- Synthesis method of 2, 2 '-bisdiphenylphosphino-1, 1'-binaphthalene
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The invention relates to a synthesis method of 2, 2 '-bisdiphenylphosphino-1, 1'-binaphthalene, which is realized by the following steps: step 1, carrying out BUCHERER reaction on 1, 1 '-binaphthyl-2-naphthol to generate 1, 1'-binaphthyl-2, 2 '-diamine; 2, subjecting 1, 1 '-binaphthyl-2, 2'-diamine to a Sandmeyer reaction to generate binaphthyl dibromide; and 3, carrying out a Grignard reaction onthe binaphthyl dibromide and diphenyl phosphine chloride to generate 2, 2 '-bisdiphenylphosphino-1, 1'-binaphthalene (BINAP). Bulk chemical raw materials are used and are low in price and easy to obtain, and the production cost is effectively reduced; the method has the advantages of easily available raw materials, high reaction yield, simple post-treatment, facilitation of industrial amplification, and strong industrial application prospect.
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Paragraph 0027-0029
(2020/09/12)
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- AROMATIC COMPOUNDS AND ORGANIC ELECTRONIC DEVICE USING THE SAME
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The present invention relates to an organic electronic device wherein an organic substance layer has a novel compound which improves the service life, efficiency, driving voltage reduction, and stability of the organic electronic device. More specifically, in the present invention, the organic electronic device is an electrode using holes and/or electrons and a device which needs the exchange of electric charges between organic substances. The organic electronic device is divided largely into two devices by an operation principle.
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Paragraph 0384; 0389; 0390
(2017/01/09)
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- Catalytic, Enantioselective Sulfenylation of Ketone-Derived Enoxysilanes
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A catalytic, enantioselective, Lewis base-catalyzed α-sulfenylation of silyl enol ethers has been developed. To avoid acidic hydrolysis of the silyl enol ether substrates, a sulfenylating agent that did not require additional Br?nsted acid activation, namely N-phenylthiosaccharin, was developed. Three classes of Lewis bases - tertiary amines, sulfides, and selenophosphoramides - were identified as active catalysts for the α-sulfenylation reaction. Among a wide variety of chiral Lewis bases in all three classes, only chiral selenophosphoramides afforded α-phenylthio ketones in generally high yield and with good enantioselectivity. The selectivity of the reaction does not depend on the size of the silyl group but is highly sensitive to the double bond geometry and the bulk of the substituents on the double bond. The most selective substrates are those containing a geminal bulky substituent on the enoxysilane. Computational analysis revealed that the enantioselectivity arises from an intriguing interplay among sterically guided approach, distortion energy, and orbital interactions.
- Denmark, Scott E.,Rossi, Sergio,Webster, Matthew P.,Wang, Hao
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supporting information
p. 13016 - 13028
(2015/09/15)
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- Oxidative skeletal rearrangement of 1,1′-binaphthalene-2,2′- diamines (BINAMs) via C-C bond cleavage and nitrogen migration: A versatile synthesis of U-shaped azaacenes
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An oxidative skeletal rearrangement of 1,1′-binaphthalene-2,2′- diamines (BINAMs) that involves the cleavage of a strong C-C single bond of the binaphthalene unit and the nitrogen migration has been discovered. The unprecedented rearrangement enables access to a series of U-shaped azaacenes otherwise difficult to prepare in a selective manner by classical methods. Moreover, physicochemical properties of the unique azaacenes have been comprehensively investigated. This journal is the Partner Organisations 2014.
- Takeda, Youhei,Okazaki, Masato,Minakata, Satoshi
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supporting information
p. 10291 - 10294
(2014/08/18)
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- CuCl2 and FeCl3 as a new and efficient catalyst for the oxidative coupling of aryl amines into 1,1′-binaphthalene-2,2 /-diamines in the ionic liquid media
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A practical synthesis of 1,1′-binaphthalene-1,1′-diamines (BINAM) from a-naphthylamine is described here. The facile purification procedure of the method makes it amenable to gram scale synthesis of 1,1′-binaphthalene-1,1′-diamines with fairly high optical purity and yield of product.
