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1.
Prof. Dr. Yutaka Matsuo Hiromi Oyama Dr. Iwao Soga Dr. Toshihiro Okamoto Dr. Hideyuki Tanaka Dr. Akinori Saeki Prof. Dr. Shu Seki Prof. Dr. Eiichi Nakamura 《化学:亚洲杂志》2013,8(1):121-128
The efficient nucleophilic addition of aryl Grignard reagents (aryl=4‐MeOC6H4, 4‐Me2NC6H4, Ph, 4‐CF3C6H4, and thienyl) to C60 in the presence of DMSO produced 1,2‐arylhydro[60]fullerenes after acid treatment. The reactions of the anions of these arylhydro[60]fullerenes with either dimethylphenylsilylmethyl iodide or dimethyl(2‐isopropoxyphenyl)silylmethyl iodide yielded the target compounds, 1‐aryl‐4‐silylmethyl[60]fullerenes. The properties and structures of these 1‐aryl‐4‐silylmethyl[60]fullerenes (aryl=4‐MeOC6H4, thienyl) were examined by electrochemical studies, X‐ray crystallography, flash‐photolysis time‐resolved microwave‐conductivity (FP‐TRMC) measurements, and electron‐mobility measurements by using a space‐charge‐limited current (SCLC) model. Organic photovoltaic devices with a polymer‐based bulk heterojunction structure and small‐molecule‐based p–n and p–i–n heterojunction configurations were fabricated by using 1‐aryl‐4‐silylmethyl[60]fullerenes as an electron acceptor. The most efficient device exhibited a power‐conversion efficiency of 3.4 % (short‐circuit current density: 8.1 mA/ cm2, open‐circuit voltage: 0.69 V, fill factor: 0.59). 相似文献
2.
Pamela G. Alsabeh Dr. Rylan J. Lundgren Dr. Robert McDonald Dr. Carin C. C. Johansson Seechurn Dr. Thomas J. Colacot Prof. Dr. Mark Stradiotto 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(6):2131-2141
An examination of the [{Pd(cinnamyl)Cl}2]/Mor‐DalPhos (Mor‐DalPhos=di(1‐adamantyl)‐2‐morpholinophenylphosphine) catalyst system in Buchwald–Hartwig aminations employing ammonia was conducted to better understand the catalyst formation process and to guide the development of precatalysts for otherwise challenging room‐temperature ammonia monoarylations. The combination of [{Pd(cinnamyl)Cl}2] and Mor‐DalPhos afforded [(κ2‐P,N‐Mor‐DalPhos)Pd(η1‐cinnamyl)Cl] ( 2 ), which, in the presence of a base and chlorobenzene, generated [(κ2‐P,N‐Mor‐DalPhos)Pd(Ph)Cl] ( 1 a ). Halide abstraction from 1 a afforded [(κ3‐P,N,O‐Mor‐DalPhos)Pd(Ph)]OTf ( 5 ), bringing to light a potential stabilizing interaction that is offered by Mor‐DalPhos. An examination of [(κ2‐P,N‐Mor‐DalPhos)Pd(aryl)Cl] ( 1 b – f ) and related precatalysts for the coupling of ammonia and chlorobenzene at room temperature established the suitability of 1 a in such challenging applications. The scope of reactivity for the use of 1 a (5 mol %) encompassed a range of (hetero)aryl (pseudo)halides (X=Cl, Br, I, OTs) with diverse substituents (alkyl, aryl, ether, thioether, ketone, amine, fluoro, trifluoromethyl, and nitrile), including chemoselective arylations. 相似文献
3.
