贫电子环丙烷衍生物与胂叶立德的反应研究

The reaction of electron-deficient cyclopropane derivatives, cis-1-methoxycarbonyl-2-aryl-6,6-dimethyl-5,7dioxospiro[2,5]octa-4,8-diones with benzoylmethylenetriphenylarsorane (2) and methoxycarbonylmethylenetriphenylarsorane (4) was found to form cis,trans-l-methoxycarbonyl-2-aryl-3-benzoyl-7,7-dimethyl-6,8-dioxospiro[3,5]nona-5,9-dione (3a-3e) and trans,cis,trans-5-[2‘-methoxycarbonyl-2‘-(triphenylarsoranylidene)acetyl]-6oxo-3-aryl-tetrahydro-pyran-2,4-dicarboxylic acid dimethyl esters (5a-5c) respectively with high stereoselectivity. The possible reaction mechanisms for the formation of the different products were also orooosed.     

Diketopyrrolopyrrole-based conjugated polymers as additives to optimize morphology for polymer solar cells

Novel random copolymers for optimizing the morphology of the active layer for high performance organic photovoltaic devices have been demonstrated. Three ternary random copolymers PTBDTDPPSi CN(3/7), PTBDTDPPSi CN(5/5), PTBDTDPPSi CN(7/3) were prepared by polymerization of electron-donating thienyl-substituted benzodithiophene(TBDT) with 2,5-bis[8-(1,1,3,3,5,5,5-heptamethyltrisiloxane-3-yl)octly]-pyrrolo[3,4-c]pyrrole-1,4-dione(DPPSi) and 2,5-dio[5-(5-cyano-5,5-dimethyl-pentyl)]-3,6-dithiophen-2-yl-pyrrolo[3,4-c]pyrrole-1,4-dione(DPPCN) of different ratios. The DPPCN block can well-tune the light absorption and molecular packing, while the DPPSi block is in favor of enhancing the charge mobility. And the formation of organic Si―O―Si networks is beneficial to stabilize the morphology of the active layer. These new copolymers have narrow bandgaps and broaden visible light absorption from 500 nm to 1000 nm. Careful balance of the contents of the trimethoxysilyl group and the cyano group can well-tune the surface energy and morphology of the copolymers. Incorporation of these novel copolymers as additives into the blend of poly(3-hexylthiophene)(P3HT) and [6,6]-phenyl-C60-butyric acid methyl ester(PC_(61)BM) is found to effectively broaden the light absorption, improve the compatibility and morphology of the active layer. As a result, some devices with certain ratios of these copolymers as additives achieve the enhanced efficiency compared with the device based on pristine P3HT:PC_(61)BM.     

C–H Arylation using acyl thiourea ligands: Applications in the synthesis of 3,6-diaryl-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazoles

Synthesis of a series of new 3,6-diaryl-[1,2,4]triazolo[3,4-b] [1,3,4]thiadiazoles(5a–o) was achieved by phophine free, C–H arylative cross-coupling of 6-aryl-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazoles(4a–o)with suitably substituted iodoanilines using 1-(2-naphthoyl)-3-(4-bromophenyl)thiourea as a ligand.The requisite triazolothiadiazoles(4a–o) were obtained by the condensation of 4-amino-1,2,4-triazole-3-thiol(3) with suitably substituted aromatic acids in the presence of phosphoryl chloride.     

Photochromic reactions of pyrryl substituted fulgides and fulgimides

Photochromic behaviour of six pyrryl substituted fulgides and one fulgimide has been examined. The substituents have significant effects on their photochromic processes. The results of steady state kinetics show that the photodecoloration of the colored form, 7,7a-dihydroindole derivatives (II) follows the first-order kinetics. The substituents have certain effects on the rate constant of the photodecoloration. As for the colored form (II), compounds with the substituent at 2- or 3-position have larger rate constants of the decoloration than those of non-substituted ones. The photocoloration reactions are more complicated and do not fit the simple kinetics. Introduction of the electron donating substituent into the 2- or 3-position leads to bathochromic shift of the maximum of absorption (λmax) of 7,7a-dihydroindole derivatives. For example, the λmax of compound II 7 is 720 nm in acetonitrile. The increasing of the polarity of the solvent caused a remarkable bathochromic shift of λmax of the colored     

