Solid-state synthesis and characterization of novel aluminophosphates,A3Al2P3O12 (A = Na,K, Rb,Tl): influence of A+ ions on the coordination of aluminum

Four aluminophosphates, A3Al2P3O12 (A = Na, K (1), Rb (2), Tl (3)), have been synthesized by solid-state reactions and characterized by X-ray diffraction and NMR and IR spectroscopic techniques. Aluminum has trigonal bipyramidal coordination in the thallium compound and tetrahedral coordination in the others. Potassium, rubidium and thallium analogues have been structurally characterized by single-crystal X-ray diffraction and found to possess three-dimensional (Al2P3O12)3- anionic frameworks with channels occupied by A+ countercations. These frameworks are built from corner connections of PO4 tetrahedra with AlO4 tetrahedra in 1 and 2 and with AlO5 trigonal bipyramids in 3. Pertinent crystal data are as follows: for 1, orthorhombic space group Pna2(1), a = 8.685(2) A, b = 16.947(2) A, c = 8.458(3) A, Z = 4; for 2, orthorhombic space group Cmc2(1), a = 17.164(2) A, b = 8.6270(6) A, c = 8.8140(14) A, Z = 4; for 3, orthorhombic space group Pna2(1), a = 6.1478(15) A, b = 10.396(3) A, c = 17.787(5) A, Z = 4. Compound 3 is a rare example of an oxide possessing aluminum exclusively in trigonal bipyramidal coordination.     

Synthesis, dual fluorescence, and fluoroionophoric behavior of dipyridylaminomethylstilbenes

The synthesis, dual fluorescence, and fluoroionophoric behavior of two donor-sigma spacer-acceptor (D-s-A) compounds, trans-4-(N,N-bis(2-pyridyl)amino)methylstilbene (1H) and trans-4-(N,N-bis(2-pyridyl)amino)methyl-4'-cyanostilbene (1CN), are reported and compared to that of trans-4-(N,N-bis(2-pyridyl)amino)methyl-4'-(N,N-dimethylamino)stilbene (1DPA). To gain insights into the dual fluorescence properties for 1H and 1CN in polar but not in nonpolar solvents, model compounds resulting from a replacement of the stilbene group by alkyl (2R) or xylyl (2X) groups or from a replacement of the dipyridylamino (dpa) group by dianisoleamino (3AA), diethylamino (3EE), methylanilino (3MP), or diphenylamino (3PP) groups also have been investigated. In addition to 1H and 1CN, all four compounds of 3 display dual fluorescence. The locally excited (LE) fluorescence mainly results from the stilbene group and the ICT fluorescence from the through-bond interactions between the amino donor and the stilbene acceptors. In the presence of transition metal ions such as Zn(II), Ni(II), Cu(II), and Cd(II), the ICT processes are switched from dpa (D) --> stilbene (A) in 1H and 1CN to stilbene (D) --> dpa/metal ion (A) in their complexes. Whereas the ICT states for the complexes are generally nonfluorescent, an exception was found for the case of 1H/Zn(II). As a result, substituent-dependent fluoroionophoric behavior has been demonstrated by 1H, 1CN, and 1DPA in response to Zn(II).     

Methylation of 1, 2, 3, 4-tetrahydroacridine by butyllithium,and the preparation of tetrahydroacridyl aryl carbinols

A number of aryl 4-(1, 2, 3, 4-tetrahydroacridyl) carbinols have been synthesized via the 4-lithio derivative of 1, 2, 3, 4-tetrahydroacridine. Some of them have been dehydrated to the corresponding arylidines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1239–1241, September, 1970.     

Efficient,scalable kinetic resolution of cis-4-benzyloxy-2,3-epoxybutanol

A new enzyme catalysed kinetic resolution of cis-4-benzyloxy-2,3-epoxybutanol has been reported. Efficient, scalable separation of the optically active alcohol from its ester derivative has been solved with liquid–liquid and solid–liquid extraction methods using commercial organic solvents and supercritical carbon dioxide. cis-4-Benzyloxy-2,3-epoxy-1-butanol enantiomers were applied for the enantioselective synthesis of (2S,3S,1′S)- and (2R,3R,1′R)-3-[2′-(dibenzylamino)-1′-hydroxyethyl]-2-phenyloxetane.     