- Montazeri, Naser,Tavana, Mahdie,Yousefian, Soghra,Firooz, Farzane Taj
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experimental part
p. 840 - 842
(2012/07/31)
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- Acid-catalyzed [3,3] sigmatropic rearrangement of N-Cbz-diaryl hydrazide for the synthesis of mono-N-Cbz-1,1′-biaryl-2,2′-diamine
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N-Cbz-Diaryl hydrazides undergo acid-catalyzed [3,3] sigmatropic rearrangement to afford N-Cbz-1,1′-biaryl-2,2′-diamines. The resultant products can be versatile synthetic platforms for a wide variety of C2- and/or nonsymmetric axially chiral ligands and organocatalysts. N-Cbz-Diaryl hydrazides bearing either a neutral or electron-donating group underwent highly efficient acid-catalyzed [3,3] sigmatropic rearrangement to afford N-Cbz-1,1′-biaryl-2,2′-diamines. The resultant products allow elaboration of various new C2- and/or nonsymmetric axially chiral ligands or organocatalysts.
- Suh, Sung-Eun,Park, In-Keol,Lim, Byeong-Yun,Cho, Cheon-Gyu
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scheme or table
p. 455 - 457
(2011/03/22)
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- Iron(III)-promoted oxidative coupling of naphthylamines: Synthetic and mechanistic investigations
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A facile route to the synthesis of 1,1′-binaphthyl-4,4′- diamines (naphthidines) and 1,1′-binaphthyl-2,2′-diamines (BINAMs) was developed by the oxidative homocoupling of 1- and 2-naphthylamines, respectively, using FeCl3 as oxidant and K2CO3 as base in 1,2-dichloroethane under ambient conditions. A preliminary mechanistic investigation was performed by the ESR spectroscopy and intermediate-trapping technique.
- Li, Xin-Le,Huang, Jin-Hua,Yang, Lian-Ming
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supporting information; experimental part
p. 4950 - 4953
(2011/11/29)
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- A simple and neutral receptor acting as a sensitive and switch-on fluorescent chemosensor for H2PO4-
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A novel artificial anion chemosensor 1 based on 2, 2'-di (4-nitrophenylurea-β-N-yl) -1, 1'-binaphthyl is designed and synthesized for sensing anions including halide ions and oxoanions. The fluorescent emission of the binaphthyl of receptor 1, forming the hydrogen bonding with anions as the sensing mechanism, is monitored in DMSO for detecting anions. In brief, while most of the anion chemosensors are switch-off fluorescent chemosensor, or non-fluorescent sensor, receptor 1 exhibits obviously the switch-on emission during the complexation with H2PO4-. Springer Science+Business Media, LLC 2009.
- Huang, Weiwei,Su, Hongyan,Yao, Sikai,Lin, Hai,Cai, Zunsheng,Lin, Huakuan
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scheme or table
p. 1697 - 1702
(2012/07/17)
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- M-CPBA/TFA: An efficient nonmetallic reagent for oxidative coupling of 1,2-diarylethylenes
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A mild synthesis of a series of phenanthrenes with different substituents on the phenanthrene ring is described. The method involves intramolecular oxidative coupling of a variety of 1,2-diarylethylene derivatives in the presence of m-chloroperoxybenzoic acid (m-CPBA) in trifluoroacetic acid (TFA) to yield phenanthrenes in high yields. The present approach solves a key step for the synthesis of polycyclic structures related to an alkaloid tylophorine.
- Wang, Kailiang,Hu, Yanna,Wu, Meng,Li, Zheng,Liu, Zhihui,Su, Bo,Yu, Ao,Liu, Yu,Wang, Qingmin
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experimental part
p. 9135 - 9140
(2011/01/12)
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- A simple and efficient oxidative coupling of aromatic nuclei mediated by manganese dioxide
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Oxidative intramolecular coupling of the aryl rings of various stilbenes for direct construction of the phenanthrene ring system is promoted efficiently by manganese dioxide-trifluoroacetic acid at room temperature in excellent yields. This approach is also applied to the intermolecular biaryl coupling of 2-naphthols, 2-naphthalenethiol, 2-naphthylamine, a phenol ether and a phenol under very mild conditions. An electron-transfer mechanism is proposed in which manganese dioxide acts as a two-electron oxidant.
- Wang, Kailiang,Hu, Yanna,Li, Zheng,Wu, Meng,Liu, Zhihui,Su, Bo,Yu, Ao,Liu, Yu,Wang, Qingmin
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experimental part
p. 1083 - 1090
(2010/06/13)
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- Synthesis of primary aryl amines through a copper-assisted aromatic substitution reaction with sodium azide
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(Figure Presented) A method is presented by which aryl halides and azides are converted to the corresponding primary aryl amines with copper(I) and sodium azide.
