 2,2′-dihydroxy-1,1′-binaphthalene (BINOL) as the starting material. The reaction sequence is completely stereoconservative and (S)-11 is obtained with no loss of enantiopurity from pure (S)-BINOL. (R)-11 can be alternatively obtained by resolution of racemic 11 using the chiral (S)-benzylaminato Pd(II)-complex 19 as the resolving agent. The S-methyl or the S-i-propyl derivatives 14 have been used as chiral ligands in the Rh(I)-catalyzed asymmetric hydroformylation of styrene and in the hydrogen transfer reduction of acetophenone with modest success (up to 20% ee). In the presence of suitable Pd-complexes the same ligands provide higher ees in the hydrosilylation of styrene (50% ee) and in the allylic alkylation of 1,3-diphenylprop-2-enyl acetate (60% ee).
- Gladiali,Medici,Pirri,Pulacchini,Fabbri
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p. 670 - 678
(2007/10/03)
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- Application of flash vacuum pyrolysis to the synthesis of sulfur- containing heteroaromatic systems
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The FVP method of ethynyl and chlorovinyl materials is applied to the ready formation of sulfur-containing fused heteroaromatic systems. The pyrolysis of the chlorovinyl materials is assumed to involve a mechanism different from that of the ethynyl materials.
- Imamura, Koichi,Hirayama, Daigo,Yoshimura, Hitoshi,Takimiya, Kazuo,Yoshio, Aso,Otsubo, Tetsuo
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p. 2789 - 2792
(2007/10/03)
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- Synthesis of structurally modified atropisomeric biaryl dithiols. Observations on the Newman-Kwart rearrangement
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The preparation of a number of biaryldithiols from biaryldiols is discussed. A key reaction is the Newman-Kwart thermorearrangement of bisthiocarbamates and crucial variables of temperature and reaction time have been identified. Alternative approaches to 3,3'-disubstituted dithiols via ortho metallation are presented. The benefit of using such disubstituted compounds is illustrated with representative examples of the stereochemical features of the derived carbanions in reactions with prochiral electrophiles.
- Cossu, Sergio,De Lucchi, Ottorino,Fabbri, Davide,Valle, Giovanni,Painter, Gavin F.,Smith, Robin A.J.
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p. 6073 - 6084
(2007/10/03)
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- Conformational polymorphism and thermorearrangement of 2,2′-bis-O-(N,N-dimethylthiocarbamato)-1,1′-binaphthalene. A facile synthesis of 1,1′-binaphthalene-2,2′-dithiol
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The title compound was found to exhibit conformational polymorphism which greatly influenced the efficiency of the thermorearrangement to 2,2′-bis-S-(N,N-dimethylthiocarbamato)-1,1′-binaphthalene. Recognition of this phenomenon has allowed a reproducible synthesis of 1,1′-binaphthalene-2,2′ dithiol.
- Bandarage, Upul K.,Simpson, Jim,Smith, Robin A. J.,Weavers, Rex T.
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p. 3463 - 3472
(2007/10/02)
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- Preparation of Enantiomerically Pure 1,1'-Binaphthalene-2,2'-diol and 1,1'-Binaphthalene-2,2'-dithiol
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A practical preparation of enantiomerically pure 1,1'-binaphthalene-2,2'-diol (1) and 1,1'-binaphthalene-2,2'-dithiol (2) is reported.Enantiopure 2 is obtained from enantiopure 1 via Newman-Kwart rearrangement of the thiocarbamoyl derivative 5 under controlled reaction conditions.The enantiopure starting diol 1 was obtained by a simple and inexpensive method engaging condensation of thiophosphoryl chloride and (S)-(-)-α-methylbenzylamine in pyridine and reaction of the resulting phosphoramidate 3 with racemic binaphthol 1 to give quantitatively a 1:1 mixture of diasteroisomers 4 that were cleanly separated by a single recrystallization from a chloroform-ethanol mixture in very high yield.The procedures can be scaled up easily.
- Fabbri, Davide,Delogu, Giovanna,Lucchi, Ottorino De
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p. 1748 - 1750
(2007/10/02)
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- Syntheses of Dibenzodiselenin and Related Novel Chalcogenide Heterocyclic Compounds
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Reaction of 2,2'-dilithio-1,1'-binaphthyl with selenium followed by air oxidation gives a mixture of dinaphthoselenophene and dimer and oligomers of 2,2'-diseleno-1,1'-binaphthyl. 2,2'-Dilithio-1,1'-biphenyl reacts with selenium to afford dibenzodiselenin.Structures of the dimeric 2,2'-diseleno-1,1'-binaphthyl and dibenzodiselenin have been confirmed by X-ray crystallographic analyses.Similar reaction of 2,2'-dilithio-1,1'-binaphthyl with sulfur or tellurium gives a mixture of dinaphthothiophene and dinaphthodithiin or a mixture of dinaphthotellurophene and oligomer of 2,2'-ditelluro-1,1'-binaphthyl, respectively.Dibenzotellurophene and oligomer of 2,2'-ditelluro-1,1'-biphenyl are obtained from reaction of 2,2'-dilithio-1,1'-biphenyl with tellurium.
- Murata, Shizuaki,Suzuki, Toshiyasu,Yanagisawa, Akira,Suga, Seiji
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p. 433 - 438
(2007/10/02)
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- Enantioselective oxidation of thioethers. A route to the resolution of -2,2'-dithiol
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A route to the resolution of racemic -2,2'-dithiol 2 is described, involving the transformation of 2 into a series of dithioethers.The latter are subjected to asymmetric oxidation to monosulfoxides by a procedure developed in our laboratory.For some of the thioethers examined the oxidation is highly diastereo- and/or enantioselective.The resolved 2 is then obtained from the optically pure monosulfoxides either by oxidation to the bis-sulfoxides followed by a Pummerer reaction or by a deoxygenation to the dithioether and subsequent reduction.In both cases enantiomerically pure 2 (e.e. > 98percent) was obtained.Keywords: enantioselective oxidation / optical resolution / thioethers / -2,2'-dithiol
- Furia, F. di,Licini, G.,Modena, G.,Valle, G.
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p. 734 - 744
(2007/10/02)
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- SYNTHESIS OD 1,1'-DIBENZO- AND 1,1'-DINAPHTHO-2,2'-DITHIOLS FROM THE RESPECTIVE THIOPHENES
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The title compounds 1 and 2 were prepared from the respective, inexpensive and readily available thiophenes vis reaction with lithium and sulfur monochloride, followed by reduction with lithium alumoinium hydride.
- Cossu, Sergio,Delogu, Giovanna,Lucchi, Ottorino De,Fabbri, Davide,Fois, Maria Paola
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p. 3431 - 3436
(2007/10/02)
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- The Synthesis of Dinaphthothiophenes
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The synthesis of dinaphthothiophene (6), dinaphthothiophene (15), dinaphthothiophene (20), dinaphthothiophene (26), dinaphthothiophene (37) and dinaphthothiophene (45) has been accomplished.
- Tedjamulia, Marvin L.,Tominaga, Yoshinori,Castle, Raymond N.,Lee, Milton L.
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p. 1143 - 1148
(2007/10/02)
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