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1.
Iododerivatives of N‐methylcarbazole ( 1 ), N‐phenylcarbazole ( 2 ), N‐benzylcarbazole ( 3 ), 2‐methoxy‐N‐methylcarbazole ( 4 ) and 3‐acetamido‐N‐ethylcarbazole ( 5 ) are synthesised. N‐Iodosuccinimide (NIS) in tetrahydrofurane/H2SO4 (catalyst), a mixture of KIO3 ‐ KI ‐ H2SO4 (catalyst) in ethanol and a mixture of KIO3 ‐ KI in glacial AcOH as iodinating agents have been used and their uses have been compared. The preparation, isolation and characterization of compounds 1a, 1b, 1c, 1d, 2a, 2b, 3a, 3b, 4a, 4b, 4c and 5a are reported (mp, tR, Rf, 1H‐nmr, 13C‐nmr, IR and ms). All of them are described for the first time except 3,6‐diiodo‐N‐phenyl‐carbazole ( 2b ). Semiempirical PM3 calculations have been performed to predict reactivity of N‐substituted carbazoles and their iododerivatives. Theoretical and experimental results are discussed briefly.  相似文献   

2.
From the crude mixtures of isomeric 4‐nitrophenylthieno[2,3‐b]pyridines ( 3 ) previously reported [1] were isolated three analytically pure samples, viz. the 2‐isomer (yellow needles, mp 258°, 3a ), the 6‐isomer (red prisms, mp 182°, 3e ), and a ternary mixture of the 2‐, 3‐, and 4‐isomers (orange needles, mp 213°, 3a:3b:3c = 1.3:1.0:0.5). The 258° compound was identified as either 3a or 3b by its 1H nmr spectrum and definitively as the former by its x‐ray crystallographic analysis. The isomeric identities of the 182° and 213° samples were established from their 1H nmr spectra only. No 5‐isomer ( 3d ) was identified. Semi‐quantitatively, relative isomeric yields fit the pattern 2‐ (64%)>>6‐ (14%)≥3‐ (12%)>4‐ (6%)≥5‐(≤4%). Crystallographic data for 3a are presented.  相似文献   

3.
Neutral classes of amide‐based macrocycle have been synthesized and the anion binding abilities are assessed by UV‐vis titration and 1H nmr experiments. Results indicate that higher anion binding abilities are observed for H2PO4?, F? and AcO?, but almost no affinity for Cl?, Br?, I? and OH?. The 1H nmr spectra shows that the interactions between the receptors and fluoride anion depend on two factors, respectively: one is depend on hydrogen bonding, the other on deprotonation.  相似文献   

4.
In this study, synthesis of new ligands, 8-hydroxy-3-[p-(3′,4′-dicyanophenoxy)-phenyl]coumarin and 8-hexyloxy-3-[p-(3′,4′-dicyanophenoxy)-phenyl]coumarin, and their phthalocyanines, 2,9,16,23-tetrakis[8-hexyloxy-3-(4-oxyphenyl)coumarin]-metal-free and metallophthalocyanines {M[Pc(OBzCou)4] (M = 2H, Zn(II), Co(II); Bz: benzene; Cou: coumarin)} were synthesised. The novel chromogenic compounds were characterised by elemental analysis: 1H NMR, 13C NMR, MALDI-TOF, IR and UV–vis spectral data. The effect of coumarin substituents on the photophysical properties of metal-free (H2Pc) and zinc phthalocyanines (ZnPc) derivatives has been examined. Spectrophotometric measurements revealed that coumarin-substituted ZnPc derivatives were in the unaggregated form, whereas those of H2Pc species were in aggregated form. It means that substitution of coumarin derivative prevents the cluster formation in the presence of zinc ion in the centre of Pc.  相似文献   

