Proton-ionizable crown compounds. 13. Synthesis and structural studies of crown compounds containing the triazole subcyclic unit and lipophilic substituents

Eight new macrocyclic polyether ligands containing the proton-ionizable triazole subcyclic unit have been prepared. Most of these compounds contain octyl, benzo or cyclohexano lipophilic groups. The unsubstituted triazolo-18-crown-6 ( 5 ) formed an unusual complex with silver ion. The crystal structure of this silver complex showed one crown complexed with one silver cation and two associated silver nitrate molecules. The new lipophilic triazolo-crowns are being tested as cation carriers for alkali and other metal cations in a bulk liquid membrane system.     

Synthesis of new proton-ionizable and neutral macrocyclic,macrobicyclic and macrotricyclic crown compounds containing dibenzo-16-crown-5 units

Fifteen new macrocyclic, macrobicyclic and macrotricyclic crown ether compounds with sym-dibenzo-16-crown-5 units have been prepared. The series includes macrocyclic polyether and bis(crown ether) compounds with proton-ionizable carboxylic or phosphonic acid monoethyl ester groups and bis(crown ether) and macrotricyclic polyether compounds with two sym-dibenzo-16-crown-5 units linked by amide, diamide, or diester functions.     

Proton-ionizable crown compounds. 10. Preparation and structural studies of macrocyclic ligands containing two sulfonamide units and with seventeen to twenty-six ring members

Eight new macrocylic ligands each containing two sulfonamide groups have been prepared. Six of these compounds have both the sulfur and nitrogen atoms of the sulfonamide units substituted with aromatic rings. The nitrogen atoms of the other two compounds have alkyl ring connections. X-ray crystal structure data were obtained for new macrocyclic compounds of 20 and 23 ring members. Each crystal structure showed two molecules in the asymmetric unit. Molecule A of 5 and both molecules of 7 exist in a compact conformation suggesting that they could wrap around a metal ion during complexation. Some of these compounds will be used as cation carriers in a bulk liquid membrane system.     

Proton-ionizable crown compounds. 9. Synthesis and structural studies of new 14-crown-4 compounds containing a pyridine or 4-pyridone subcyclic unit

Four new 14-crown-4 macrocyclic ligands containing either a pyridine or a 4-pyridone subcyclic unit have been prepared. Two of the 4-pyridono-crowns contained lipophilic hydrocarbon substituents. The starting octyl- and benzyl-substituted 4-oxa-1,7-heptanediols were prepared from the 2-octyl- or 2-benzyl-1,3-propane-diol. When the two substituted 4-oxa-1,7-heptanediols were treated with tosyl chloride, both the expected 2-substituted-4-oxaheptane-1,7-ditosylates and the ditosylate of the dimeric diol were isolated. X-ray structure determinations were carried out on two of the new 14-crown-4 compounds.     

Synthesis of macroheterocycles — Analogs of dibenzo-crown compounds. 4. 15–18-Membered pyridine-containing crown compounds

By condensation of bridged, aromatic diamines, derivatives of o-aminophenol or o-aminothiophenol, with the diacyl chloride of 2,6-pyridinedicarboxylic acid under high dilution, 15–18-membered macrocyclic diamides containing a pyridine nucleus have been synthesized. The synthesized compounds were characterized by IR and PMR spectroscopy.See [1] for Communication 3 in this series.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1559–1562, November, 1989.     

含呋喃环Schiff碱型大环化合物的合成及其与Ba^2+,Sr^2+配合行为

利用Mn^2+，Ba^2+及Sr^2+作为模板离子，合成了一类新型的含呋喃环系 Schiff碱型大环化合物，如L^1和配合物L^2Ba(ClO4)2，L^3Ba(ClO4)2和L^4Ba (ClO4)2.L^2-L^4的Ba^2+配合物经与NaSO4水溶液反应解络，得到自由配体L^2， L^3和L^4，配体L^2和L^3分别与Sr^2+作用，得到配合物L^2Sr(ClO4)2和L^3Sr (ClO4)2。上述大环配体和各种配合物均经元素分析，IR，^1H NMR，MS等证实了它 们的结构和组成。     

Proton-Ionizable crown compounds. 8. Synthesis and structural studies of macrocyclic polyether ligands containing a 4-thiopyridone subcyclic unit