- Markiewicz, John T.,Wiest, Olaf,Helquist, Paul
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supporting information; experimental part
p. 4887 - 4890
(2010/10/19)
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- TLC plates as a convenient platform for solvent-free reactions
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Solvent-free oxidative couplings of naphthols have been optimized by co-spotting catalysts and substrates directly on silica TLC plates and heating, followed by chromatography, staining, and qualitative visualization. The Royal Society of Chemistry.
- Stoddard, Jonathan M.,Nguyen, Lien,Mata-Chavez, Hector,Nguyen, Kelly
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p. 1240 - 1241
(2008/02/02)
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- Enantiodiscrimination and enantiocontrol of neutral and cationic Pt II complexes bearing the Tropos biphep ligand: Application to asymmetric lewis acid catalysis
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(Chemical Equation Presented) The stereochemically stable, enantiopure biphep-Pt complexes can be employed as an atropos asymmetric catalyst at 50°C or below. Both enantiomeric forms of this complex can be obtained by using either the chiral diamine (R)-dabn or its diamide (R)-dabnTf followed by chirally controlled formation of the single biphep-Pt enantiomer at higher (> 60°C) temperatures (see scheme; Tf=trifluoromethanesulfonate).
- Mikami, Koichi,Kakuno, Hitomi,Aikawa, Kohsuke
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p. 7257 - 7260
(2007/10/03)
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- New ligands for enantioselective recognition of chiral carboxylates based on 1,1′-binaphthalene-2,2′-diamine
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Simple bis(arylureido)binaphthalenes and (arylamido)binaphthalenes have been synthesized in both racemic as well as optically active forms. One of these compounds has been found to complex chiral anions with modest enantioselectivity.
- Stibor, Ivan,Holakovsky, Roman,Mustafina, Asiya R.,Lhotak, Pavel
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p. 365 - 383
(2007/10/03)
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- Copper(II)-mediated oxidative coupling of 2-aminonaphthalene homologues. Competition between the straight dimerization and the formation of carbazoles
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Whereas the Cu(II)-mediated oxidative coupling of 2-aminonaphthalenes 7a and 7b results in the clean formation of 1,1′-binaphthyls 13a and 13b, respectively, their higher homologues and congeners 8 - 12 have been found to exhibit a different reaction pattern. Thus, 2-aminoanthracene (8) gave a ～1:1 mixture of the expected bianthryl derivative 15 and the carbazole 16, whereas the 9-aminophenanthrene (10), 3-phenyl-1-aminonaphthalene (11), and 2-aminochrysene (12) produced almost exclusively the corresponding carbazoles 19, 20, and 21, respectively. By contrast, the isomeric 3-aminophenanthrene (9) gave rise to the azo compound 17 as a result of the preferential oxidation on the nitrogen. The carbazoles have been shown to arise directly from the coupling reactions rather than from the primarily formed binaphthyls. Alternatively, carbazole 19 can also be prepared from 1b on reaction with hydrazine. On the other hand, treatment of 3a with hydrazine resulted in the formation of a ～2:7 mixture of amine 11 and arylhydrazine 22. 2,2′-Diamino-1,1′-bianthryl (15) has been resolved into enantiomers via Cocrystallization with (-)-N-benzylcinchonidinium chloride and shown to have (R)-(-)-15 configuration by X-ray crystallography.
- Vyskocil,Smrcina,Lorenc,Tislerova,Brooks,Kulagowski,Langer,Farrugia,Kocovsky
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p. 1359 - 1365
(2007/10/03)
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- Process for producing an optically active ruthenium-phosphine complex and process for producing an optically active alcohol by using the complex
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Provided is a process for preparing an optically active ruthenium-phosphine complex represented by the following formula (1): wherein L represents a bidentate ligand compound of a tertiary phosphine; X represents a halogen atom; and * means chiral center (L* is an optically active substance), which comprises reacting a ruthenium-phosphine complex represented by: RumXnLpAq or [RuX(D)(L)]X wherein, X and L have the same meanings as described above (L is a racemic modification); A represents triethylamine (Et3N), etc.; and m, n, p and q each stands for an integer and D represents benzene, etc. with ? equivalent of a specific optically active chiral diamine, thereby inactivating one of the enantiomers; and then with a specific optically active diamine derivative, thereby activating the other enantiomer.