5.
5,10, 15-Triphenyl-20-{2- [α- (adenine-9 ) acetylamino]} phenyl porphyrin ( 1 ), 5,10, 15-triphenyl-20-{2-[α-(cytosine-1)acetylamino]} phenyl porphyrin (2), 5, 10, 15-triphenyl-20-{4-[α-(cytosine-1)ethoxy]} phenyl porphyrin (3) and their zinc complexes Zn-1, Zn-2 and Zn-3 have been prepared and characterized by ^1H NMR spectra, elemental analyses, electronic absorption spectra and mass spectra (FAB). Intramolecular π-π interactions and intramolecular metal-~ interaction for 1, 2, Zn-1,and Zn-2 have been investigated by several methods. ^1H NMR studies demonstrate that the porphyrin π-system in 1 and 2 is parallel to the adenine and the cytosine aromatic ring, respectively. The electronic absorption spectral properties of free porphyrin derivatives and their zinc complexes have been compared with those of H2TPP and ZnTPP. The results show that the UV-vis spectra of 1 and 2 are the same as that of H2TPP,whereas the spectra of their zinc complexes show 7 nm red shifts of the Soret bands compared to that of ZnTPP. The emission spectra of Zn-1 and Zn-2 are independent of excitation wavelength. From combination of the evidence of absorption and emission spectra it is suggested the existence of intramolecular metal-π interaction in Zn-1 and Zn-2. The results of conformational analysis agreed quite nicely with that of experiments, thus it was further to validate the experimental conclusions.  相似文献   

6.
Carbazole ( 1 ) undergoes electrophilic aromatic substitution with various iodinating reagents. Although, 3‐iodocarbazole ( 1b ) and 3,6‐diiodocarbazole ( 1d ) obtained by iodination of carbazole were isolated and characterized sometime ago, 1‐iodocarbazole ( 1a ), 1,6‐diiodocarbazole ( 1c ) and 1,3,6‐triiodocarbazole ( 1e ) had never been isolated from the reaction mixture. The preparation and subsequent isolation and characterization of 1a, 1b, 1c, 1d and 1e are reported (mp, tr, Rf, 1H‐nmr, 13C‐nmr and ms). As iodinating reagents, NaIO4/I2 and NaIO4/KI mixtures in (i) ethanol doped with catalytical amount of sulfuric acid and in (ii) acetic acid, and N‐odosuccinimide and N‐iodosuccinimide‐silica gel in dichloromethane and in chloroform have been used and their uses have been compared. The iodination reaction of different carbazole derivatives such as 2‐acetoxycarbazole ( 2 ), 3‐bromocarbazole (3) and 3‐nitrocarbazole ( 4 ) was also studied and the corresponding iododerivatives, 2a, 2b, 2c, 3a, 3b, 4a and 4b , are described for the first time. Semiempirical PM3 calculations have been performed in order to predict reactivity of carbazole ( 1 ), substituted carbazoles (2‐4) and iodocarbazoles ( 1a‐1e, 2a‐2c, 3a‐3b, 4a and 4b ) (Scheme 1). Theoretical and experimental results are discussed briefly.  相似文献   

7.
The effects of alkyloxy substituents attached to one phthalocyanine ligand of three heteroleptic bis(phthalocyaninato) yttrium complexes Y(Pc)[Pc(α‐OCH3)4] ( 1 ), Y(Pc)[Pc(α‐OCH3)8] ( 2 ), and Y(Pc)[Pc(β‐OCH3)8] ( 3 ), as well as their reduction products {Y(Pc)[Pc(α‐OCH3)4]}? ( 4 ), {Y(Pc)[Pc(α‐OCH3)8]}? ( 5 ), and {Y(Pc)[Pc(β‐OCH3)8]}? ( 6 ) [H2Pc(α‐OCH3)4=1,8,15,22‐tetrakis(methyloxy)phthalocyanine; H2Pc(α‐OCH3)8=1,4,8,11,15,18,22,25‐octakis(methyloxy)phthalocyanine; H2Pc(β‐OCH3)8=2,3,9,10,16,17,23,24‐octakis(methyloxy)phthalocyanine] are studied by DFT calculations. Good consistency is found between the calculated results and experimental data for the electronic absorption, IR, and Raman spectra of 1 and 3 . Introduction of electron‐donating methyloxy groups on one phthalocyanine ring of the heteroleptic double‐deckers induces structural deformation in both phthalocyanine ligands, electron transfer between the two phthalocyanine rings, changes in orbital energy and composition, shift of electronic absorption bands, and different vibrational modes of the unsubstituted and substituted phthalocyanine ligands in the IR and Raman spectra in comparison with the unsubstituted homoleptic counterpart Y(Pc)2. The calculations reveal that incorporation of methyloxy substituents at the nonperipheral positions has greater influence on the structure and spectroscopic properties of bis(phthalocyaninato) yttrium double‐deckers than at the peripheral positions, which increases with increasing number of substituents. Nevertheless, the substituent effect of alkyloxy substituents at one phthalocyanine ligand of the double‐decker on the unsubstituted phthalocyanine ring and on the whole molecule and the importance of the position and number of alkyloxy substituents are discussed. In addition, the effect of reducing 1 – 3 to 4 – 6 on the structure and spectroscopic properties of the bis(phthalocyaninato) yttrium compounds is also discussed. This systemic DFT study is not only useful for understanding the structure and spectroscopic properties of bis(phthalocyaninato) rare earth metal complexes but also helpful in designing and preparing double‐deckers with tunable structure and properties.  相似文献   