Ryo Nadano Dr. Kohei Fuchibe Dr. Masahiro Ikeda Hiroki Takahashi Junji Ichikawa Prof. Dr. 《化学:亚洲杂志》2010,5(8):1875-1883
1‐(Trifluoromethyl)vinylation is accomplished in two protocols by the in situ generation of thermally unstable 3,3,3‐trifluoroprop‐1‐en‐2‐yllithium ( 1 ): 1) a rapid lithium–halogen‐exchange reaction of 2‐bromo‐3,3,3‐trifluoroprop‐1‐ene ( 2 ) takes effect with sec‐BuLi at ?105 °C to generate vinyllithium 1 , which reacts with more reactive electrophiles, such as aldehydes and N‐tosylimines before its decomposition, to afford 2‐(trifluoromethyl)allyl alcohols and N‐[2‐(trifluoromethyl)allyl] sulfoamides in good yield; 2) treatment of 2 with nBuLi at ?100 °C causes a slow lithium–halogen exchange of 2 , which gives rise to a mixture of 1 and nBuLi. Vinyllithium 1 is preferentially trapped with less reactive electrophiles, such as N,N‐dimethylamides in the presence of BF3?OEt2, to afford 1‐(trifluoromethyl)vinyl ketones in good yield. Versatility of the products toward syntheses of CF3‐containing ring‐fused cyclopentenones is also demonstrated by the Pauson–Khand reaction and the Nazarov cyclization. 相似文献
4.
New Pyrazolyl‐Nicotinic Acids,Methyl Esters,and 1,3,4‐Oxadiazolyl‐pyrazolyl‐pyridine Tricyclic Scaffold Derivatives from 6‐Hydrazinylnicotinic Acid Hydrazide Hydrate 下载免费PDF全文
H. G. Bonacorso G. R. Paim L. M. F. Porte E. P. Pittaluga S. Cavinatto A. R. Meyer M. A. P. Martins N. Zanatta 《Journal of heterocyclic chemistry》2014,51(4):1171-1178
This paper describes an efficient approach for the synthesis of a new series of 6‐[3‐alkyl(aryl/heteroaryl)‐5‐trifluoromethyl‐1H‐pyrazol‐1‐yl]nicotinic acids (where alkyl = CH3; aryl = Ph, 4‐OCH3Ph, 4,4′‐BiPh; and heteroaryl = 2‐Furyl) from the hydrolysis reaction of alkyl(aryl/heteroaryl)substituted 2‐(5‐trifluoromethyl‐5‐hydroxy‐4,5‐dihydro‐1H‐pyrazol‐1‐yl)‐5‐(5‐trifluoromethyl‐5‐hydroxy‐4,5‐dihydro‐1H‐1‐carbonylpyrazol‐1‐yl)pyridines, under basic conditions and at 70–95% yields. In a subsequent step, the esterification reaction of pyrazolyl‐nicotinic acids done in thionyl chloride and methanol led to the isolation of a series of methyl 6‐[alkyl(aryl/heteroaryl)‐5‐trifluoromethyl‐1H‐pyrazol‐1‐yl] nicotinates as stable hydrochloride salts at 64–84% yields, which could be easily converted to hydrazides to give new oxadiazolyl‐pyrazolyl‐pyridine tricyclic scaffolds at good yields from a [4 + 1] cyclocondensation reaction with 1,1,1‐triethoxyethane and 1‐(triethoxymethyl)benzene as the reagent/solvent. 相似文献
5.
Helio G. Bonacorso Rosália Andrighetto Nícolas Krüger Jussara Navarini Alex F. C. Flores Marcos A. P. Martins Nilo Zanatta 《Journal of heterocyclic chemistry》2013,50(Z1):E193-E199
This article reports a convenient and general method for the regioselective synthesis of a new series of 2‐alkyl(aryl)‐8‐methyl‐4‐trifluoromethyl‐7‐aminoquinolines in 86–93% yields, from cycloaromatization reactions of N‐(oxotrifluoroalkenyl)‐2,6‐diaminotoluenes in a strongly acidic medium polyphosphoric acid and absence of solvent. The enaminoketone intermediates were easily isolated from the reaction of 4‐alkoxy‐4‐alkyl(aryl)‐1,1,1‐trifluoroalk‐3‐en‐2‐ones [CF3C(O)CH═C(R)OR1, where R = H, Me, Ph, 4‐FPh, 4‐BrPh, 4‐MePh, and R1 = Me, Et] with 2,6‐diaminotoluene (2,6‐DAT) in methanol under mild conditions, in 46–70% yields. Another synthetic route also allowed the regioselective synthesis of 2‐aryl(heteroaryl)‐4‐methyl‐4‐trifluoromethyl‐7‐aminoquinolines from direct cyclocondensation reactions of 4‐alkoxy‐4‐aryl(heteroaryl)‐1,1,1‐trifluoroalk‐3‐en‐2‐ones with 2,6‐diaminotoluene in methanol under mild conditions, in 21–36% yields. 相似文献
6.
