Macrocycle opening in crown ethers

Macrocycle opening in derivatives of benzocrown ethers under the action of amines is affected by the nature of the heteroatoms in the macrocycle, the nature of the functional group in the benzene ring of the crown ether, and the length, branching, and number of hydrocarbon radicals at the amine nitrogen atom. A distinguishing feature of this reaction is the template effect of MeNH₃ ⁺, Me₂NH₂ ⁺, Na⁺, and K⁺ ions.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 687–692, March, 1996.For Part I see Ref. 1.     

Macrocycle opening in formyl derivatives of benzocrown ethers under the action of methylamine

A new method for synthesizing nitrogen-containing podands by nucleophilic regioselective cleavage of the macrocycle in formyl derivatives of benzocrown ethers by heating with methylamine and methylammonium chloride has been developed. This reaction is the first example of crown ether opening by a nitrogen-containing nucleophile.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 950–953, May, 1995.     

New methodology for the synthesis of benzoazacrown ethers by transformation of the macrocycle of benzocrown ethers

The review summarizes the results of studies aimed at constructing new promising macrocyclic ligands that bind metal and ammonium ions. A new approach to the synthesis of formyl and nitro derivatives of 1-aza-2,3-benzocrown ethers possessing considerable synthetic potential is described. The review presents a radically new methodology for the synthesis of such benzoazacrown ethers based on stepwise transformations of the macrocycle of readily accessible benzocrown ethers. The main structural factors and necessary conditions enabling stepwise transformations of the macrocycle of crown ethers into azacrown ethers were revealed. For the first time, the ability of N-methylbenzoazacrown ethers to form complexes was found, which is much superior to that of widely used N-phenylazacrown ethers and benzocrown ethers with the same size of the macrocycle.     

Synthesis of thiaazapodands from 4′-nitrobenzothiacrown ethers

A series of thiaazapodands were synthesized from 4′-nitrobenzothiacrown ethers by nucleophilic regioselective opening of the macrocycle on heating with methylamine in up to 94% yield. Dedicated to Academician V. A. Tartakovsky on his 75th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1479–1481, August, 2007.     

Macrocycle opening in crown compounds

The regioselective nucleophilic opening of the macrocycle of 4′-nitrobenzo-15-crown-5 ether under the action of amines with various structures to form nitrogen-containing podands was studied. A distinguishing characteristic feature of this reaction with aminoalcohols is the ability of the latter to form hydrogen bonds, resulting in an increase in the degree of conversion into podands.     

Synthesis and characterization of new aromatic polyamides bearing crown ethers or their dipodal counterparts in the pendant structure. I. Benzo‐12‐crown‐4 and ortho‐bis(2‐ethoxyethoxy)benzene

Two novel isophthalic diacid‐based monomers have been synthesized by inclusion in ring position 5 of a functionalized benzoylamine moiety. The functionalization includes a 12‐crown‐4 ether group fused with the benzene subunit and a dipodand substructure, formally a disubstitution of the benzene ring, with two sequences of ethyl‐terminated ethylene oxide units, which represent the open‐chain counterpart of the alicylic crown moiety. The polycondensation of the two diacids with five aromatic diamines yielded 10 new polyamides with crown or podand pendant substructures. The polyamides had previously been chemically characterized by NMR, IR, and elemental analysis. The polymers showed high glass transition temperatures of up to 349 °C, good thermal stability (T_{donset, N2} ≈ 400 °C), and improved solubility in organic solvents. The presence of acyclic or alicyclic oxyethylene sequences as crown ether or podand substructures and an additional amide side group per repeat unit made the polymers essentially amorphous and improved their water absorption ability in comparison with nonsubstituted polyamides. Water uptake values as high as 12% were observed at 65% relative humidity. All the polyamides showed a good film‐forming ability, and the mechanical properties of these films are considered to be satisfactory for experimental aromatic polyamides. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2270–2281, 2006     

Periphery-modified crown ethers. Synthesis of bis-5,8-dimethoxy-1,4-methanonaphthalene-fused crown ethers

The easily accessible and multi-functionalized 5,8-dimethoxy-6,7-dihydroxy methyl-1,4-dihydro-1,4-methanonaphthalene (1) has been utilized as the basic building material to synthesize the symmetric bis-methanonaphthalene-fused crown ethers 14a-d (BMN-16-crown-4, BMN-22-crown-6, BMN-28-crown-8, and BMN-34-crown-10), that are constructed based on the connection between the α,β-bis-benzylic carbon atoms of diol 1 and oligoethylene glycols (9a-d) via two synthetic routes keyed upon the method of Williamson ether synthesis.     