Abkömmlinge der 3-Chinolincarbonsäure mit Sauerstoffsubstitution in Stellung 4, 5 and 8: Synthese,Reaktionen, NMR.-Studien

Derivatives of 3-Quinolinecarboxylic Acid with Oxygen Substitution in Positions 4, 5 and 8: Synthesis, Reactions, NMR. Studies Starting from either 1, 4-dibenzyloxybenzene (7) or 2, 5-dimethoxyaniline ( 16 ), synthetic routes have been developed to benzenoid and quinoid derivatives of 4-oxo-1, 4-dihydro-3-quinolinecarboxylic acid with O-bearing substituents in the positions 5 and 8 (compounds 12 - 15 , 19 , 20 , 23 , and 24 ). With the 1-ethyl-4, 5, 8 trioxo acid 14 as a dienophile, a series of linear tricyclic diene adducts ( 29 - 32 ) has been prepared, the structures of which were further modified by aromatization, reduction or dehydrogenation (compounds 33 - 40 ). A series of benzenoid and quinoid compounds with an additional substituent in position 6 or 7 (Table 1) has been derived mainly from the quinone 14 , primarily by addition of nucleophiles and eventually subsequent steps, and by aromatic electrophilic substitution of the 1-ethyl-5, 8-dimethoxy acid 23 . The substitution pattern of some of these compounds has been elucidated by detailed ¹³C-NMR. studies (Table 2) and/or nuclear Overhauser-effect studies (Table 3). Correlations, based essentially on chemical arguments, allowed to define the structures of most of the residual new compounds (Table 4).     

Diels-alder reactions of 3, 6-diphenyl-1, 2, 4, 5-tetrazine and 3, 6-di(2-pyridyl)-1, 2, 4, 5-tetrazine with some 1-morpholinocycloalkenes

The reactions of 3, 6-diphenyl-1, 2, 4, 5-tetrazine 1 and 3, 6-di(2-pyridyl)-1, 2, 4, 5-tetrazine 2 with the enamines 3a-d derived from morpholine and the 5-,6-,7- and 8-membered cyclic ketones have been investigated. A number of pyridazine derivatives 4–7 most of which are new have been reported. Moreover, a novel procedure for the aromatization of pyridazines 5a-d to the corresponding pyridazine 7b-d via oxidative elimination using hydrogen peroxide is described. The structures of products 4–7 were confirmed by spectral methods and elemental analysis.     

1, 4-Dimethylcyclohex-3-enyl Methyl Ketone,a monoterpenoid with a novel skeleton

1, 4-Dimethylcyclohex-3-enyl methyl ketone ( 1 ) has been isolated from the oil of Juniperus communis L . (fruit). This is the first reported occurrence of this skeleton in nature. A curious effect on the NMR.-spectrum of the compound ( 1 ) by the shift agent, Eu(fod)₃, is described.     

Oxazolidines. 2. Synthesis of 2-methyloxazolidines by cyclization of vinyl ethers of 1, 2-amino alcohols

A study has been made of the catalytic activity of a number of proton acids and Lewis acids, amongst which mercury salts were particularly active, in the cyclization of N-phenylethanolamine vinyl ether to 2-methyl-3-phenyloxazolidine. A method for the preparative synthesis of 2-methyloxazolidines has been developed.For Communication 1, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 536–538, April, 1986.     

Chemistry of the podocarpaceae—III A new lignan, seco-isolariciresinol and further constituents of the heartwood of Podocarpus spicatus

A new lignan for which the name seco-isolariciresinol is proposed, has been isolated from the heartwood of Podocarpus spicatus. The structure has been shown to be 2:3-bis(4′-hydroxy-3′- methoxybenzyl)-butan-1:4-diol (II, R = H), and confirmed by an absolute synthesis from (−)-matairesinol (I, R = H). A further examination of the extractives of the heartwood has resulted in the isolation of the minor constituents, (+)-taxifolin, (+)-aromadendrin, kaempferol and sequoyitol, in addition to the previously reported compounds, matairesinol, -conidendrin, quercetin, genistein and podospicatin.     

Reaction of 4-hydrazinoquinolines with β-diketones. Synthesis and spectroscopy (1h, 13c nmr,ms) of some pyrazolylquinolines

A series of 4-pyrazolylquinolines have been prepared from 4-hydrazinoquinolines and β-dicarbonyl compounds and the previously proposed diazepine structure for the reaction products has been ruled out. A ¹³C nmr study established the 3-position of the methyl group when two isomers were possible. Finally, a careful ¹H nmr study of 2- and 4-pyrazolylquinolines led to the conclusion that intramolecular hydrogen bonds between aromatic (or heteroaromatic) C-H and pyridine like nitrogens is the factor that determines the conformation of these compounds.     