Acidichromism of indolinospirooxazines in isopropanol

1,3,3-tnmethyl-spiro[mdolino-2,3'-[2H]naphtho[2,1-b] [1,4]oxazine(SP1) and 1,3,3-trimen-thyl-9-methoxy-spiro[indolino2,3'-[2H]naphtho[2,1-b] [ 1,4]oxazine] (SP2) react with hydrochloric acid to form the complex SP HCl in isopropanol solution at room temperature The absorption maxima of these complexes are 440 and 463 nm respectively In acidic media,the opening form of spirooxazine can react with hydrochloric acid to form the complex PMC HCl via zwittenon form The absorption spectra of PMC HCl are obviously hypsochromic shifted compared with the reported spectra of the complex in neutral media In the mean time,the thermal stability of the complex is increased.The first order kinetics for the decoloration process of the acidichromic product of the opening form was determined and the lifetimes of these products are 180 and 200 s,respectively.     

Fe_3O_4@MCM-48–SO_3H:合成苯并[f]色烯并[2,3-d]嘧啶酮的高效、可磁性分离纳米催化剂(英文)

Sulfonic acid groups were grafted onto three different types of synthesized magnetic nanoparticles, namely Fe3O4, Fe3O4@SiO2, and Fe3O4@MCM-48. The sulfonic acid-functionalized nanoparticles were evaluated as catalysts for the synthesis of 5-aryl-1H-benzo[f]chromeno[2,3-d]pyrimidine-2,4(3H,5H)-dione derivatives in terms of activity and recyclability. Their catalytic activities were compared with that of the homogeneous acid catalyst 1-methylimidazolium hydrogen sulfate([HMIm][HSO4]). The activity of Fe3O4@MCM-48–SO3H was comparable to those of the other heter-ogeneous and homogeneous catalysts.     

Synthesis of 6-aryl substituted 3-(5''''-phenyl-2H-tetrazole-2''''-methylene)-S-triazolo[3,4-b]-1,3,4-thiadiazoles

In this paper , 10 novel 6-aryl-3-(5'-phenyl-2H-tetrazole-2'-methylene)-S-triazolo[3, 4-b]-1,3,4-thiadiazoles have been synthesized by the condensation of 3-(5'-phenyl-2H-tetrazole-2'-methylene)-4-amino-5-mercapto-1,2,4-triazole with various aromatic carboxylic acids in the presence of phosphorus oxychloride. The structure of these compounds was determined by elemental analysis , UV, IR, 1H NMR and MS. Their spectral properties were also discussed.     

Michael-Addition Reaction of Malononitrile with α,β-Unsaturated Cycloketones Catalyzed by KF／Al2O3

A series of KF/Al2O3 catalyzed Michael-addition reactions between malononitrile and α,β-unsaturated cycloketones in DMF solution were studied. At room temperature, 2-cyano-3-aryl-3-(1,2,3,4-tetrahydronaphthalen-1-one-2-yl) propionitrile derivatives were synthesized by the reaction between 2-arylmethylidene-1,2,3,4-tetra-hydronaphthalen-1-one and malononitrile. However, if the temperature was increased to 80℃, 2-amino-3-cyano-4-aryl-4H-benzo[h]chromene derivatives were obtained in high yields. When the α,β-unsaturated ketones were replaced by 2,6-biarylmethylidenecyclohexanone or 2,5-biarylmethylidenecyclopentanone, another series of 2-amino-3-cyano-4H-pyran derivatives was isolated successfully. The structures of the products were confirmed by X-ray diffraction analysis.     