Photochromic crown ethers

An amphiphilic crown-containing styryl dye (1) was synthesized, and the effects of irradiation, temperature, and alkali and alkali-earth metal ions on the conductivity and optical spectra of its solutions in dioctyl phthalate were studied. Compound1 in thetrans-form almost completely exists as ion pairs (IP). Irradiation at a long-wavelength absorption maximum (λ_max) results in a reversible increase in the conductivity and, hence, a degree of dissociation of IP (α); these parameters decrease when complexes with metal ions are formed. The relaxation times for the photoinduced conductivity coincide with a decrease in the extinction within experimental error in the 20–60°C temperature range. The photoinduced increase in α is caused bytrans—cis-isomerization and an increase in steric hindrances for the interaction of the ClO₄ ⁻ anion with the N⁺ atom of benzothiazolium in thecis-form of1. The activation energies for the darkcis—trans-relaxation, absolute α values, and thermodynamic parameters of dissociation of IP in thetrans-form, as well as the α values in a photostationary mixture ofcis—trans-isomers, were estimated. The decrease in α after binding with metal ions is likely caused by the redistribution of the positive charge to benzothiazolium through the conjugated system of1. Correlations between the decrease in conductivity (decrease in α) and the hypsochromic shift Δλ_max after the formation of complexes between1 and metal ions were observed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1296–1301, July, 1997.     

Comparative photophysical behaviour of naphthalene-linked crown ethers and aza crown ethers of varying cavity dimensions

A comparative time-resolved emission studies of several naphtho-crown ethers I–V, where metal ions can be complexed in a predetermined orientation with respect to the naphthalene (Naph) π-plane and naphthalene-linked aza crown ethers (L1 and L2) have been presented. In both the systems, crown ethers and aza crown ethers, naphthalene fluorescence gets quenched. In the systems I to V, the quenching is mainly due to efficient spin-orbit coupling (SOC) leading to greater population of the lowest triplet state of naphthalene. This SOC depends on the orientation of the crown ring with respect to the Naph-π-plane. However, in the systems L1 and L2, the quenching is due to photoinduced electron transfer (PET) from nitrogen lone pair of the aza crown ring to naphthalene moiety and consequent exciplex formation. The results have been interpreted using the time-resolved emission studies of all the compounds in various solvents, their alkali metal ion complexes, and protonated ligands.     

Synthesis of novel crown ethers. Part 1. Coumestan and coumestan analog derivatives of crown ethers

The presented ethylenedioxy compounds5a,5d,6a and6c are examples of novel cyclic ethers, while macrocyclic polyethers represent new crown ether analogues. New coumestan-crowns5a-f, derivatives of 6,7-dihydroxy-3,4-dihydro-2H-dibenzofuran-1-one and 6,7-dihydroxy-3,3-dimethyl-3,4-dihydro-2H-dibenzofuran-1-one6a-e were synthesized from the correspondingo-dihydroxy compounds3a-b,4a-b and ditosylates or dichlorides of di- or triethylene glycol in the presence of K₂CO₃, in DMF/H₂O (15/1) solutions at 65–75 °C for 35 hours. The structure of the macrocyclic ethers obtained were confirmed by¹H-NMR,¹³C-NMR, IR spectra and elemental analyses.Presented at the Sixth International Seminar on Inclusion Compounds, Istanbul, Turkey, 27–31 August, 1995.     

Synthesis and characterization of new aromatic polyamides bearing crown ethers or their dipodal counterparts in the pendant structure. II. Benzo‐15‐crown‐5 and ortho‐bis[2‐(2‐ethoxyethoxy)ethoxy]benzene

This article describes the synthesis and characterization of two diacid monomers, each containing a benzo‐15‐crown‐5 subunit or its dipodal counterpart. Both novel monomers were reacted with technical aromatic diamines with Yamazaki's direct polyamidation method to render modified polyisophthalamides with high molecular weights containing side moieties of cyclic and acyclic ethylene oxide sequences. All the polymers were soluble in aprotic polar solvents and showed high glass‐transition temperatures in the range of 190–345 °C. The polymers with side crown ethers showed much higher glass‐transition temperatures than those with acyclic linear side ethylene oxide arms. The chemical composition, particularly with respect to the diamine and the open or closed character of the pendent ethylene oxide sequence, also affected other general properties such as the mechanical resistance, mechanical modulus, or water absorption. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4063–4075, 2006     

The complexation of alkali metal ions by crown ethers,aza crown ethers,and cryptands in propylene carbonate

The reactions between alkali metal ions and crown ethers, aza crown ethers, and cryptands in propylene carbonate were studied by potentiometric and calorimetric titrations. The most stable complexes formed by macrocyclic and macrobicyclic ligands are when the ligand and cation dimensions are comparable. On comparing the complex stabilities of crown ethers and aza crown ethers of the same size, crown ethers were, on the whole, found to form the most stable complexes, with the exception of the lithium cation. Enthalpic factors are responsible. Substitution of the amino group protons of the aza crown ethers by benzyl groups leads to a high increase in values of the reaction enthalpy. This effect is partly compensated by entropic contributions. The bulky benzyl groups reduce the ligand solvent interactions and induce a ligand conformation with the lone pair of electrons from the nitrogen donor atoms which are more or less directed inside the cavity. The thermodynamic data for the transfer from methanol to propylene carbonate indicate that the ligands containing nitrogen show specific interactions with methanol.This paper is dedicated to Professor H. Strehlow on the occasion of his 70th birthday.     