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- Chiral enrichment of 2-amino-2'-hydroxy-1,1'-binaphthyl
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A new synthetic procedure for the formation of 2-amino-2'-hydroxy-1,1'- binaphthyl, and a new purification procedure through the formation of Schiff bases, purification of the Schiff bases, and breakdown of the Schiff bases through amine exchange, are described. Through the new purification procedure, greater than 99% purity of the compound can be obtained easily and reliably. A set of procedures were examined to compare the efficiency and reliability to resolve 2-amino-2'-hydroxy-1,1'-binaphthyl into enantiomers. A new procedure was discovered to enrich enantiomeric excess from less than 10% to 95-99% in one step. Even a racemic mixture from an achiral procedure can be enriched to 67% e.e. in about 4% yield. The X-ray crystal structure of the racemic mixture [rhombohedral, space group Iba2, a=15.718(2) A, b=21.703(2) A, c=8.5398(9) A, V=2913.2(5) A3, RI=0.0705, Z=8, d(calcd)=1.301 g/cm3, F(000)=1200 e] was solved to elucidate the intriguing behavior of this compound.
- Mahmoud, Hussein,Han, Ying,Segal, Brent M.,Cai, Lisheng
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p. 2035 - 2042
(2007/10/03)
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- Dilithium diamides [{Li(OC4H8)}2{C20H 12(NR)2}] (R = SMe3 or CH2But) derived from R-, S- or R,S-2,2′-diamino-1,1′-binaphthyl derivatives
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The dilithium diamides [{Li(thf)}2{C20H12(NR)2}] (R = SiMe3 1 or CH2But 2, thf = tetrahydrofuran) were prepared from R,S-2,2′-diamino-1,1′-binaphthyl, C20H12(NH2)2, via C20H12[N(H)SiMe3]2 or C20H12[NHC(O)But]2 and C20H12[N(H)CH2But]2, respectively, and were transformed into SiCl2[C20H12(NR)2] by treatment with SiCl4. The crystal structures of 1 and 2 were determined. They are monomers, having a Li(1)N(1)Li(2)N(2) buckled ring, with Li(1)-N(2) ca. 0.2 A shorter than Li(1)-N(1), the two groups R cis to one another, and N(1)-C(1) η2 bonded to Li(1). The R and S enantiomers were similarly prepared and their optical stability was demonstrated by their hydrolysis to R- and S-C20H12(NH2)2, respectively. Evidence is provided for the structures of [M{C20H12[N(SiMe3)]2}] (M = Ge or Sn), obtained by conversion of the stannylene into the crystallographically characterised [{Sn[(NSiMe3)2C20H12](μ-O)} 3].
- Drost, Christian,Hitchcock, Peter B.,Lappert, Michael F.
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p. 3595 - 3601
(2007/10/03)
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- Synthesis and resolution of racemic 2-amino-2′-hydroxy-1,1′-binaphthyl
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The title compound 3 has been prepared via a highly selective, Cu(II)-mediated cross-coupling of 2-aminonaphthalene 1 and 2-naphthol 2 and resolved into enantiomers via crystallization of diastereoisomeric salts with (1S)-(+)-10-camphorsulfonic acid. The method has been optimized and the use of chromatography eliminated.
- Smrcina, Martin,Vyskocil, Stepan,Polivkova, Jana,Polakova, Jana,Kocovsky, Pavel
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p. 1520 - 1524
(2007/10/03)
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- Selective Cross-Coupling of 2-Naphthol and 2-Naphthylamine Derivatives. A Facile Synthesis of 2,2',3-Trisubstituted and 2,2',3,3'-Tetrasubstituted 1,1'-Binaphthyls
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The novel 1,1'-binaphthyls with OH and/or NHR (R = H or Ph) groups in the 2,2'-positions and with additional methoxycarbonyl group(s) in the 3- or 3,3'-positions (13-18) have been synthesized from their respective precursors 1-5 by the CuCl2/t-BuNH2-mediated oxidative cross-coupling.In most cases, the chemoselectivity was good, and the cross-coupled products 11-18 were obtained in fair to excellent yields.Binaphthyls 6-10, resulting from the selfcoupling, and carbazoles 19-23 have been identified as byproducts.Ab initio calculations and electrochemical measurements have been employed to account for the observrd selectivity.
