Attachment of neutrals during tandem mass spectrometry of sulfonic acid dyes and intermediates in an ion trap

Several positional isomers of 2-(2-quinolinyl)-1H-indene-1,3(2H)-dione mono- and disulfonic acids prepared as reference materials for development of analytical methods involved in FDA certification of D&C Yellow No. 10 (Quinoline Yellow) were found consistently to show [MH + 14](+) ions when their electrospray- or atmospheric pressure chemical ionization-prepared MH(+) ions were subjected to collisional activation. The source of these ions was found to be the methanol used as solvent in these procedures which combined with their [MH - H(2)O](+) ions under chemical ionization conditions. The reaction was found to be sensitive to their isomeric and chemical structures and other examples of this process are reviewed.     

Preparative separation of di- and trisulfonated components of Quinoline Yellow using affinity-ligand pH-zone-refining counter-current chromatography

Four positionally isomeric 2-(2-quinolinyl)-1H-indene-1,3(2H)-dionedisulfonic acids (SA) and one triSA, components of the color additive Quinoline Yellow (QY, Color Index No. 47005), were isolated from the dye mixture by affinity-ligand pH-zone-refining counter-current chromatography (CCC) through complementary use of ion-exchange and ion-pair reagents as the ligand. The added ligands facilitated the partitioning of the very polar polysulfonated components into the organic stationary phase of the two-phase solvent systems that consisted of isoamyl alcohol–methyl tert-butyl ether–acetonitrile–water (3:5:1:7), (3:4:1:7) or (3:1:1:5). Thus, separation of a 5-g portion of QY using sulfuric acid as the retainer and dodecylamine as the ligand (an ion-exchange reagent, 20% in the stationary phase), resulted in 1.21 g of 6′,5-diSA and 1.69 g of 6′,8′,5-triSA, both of over 99% purity. A minor component, 8′,4-diSA, not previously reported was also obtained (4.8 mg of over 94% purity) through a similar separation of a different batch of QY using hydrochloric acid as the retainer and 10% dodecylamine as the ligand in the stationary phase. Two components that co-eluted (0.55 g) in the 5 g separation were separated when trifluoroacetic acid was used as the retainer and tetrabutylammonium hydroxide (an ion-pair reagent) as the ligand. The separation resulted in 20.7 mg of 6′,4-diSA, not previously reported, and 111.8 mg of 8′,5-diSA, both of over 98% purity. The isolated compounds were characterized by high-resolution mass spectrometry and proton nuclear magnetic resonance with correlated spectroscopy assignments.     

Characterisation of the surface Lewis acid-base properties of poly(butylene terephthalate) by inverse gas chromatography

Two modes of high-speed counter-current chromatography (HSCCC) were applied to separate 3- and 4-sulfophthalic acid from a mixture. Conventional HSCCC was useful for the separation of up to several hundred milligram quantities of these positional isomers, while pH-zone-refining CCC was implemented successfully to separations at the multigram level. The conventional HSCCC separations were performed with a standard J-type HSCCC system that has a superior resolution but a lower level of retention of the stationary phase of the biphasic solvent system used (acidified n-butanol-water). The pH-zone-refining CCC separations were performed with an X-type HSCCC system (a cross-axis system) that has a higher capability for retention of the stationary phase. The purified positional isomers (over 99% pure as determined by HPLC) were characterized by 1H NMR and negative ion electrospray ionization mass spectrometry.     

Structural assignment of isomeric 2-(2-quinolinyl)-1H-indene-1,3(2H)-dione mono- and disulfonic acids by liquid chromatography electrospray and atmospheric pressure chemical ionization tandem mass spectrometry

Positionally isomeric 2-(2-quinolinyl)-1H-indene-1,3(2H)-dione mono- and disulfonic acids give rise to similar electrospray ionization (ESI) and atmosphere pressure chemical ionization (APCI) mass spectra, which show very abundant MH(+) ions and negligible fragmentation. The MH(+) ions of these isomeric acids exhibit notably different behavior under collision-induced dissociation (CID) conditions. The acids with a sulfonic group at position 8' in the quinoline moiety, adjacent to the N-atom, exhibit highly abundant [MH - H(2)SO(3)](+) ions (m/z 272 for the mono- and m/z 352 for the disulfonic acids), which are of lower abundance in the CID spectra of isomers with the SO(3)H group at other positions, remote from the nitrogen atom. The latter isomers undergo efficient eliminations of SO(3) and HSO(3). The isomeric diacids with one SO(3)H group at position 4 of the indene-1,3(2H)-dione moiety, adjacent to one of the carbonyl groups, undergo highly efficient elimination of H(2)O. Mechanistic pathways, involving interactions between adjacent groups, are proposed for the above regiospecific fragmentations. Pronounced different behavior has been also observed in negative ion tandem mass spectrometric measurements of the sulfonic acids. The distinctive behavior of the isomeric acids was strongly pronounced when the measurements were performed with an ion trap mass spectrometer (LCQ), and much less so with a triple-stage quadrupole instrument (TSQ).     