Three new proton-ionizable macrocyclic polyether ligands containing the 4-pyridone subcyclic group have been prepared. Two of these ligands contain lipophilic n-octyl substituents, the other ligand contains a phenyl substituent. The 15-crown-5 ligand containing both a 4-pyridone subcyclic unit and an n-octyl substituent selectively transported lithium cations in a water-methylene chloride-water bulk liquid membrane system. Five crown compounds containing the 4-pyridone subcyclic unit were converted to the 4-thiopyridono-crown compounds when treated with Lawesson's Reagent. The crystal structure of 4-thiopyridono-18-crown-6 shows a carbon-sulfur double bond and a molecule of water hydrogen bonded inside the macrocycle cavity.     

Proton-ionizable crown compounds. 20. The synthesis of polyazatriazolo-, polyazabistriazolo- and bispyridono-crown ligands containing lipophilic hydrocarbon substituents

Four new macrocyclic polyaza-crown compounds containing a triazole subcyclic group and two to five lipophilic hydrocarbon substituents have been prepared from the appropriate polyamine and N-THP-protected 2,5-triazoledimethyl dichloride. N,N,N',N'-Tetrabenzyltetraazabistriazolo-18-crown-6 was prepared from N,N'-dibenzylethylenediamine and N-THP-protected 2,5-triazoledimethyl dichloride. Biscyclohexano-bispyridono-18-crown-6 was prepared from trans- 1,2-cyclohexanediol and THP-protected 4-hydroxy-2,6-pyridinedimethyl ditosylate.     

New one step synthesis of crown compounds containing a 1,3,4‐thiadiazole moiety

New macrocyclic polyether compounds containing a 2,5‐bis(2‐hydroxyphenyl)‐1,3,4‐thiadiazole moiety have been prepared by a nucleophilic substitution reaction involving ethylene or polyethylene glycol ditosylate and a bisphenol, the 2,5‐bis(2‐hydroxyphenyl)‐1,3,4‐thiadiazole, with solid anhydrous carbonate as a base. The structures of the macrocycles obtained were firmly established by ¹H and ¹³C nmr spectroscopy and their mass spectra.     

Studies on the synthesis of heterocyclic compounds. XIII. The synthesis of macrocyclic tetraesters from 1,2-cyclohexane- and 2,3-butanediols

A new series of macrocyclic compounds containing 1,2-cyclohexanediols and 2,3-butandiol sub-unit have been prepared treating the stannolanic and stibolanic derivatives with diacyl chlorides. The structures of the compounds prepared have been determined by elemental analysis and spectroscopic data.     

Studies on the synthesis and properties of open-chain and macrocyclic crown compounds

Eight new open-chain crown compounds (1–8) and two new macrocyclic crown ethers (9 and10) were synthesized from 1,5-bis(2-aminophenoxy)-3-oxapentane (15) and 1,8-bis(2-aminophenoxy)-3,6-dioxaoctane (16) which were prepared by the catalytic hydrogenation of the corresponding bis(2-nitrophenoxy) derivatives13 and14. The fluorescent property investigation of two open-chain crown ethers (7 and8) indicated that they exhibit complexing effects on Ag⁺ and Mn²⁺ cations and can be used as fluorescent reagents for the microanalysis of the metal cations. The pyrolysis kinetics measurement for compounds5 and6 in nitrogen and air was carried out, and their reaction orders and activation energy were obtained. They are one-step and two-step pyrolysis reactions in nitrogen and air, respectively.     

Synthetic approaches toward macrocyclic sulfonyl crown formazans

Coupling of diazonium salts with ethyl sulfonylpyruvates 1–3 or arenesulfonylacetic acids 14,15 afforded good yields of the corresponding 1,5-symmetrically disubstituted-3-sulfonylformazans 4–11. The new sulfonyl macrocyclic crown formazans 25–32 were prepared by coupling of the appropriate bisdiazonium salts 22–24 with compounds 1–3 or 14,15. © 1996 John Wiley & Sons, Inc.     

Proton-ionizable crown compounds. 19. The synthesis of chiral dialkyl-substituted triazolo-18-crown-6 macrocycles

Four new chiral macrocyclic polyether ligands containing the proton-ionizable triazole subcyclic unit have been prepared. The triazolo-crowns contain two isopropyl, two isobutyl, two (S)-sec-butyl or two benzyl substituents on chiral macro ring carbon atoms. A racemic triazolo-18-crown-6 containing two (1-naphthoxy)methyl substituents was also prepared.     