8.
A novel series of double‐decker lanthanide(III) bis(phthalocyaninato)–C60 dyads [LnIII(Pc)(Pc′)]–C60 (M=Sm, Eu, Lu; Pc=phthalocyanine) ( 1 a – c ) have been synthesized from unsymmetrically functionalized heteroleptic sandwich complexes [LnIII(Pc)(Pc′)] (Ln=Sm, Eu, Lu) 3 a – c and fulleropyrrolidine carboxylic acid 2 . The sandwich complexes 3 a – c were obtained by means of a stepwise procedure from unsymmetrically substituted free‐base phthalocyanine 5 , which was first transformed into the monophthalocyaninato intermediate [LnIII(acac)(Pc)] and further reacted with 1,2‐dicyanobenzene in the presence of 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU). 1H NMR spectra of the bis(phthalocyaninato) complexes 3 a – c and dyads 1 a – c were obtained by adding hydrazine hydrate to solutions of the complexes in [D7]DMF, a treatment that converts the free radical double‐deckers into the protonated species, that is, [LnIII(Pc)(Pc′)H] and [LnIII(Pc)(Pc′)H]–C60. The electronic absorption spectra of 3 a – c and 1 a – c in THF exhibit typical transitions of free‐radical sandwich complexes. In the case of dyads 1 a – c , the spectra display the absorption bands of both constituents, but no evidence of ground‐state interactions could be appreciated. When the UV/Vis spectra of 3 a – c and 1 a – c were recorded in DMF, typical features of the reduced forms were observed. Cyclic voltammetry studies for 3 a – c and 1 a – c were performed in THF. The electrochemical behavior of dyads 1 a – c is almost the exact sum of the behavior of the components, namely the double‐decker [LnIII(Pc)(Pc′)] and the C60 fullerene, thus confirming the lack of ground‐state interactions between the electroactive units. Photophysical studies on dyads 1 a – c indicate that only after irradiation at 387 nm, which excites both C60 and [LnIII(Pc)(Pc′)] components, a photoinduced electron transfer from the [LnIII(Pc)(Pc′)] to C60 occurs.  相似文献   

9.
A series of eleven new 2‐methylthio‐3H‐7‐[(o‐; m‐ and p‐substituted) phenoxy]‐4‐(p‐substituted‐phenyl)‐[1,5]benzodiazepines, which have potentially useful pharmacological activities, has been synthesized by condensing the 4‐[(o‐; m‐ and p‐R1)phenoxy]‐1,2‐phenylendiamines with 3,3‐dimercapto‐1‐(p‐R2‐phenyl)‐2‐propen‐1‐one. Afterward the lH‐[1,5]benzodiazepine‐2‐thiones obtained were treated with sodium hydride and methyl iodide. The structure of all products was corroborated by ir, 1H nmr, 13C nmr and ms.  相似文献   

10.
The 1H and 13C nmr spectra of 1,4,5,7-tetrahydro-3H-2,6-benzodiselenine (1) and three 4-spiro derivatives 2–4 as well as the 77Se nmr spectra of 2 have been recorded at different temperatures in order to investigate their conformational behavior. It was found that in analogy to corresponding dithionins the molecules adopt a chiral ground state conformation (Figure 2), and coalescence effects are due to racemization.  相似文献   

11.
The study of inter‐conversion between molecules, especially biologically and pharmaceutically important molecules, is extremely important. This study reports the inter‐conversion between two azo‐derivtives: azo‐6‐aminouracils to azo‐barbituric acids. We successfully converted the 1,3‐dimethyl‐5‐(arylazo)‐6‐aminouracils ( Uazo‐1 to Uazo‐4 ) to 1,3‐dimethyl‐5‐(arylazo)‐barbituric acids ( BAazo‐1 to BAazo‐4 ) (where aryl?C6H5‐( 1 ); p‐MeC6H4‐( 2 ), p‐ClC6H4‐( 3 ), and p‐NO2C6H4‐( 4 )) following an acid‐hydrolysis path. The products were characterized using spectroscopic tools like UV‐vis, IR, and NMR spectroscopy. UV‐vis spectra of the as‐prepared dyes reveal that in contrast to the azo‐6‐aminouracils they are hardly responsive towards solvatochromism. IR spectra exhibit three characteristic >C?O frequencies for as‐prepared azobarbituric acids instead of two for mother azo‐6‐aminouracils. 1H NMR spectra which reflect the existence of solution species evidence the absence of >C?NH group (characteristic imido‐H at the 6‐position of hydrazone species of azo‐6‐aminouracils) and consequence presence of >C?O group at the same position in as‐prepared azobarbituric acids. They exhibit structural emissions in the range of 400–440 nm upon excitation at 360 nm. The determined acid dissociation constant (pKa) values of BAazos increase according to the following sequence: BAazo ‐ 2 > 1 > 3 > 4 .  相似文献   