Synthesis,characterization, reactivity,and electrochemical studies of manganese(IV) complexes of bis(2-hydroxy-1-naphthaldehyde)adipoyldihydrazone

Manganese(IV) complexes [Mn^IV(npah)(H₂O)₂] (1) and [Mn^IV(npah)(A)₂]?·?nH₂O (where A?=?py (2), 2-pic (3), 3-pic (4), 4-pic (5)) and Mn^IV(npah)(NN)] (NN?=?bpy (6) and phen (7)) have been synthesized from bis(2-hydroxy-1-naphthaldehyde)adipoyldihydrazone in methanol. The composition of the complexes has been established by elemental analyses. Complex 3 has been characterized by mass spectral data also. Structural assessment of the complexes has been based on data from molar conductance, magnetic moment, electronic, electron paramagnetic resonance, and infrared (IR) spectral studies. Molar conductances of the complexes in DMSO suggest non-electrolytes. Magnetic moment and EPR studies suggest +4 oxidation state for manganese in these complexes. Electronic spectral studies suggest six-coordinate octahedral geometry around the metal ions. IR spectra reveal that H₄npah coordinates to the metal in enol form. Reaction of the complexes with benzyl alcohol and SO₂ has been investigated. Cyclic voltammetric studies of the complexes have also been carried out.     

Convergent synthesis of a common pentasaccharide-repeating unit corresponding to the O-specific polysaccharide of Escherichia coli O4:K3, O4:K6, and O4:K12

A convergent chemical synthesis of a pentasaccharide found in the O-specific polysaccharide of Escherichia coli O4:K3, O4:K6, and O4:K12 has been achieved in excellent yield. A [3+2] block synthetic strategy has been adopted to couple a disaccharide donor 11 with a trisaccharide acceptor 10 for the construction of the pentasaccharide derivative 12 which on deprotection furnished target pentasaccharide 1 as its 4-methoxyphenyl glycoside. Disaccharide thioglycoside donor 11 and trisaccharide acceptor 10 were prepared from suitably protected monosaccharide intermediates. Yields were excellent in all steps.     

Synthesis of 3-cyano-4, 6-diaryl-3, 4-dihydropyridine-2-thionks

3-Cyano-4, 6-diaryl-3, 4-dihydropyridine-2-thiones have been synthesized for the first time by the condensation of arylideneacetophenones or 1-piperidino-1-phenyl-2-benzoylethane with cyanothioacetamide and the 1, 1-dicyano-2-aryl-3-benzoylpropane with hydrogen sulfide in the presence of bases. It has been established by PMR spectroscopy that 3-cyano-3,4-dihydropyridine-2-thiones exist in solutions in the form of mixture of cis and trans isomers.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1515–1520, November, 1983.     

Organocadmium aminoalcoholates: synthesis, structure, and materials chemistry

The novel methylcadmium aminoalkoxides MeCd(dmae) (Hdmae = dimethylaminoethanol), MeCd(bdmap) [Hbdmap = 1,3- bis-(dimethylamino)-propan-2-ol], and MeCd(tdmap) [tdmap = 1,3- bis(dimethylamino)-2-(dimethylaminomethyl)-propan-2-ol] have been synthesized and structurally characterized. MeCd(dmae) (1) forms a tetrameric heterocubane with a Cd4O4 core, while MeCd(bdmap) (2) is trimeric and MeCd(tdmap) (3) is a dimer. Only in the case of MeCd(dmae) are all the ligand donors fully utilized. In solution, MeCd(tdmap) undergoes a Schlenk equilibrium, with Me2Cd and Cd(tdmap)2 evident at 218 K. The structure and solution-state chemistry of Cd(tdmap)2 (5) have been independently studied and, in the solid-state, found to exist as a dimer whose coordination number at cadmium (CN = 6) is greater than in the organocadmium complexes (CN = 4, 5). MeCd(tdmap) has been used as a single-source precursor for CdO films by LPCVD with a glass substrate temperature of only 140 degrees C. Evidence is also presented for the formation of a heterometallic precursor, [(MeZn)(MeCd)(tdmap)2] (6), which has been used to deposit films of CdO mixed with ZnO by LPCVD at 140 degrees C. The structure of Me4Cd4(tdmap)2Cl2 (4), obtained serendipitously, is also included. Crystal data: 1, C20H52Cd4N4O4, FW 862.26, triclinic, P1, a = 11.47560(10), b = 13.55400(10), c = 21.5966(2) A, alpha = 99.7869(4), beta = 90.7476(4), gamma = 98.7823(4) degrees, V = 3268.82(5) A(3), Z = 4; 2, C27H67Cd3N6O3, FW 861.07, triclinic, P1, a = 11.4148(2), b =13.1886(2), c = 14.3139(3) A, alpha = 102.1962(10), beta = 108.3064(10), gamma = 100.8446(10) degrees, V = 1923.09(6) A(3), Z = 4; 3, C22H54Cd2N6O2, FW 659.51, monoclinic, P2(1)/n, a = 10.2912(1), b = 13.46930(1), c = 11.79130(1) A, beta = 112.8051(1) degrees, V = 1506.59(2) A(3), Z = 2; 4, C24H60Cd4Cl2N6O2, FW 985.28, monoclinic, P2(1)/c, a = 10.89780(10), b = 20.3529(2), c = 16.5317(2) A, beta = 94.8550(10) degrees, V = 3653.61(7) A(3), Z = 4; 5, C40H96Cd2N12O4, FW 1034.09, orthorhombic, P2(1)cn, a = 12.33290(10), b = 14.25060(10), c = 29.9003(2) A, V = 5255.01(7) A(3), Z = 4.     