Lithium phenylacetylide ( 1a ) and N2O4 ( 2 ) at −78° yield diphenylbutadiyne ( 6a ) by oxidative coupling, phenylacetylene ( 7a ) by oxidation and then solvent H‐abstraction, and benzoyl cyanide ( 8 ) by dimerizative‐rearrangement of nitroso(phenyl)acetylene ( 23 ). Nitro(phenyl)acetylene ( 3 , R=Ph) is not obtained. Benzonitrile ( 9 ), a further product, possibly results from hydrolytic decomposition of nitroso(phenyl)ketene ( 27 ) generated from phenylacetylenyl nitrite ( 26 ). Phenylacetylene ( 7a ) and 2 give, along with (E)‐ and (Z)‐1,2‐dinitrostyrenes ( 34 and 35 , resp.), 3‐benzoyl‐5‐phenylisoxazole ( 10 ), presumably as formed by cycloaddition of benzoyl nitrile oxide ( 40 ) to 7a . Further, 2 reacts with other lithium acetylides ( 1b – 1e ), and with sodium, magnesium, zinc, copper, and copper lithium phenylacetylides, 1f – 1l , to yield diacetylenes 6a – 6c and monoacetylenes 7a – 7c . Conversions of metallo acetylide aggregates to diacetylenes are proposed to involve generation and addition reactions of metallo acetylide radical cationic intermediates in cage, further oxidation, and total loss of metal ion. Loss of metal ions from metallo acetylide radical cations and H‐abstraction by non‐caged acetylenyl radicals will give terminal acetylenes. The principal reactions (75–100%) of heavy metal acetylides phenyl(trimethylstannyl)acetylene ( 44 ) and bis(phenylacetylenyl)mercury ( 47 ) with 2 are directed nitrosative additions (NO+) and loss of metal ions to give nitroso(phenyl)ketene ( 27 ), which converts to benzoyl cyanide ( 8 ). 相似文献
7.
Ming‐Zhong Wang Cong‐Ying Zhou Man‐Kin Wong Dr. Chi‐Ming Che Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(19):5723-5735
Ruthenium porphyrins (particularly [Ru(2,6‐Cl2tpp)CO]; tpp=tetraphenylporphinato) and RuCl3 can act as oxidation and/or Lewis acid catalysts for direct C‐3 alkylation of indoles, giving the desired products in high yields (up to 82 % based on 60–95 % substrate conversions). These ruthenium compounds catalyze oxidative coupling reactions of a wide variety of anilines and indoles bearing electron‐withdrawing or electron‐donating substituents with high regioselectivity when using tBuOOH as an oxidant, resulting in the alkylation of N‐arylindoles to 3‐{[(N‐aryl‐N‐alkyl)amino]methyl}indoles (yield: up to 82 %, conversion: up to 95 %) and the alkylation of N‐alkyl or N‐H indoles to 3‐[p‐(dialkylamino)benzyl]indoles (yield: up to 73 %, conversion: up to 92 %). A tentative reaction mechanism involving two pathways is proposed: an iminium ion intermediate may be generated by oxidation of an sp3 C? H bond of the alkylated aniline by an oxoruthenium species; this iminium ion could then either be trapped by an N‐arylindole (pathway A) or converted to formaldehyde, allowing a subsequent three‐component coupling reaction of the in situ generated formaldehyde with an N‐alkylindole and an aniline in the presence of a Lewis acid catalyst (pathway B). The results of deuterium‐labeling experiments are consistent with the alkylation of N‐alkylindoles via pathway B. The relative reaction rates of [Ru(2,6‐Cl2tpp)CO]‐catalyzed oxidative coupling reactions of 4‐X‐substituted N,N‐dimethylanilines with N‐phenylindole (using tBuOOH as oxidant), determined through competition experiments, correlate linearly with the substituent constants σ (R2=0.989), giving a ρ value of ?1.09. This ρ value and the magnitudes of the intra‐ and intermolecular deuterium isotope effects (kH/kD) suggest that electron transfer most likely occurs during the initial stage of the oxidation of 4‐X‐substituted N,N‐dimethylanilines. Ruthenium‐catalyzed three‐component reaction of N‐alkyl/N‐H indoles, paraformaldehyde, and anilines gave 3‐[p‐(dialkylamino)benzyl]indoles in up to 82 % yield (conversion: up to 95 %). 相似文献
8.