12.
Regioselective reactions of morpholine‐1‐carbothioic acid (2‐phenyl‐3H‐quinazolin‐4‐ylidene) amide ( 1 ) with electrophiles and nucleophiles were studied. The compound ( 1 ) reacts with alkyl halides in basic medium to afford S‐substituted isothiourea derivatives, with amines to give 1,1‐disubstituted‐3‐(2‐phenyl‐3H‐quinazolin‐4‐ylidene) thioureas and l‐substituted‐3‐(2‐phenyl‐quinazolin‐4‐yl) thioureas via transami‐nation reaction. The reaction of ( 1 ) with amines in the presence of H2O2 provided N4‐disubstituted‐N'4‐(2‐phenylquinazolin‐4‐yl)morpholin‐4‐carboximidamide via oxidative desulfurization. Estimation of reactivity sites on ( 1 ) was supported using the ab initio (HF/6‐31G**) quantum chemistry calculations. The ir, 1H nmr, 13C nmr, mass spectroscopy and x‐ray identified the isolated products.  相似文献   

13.
The compounds 5‐ethoxycarbonyl‐1,6‐dimethyl‐4‐(3‐nitrophenyl)‐3,4‐dihydropyrimidin‐2(lH)‐one (5) and 5‐ethoxycarbonyl‐1‐phenyl‐6‐methyl‐4‐(3‐nitrophenyl)‐3,4‐dihydropyrimidin‐2(lH)‐one (1) were prepared by the Biginelli condensation method and they converted to eight N‐3 substituted dihydropyrimidines using NaH and various electrophiles (ClCO2Et, TsCl, Ac2O, AcCl and PhCOCl). Compound (1) was mono‐brominated at the C6‐methyl group using bromine solution. Reaction of the bromo derivative with amino nucleophiles such as methyl amine and cyclohexyl amine produced two pyrrolo‐pyrimidine derivatives. All the compounds except 5‐ethoxycarbonyl‐1‐phenyl‐6‐methyl‐4‐(3‐nitrophenyl)‐3,4‐dihydropyrimidin‐2(lH)‐one ( 4 ) were purified by recrystallization methods. The structure of all the new compounds was confirmed using FT‐ir,1H nmr, 13C nmr spectral and elemental analyses methods.  相似文献   

14.
A selected series of 2‐(4‐methylpyridin‐2‐yl)‐1H‐benzimidazole derivatives, bases and cyclic mono‐ and bis‐salts, were synthesized. Complete '1H nmr characterization is reported. Ambiguous assignments were solved using 1H‐1H NOESY analysis. Significant ir and 1H nmr data are presented concerning: i) tautomeric equilibrium of imidazole hydrogen; ii) hydrogen bonds; iii) conformational inversion of partially saturated rings.  相似文献   

15.
The synthesis of new pyrazolo[4,3‐c]β‐carbolines ( 8a,b ) is achieved by condensation of the appropriate aldehyde with 3‐(4‐amino‐1,3‐dimethylpyrazol‐5‐yl)indole ( 4 ) under Pictet‐Spengler reaction conditions. Regioselective cyclization occurred at the usual indole C‐2 position as evidenced from the 1H‐and 13C nmr spectra of 8a,b which lack the pyrrolic H‐2 signal, present in 4 (δ 7.26, 1H, d, Jch‐NH = 2‐5 Hz).  相似文献   