- Smrcina, Martin,Vyskocil, Stepan,Maca, Bohumil,Polasek, Miroslav,Claxton, Thomas A.,et al.
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p. 2156 - 2163
(2007/10/02)
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- Synthesis of Optically Active 2,2'-Dihalo-1,1'-binaphthyls via Stable Diazonium Salts
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Optically pure 2,2'-dibromo-1,1'-binaphthyl (DBBN) (5) and optically pure 2,2'-diiodo-1,1'-binaphthyl (DIBN) (6) are synthesized in preparative quantities starting from 2-naphthol.These compounds are useful for the preparation of chiral, bidentate ligands based on the 1,1'-binaphthyl system.The synthesis proceeds through a common optically active precursor, 2,2'-diamino-1,1'-binaphthyl ((R)-(+)-DABN) (2), and involves the preparation and subsequent decomposition of stable diazonium metal complexes (3 and 4).The effects of several variables, including the nature of the metal M, on these reactions is discussed, and comparison to related procedures reported in the literature is made.
- Brown, Kenneth J.,Berry, Matthew S.,Murdoch, Joseph R.
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p. 4345 - 4349
(2007/10/02)
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- ENANTIOSELECTIVE REARRANGEMENT OF 2,2'-HYDRAZONAPHTHALENE
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2,2'-Hydrazonaphthalene rearranges in the presence of (+)-camphor-10-sulfonic acid to give 2,2'-diamino-1,1'-binaphthyl with optical yields up to 15percent in the (-)-enantiomer.Enantioselectivity is dependent on temperature and solvent.
- Sannicolo, Franco
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p. 119 - 120
(2007/10/02)
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- Heavy-Atom Kinetic Isotope Effects in the Acid-Catalysed and Thermal Rearrangements of 2,2'-Hydrazonaphthalene. Transition-State Differences in their Concerted Rearrangements
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Acid-catalyzed (70percent aqueous dioxane at 0 deg C) and thermal rearrangement (95percent ethanol at 80 deg C) of 2,2'-hydrazonaphthalene (1) into 2,2'-diamino-1,1'-binaphthyl (2) have been shown to be concerted, -sigmatropic shifts.This was accomplished by measuring the nitrogen and carbon kinetic isotope effects (KIE), for which purpose mixtures of 1 with 1 and 1 were used.KIE were calculated from whole-molecule mass ratios, measured by multiscan mass spectrometry, in the bis(trifluoroacetyl) derivative of product 2, isolated after low and high conversions.The results (averaged) were, for two isotopic atoms, k(14N)/k(15N') = 1.0904, k(12C)/k(13C) = 1.0086 in the one-proton, acid-catalyzed rearrangement and 1.0611 and 1.0182, respectively, in the neutral, thermal rearrangement.These results indicate that although the rearrangements are concerted processes, the breaking of the N-N bond and the forming of the C-C bond proceed to different extents in the transition states.Furthermore, the differences in the timing of these events is greater in the acid-catalyzed than in the thermal rearrangement, a difference which may be attributable to earlier C-C bonding in the polar transition state of the former.
- Shine, Henry J.,Gruszecka, Ewa,Subotkowski, Witold,Brownawell, Marilyn,Filippo, Joseph San, Jr.
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p. 3218 - 3223
(2007/10/02)
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- AXIALLY DISSYMMETRIC bis(AMINOPHOSPHINE)S DERIVED FROM 2,2 prime -DIAMINO-1,1 prime -BINAPHTHYL. SYNTHESIS AND APPLICATION TO RHODIUM(I)-CATALYZED ASYMMETRIC HYDROGENATIONS.
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Axially dissymmetric bisphosphine ligands, (R)- and (S)-2,2 prime -bis(diphenylphosphinoamino)-1,1 prime -binaphthyl (BDPAB) and (R)-2,2 prime -bis left bracket N-(diphenylphosphino)methylamino right bracket -1,1 prime -binaphthyl (Me-BDPAB) were conveniently prepared from 2,2 prime -diamino-1,1 prime -binaphthyl. The rhodium(I)-catalyzed asymmetric hydrogenation of alpha -acylamidoacrylic acids and esters gave the corresponding amino acids of up to 95% optical purity. The sign of the centro-chirality of the product amino acids was always the same to that of axial chirality of the ligand in both cases of BDPAB and Me-BDPAB.
- Miyano,Nawa,Mori,Hashimoto
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p. 2171 - 2176
(2007/10/02)
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