Selective lithium ion extraction with chromogenic monoaza crown ethers

Two chromogenic monoaza crown ethers were synthesized and investigated for their lithium extraction capabilities. The chromogenic monoaza 14-crown-4 compound exhibited the best selectivity for lithium over sodium; ca. 2800, with a detection limit of 0.08 ppm.     

Investigations on 2,3′-biquinolines. 18. New convenient one-pot synthesis of 1′-alkyl-1′,4′-dihydro-2,3′-biquinolyl-4′-thiones and their conversion into 1′-alkyl-1′,4′-dihydro-2,3′-biquinolyl-4′-ones

A method has been developed for the one pot synthesis of 1′-alkyl-1′,4′-dihydro-2.3′-biquinolyl-4′-thiones based on the reduction of 1-alkyl-3-(2-quinolyl)quinolinium halides with sodium borohydride and subsequent thiolation. 1′-Alkyl-1′,4′-dihydro-2,3′-biquinolyl-4′-ones were obtained in close to quantitative yield by the oxidation of 1′-alkyl-1′, 4′-dihydro-2,3′-biquinolyl-4′-thiones. For Part 17 see [1]. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 67–70, January, 2006.     

Mass spectrometry of crown ethers

The mass spectra of benzo-15-crown-5 and benzo-l8-crown-6 were investigated by mass spectrometry with different inlet systems, such as direct introduction, gas chromatography and liquid chromatography inlets. Different ionisation methods such as electron impact, chemical ionisation, electron capture or negative ion chemical ionisation were also studied. The results and the specific problems encountered for this group of substances are discussed based on the spectra obtained.Presented at the Sixth International Seminar on Inclusion Compounds, Istanbul, Turkey, 27–31 August, 1995.     

Photoinduced template synthesis of cyclobutane-containing crown ether

The photoinitiated [2+2]-cycloaddition of 1,5-bis[2-(3-phenyl-3-oxoprop-1-en-1-yl)phenoxy]-3-oxapentane in solution was studied. In the presence of potassium cations, the reaction is intramolecular and gives crown ether containing the γ-truxin-type cyclobutane fragment (anti, head-to-head) as the major product. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 204–206, January, 2008.     

Transfer activity coefficients of crown ethers and their complexes with univalent metal ions between pairs of polar organic solvents

From a comparison of transfer activity coefficients, [(LM⁺)]_PC,2 between propylene carbonate and solvent S₂ of alkali or silver ions complexed with dibenzo-substituted crown ethers (L=DB-18-cr-6, DB-21-cr-7, DB-24-cr-8, DB-30-cr-10) it can be concluded that in the complex LM⁺ both L and M⁺ are solvated, particularly in solvents of high donicity, e.g., N,N-dimethylformamide. From the abnormally low ionic mobility of DB-30-cr-10K⁺ in acetonitrile and the high value of the association constant of the ion pair DB-30-cr-10KBr it is concluded that the outer solvent shell is stripped upon formation of the ligand separated ion pair. A linear relation is found between [log (LM⁺)]_PC,2 and [log(M⁺)]_PC,2 only when L is 18-cr-6, B-18-cr-6, or DB-18-cr-6. Deviation from the linearity of complexes of the larger dibenzo crown ethers is attributed to the flexibility of L. It is shown that solution of 18-cr-6, DB-18-cr-6 and DB-30-cr-10 is enthalpy assisted to a greater extent in acetonitrile than in methanol, while the entropy of solution is more favorable in the latter.     

Investigations on 2,3′-Biquinoline. 17. Regioselectivity of the Halogenation of 2,3′-Biquinoline Derivatives

A method has been developed for the synthesis of bromo and chloro derivatives of 2,3′-biquinoline and 2,3′-biquinolones based on the bromination and chlorination in various media. It was found that the bromination of 2,3′-biquinoline in strongly acidic medium occurred on the 2-quinoline fragment and in weak acid on the 3-quinoline and that it takes place via a stage of formation of a dihydro derivative. 1′-Alkyl-1′, 4′-dihydro-2,3′-biquinolin-4′-ones and 1′-alkyl-1′,2′-dihydro-2,3′-biquinolin-2′-ones are halogenated at position 6′. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1372–1377, September, 2005.     

Luminescence of lanthanides in complexes with chromophoric crown ethers

Spectral luminescence characteristics, viz., quantum yields and luminescence lifetime, of the Yb³⁺ and Nd³⁺ ions in aqueous-methanolic solutions of their complexes with chromophoric benzo-15-crown-5 derivatives were determined. The efficient 4f-luminescence (_exc = 337 nm) is due to the intramolecular transfer of the excitation energy from the chromophoric moiety of the molecule to the Ln³⁺ ion.