Application of pH-Zone-Refining Countercurrent Chromatography in the Preparative Separation of Alkaloids from Traditional Chinese Medicine

pH-Zone-refining countercurrent chromatography (CCC) is a recently developed new preparative separation method based on conventional CCC. The method uses a retainer base (or acid) in the stationary phase to retain the analyses in the column and an eluent acid (or base) to elute the analyses according to their pKa values and hydrophobicities. It produces a succession of highly concentrated rectangular peaks with minimum overlap similar to those observed in displacement chromatography. pH-zone-refining CCC has important advantages over the conventional CCC including an over 10-fold increase (up to 10 gram or more) in sample loading capacity, high concentration of fractions, and concentration of minor impurities. pH-zone-refining CCC has been successfully applied to the preparative separation of a variety of compounds including both acidic and basic derivatives of amino acid, hydroxyxanthene dyes, peptides, alkaloids, indole auxins, structural, geometrial and optical isomers.     

Synthesis,nature of electronic transitions,and absorption spectra of the dye based on 4-(methyl-1-{2-[4-(1-methyl-2-oxo-1,2-dihydroquinolin-3-yl)phenyl]-2-oxoethyl}pyridinium bromide

The reaction of 3-(4-bromoacetylphenyl)-1-methylquinolin-2(1Н)-one with pyridine and 4-methylpyridine has afforded the corresponding pyridinium salts. Condensation of 4-methyl-1-{2-[4-(1-methyl-2-oxo-1,2-dihydroquinolin-3-yl)phenyl]-2-oxoethyl}pyridinium bromide with 4-dimethylaminobenzaldehyde has given a new biscyanine dye, 1-{1-[4-(1,2-dihydro-1-methyl-2-oxo-3-quinolinyl)benzoyl]-2-[4-(dimethylamino)-phenyl]ethynyl}-4-{2-[4-(dimethylamino)phenyl]ethynyl}pyridinium bromide. Its electronic spectrum has been analyzed, and quantum-chemical simulation of spatial and electronic structure of its possible isomers has been performed.     

Preparative separation of isomeric and stereoisomeric dicarboxylic acids by pH-zone-refining counter-current chromatography

This work involves the preparative separation of some isomeric dicarboxylic acids using pH-zone-refining counter-current chromatography (CCC), a relatively new preparative technique for the separation of ionizable compounds. The paper concentrates especially on the separation of a synthetic mixture of closely related cis and trans pairs of 1-methyl- and 1,3-dimethyl-1,3-cyclohexanedicarboxylic acids. The elution sequence of the isomers is discussed in terms of their relative acidities (pK(a) values) in solution and gas phase, hydrophobicities, and steric configuration. Two possible explanations are suggested for the mechanism of separation. They both involve the amount of retainer acid used, as it affects the separation and plays a role in the chemohydrodynamic equilibrium of the dicarboxylic acids in the column.     

手性2-(2-吡啶基)-4-羧乙基-1,3-噻唑烷的合成及应用研究

以分级结晶和柱层析法对手性配体2-(2-吡啶基)-4-羧乙基-1,3-噻唑烷(A)进行了异构体分离提纯。将其与[Rh(COD)Cl]_2制备的原位催化剂用于催化苯乙酮及其它几种芳香酮的不对称硅氢化反应,化学收率达90％左右,光学纯度达80％e.e.左右,噻唑烷环上的C_2构型对催化反应结果无影响,C_4位上酯基的影响也不大。     

Synthesis and molecular and crystal structure of 1-allyl-4-[2-cyano-2-(indan-1,3-dione-2-ylidene)ethylidene] -1, 4-dihydroquinoline

The reaction of 1-allyl-4-methylquinolinium bromide with 2-dicyanomethyleneindan-1,3-dione in the presence of a two-fold excess of triethylamine affords 1-allyl-4-[2-cyano-2-(indan-1,3-dione-2-ylidene) ethylidene]-1,4-dihydrogtiinoline, a representative of a new class of merocyanines. The structure of this compound has been established by X-ray structural analysis. A substantial intramolecular charge transfer and a hydrogen bond between the vinyl hydrogen atom and the indandione oxygen atom have been found.Dedeased in 1995Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 173–176, January, 1996.     