Simon Janich Dr. Roland Fröhlich Dr. Atsushi Wakamiya Dr. Shigehiro Yamaguchi Prof. Dr. Ernst‐Ulrich Würthwein Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(40):10457-10463
Treatment of tetramethylsuccinonitrile 1 with aryl lithium compounds and subsequent quenching with chlorotrimethylsilane yields 5‐aryl‐3,3,4,4‐tetramethyl‐N‐(trimethylsilyl)‐3,4‐dihydropyrrol‐2‐imines 2 a – c in 49–71 % yield. Attempts to crystallise 2 a – c in the presence of wet air yielded the tetraaryl tetradecahydroporphyrazins 3 a – c in yields of 4–84 % as single diastereomers. X‐ray diffraction studies of 3 b and c showed that only the isomer with four aryl substituents pointing in the same direction was formed. The resulting four‐bladed pinwheel‐like structures were characterised by four intramolecular aromatic interactions, in which each phenyl ring points with its edge towards the centre of a neighbouring phenyl moiety, resembling the arrangement of benzene molecules in T‐shaped dimers. Temperature‐dependent NMR spectra give insight into the dynamic properties of the aryl substituents. Quantum chemical calculations that included dispersion corrections indicated the importance of aryl–aryl interactions for the diastereoselectivity of the reaction and for the structural properties of the single isomers observed. 相似文献
9.
Jonathan D. Webb Véronique S. Laberge Stephen J. Geier Douglas W. Stephan Prof. Dr. Cathleen M. Crudden Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(16):4895-4902
We report herein that the reaction between a series of Hantzsch’s ester analogues 1 a – d with the Lewis acidic species B(C6F5)3 results in facile transfer of hydride to boron. The main products of this reaction are pyridinium borohydride salts 2 a – d , which are obtained in high to moderate yields. The N‐substituted substrates (N‐Me, N‐Ph) reacted in high yield 90–98 % and the connectivity of the products were confirmed by an X‐ray crystallographic analysis of the N‐Me borohydride salt 2 a . Unsubstituted Hanztsch’s ester 1 a reacted less effectively generating only 60 % of the corresponding borohydride salt, with the balance of the material sequestered as the ester‐bound Lewis acid–base adduct 3 a . Formation of the Lewis acid–base adduct could be minimized by increasing the steric bulk about the ester groups as in 1 d . The connectivity of the carbonyl‐bound adduct was confirmed by an X‐ray crystallographic analysis of 3 e the product of the reaction of methyl ketone 1 e with B(C6F5)3. We also explored the generation of these pyridinium salts by employing frustrated Lewis pair methodology. However, the reaction of mixtures of the corresponding pyridine and B(C6F5)3 with hydrogen gas only resulted in formation of trace amounts of the pyridinium borohydride, along with the Lewis acid–base adduct of the starting material and B(C6F5)3. The 1,2‐dihydropyridine adduct was the final product of this reaction. This was ascribed to the low basicity of the pyridine nitrogen and the complicating formation of an ester bound Lewis acid–base adduct. 相似文献
10.
Carine Maaliki Dr. Christine Lepetit Dr. Yves Canac Dr. Christian Bijani Carine Duhayon Prof. Remi Chauvin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(25):7705-7714
Two types of imidazoliophosphane with additional electron‐withdrawing substituents, such as alkoxy or imidazolio groups, are experimentally described and theoretically studied. Diethyl N,N′‐2,4,6‐methyl(phenyl)imidazoliophosphonite is shown to retain a P‐coordinating ability toward a {RhCl(cod)} (cod=cycloocta‐1,5‐diene) center, thus competing with the cleavage of the labile C? P bond. Derivatives of N,N′‐phenylene‐bridged diimidazolylphenylphosphane were isolated in good yield. Whereas the dicationic phosphane proved to be inert in the presence of [{RhCl(cod)}2], the monocationic counterpart was shown to retain the P‐coordinating ability toward a {RhCl(cod)} center, thus competing with the N‐coordinating ability of the nonmethylated imidazolyl substituent. The ethyl phosphinite version of the dication, thus possessing an extremely electron‐poor PIII center, was also characterized. According to the difference between the calculated homolytic and heterolytic dissociation energies, the N2C???P bond of imidazoliophosphanes with aryl, amino, or alkoxy substituents on the P atom is shown to be of dative nature. The P‐coordinating properties of imidazoliophosphanes with various combinations of phenyl or ethoxy substituents on the P atom and those of six diimidazolophosphane derivatives with zero, one, or two methylium substituents on the N atom, were analyzed by comparison of the corresponding HOMOs and LUMOs and by calculation of the IR C?O stretching frequencies of their [RhCl(CO)2] complexes. Comparison of the νCO values allows the family of the electron‐poor Im+PRR′ (Im=imidazolyl) potential ligands to be ranked in the following order versus (R,R′): P(OEt)3<(Ph,Ph)<(Ph,OEt)<(OEt,OEt)<PF3<(Ph,Im)<(Ph,Im+)<(OEt,Im+). The (Ph,Im) representative is therefore the least electron‐donating phosphane for which coordinating behavior toward a RhI center has been experimentally evidenced to date. Ultimate applications in catalysis could be envisaged. 相似文献
11.