Synthesis,Structure and Luminescent Property of a Zn(Ⅱ) Complex with Mixed Multi-N Donor and 2,5-Dihydroxy-terephthalic Acid Ligands

A new complex, [Zn_2(HL)_2(2,5-OH-pbda)]n(1, L = 1-(1 H-imidazol-4-yl)-4-(4 Htetrazol-5-yl)benzene(H_2L) and 2,5-OH-H_2 pbda = 2,5-dihydroxy-terephthalic acid), has been hydrothermally prepared and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and PXRD. Complex 1 crystallizes in monoclinic, space group P2_1/n with a = 8.8101(10), b = 17.105(2), c = 9.4014(11) ?, β = 105.704(2)o, V = 1363.9(3) ?`3, Z = 4, C_(14)H_9N_6O_3Zn, M_r = 374.64, D_c = 1.824 g/cm~3, μ = 1.831 mm~(-1), S = 1.042, F(000) = 756, the final R = 0.0309 and w R = 0.1003 for 3130 observed reflections(I 2σ(I)). The H_2L ligand was deprotonated to be an HL-anion, and coordinated with Zn~(2+) to form two-dimensional(2D) Zn_2(HL~-)_2~(2+) sheets, which were pillared by the 2,5-OH-pbda2-ligands to form a three-dimensional(3D) dmc net with Point(Schl?fli) symbol of(4·82)(4·85). The large vacancy of the dmc net is filled via mutual interpenetration of another independent framework, leading to the formation of a 2-fold interpenetrating architecture. Solid state luminescent property of 1 has been investigated.     

A convenient synthesis of 2-aryl substituted benzo[f] [1,2,4]triazolo[1,5-a]azepine derivatives

A convenient synthetic pathway to 2-aryl-5,6-dihydro-4H-benzo[f][1,2,4]triazolo[1,5-α]azepine derivatives 7 was developed. The synthesis was based on the cycloaddition of the 1,2,3,4-tetrahydronaphthalene a-acetoxy azo compounds 3 with Ar-CN in the presence of AlCl3 and the consecutive ring enlargement.     

Structures and photochromic properties of fulgides based on naphtho[1,2-<Emphasis Type="Italic">b</Emphasis>]furan and benzo[<Emphasis Type="Italic">g</Emphasis>]indole

The novel heterocyclic fulgides, i.e. 3-isopropylidene-4-{1-[5-methoxy-1-(4-methoxy-phenyl)-2-methyl-1H-benzo[g]indol-3-yl]ethylidene}dihydrofuran-2,5-dione and 3-isopropylidene-4-[1-(1-benzyl-5-methoxy-2-methyl-1H-benzo[g]indol-3-yl)ethylidene]dihydrofuran-2,5-dione, were prepared and isolated as E-isomers. Photochromism, E-configuration, and high resistance to photocoloration—photobleaching of solutions of these fulgides as well as 3-isopropylidene-4-[1-(5-methoxy-2-methylnaphtho[1,2-b]furan-3-yl)ethylidene]dihydro-furan-2,5-dione and 3-isopropylidene-4-[1-(5-methoxy-2-methyl-1-phenyl-1H-benzo[g]indol-3-yl)ethylidene]dihydrofuran-2,5-dione synthesized previously were shown by X-ray diffraction analysis, ¹H NMR spectroscopy and electronic absorption spectroscopy. The novel fulgides show fluorescence and high thermal stability of photogenerated cyclic form. Repeated photo-coloration—photobleaching is accompanied by reversible photoinduced E—Z isomerization. Benzo[g]indolyl fulgides are characterized by the longer wavelength absorption of both original (E) and photoisomeric cyclic (C) forms as compared to naphthofuran fulgide.     

Synthesis of photochromic bisfulgimides by the condensation of (3<Emphasis Type="Italic">Z</Emphasis>)-3-[1-(2,5-dimethyl-3-thienyl)-ethylidene]-4-isopropylidene-2,5-furandione with aromatic diamines

The first representatives of thiophene derivatives with two fulgimide fragments in one molecule have been obtained by the condensation of (3Z)-3-[1-(2,5-dimethyl-3-thienyl)ethylidene]-4-isopropylidene-2,5-furandione with aromatic diamines. The photochromic properties of the obtained compounds have been investigated and the effect of a spacer, linking the two fulgimide fragments, on the reaction rates of photocoloration and photodecoloration of these compounds has been studied.     