New 4-quinaldinol derivatives XVII. 2-Methyl-3-(3-chloro-2-buten-1-yl)-4-hydroxyquinoline-6-carboxylic acid and some of its transformations

1-(2-Methyl-4-hydroxy-6-carboxy-3-quinolinyl)-3-butanone and 1-(2-methyl-4-chloro-6-carboxy-3-quinolinyl)-3-butanone were obtained by the acid hydrolysis of 2-methyl-3-(3-chloro-2-buten-1-yl)-4-hydroxy(chloro)quinoline-6-carboxylic acids and their esters.See [6] for communication XVI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1681–1682, December, 1971.     

手性2-(2-吡啶基)-4-羧乙基-1, 3-噻唑烷的合成及应用研究

以分级结晶和柱层析法对手性配体2-(2-吡啶基)-4-羧乙基-1,3-噻唑烷(A)进行了异构体分离提纯。将其与[Rh(COD)Cl]~2制备的原位催化剂用于催化苯乙酮及其它几种芳香酮的不对称硅氢化反应, 化学收率达90%左右, 光学纯度达80%e.e.左右, 噻唑烷环上的C~2构型对催化反应结果无影响, C~4位上酯基的影响也不大。     

3-[2-(8-Quinolinyl)benzoxazol-5-yl]alanine derivative—a specific fluorophore for transition and rare-earth metal ion detection

A novel aromatic amino acid, 3-[2-(8-quinolinyl)benzoxazol-5-yl]alanine derivative was synthesized as a potential Zn(II) and rare-earth metal, Eu(III) and Tb(III), ion chemosensor. The fluorophore was obtained using lead tetraacetate in DMSO to oxidize the Schiff base obtained from N-Boc-3-amino-tyrosine methyl ester and quinoline-8-carboxaldehyde. Preliminary photophysical properties of this ligand show that it possesses the properties necessary to be an effective chemosensor for Zn²⁺, Tb³⁺ and Eu³⁺ ions.     

Synthesis and Crystal Structure of 5-Cyclopropyl- 10-（4-fluorophenyl）-7,7-dimethyl-7,8-dihydro-5H- indeno[1,2-b]quinoline-9,11（6H,10H）-dione

The title compound 5-cyclopropyl-10-(4-fluorophenyl)-7,7-dimethyl-7,8-dihydro- 5H-indeno[1,2-b]quinolne-9,11(6H,10H)-dione was obtained by the reaction of 4-fluorobenzal- dehyde, 2H-indene-1,3-dione and 3-(cyclopropylamino)-5,5-dimethylcyclohex-2-enone in the presence of acetic acid under microwave irradiation. Its structure was confirmed by IR and 1H- NMR spectra. The crystal is of monoclinic, space group P21/c with a = 14.138(3), b = 8.952(2), c = 17.140(3) , β = 102.253(3)o, C27H24FNO2, Mr = 413.47, Z = 4, V = 2119.9(8) 3, Dc = 1.296 g/cm3, μ(MoKα) = 0.087 mm-1, F(000) = 872, the final R = 0.0425 and wR = 0.0905 for 2336 observed reflections (I > 2σ(I)). X-ray analysis revealed that the pyridine ring adopts a boat conformation and the six-membered ring fused with it assumes a twist boat conformation.     

Study of the reactivity of subtituted phthalic acids and anhydrides in condensation reactions with N-carboxymethylpyridinium salts and the synthesis of novel N-(1H-indene-1,3(2H)-dion-2-Yl)pyridinium betaines

Reaction of substituted phthalic acids or their anhydrides (including pyromellitic dianhydride) with salts of N-carboxymethylpyridinium and substituted N-carboxymethylpyridinium in the presence of acetic anhydride and triethylamine in acetonitrile or acetic acid solutions gave a series of novel N-(1H-indene-1,3(2H)-dion-2-yl)pyridinium betaines. Electron acceptors substitutents in the phthaloyl and pyridine rings were found to increase and electron donor substituents-to decrease the reactivity.Riga Technical University, Riga LV-1048, LatviaTranslated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12. pp. 1647–1654, December, 1999.     