含氮大环化合物的研究

总结十五年来在氮杂冠醚和大环多胺的合成和性质研究方面的主要成果：氮杂冠醚和大环多胺合成的方法学研究,氮杂冠醚和大环多胺的NMR研究,含氮杂冠醚结构单元的吲哚啉螺苯并吡喃类信息接受体的合成和性质研究,桥连环糊精二聚体的分子识别研究。     

Complexation properties of macrocyclic polyether-diester compounds containing furan and benzene subcyclic units

A new series of macrocyclic polyether-diester ligands containing a furan subcyclic unit is reported. In contrast to other macrocyclic ligands, the twenty-four membered ring diester compounds containing either a furan or benzene subcyclic unit complex more strongly with benzylammonium perchlorate than do the eighteen membered ring compounds.     

The preparation of macrocyclic polyether-diester compounds by transesterification including the preparation of two new nitrogen containing diester-crown compounds

Macrocyclic polyether-diester compounds have been prepared by reacting oligoethylene glycols with the appropriate dimethyl esters in the presence of catalytic amounts of alkali metal methoxides. The methanol by-product was removed by molecular sieves. Product yields were improved for the preparation of all macrocyclic compounds except a compound containing a furan subcyclic group ( 4 ). Six new macrocyclic diester compounds ( 7-12 ) could only be prepared using the base catalyzed transesterification process since the acid chloride synthetic method failed or the acid chloride could not be made. The formation of compounds 5 and 6 from dimethyl 2, 6-pyridine dicarboxylate ( 17 ) and the triethylene and tetraethylene glycols proceded by way of half-transesterified intermediates. These intermediates were also observed for the base catalyzed decomposition of 5 and 6 in methanol to form the glycol and the diester 17 .     

Synthesis of novel disulfide-bridged dilactam crown ethers

The novel macrocyclic dilactams with redox-switched disulfide linkage were synthesized.These compounds were obtained from 2,2'-dithiodibenzoyl chloride in the macrocyclization step by fast addition method in moderate yields.     

Macrocyclic polyether-diester compounds as phase-transfer catalysts

Three new macrocyclic polyether-diester have been prepared. The catalytic activity of these compounds has been tested in the Br/I exchange reactions of octyl bromide with different ionic diameter cations.     

Supramolecular compounds of cucurbituril with molybdenum and tungsten chalcogenide cluster aqua complexes

The review surveys the synthesis and structures of a new class of supramolecular compounds composed of the macrocyclic cavitand cucurbituril and molybdenum or tungsten chalcogenide clusters. The structural motifs of supramolecular compounds and factors influencing their formation are considered.     

Diastereoisomeric singly bridged cyclophosphazene-macrocyclic compounds

31P NMR spectroscopy and added chiral shift reagent (CSR) or chiral solvating agent (CSA) have been used to show that unsymmetrically substituted singly bridged macrocyclic phosphazene compounds exist as 1:1 diastereoisomers of two racemic mixtures, in contrast to previous work (ref 2) on symmetrically substituted diastereoisomeric analogues, which exist as meso and racemic forms. The cis-ansa cyclotriphosphazatriene-macrocycle, 1, is meso and monosubstitution of the >P(O-macrocycle)Cl group with 2-naphthol gives a racemic product (7), in which the macrocyclic ring exists in a trans-ansa configuration. Reaction of 7 with the di-secondary amine, piperazine, gives an unsymmetrically disubstituted racemic compound (8) having a cis-ansa configuration of the macrocyclic ring. Reaction of 8 with a further quantity of 1 forms a singly bridged derivative (9) with the macrocyclic rings in cis-trans configurations, and further reaction of 9 with pyrrolidine gives compound 10 with the macrocyclic rings in cis-cis configurations. Both 9 and 10 have four stereogenic centers giving rise to diastereoisomeric compounds existing as mixtures of two racemates. The results are consistent with inversion of configuration at phosphorus at each step of the reaction of >P(OR)Cl groups with nucleophile Z (i.e., Z = naphthoxy, piperazino, pyrrolidino) to form >P(OR)Z derivatives.