Methoxyl-induced fluorescence quenching in N,N′-bridged 9H-dipyrrinones and an X-ray crystal structure

Strongly fluorescent dipyrrinones can be prepared by bridging the pyrrole and lactam nitrogens with a carbonyl group, from reaction with N,N′-carbonyldiimidazole in the presence of a strong, non-nucleophilic base. The yellow, N,N′-carbonyl-bridged dipyrrinones typically have fluorescent quantum yields (φ_F) approaching 1.0. Thus, in chloroform, N,N′-bridged 9H-dipyrrinones with β-alkyl substituents: 2,3-diethyl-7,8-dimethyl has φ_F = 0.90 (λ_em = 465 nm) and 2,3-dimethyl-7,8-dimethoxy has φ_F = 0.84 (λ_em = 482 nm). In contrast, 2,3-dimethoxy-7,8-dimethyl and 2,3,7,8-tetramethoxy show red-shifted λ_em but with strongly reduced φ_F: φ_F = 0.10 (λ_em = 511 nm) and 0.08 (λ_em = 511 nm), respectively. Methoxy substituents on the lactam, but not the pyrrole ring act to quench the fluorescence and shift the emission and excitation wavelengths bathochromically. The first X-ray crystal structure of an N,N′-carbonyl-bridged dipyrrinone was obtained from 7,8-dimethoxy-2,3-dimethyl-10H-dipyrrin-1-one. Correspondence: David A. Lightner, Department of Chemistry, University of Nevada, Reno, Nevada 89557-0020, USA.     

Host proficiency of N,N′-bis(9-phenyl-9-thioxanthenyl)ethylenediamine for pyridine and the methylpyridine guests – a competition study

N,N′-Bis(9-phenyl-9-thioxanthenyl)ethylenediamine proved to be an extremely efficient host compound for pyridine and the isomeric methylpyridines. Furthermore, this host displayed selective behaviour during equimolar guest competitions, consistently favouring 3-methylpyridine in binary, ternary and quaternary experiments. Selectivity orders were 3-methylpyridine >> 4-methylpyridine > 2-methylpyridine, and 3-methylpyridine > pyridine > 4-methylpyridine > 2-methylpyridine, for equimolar ternary and quaternary solutions, respectively. When guest concentrations in binary competitions were varied, 3-methylpyridine remained the favoured guest, even at low 3-methylpyridine concentrations. Single crystal X-ray diffraction showed that all four complexes were isostructural (monoclinic, P2₁/n) while guests occupy discrete cavities in the crystal. Only 3-methylpyridine experiences (guest methyl)C–H???π(host) and (guest methyl)C–H???H–Ar(host) interactions, explaining the observed affinity of the host for this guest. DSC analyses provided further affirmation for the host preference: endotherm peak temperatures for the guest release processes correlated directly with the selectivity order for the three methylpyridine isomers.     

N,N′-Diacylated imidazolidines and hexahydropyrimidines

A method for the preparation ofN-monoacyl imidazolidines and hexahydropyrimidines (as hydrochlorides) by interaction of monoacylated derivatives of ethylenediamine and trimethylenediamine with chloromethyl methyl ether was developed. Also a method for the preparation ofN,N-diacylimidazolidines and hexahydropyrimidines either by acylation of their monoacyl derivatives or by reaction of the correspondingN,N-diacyl alkylenediamine derivatives with dimethoxymethane, diacetoxymethane, 1,3,5-trioxane or chloromethyl methyl ether was designed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1452–1456, August, 1994.     

Improved Syntheses of N‐Desmethylcitalopram and N,N‐Didesmethylcitalopram

An improved and efficient synthesis of N‐desmethylcitalopram (2) and N,N‐didesmethylcitalopram (3) is presented. The method involved N‐demethylation of citalopram (1) using 1‐chloroethyl chloroformate to give 2 in 87% yield. Synthesis of 3 was accomplished by alkylation of 8 with 1‐(3‐bromopropyl)‐2,2,5,5‐tetramethyl‐1‐aza‐2,5‐disilacyclopentane (9).     

