Presence Of Metallic Sodium Research Articles

The syntheses of 2-hydroxybenzothiazole substituted cyclotriphosphazenes: Spectroscopic characterizations

The nucleophilic substitution reactions of mono- and bis-spiro-2,2’-dioxybiphenyl cyclotriphosphazenes (1a and 1b) with 2-hydroxybenzothiazole (2) were performed in the presence of metallic sodium in THF. Two novel 2-oxybenzothiazole-substituted spiro-2,2′-dioxybiphenyl cyclotriphosphazene derivatives (3a and 3b) were obtained from these reactions. Both compounds (3a, 3b) have been characterized by elemental analysis as well as by 1H, 13C and 31P NMR spectroscopy. Compounds 3a and 3b are reported for the first time in this study.

Synthesis, Structure, and Biological Activity of Magnesium(II), Zinc(II), Cobalt(II), and Copper(II) Bis(4-aryl-1-ethoxy-1-oxobutane-2,4-dionates)

The condensation of aryl methyl ketones with diethyl oxalate in the presence of metallic sodium or sodium hydride gave sodium 4-aryl-1-ethoxy-1,4-dioxobut-2-en-2-olates, and metal exchange of the latter with magnesium(II), zinc(II), cobalt(II), and copper(II) salts afforded the corresponding metal bis(4-aryl-1-ethoxy-1-oxobutane-2,4-dionates). The obtained complexes were tested for antibacterial activity against gram-positive and gram-negative bacteria by the agar diffusion method.

Visible Light assisted Photocatalytic Acitivity of Zinc Titanate in Presence of Metallic Sodium

Zinc titanate powder was synthesizd by an organic free co-precipitation peroxide technique. Zinc chloride and titanium (IV) isopropoxide were used as the primary material with the ratio of Zn:Ti was 1:1 and the later compound was prepared by mixing titanium chloride with isopropanol. The stoichiometric ratio of the synthesized zinc titanate was measured by using AAS. The synthesized powder was calcined at 800°C for 3 hours using the X-ray diffraction and the calcined zinc titanate powder crystalline phase formation was found to be cubic. FTIR was used for studying the bonding characteristics of ZnO and TiO2. Disintegration temperature was analyzed by means of Thermogravimetric analysis. The photocatalytic activity was measured based on the degradation of methyl orange in aqueous solution in the presence of metallic sodium. The results showed that ZnTiO3 particle exhibited good photocatalytic activity under visible range radiation.

Easy and controlled synthesis of nitrogen-doped carbon

A novel synthesis of N-doped carbon with not only a high surface area (∼1000m2g−1) but also with a controlled amount of N-doping is reported from the solvothermal reduction of hexachlorobenzene (HCB) and pentachloropyridine (PCP), without the emission of harmful byproducts. In the presence of metallic sodium as a reducing agent, the N-doping amount can be regulated up to 0.12 of N/C atomic ratio by simply altering the initial HCB and PCP ratios. The mechanism is proposed where the chlorine in the HCB and PCP is reacted with metallic sodium by producing NaCl, and the N-doped carbon is synthesized as the activated carbon edges of C5N and C6 rings being bonded together. The surfaces of the prepared N-doped carbons are modified through heat-treatment and this dramatically improves the mechanical and electrical properties. The dominant doping phases of N are pyridinic-N and amide or amine groups; however, the amide or amine groups are eliminated and graphitic-N is newly generated through heat-treatment.

Synthesis and structural characterization of 1-(3-aminopropyl)silatrane and some new derivatives

The research goal was to synthesize and structurally characterize a silatrane intended to be subsequently incorporated into metal complex structures. 3-Aminopropyltrialkoxysilane was reacted with triethanolamine in 1:1 molar ratio, either in bulk, in the presence of metallic sodium, or in a solvent mixture. 1-(3-Aminopropyl)silatrane in carbamate form or having free amine groups was obtained. The latter was reacted with 2-hydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde and CoCl2 or with CoCl2 only. The crystalline reaction products were characterized by elemental and spectral (FTIR and 1H NMR) analyses and single crystal X-ray diffractometry, which revealed the formation of new, either sought (1-(3-aminopropyl)silatrane, 1-(3-salicyliminopropyl)silatrane) or unexpected (N-carboxylated 1-(3-aminopropyl)silatrane and 1-chlorocobaltrane) structures.

ChemInform Abstract: Borylation of α-Hydroxyalkylphosphine Oxides in the Presence of Strong Bases.