1,3-二-(3,3-二甲基-2-甲烯假吲哚)方酸菁染料的合成及其晶体结构

合成了两个新型方酸菁染料3和5。在催化下,2,3,3-三甲基假吲哚不需N- 烷基化,可直接与方酸反应。反应过程中发生了明显的质子转移。结晶学数据表明,分子3的整体位于同一平面;溶剂苯规则地排在方酸四碳的周围, 后者酷似电子陷肼。染料5有良好的水溶性。     

Thermal reactions of 2-(2-oxo-3-nitro-4-quinolinyl)malonates

Depending on the ester substituent, diethyl 2-(3-nitro-2-oxo-4-quinolinyl)malonates 2 give upon thermolysis ethyl 2-(3-nitro-2-oxo-4-quinolinyl)acetates 4, whereas dimethyl 2-(3-nitro-2-oxo-4-quinolinyl)-malonates 3 cyclize to give 1-methoxycarbonylisoxazolo[3,4-c]quinolin-4(5H)-ones 5. The necessary reaction conditions can be obtained easily with the help of differential scanning calorimetry.     

Synthesis of New Functionally Substituted Indenes,Benzofurans, and 2,5-Benzodiazocin-1(2H)-ones

Russian Journal of Organic Chemistry - The synthesis of new functionally substituted 1H-indene-1,3(2H)-diones, indenobenzofurans, and 2,5-benzodiazocines is described. The condensations of...     

Preparative separation of 1,3,6-pyrenetrisulfonic acid trisodium salt from the color additive D&C Green No. 8 (pyranine) by pH-zone-refining counter-current chromatography

In developing analytical methods for batch certification of the color additive D&C Green No. 8 (G8), the U.S. Food and Drug Administration needed the trisodium salt of 1,3,6-pyrenetrisulfonic acid (P3S) for use as a reference material. Since P3S was not commercially available, preparative quantities of it were separated from portions of a sample of G8 that contained ～3.5% P3S. The separations were performed by pH-zone-refining counter-current chromatography using dodecylamine (DA) as the hydrophobic counterion. The added DA enabled partitioning of the polysulfonated components into the organic stationary phase of the two-phase solvent system used, 1-butanol-water (1:1). Thus, a typical separation that involved 20.3g of G8, using sulfuric acid as the retainer acid and 20% DA in the stationary phase and 0.1M sodium hydroxide as the mobile phase, resulted in ～0.58 g of P3S of greater than 99% purity. The identification and characterization of the separated P3S were performed by elemental analyses, proton nuclear magnetic resonance, high-resolution mass spectrometry, ultra-violet spectra, and high-performance liquid chromatography.     

Binary systems of C60 with positional isomers 1,2- and 1,3-C6H4Br2

Thermodynamic properties of binary systems of C₆₀ with 1,2- and 1,3-dibromobenzenes have been studied by means of differential scanning calorimetry (DSC). Solid solvates with the compositions C₆₀3(1,2-C₆H₄Br₂); C₆₀2(1,3-C₆H₄Br₂) and C₆₀0.6(1,3-C₆H₄Br₂) have been found. The solvates have been characterised by their enthalpies and temperatures of incongruent melting transition and in part by X-ray powder data. It has been shown that positional isomers 1,2- and 1,3- of the substituted benzenes formed two series of “typical” phase diagrams. Solubility behaviour of C₆₀ in positional isomers has been discussed.     

Sc(OTf)3-catalyzed or t-BuOK promoted tandem reaction of 2-(2-(alkynyl)benzylidene)malonate with indole

Tandem reaction of 2-(2-(alkynyl)benzylidene)malonate with indole was investigated. (Z)-1-Benzylidene-3-(1 H-indol-1-yl)-1 H-indene-2,2(3 H)-dicarboxylate was generated in the presence of t-BuOK at room temperature; whereas 3-((1 H-indol-3-yl)(2-(alkynyl)aryl)methyl)-1 H-indole was obtained when Sc(OTf)3 was utilized as catalyst at 50 degrees C.