Preparation and Characterization of N,N′-Dialkyl-1,3-propanedialdiminium Chlorides,N,N′-Dialkyl-1,3-propanedialdimines,and Lithium N,N′-Dialkyl-1,3-propanedialdiminates

We describe convenient preparations of N,N′-dialkyl-1,3-propanedialdiminium chlorides, N,N′-dialkyl-1,3-propanedialdimines, and lithium N,N′-dialkyl-1,3-propanedialdiminates in which the alkyl groups are methyl, ethyl, isopropyl, or tert-butyl. For the dialdiminium salts, the N₂C₃ backbone is always in the trans-s-trans configuration. Three isomers are present in solution except for the tert-butyl compound, for which only two isomers are present; increasing the steric bulk of the N-alkyl substituents shifts the equilibrium away from the (Z,Z) isomer in favor of the (E,Z), and (E,E) isomers. For the neutral dialdimines, crystal structures show that the methyl and isopropyl compounds adopt the (E,Z) form, whereas the tert-butyl compound is in the (E,E) form. In aprotic solvents all four dialdimines (as well as the lithium dialdiminate salts) adopt cis-s-cis conformations in which there presumably is either an intramolecular hydrogen bond (or a lithium cation) between the two nitrogen atoms.     

Synthesis of N,N′-di(tert-butyl)bispidin-9-ones

Condensation of 1,3,5-tri(tert-butyl)-1,3,5-triazacyclohexane with acetone gave 3,7-di(tert-butyl)-1,5-bis[(tert-butylamino)methyl]bispidin-9-one. Reactions with ethyl methyl ketone and other ketones of the formula RCH₂COCH₃ yielded 5-R-3,7-di(tert-butyl)-1-[(tert-butylamino)methyl]bispidin-9-ones, while reactions with diethyl ketone and other symmetrical ketones of the formula RCH₂COCH₂R afforded 1,5-R-3,7-di(tert-butyl)bispidin-9-ones.     

Host selectivity behaviour of trans-N,N′-bis(9-phenyl-9-xanthenyl)cyclohexane-1,2-diamine and trans-N,N′-bis(9-phenyl-9-thioxanthenyl)cyclohexane-1,2-diamine when presented with six-membered heterocyclic guest mixtures

Two compounds, trans-N,N′-bis(9-phenyl-9-xanthenyl)cyclohexane-1,2-diamine (1,2-DAX) and trans-N,N′-bis(9-phenyl-9-thioxanthenyl)cyclohexane-1,2-diamine (1,2-DAT), were assessed for their host ability in the presence of four heterocyclic guest species, namely pyridine (PYR), piperidine (PIP), morpholine (MOR) and dioxane (DIO). Each of these guests formed single solvent complexes with both host compounds. When 1,2-DAX and 1,2-DAT were recrystallized from various guest mixtures, it was shown that their selectivity orders were identical, DIO (46.6%)?>?MOR (23.0%)?>?PYR (18.9%)?>?PIP (11.5%) and DIO (85.9%)?>?MOR (23.7%)?>?PYR (8.9%)?>?PIP (8.5%), respectively, but that the thio host derivative possessed a significantly enhanced preference for DIO compared with its oxygen analogue. Additional experiments in order to investigate the various parameters at play in these complexation experiments involved single crystal diffraction experiments and thermal analyses.

     

Thermal and FTIR spectral studies of N,N′-diphenylguanidine

Thermal decomposition of N,N??-diphenylguanidine (DPG) was investigated by simultaneous TG/DSC-FTIR techniques under nonisothermal conditions. Online FTIR measurements illustrate that aniline is a major product of DPG decomposition. The observation that the activation energy depends on the extent of conversion indicates that the DPG decomposition kinetics features multiple processes. The initial elimination of aniline from DPG involves two pathways because of the isomerization of DPG. Mass spectrometry and thin film chromatography suggest that there are two major intermediate products with the major one of C₂₁N₃H₁₇. The most probable kinetic model deduced through multivariate nonlinear regression method agrees well with the experimental data with a correlation coefficient of 0.9998. The temperature-independent function of conversion f(??), activation energy E and the pre-exponential factor A of DPG decomposition was also established through model-fitting method in this research.     