Investigation of reactions of the organozinc reagents prepared from zinc and dialkyl dibromomalonates with the derivatives of 2-arylmethyleneindan-1,3-dione and 5-arylmethylene-2,2-dimethyl-1,3-dioxane-4,6-dione

Organozinc compounds prepared from dialkyl dibromomalonates and zinc react with 2-arylmethyl-eneindan-4,6-diones, 5-arylmethylene-2,2-dimethyl-1,3-dioxane-4,6-diones, as well as with 2-[4-(1,3-dioxoindan-2-ylidenemethyl)phenyl]methyleneindan-1,3-dione and 5-[4-(2,2-dimethyl-4,6-dioxo-1,3-dioxane-2-ylidenemethyl)phenyl]methylene-2,2-dimethyl-1,3-dioxane-4,6-diones to form dialkyl 3-aryl-1′3′-dioxaspiro(cyclopropane-2,2′-indan)-1,1-dicarboxylates, dimethyl 3-aryl-6,6-dimethyl-5,7-dioxa-4,8-dioxaspiro[2,5]octan-2,2-dicarboxylates, dialkyl 2-{4-[3,3-bis (alkoxycarbonyl)-1′,3′-dioxaspiro(cyclopropane-2,2′-indan)-1-yl]phenyl}-1′,3′-dioxaspiro[cyclopropane-2,2′-indan]-1,1-dicarboxylates, and dialkyl 2-{4-[2,2-bis(alkoxycarbonyl)-6,6′-dimethyl-4,8-dioxo-5,7-dioxaspiro[2,5]oct-1-yl]phenyl}-6,6-dimethyl-4,8-dioxo-5,7-dioxaspiro[2,5]octan-1,1-dicarboxylate respectively.     

The mechanisms of photochromic transformations of 2-indolylfulgides

Photochromic properties of 2-indolylfulgides, namely, Z-3-[1-(1,3-dimethyl-1H-indol-2-yl)ethylidene]-4-isopropylidenetetrahydrofuran-2,5-dione andE-3-isopropylidene-4-(1-methyl-1H-indol-2-ylmethylidene)tetrahydrofuran-2,5-dione, were studied. The quantum yields of their photochemical isomerizations in toluene and the rate constant of the dark ring-opening in ethanol were determined. The fluorescence spectra of the open and cyclic forms of 2-indolylfulgides were measured. It was assumed that the excited-stateZ-isomer can be transformed into a cyclic isomer without intermediacy of anE-isomer in the ground state. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1026–1029, June, 2000.     

Synthesis, structures, and photochromic properties of 2-methylthieno[3,2-b][1]benzothiophen-3-ylfulgide

The novel heterocyclic fulgide, 3-(1-methylethylidene)-4-[1-(2-methylthieno[3,2-b]-[1]benzothiophen-3-yl)ethylidene]dihydrofuran-2,5-dione, was obtained and isolated as a Z-isomer. Its structure was confirmed by electronic absorption spectroscopy, ¹H NMR spectroscopy, and X-ray diffraction analysis. The novel thienothiophene fulgide is photochromic in both solutions and the crystalline state. Its colored cyclic form resists photodegradation and is thermally stable. When benzothiophene is annulated with the thienyl fragment, the long-wavelength absorption peak of the cyclic isomer of the novel fulgide experiences a bathochromic shift compared to the earlier described 3-thienylfulgide. The TD B3LYP/6-311G**-calculated spectroscopic characteristics of the fulgide isomers suggest the formation of their photostationary mixture under irradiation with λ = 365 nm. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2318–2324, December, 2007.     