Dimitrije Djukanovic Benjamin Heinz Dr. Francesca Mandrelli Dr. Serena Mostarda Dr. Paolo Filipponi Dr. Benjamin Martin Prof. Dr. Paul Knochel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(56):13977-13981
The continuous flow reaction of various aryl or heteroaryl bromides in toluene in the presence of THF (1.0 equiv) with sec-BuLi (1.1 equiv) provided at 25 °C within 40 sec the corresponding aryllithiums which were acylated with various functionalized N,N-dimethylamides including easily enolizable amides at −20 °C within 27 sec, producing highly functionalized ketones in 48–90 % yield (36 examples). This method was well suited for the preparation of α-chiral ketones such as naproxene and ibuprofen derived ketones with 99 % ee. A one-pot stepwise bis-addition of two different lithium organometallics to 1,1,3,3-tetramethyurea (TMU) provided unsymmetrical ketones in 69–79 % yield (9 examples). 相似文献
12.
Reactivity of TpMe2‐Supported Yttrium Alkyl Complexes toward Aromatic N‐Heterocycles: Ring‐Opening or CC Bond Formation Directed by CH Activation 下载免费PDF全文
Dr. Weiyin Yi Prof. Dr. Jie Zhang Shujian Huang Prof. Dr. Linhong Weng Prof. Dr. Xigeng Zhou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(3):867-876
Unusual chemical transformations such as three‐component combination and ring‐opening of N‐heterocycles or formation of a carbon–carbon double bond through multiple C–H activation were observed in the reactions of TpMe2‐supported yttrium alkyl complexes with aromatic N‐heterocycles. The scorpionate‐anchored yttrium dialkyl complex [TpMe2Y(CH2Ph)2(THF)] reacted with 1‐methylimidazole in 1:2 molar ratio to give a rare hexanuclear 24‐membered rare‐earth metallomacrocyclic compound [TpMe2Y(μ‐N,C‐Im)(η2‐N,C‐Im)]6 ( 1 ; Im=1‐methylimidazolyl) through two kinds of C–H activations at the C2‐ and C5‐positions of the imidazole ring. However, [TpMe2Y(CH2Ph)2(THF)] reacted with two equivalents of 1‐methylbenzimidazole to afford a C–C coupling/ring‐opening/C–C coupling product [TpMe2Y{η3‐(N,N,N)‐N(CH3)C6H4NHCH?C(Ph)CN(CH3)C6H4NH}] ( 2 ). Further investigations indicated that [TpMe2Y(CH2Ph)2(THF)] reacted with benzothiazole in 1:1 or 1:2 molar ratio to produce a C–C coupling/ring‐opening product {(TpMe2)Y[μ‐η2:η1‐SC6H4N(CH?CHPh)](THF)}2 ( 3 ). Moreover, the mixed TpMe2/Cp yttrium monoalkyl complex [(TpMe2)CpYCH2Ph(THF)] reacted with two equivalents of 1‐methylimidazole in THF at room temperature to afford a trinuclear yttrium complex [TpMe2CpY(μ‐N,C‐Im)]3 ( 5 ), whereas when the above reaction was carried out at 55 °C for two days, two structurally characterized metal complexes [TpMe2Y(Im‐TpMe2)] ( 7 ; Im‐TpMe2=1‐methyl‐imidazolyl‐TpMe2) and [Cp3Y(HIm)] ( 8 ; HIm=1‐methylimidazole) were obtained in 26 and 17 % isolated yields, respectively, accompanied by some unidentified materials. The formation of 7 reveals an uncommon example of construction of a C?C bond through multiple C–H activations. 相似文献
13.