Phosphate and arsenate electro-insertion processes into a N,N,N′,N′-tetraoctylphenylenediamine redox liquid

The electro-insertion of ions is a well-known phenomenon, which allows the transfer of anions or cations across phase boundaries to be monitored and driven electro-chemically. Extremely hydrophilic anions, such as phosphate and arsenate, are not usually observed to undergo electro-insertion. It is shown here that at organic redox liquid|water|electrode triple interfaces these anions can be forced electro-chemically to transfer into organic media.The transfer process of phosphate anions from aqueous buffer solutions into organic microdroplets of the redox liquid N,N,N^′,N^′-tetraoctylphenylenediamine (TOPD) is pH and concentration sensitive. It is shown that phosphate is transferred in the form of PO₄HK⁻ in the presence of phosphate buffer. Two distinct potential regions are identified and attributed to (i) interfacial redox processes at the liquid|liquid interface associated with deprotonation and (ii) bulk redox processes associated with anion transfer from the aqueous to the organic phase.The comparison of phosphate and arsenate electro-insertion processes suggests that arsenate is less hydrophilic and transferred into the organic phase preferentially.     

Potential facile separation strategy for mixtures of 3- and 4-methylpyridine by employing N,N′-bis(9-phenyl-9-xanthenyl)ethylenediamine as an alternative host compound

In the present work, a plausible host candidate is provided for the separation of 3-methylpyridine (3MP) from 4-methylpyridine (4MP), isomers that are extremely difficult to separate by conventional means. Host compound N,N′-bis(9-phenyl-9-xanthenyl)ethylenediamine (H2), when recrystallized from an equimolar mixture of 3MP and 4MP, contained 91.6% 3MP, a significantly improved outcome compared with the alternate host compound N,N′-bis(9-phenyl-9-thioxanthenyl)ethylenediamine (H1) which only enclathrated 70% of this isomer in the same experimental conditions. Single crystal diffraction and thermoanalytical experiments were conducted in order to investigate this preference for 3MP by considering both host?guest interactions and relative complex stabilities. Many of the guest components in 3(H2)·5(3MP)·0.268(O) experienced at least one other short contact measuring less than the sum of the van der Waals radii of the involved atoms, an observation that may explain the selectivity of H2 for this guest since this was not the case in complexes containing PYR and 4MP. Results from the thermal analyses were less informative.

     

Synthesis and Structural Elucidation of N,N ’-Ditosyl-1,11-diaza-4,8,14,18-tetraselena-cycloicosane and its Copper and Platinum Complexes

The reaction of 1,2-diselenacyclopentane with N,O,O-tri-(toluene-p-sulphonate)-diethanolamine afforded a new seleno-azacrown ether, i.e. N,N′-ditosyl-1,11-diaza-4,8,14,18-tetraselena cycloicosane (1), in 19% yield, which was comprehensively characterized by elemental analysis, UV–Vis, ¹H NMR and mass spectroscopy. The reaction of 1 with copper(II) perchlorate (Cu(ClO₄)₂) and platinum(IV) tetrachloride (PtCl₄) gave its corresponding copper (2) and platinum complexes (3), respectively. The crystallographic investigations showed that the disparity of metal ion led not only to the distinct crystal system and space group, i.e. monoclinic system (C2/c) for 2 and triclinic system (P-1) for 3, but also the different coordination modes of copper and platinum ions with 1, i.e. normal coordination mode for 2 and ring-contracted coordination mode for 3. Moreover, the metal ions in the crystals 2 and 3 were found in Cu(I) and Pt(II) forms, respectively, although Cu(II) and Pt(IV) were used at the initial stage of coordination reaction.     