4-Hydroxy-2-quinolones 148. Synthesis and antitubercular activity of 1-hydroxy-3-oxo-6,7-dihydro-3H,5H-pyrido[3,2,1-<Emphasis Type="Italic">ij</Emphasis>]quinoline-2-carboxylic acid N-R-amides

An improved method for the preparation of ethyl 1-hydroxy-3-oxo-6,7-dihydro-3H,5H-pyrido[3,2,1-ij]quinoline-2-carboxylate has been proposed and a series of hetarylamides has been synthesized from it. A comparative analysis has been carried out of the antitubercular activities of the synthesized compounds with the active structural analogs 4-hydroxy-2-oxo-1,2-dihydroquinoline-3 and 1-hydroxy-3-oxo-5,6-dihydro-3H-pyrrolo[3,2,1-ij]quinoline-2-carboxamides studied before. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1189–1202, August, 2008.     

Higher Isoprenoids-XIIa: Partial syntheses from cycloartenol,cyclolaudenol-part 4: a novel method for functionalization of C-4 methyl in triterpenoids,and synthesis of cyclodeucalanone

A general method for selective oxygenation of C-4-Me in triterpenes, leading finally to 4α-carboxyl/4α-hydroxymethyl functionalities, is described. The key-step involved is phytolysis of hypoiodite derived from 3β-hydroxymethyl derivative of the triterpene. The method is illustrated by the conversion of cyclolaudanone (1) into methyl 3-oxo-cyclolaudan-29-oate (2). The latter has been converted into the known cycloeucalanone (3) by a simple sequence of reactions.     

Octahedral Co(II) and Ni(II) complexes of Schiff bases,semicarbazone and thiosemicarbazone,synthesis, biological,spectral, and thermal studies

A new series of cobalt(II) and nickel(II) complexes, [M(ligand)(H₂O)₂(Y)] (M = Co(II) or Ni(II); Y = Cl^?, Br^? or NO₃ ^?), containing the Schiff-base semicarbazone and thiosemicarbazone, HL¹ and HL², formed from 4-hydroxycoumarin-3-carbaldehyde have been synthesized. The nature of bonding and the stereochemistry of the complexes have been deduced from elemental analyses, infrared, electronic spectra, magnetic susceptibility, and conductivity measurements. An octahedral geometry has been suggested for the complexes. The metal complexes were screened for their antifungal and antibacterial activities on different species of pathogenic fungi and bacteria and their biopotency has been discussed.     

Marruboside,a new phenylethanoid glycoside from Marrubium vulgare L

A new phenylethanoid glycoside, marruboside, has been isolated from the aerial parts of Marrubium vulgare L. Its structure was established as 3,4-dihydroxy-beta-phenylethoxy-O-[beta-D-apiofuranosyl-(1-->2)-alpha-L-rhamnopyranosyl-(1-->3)]-[beta-D-apiofuranosyl-(1-->6)]-4-O-caffeoyl-beta-D-glucopyranoside, on the basis of spectroscopic evidence.     

The molecular structure of 4a, 5, 8, 8a-tetrahydro-11, 14-dimethoxy-7-methyl-4a-(3-methyl-2-butenyl)-5, 8a-o-benzeno-1, 4-naphthoquinone

A novel natural product, microphyllone, has been isolated from Ehretia microphylla² together with baurenol and ursolic acid. Spectroscopic techniques, derivative formation and finally X-ray diffraction have been utilized in the structure elucidation of microphyllone. The structure appears to be 4a, 5, 8,8a - tetrahydro -11,14- dihydroxy-7-methyl-4a-(3-methyl-2-butenyl)-5, 8a-o-benzeno-1, 4-naphthoquinone.     

Synthesis, characterization, and electrochemical and electrochromic properties of sandwich dilutetium tetraphthalocyanine

A new sandwich-tpype dilutetium tetraphthalocyanine 4 has been synthesized by the reaction of dimeric lutetium(III) phthalocyanine 3 with two equiv. of dilithium octakishexylthiophthalocyanine in amyl alcohol. Compound 3 was prepared from 4',5',4",5"-tetraiminoisoindoline(1,4,7,10-tetrathia-12-crown-4) 1, 4,5-bis(hexylthio)-1,2-diiminoisoindoline and lutetium acetate in amyl alcohol. Compounds 3 and 4 were characterized by elemental analysis, UV/visible, IR, (1)H NMR and ESR spectroscopy. The electrochemical and electrochromic properties of 3 and 4 have been examined by cyclic voltammetry. Both 3 and 4 displayed well-defined electrochromic behavior.