Diversification of ortho‐Fused Cycloocta‐2,5‐dien‐1‐one Cores and Eight‐ to Six‐Ring Conversion by σ Bond C−C Cleavage 下载免费PDF全文
Lee Eccleshare Leticia Lozada‐Rodríguez Phillippa Cooper Dr. Laurence Burroughs John Ritchie Dr. William Lewis Prof. Dr. Simon Woodward 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(35):12542-12547
Sequential treatment of 2‐C6H4Br(CHO) with LiC≡CR1 (R1=SiMe3, tBu), nBuLi, CuBr?SMe2 and HC≡CCHClR2 [R2=Ph, 4‐CF3Ph, 3‐CNPh, 4‐(MeO2C)Ph] at ?50 °C leads to formation of an intermediate carbanion (Z)‐1,2‐C6H4{CA(=O)C≡CBR1}{CH=CH(CH?)R2} ( 4 ). Low temperatures (?50 °C) favour attack at CB leading to kinetic formation of 6,8‐bicycles containing non‐classical C‐carbanion enolates ( 5 ). Higher temperatures (?10 °C to ambient) and electron‐deficient R2 favour retro σ‐bond C?C cleavage regenerating 4 , which subsequently closes on CA providing 6,6‐bicyclic alkoxides ( 6 ). Computational modelling (CBS‐QB3) indicated that both pathways are viable and of similar energies. Reaction of 6 with H+ gave 1,2‐dihydronaphthalen‐1‐ols, or under dehydrating conditions, 2‐aryl‐1‐alkynylnaphthlenes. Enolates 5 react in situ with: H2O, D2O, I2, allylbromide, S2Me2, CO2 and lead to the expected C ‐E derivatives (E=H, D, I, allyl, SMe, CO2H) in 49–64 % yield directly from intermediate 5 . The parents (E=H; R1=SiMe3, tBu; R2=Ph) are versatile starting materials for NaBH4 and Grignard C=O additions, desilylation (when R1=SiMe) and oxime formation. The latter allows formation of 6,9‐bicyclics via Beckmann rearrangement. The 6,8‐ring iodides are suitable Suzuki precursors for Pd‐catalysed C?C coupling (81–87 %), whereas the carboxylic acids readily form amides under T3P® conditions (71–95 %). 相似文献
14.
Yutaka Matsuo Ya Wang Hiroshi Ueno Takafumi Nakagawa Hiroshi Okada 《Angewandte Chemie (International ed. in English)》2019,58(26):8762-8767
(N‐Phenylfluorenylidene)acridane (Ph‐FA) compounds with electron‐withdrawing and ‐donating substituents (H, MeO, Ph, NO2, Br, F) at the para position of the phenyl group were successfully synthesized by Barton–Kellogg reactions of N‐aryl thioacridones and diazofluorene. By using the substituent on the nitrogen atom to alter the electronic properties, both the folded and twisted conformers of p‐NO2‐C6H4‐FA could be crystallographically characterized, which enabled the charge transfer from the electron‐donating acridane moiety to the electron‐accepting fluorenylidene moiety to be understood. Ground‐state mechanochromism, thermochromism, vapochromism, and proton‐induced chromism were demonstrated between the folded and twisted conformations of the conformers. Protonation and chemical oxidation of Ph‐FA gave two stable acridinium compounds, namely, the fluorenylacridinium and acridinium radical cations. The present study will contribute to the development of functional dyes and organic semiconductors. 相似文献
15.
