194-65-0

Upstream product

• 55441-97-9 <1,1'-Binaphthalene>-2,2'-diyl O,O-bis(N,N-dimethylthiocarbamate) 
• 74866-28-7 2,2'-dibromo-1,1'-binaphthyl 
• 124414-28-4 (2,2'-Dimethylthio)<1,1'-binaphthalene> 
• 88220-28-4 2-styrylnaphtho<2,1-b>thiophene 
• 16420-13-6 N,N-Dimethylthiocarbamoyl chloride 
• 602-09-5 1,1'-bi-2-naphthol 
• 162426-76-8 2-(diphenylphosphinyl)-1,1'-binaphth-2'-ol-N,N-dimethylthiocarbamate 
• 439588-87-1 C₂₀H₁₀S 
• 132548-91-5 ((R)-2'-hydroxy-[1,1'-binaphthalen]-2-yl)diphenylphosphine oxide 
• 132548-91-5 (S)-(+)-2-hydroxy-2'-diphenylphosphinoyl-1,1'-binaphthyl 
• 147923-23-7 <1,1'-Binaphthalene>-2,2'-diyl S,S-bis(N,N-dimethylthiocarbamate) 
• 124414-28-4 (2,2'-Dimethylthio)<1,1'-binaphthalene> 
• 124414-32-0 (2-Methylsulfinyl-2'-methylthio)<1,1'-binaphthalene> 
• 613-81-0 bis(2-naphthyl)sulfide 

Downstream Products

• 604-53-5 1,1'-bisnaphthalene 
• 182065-73-2 (CH₃C(CH₂P(C₆H₅)2)3)Ir(H)2(SC₂₀H₁₃) 
• 182065-79-8 (CH₃C(CH₂P(C₆H₅)2)3)Rh(H)2(SC₂₀H₁₃) 
• 182065-71-0 (CH₃C(CH₂P(C₆H₅)2)3)Ir(H)(S(C₁₀H₆)2) 
• 182065-69-6 (CH₃C(CH₂P(C₆H₅)2)3)Ir(H)(S(C₁₀H₆)2) 
• 102555-71-5 1,1'-binaphthalene-2,2'-dithiol 
• 348617-10-7 (S)-diphenyl(2'-phenyl-[1,1'-binaphthalen]-2-yl)phosphine 

Relevant academic research and scientific papers

Dinaphtho[2,1-b:1′,2′- d] thiophenes as high refractive index materials exploiting the potential characteristics of "dynamic thiahelicenes"

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.

Helicene synthesis by Br?nsted acid-catalyzed cycloaromatization in HFIP [(CF3)2CHOH]

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.

Thiolate-Initiated Synthesis of Dibenzothiophenes from 2,2′-Bis(methylthio)-1,1′-Biaryl Derivatives through Cleavage of Two Carbon-Sulfur Bonds

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.

Cyclization of 2-Biphenylthiols to Dibenzothiophenes under PdCl2/DMSO Catalysis

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.

METHOD FOR PRODUCING HETEROCYCLIC COMPOUNDS

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

Photodeoxygenation of dinaphthothiophene, benzophenanthrothiophene, and benzonaphthothiophene: S-oxides

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.

Palladium-Assisted "Aromatic Metamorphosis" of Dibenzothiophenes into Triphenylenes

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.

An efficient synthesis of dinaphthothiophene derivatives

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.

Ethynyl sulfides as participants in cascade cycloaromatizations

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.

Asymmetric synthesis of axially chiral biaryls by nickel-catalyzed Grignard cross-coupling of dibenzothiophenes

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).