Photochromism of an <Emphasis Type="Italic">N</Emphasis>-aminofulgimide-derived Schiff base

A Schiff base was synthesized from 5-methoxysalicylaldehyde and N-aminofulgimide, viz., 1-amino-3-[1-(2,5-dimethylthiophen-3-yl)ethylidene]-4-isopropylidenepyrrolidine-2,5-dione. The compound synthesized undergoes photochromic transformations typical of those of N-aminofulgimide studied earlier. A bathochromic shift of the absorption bands of the open and cyclic forms of the obtained Schiff base compared to the starting N-aminofulgimide was observed.     

Photochromic benzo[<Emphasis Type="Italic">g</Emphasis>]indolyl fulgimide with modulated fluorescence

A new photochromic fulgimide, (E)-1-(anthracen-9-ylmethyl)-3-[1-(5-methoxy-2-methyl-1-phenyl-1H-benzo[g]indol-3-yl)ethylidene]-4-(propan-2-ylidene)pyrrolidine-2,5-dione, has been synthesized and found to exhibit fluorescence. The structure of this compound and intermediate fulgenates and amidofulgenic and fulgenic acids has been determined by electronic and vibrational spectroscopy, ¹H and ¹³C NMR, and mass spectrometry. The amidofulgenic and fulgenic acids are capable of undergoing photoinduced reversible Z/E isomerization with respect to the C=C bond without subsequent cyclization, whereas fulgenates are converted to the corresponding cyclic structures. The new fluorescent fulgimide is transformed into the colored nonfluorescing cyclic isomer under UV irradiation. The reverse ring opening under visible light irradiation restores the fluorescence properties, which makes this compound a molecular fluorescence switch.     

Synthesis of 5-aryl-3-carbazoyl-1,3,4-oxadiazol-2(3H)-one. Derivatives and their ring transformation into 5-benzamido-1,2,4-triazolidine-3,5-dione derivatives

Some 5-aryl-3-carbazoyl-1,3,4-oxadiazol-2(3H)-one derivatives 6 and 9 have been synthesized in two ways. The expected thermal ring transformation into 2,5-disubstituted 1,3,4-oxadiazoles did not occur but, by acid hydrolysis of 5-aryl-3-[3-benzylidene-2-methyl(or phenyl)carbazoyl]-1,3,4-oxadiazol-2(3H)-ones 6 , a new ring transformation took place and the corresponding 4-benzamido-1-methyl(or phenyl)-1,2,4-triazolidine-3,5-dione derivatives 11 were formed. The 4-amino-1-phenyl-1,2,4-triazolidine-3,5-dione ( 19 ) has been prepared and its structure was confirmed by some reactions.     

New photochromic symmetrical and unsymmetrical bis(heteroaryl)maleimides: A spectrokinetic study

The photochromic behavior of two newly synthesized diarylethenes is here presented. The compounds studied are the symmetrical (1-benzyl-3,4-bis(2-methylbenzo[b]thiophen-3-yl)-[1H]-2,5-dihydropyrrol-2,5-dione) and the unsymmetrical (1-benzyl-3-(2-methylbenzo[b]thiophen-3-yl)-4-(2,5-dimethyl-3-thienyl)-[1H]-2,5-dihydropyrrol-2,5-dione). Upon stimulation with UV or violet light, these compounds become red-colored due to photocyclization and cyclorevert to the light yellow open form upon irradiation with visible light. In this work, absorption and fluorescence spectra, molar absorption coefficients of the ethenic and cyclized forms, fluorescence quantum yields and photochemical quantum yields of both the forward and back photoreactions were determined. Temperature, excitation wavelength and solvent effects were explored. The symmetrical compound was found to be a bistable photochrome. In contrast, the unsymmetrical molecule resulted unsuitable as photochrome because of side degradation processes occurring in competition with cyclization.     

Synthesis and spectral kinetic investigation of solutions of photochromic thienylfulgimides

A convenient method has been developed for the synthesis of previously unknown photochromic 1-amino-3-[1-(2,5-dimethyl-3-thienyl)ethylidene]-4-(1-methylethylidene)pyrrolidine-2,5-dione, from which photochromic Schiff’s bases were obtained. A spectral kinetic investigation of the photochromism of the thienylfulgimides obtained has been carried out. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1170–1175, August, 2006.