Yutaka Matsuo Ya Wang Hiroshi Ueno Takafumi Nakagawa Hiroshi Okada 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(26):8854-8859
(N‐Phenylfluorenylidene)acridane (Ph‐FA) compounds with electron‐withdrawing and ‐donating substituents (H, MeO, Ph, NO2, Br, F) at the para position of the phenyl group were successfully synthesized by Barton–Kellogg reactions of N‐aryl thioacridones and diazofluorene. By using the substituent on the nitrogen atom to alter the electronic properties, both the folded and twisted conformers of p‐NO2‐C6H4‐FA could be crystallographically characterized, which enabled the charge transfer from the electron‐donating acridane moiety to the electron‐accepting fluorenylidene moiety to be understood. Ground‐state mechanochromism, thermochromism, vapochromism, and proton‐induced chromism were demonstrated between the folded and twisted conformations of the conformers. Protonation and chemical oxidation of Ph‐FA gave two stable acridinium compounds, namely, the fluorenylacridinium and acridinium radical cations. The present study will contribute to the development of functional dyes and organic semiconductors. 相似文献
16.
H. W. Goh S. H. Goh G. Q. Xu 《Journal of polymer science. Part A, Polymer chemistry》2002,40(8):1157-1166
[60]Fullerenated poly(2‐hydroxyethyl methacrylate)s containing 0.6–3.0 wt % C60 were synthesized. These polymers are soluble in methanol and N,N‐dimethylformamide (DMF). [60]Fullerenated poly(2‐hydroxyethyl methacrylate)s with higher C60 contents are only sparingly soluble in DMF and virtually insoluble in other organic solvents. A loading of 1.2 wt % C60 in poly(2‐hydroxyethyl methacrylate) does not greatly affect its miscibility with poly(N‐vinyl‐2‐pyrrolidone), poly(1‐vinylimidazole), and poly(4‐vinylpyridine). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1157–1166, 2002 相似文献
17.
Gopa Barman Pranab Haldar Neelanjan Dutta Jayanta K. Ray 《Journal of heterocyclic chemistry》2011,48(2):463-467
Substituted pyrrolidine derivatives were synthesized in high yield by NaBH4/I2 mediated chemoselective reduction of N‐aryl‐γ‐lactam and N‐aryl‐thio‐γ‐lactam‐2,2‐dicarboxylate. With excess NaBH4/I2, carbonyl functionality of the ester groups remained unchanged. J. Heterocyclic Chem., (2011). 相似文献
18.
Seeking to further the investigation of extremely sterically congested main group metals, the synthesis of a new oligoaryl triazene (Dipp*2N3H) is reported. This was accessed by diazotization of Dipp*NH2 to access both Dipp*I and Dipp*N3 in high yield and with scalable preparations. These compounds are used as precursors to Dipp*2N3H, via a magnesium aryl, due to the difficulties in obtaining pure triazene via an aryl‐lithium species. Deprotonation of the triazene with both potassium and thallium tert‐butoxides gives the respective metal triazenides in high yield. The solid‐state structures of these complexes have been determined and three high hapticity metal arene‐π interactions, which sterically shield the metal centers, were observed in each case; spectroscopic C2v symmetry suggests these interactions are fluxional in solution. The variability of these interactions in the solid state as well as the changes in calculated steric demand of the ligand between metals point to an adaptive, flexible coordination mode. 相似文献
19.
The zwitterionic 1 : 1 intermediates generated by addition of Ph3P to acetylenic esters is trapped by 1‐[(aryl)chloromethylene]‐2‐phenylhydrazines (=N‐phenylarenecarbohydrazonoyl chlorides) to yield functionalized 3‐aryl‐1‐phenyl‐1H‐pyrazoles in good yields. 相似文献
20.
Eiji Ihara Naohiro Omura Shinsuke Tanaka Tomomichi Itoh Kenzo Inoue 《Journal of polymer science. Part A, Polymer chemistry》2005,43(19):4405-4411
The anionic polymerization of methyl methacrylate in toluene at −78 °C with lithium amides of various secondary amines (diisopropylamine, N‐isopropylaniline, N‐n‐butylaniline, indoline, and N‐ethyl‐o‐toluidine) as initiators was studied. The tacticity of the resulting poly(methyl methacrylate)s (PMMAs) was dependent on the kind of secondary amine, and highly isotactic PMMAs (91–93% mm) were obtained when lithium amides of N‐isopropylaniline and N‐n‐butylaniline were employed. The isotacticity of the PMMAs further increased up to 98% mm with initiating systems composed of the lithium amides, n‐butyllithium, and transition‐metal halides (WCl6, MoCl5, and NbCl5). © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4405–4411, 2005 相似文献