Syntheses and Characterization of Metal Complexes of L－Lysine－N，N，N＇，N＇－tetraacetic Acid and L－Lysine－N，N，N＇，N＇－tetramethylenepho sphonic Acid

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N-Lithio-N,N′,N″,N″-tetramethyldiethylenetriamine and N′-Lithio-N,N,N″,N″-tetramethyldiethylenetriamine; Oxidative Coupling of Aminomethyllithium Derivatives

N-lithio-N,N′,N″,N″-tetramethyldiethylenetriamine (I-Li) is formed from 2,5,8,11-tetramethyl-2,5,8,11-tetraazadodecane (III) or from 2,5,8,11,14,17-hexamethyl-2,5,8,11,14,17-hexaazaoctadecane (IV) with n-BuLi or sec-BuLi, respectively, its isomer N′ -lithio-N,N,N″,N″,-tetramethyldiethylene-triamine (II-Li) from tris(2-dimethylaminoethyl)amine (V) with n-BuLi. IV results from treatment of N-lithiomethyl-N,N′,N″,N″-tetramethyldiethylenetriamine (PMDTA-Li) with 1,2-dibromoethane.     

Ionic liquid based on α-amino acid anion and N7,N9-dimethylguaninium cation ([dMG][AA]): theoretical study on the structure and electronic properties

The interactions between five amino acid based anions ([AA](-) (AA = Gly, Phe, His, Try, and Tyr)) and N7,N9-dimethylguaninium cation ([dMG](+)) have been investigated by the hybrid density functional theory method B3LYP together with the basis set 6-311++G(d,p). The calculated interaction energy was found to decrease in magnitude with increasing side-chain length in the amino acid anion. The interaction between the [dMG](+) cation and [AA](-) anion in the most stable configurations of ion pairs is a hydrogen bonding interaction. These hydrogen bonds (H bonds) were analyzed by the quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analysis. Finally, several correlations between electron densities in bond critical points of hydrogen bonds and interaction energy as well as vibrational frequencies in the most stable configurations of ion pairs have been checked.     

N,N′ and N,O chelated phosphenium cations containing aminotroponiminate or aminotroponate units

New phosphenium cations stabilized by bidentate monoanionic N-isopropyl-2-(isopropylamino)troponiminate or 2-(isopropylamino)troponate units have been synthesized. These complexes were characterized by ³¹P, ¹H and ¹³C NMR spectroscopies, and the molecular structures were determined by X-ray crystallography. These data indicate the formation of N,N′- and N,O-chelate derivatives having three-coordinate phosphorous atoms included in planar heterobicycles. Moreover, computational studies support the presence of high delocalization of the positive charge into the π-conjugated carbon backbone and of the high-lying phosphorus lone-pair orbital.     

Syntheses of 6N(N′-formyl-D-phenylalanyl)-deoxyamino-β-cyclodextrin and 6N(N′-formyl-L-phenylalanyl)deoxyamino-β-cyclodextrin and their inclusion behavior

6N(N-formyl-D-phenylalanyl)-deoxyamino--cyclodextrin and 6N(N-formyl-L-phenylal-anyl)-deoxyamino--cyclodextrin (I andII) were prepared. These new hosts formed intramolecular host-guest complexes and included naphthyl derivatives preferentially with a stoichiometry of 1:1. The inclusion behavior was different between I and II because the cavity shape formed with the CD cavity and the phenylalanine moiety of I was different from that of II.     

Reactions of N-Allyl- and N-Propargyltriflimides with N,N′-Disubstituted Carbodiimides

The alkylating activity of N-allyl- and N-propargyltriflimides toward N,N′-dicyclohexyl- and N,N′-diphenylcarbodiimides has been studied. Activation of the nitrogen atom by two electron-withdrawing trifluoromethanesulfonyl groups favors cleavage of the C–N bond in the absence of a catalyst with the formation of N-substituted unsaturated ureas.

     

Poly(N,N′-dibromo-N-ethyl-benzene-1,3-disulfonamide) and N,N,N′,N′- tetrabromobenzene-1,3-disulfonamide as effective catalysts for conversion of aldehydes to 1,1-diacetates and acetals

Poly(N,N′-dibromo-N-ethyl-benzene-1,3-disulfonamide) [PBBS] and N,N,N′,N′-tetrabromobenzene-1,3-disulfonamide [TBBDA] are effective catalysts for easy preparation of 1,1-diacetates from aldehydes and acetic anhydride, and for easy preparation of acetals using diols under microwave irradiation in the presence of SiO₂.