16.
The title complex salt, (C16H36N)[MnBr(C32H16N8)] or (TBA)[MnIIBr(Pc)] (TBA is tetrabutylammonium and Pc is phthalocyaninate), has been obtained as single crystals by the diffusion technique and its crystal structure was determined using X‐ray diffraction. The high‐spin (S = ) [MnIIBr(Pc)] macrocycle has a concave conformation, with an average equatorial Mn—N(Pc) bond length of 2.1187 (19) Å, an axial Mn—Br bond length of 2.5493 (7) Å and with the MnII cation displaced out of the 24‐atom Pc plane by 0.894 (2) Å. The geometry of the MnIIN4 fragment in [MnIIBr(Pc)] is similar to that of the high‐spin (S = ) manganese(II) tetraphenylporphyrin (TPP) in [MnII(1‐MeIm)(TPP)] (1‐MeIm is 1‐methylimidazole).  相似文献   

17.
A series of twelve new 7‐chloro‐5‐[(o‐ and p‐R1)phenyl]‐1‐R2‐3H‐[1,4] benzo‐diazepin‐2‐ones, which have possible pharmacological properties were synthesized. The synthesis of all the final compounds was carried out by four steps. The structure of all final products was corroborated by ir, 1H nmr, 13C nmr and ms, and have been obtained in 35‐94% yield.  相似文献   

18.
Starting from ethyl propionylacetate, and ethyl 2‐ethylacetoacetate we prepared 4‐propyl‐7,8‐, 4‐propyl‐6,7‐, 3‐ethyl‐4‐methyl‐7,8‐ and 3‐ethyl‐4‐methyl‐6,7‐dihydroxy‐2H‐chromenones which were allowed to react with the bis‐dihalides or ditosylates of glycols in DMF/Na2CO3 to afford the 6,7‐ and 7,8‐chromenone derivatives of 12‐crown‐4, 15‐crown‐4 and 18‐crown‐6. The products were identified using ir, 13C and 1H nmr, ms and high resolution mass spectroscopy. The cation selectivities of chromenone crown ethers with Li+, Na+ and K+ cations were estimated from the steady state emission fluorescence spectra of free and cation complexed chromenone macrocyclic ethers in acetonitrile.  相似文献   

19.
Nitration of commercial full aromatic β‐carboline alkaloids nor‐harmane ( 1 ), harmane ( 2 ), harmine ( 3 ), harmol ( 4 ), and the 7‐acetylated derivative of harmol ( 5 ) is described. Advantages and disadvantages of different nitration reagents which involve acidic conditions (HNO3/H+) and neutral conditions (Cu(NO3)2; ceric ammonium nitrate) are discussed. A complete 1H and 13C‐nmr characterization including ms and also uv absorption spectra in neutral and acid media is presented. A detailed ei‐ms and ld‐tof‐ms study is enclosed because the nitro‐β‐carbolines constitute a new family of β‐carboline‐like chromophores with potential use as matrix in uv‐maldi‐tof‐ms.  相似文献   

20.
The infrared (IR) spectroscopic data and Raman spectroscopic properties for a series of 13 “pinwheel-like” homoleptic bis(phthalocyaninato) rare earth complexes M[Pc(α-OC5H11)4]2 [M = Y and Pr–Lu except Pm; H2Pc(α-OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyanine] have been collected and comparatively studied. Both the IR and Raman spectra for M[Pc(α-OC5H11)4]2 are more complicated than those of homoleptic bis(phthalocyaninato) rare earth analogues, namely M(Pc)2 and M[Pc(OC8H17)8]2, but resemble (for IR) or are a bit more complicated (for Raman) than those of heteroleptic counterparts M(Pc)[Pc(α-OC5H11)4], revealing the decreased molecular symmetry of these double-decker compounds, namely S8. Except for the obvious splitting of the isoindole breathing band at 1110–1123 cm−1, the IR spectra of M[Pc(α-OC5H11)4]2 are quite similar to those of corresponding M(Pc)[Pc(α-OC5H11)4] and therefore are similarly assigned. With laser excitation at 633 nm, Raman bands derived from isoindole ring and aza stretchings in the range of 1300–1600 cm−1 are selectively intensified. The IR spectra reveal that the frequencies of pyrrole stretching and pyrrole stretching coupled with the symmetrical CH bending of –CH3 groups are sensitive to the rare earth ionic size, while the Raman technique shows that the bands due to the isoindole stretchings and the coupled pyrrole and aza stretchings are similarly affected. Nevertheless, the phthalocyanine monoanion radical Pc′ IR marker band of bis(phthalocyaninato) complexes involving the same rare earth ion is found to shift to lower energy in the order M(Pc)2 > M(Pc)[Pc(α-OC5H11)4] > M[Pc(α-OC5H11)4]2, revealing the weakened π–π interaction between the two phthalocyanine rings in the same order.  相似文献   

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