Lithium (sodium) 2,2,5-triphenyl-5-oxo-1,3,2,5-dioxaborataphosphorinanes, forming crystals with two molecules of water, are produced when bis(hydroxymethyl)phenylphosphine oxide is reacted with isobutyl diphenylborate in the presence of metallic sodium or lithium (sodium) alcoholate.

Synthesis and some chemical conversions of acetylenic derivatives of 1,4-dioxane

The possibility has been shown of synthesizing acetylenic derivatives of 1,4-dioxane in high yield by the interaction of glycidyl ethers of acetylenic alcohols with ethylene bromohydrin in the presence of boron trifluoride etherate. Dehydrobromination of the corresponding bromohydrin was then carried out in the presence of metallic sodium in absolute diethyl ether. Acetylenic derivatives of 1,4-dioxane enter into hydrosilylation, aminomethylation, and diene condensation reactions with the formation of new derivatives of 1,4-dioxane.

4-Hydroxy-2-quinolones 146. Synthesis and structure of 1,1′-diallyl-4,4′-dihydroxy-1H,1′ H-[3,3′]biquinolinyl-2,2′-dione

The methyl ester of N-allyl-2-methoxycarbonylsuccinanilic acid is partially converted to 1,1′-diallyl-4,4′-dihydroxy-1H,1′H-[3,3t′]biquinolinyl-2,2′-dione in refluxing toluene in the presence of metallic sodium. A possible mechanism for the occurrence of these chemical processes is discussed.

The first example of the alkoxy-containing iron(ii) tris-dioximate clathrochelate: synthesis, structure, and properties

The reaction of the dichloride iron(ii) tris-dioximate clathrochelate with triethyl orthoformate in the presence of metallic sodium afforded the diethoxy-substituted macrobicyclic complex. The first alkoxy-containing clathrochelate was characterized using elemental analysis, MALDI-TOF mass spectrometry, IR, UV-Vis, 1H and 13C{1H} NMR spectroscopy, and X-ray diffraction analysis.

2,6,7-Trihydroxy-4,9-dioxodeca-2,5,7-trienoic and 2-hydroxy-2-(3-hydroxy-4-methyl-2,5-dioxocyclopent-3-en-1-ylidene)acetic acid esters: Synthesis and structural specificity

Claisen condensation of acetone and butan-2-one with diethyl oxalate in the presence of metallic sodium leads to the formation of ethyl 2,6,7-trihydroxy-4,9-dioxodeca-2,5,7-trienoate and ethyl 2-hydroxy-2-(3-hydroxy-4-methyl-2,5-dioxocyclopent-3-en-1-ylidene)acetate, respectively.

Synthesis and characterization of a model carbon-chain polymer substituted by two esters on every third atom via anionic ring-opening polymerization of a cyclopropane-1,1-dicarboxylate

Ultrapure diethyl 1,1-cyclopropanedicarboxylate (1) undergoes ring-opening polymerization when placed in the presence of small amounts of sodium thiophenolate (2) at temperatures above 80°C, and leads to the synthesis of a carbon-chain polymer substituted on every third carbon atom by ethyl ester substituents. 1 polymerizes also in the presence of 2 generated in situ from thiophenol and metallic sodium, but does not polymerize in the presence of metallic sodium alone. Polymerizations are slow and require high concentrations in monomer and initiator to obtain reasonable polymerization times. In spite of the high temperatures used in some experiments (up to 130°C), no structural subunit resulting from side reactions was detected, presumably due to the high stability of the propagating malonate carbanion. Polymers of narrow molecular weight distribution were obtained at both 80 and 130°C (M̄w/M̄n < 1,14), and absolute degrees of polymerization increased with polymer yields. These results were rationalized on the basic of a quasi-living polymerization mechanism. Thermal properties of poly(1) were determined by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). Poly(1) is stable up to 275°C and is a micro-crystalline polymer insoluble in most typical solvents, with the noticeable exception of chloroform and dichloromethane.

Borylation of ?-hydroxyalkylphosphine oxides in the presence of strong bases

Lithium (sodium) 2,2,5-triphenyl-5-oxo-1,3,2,5-dioxaborataphosphorinanes, forming crystals with two molecules of water, are produced when bis(hydroxymethyl)phenylphosphine oxide is reacted with isobutyl diphenylborate in the presence of metallic sodium or lithium (sodium) alcoholate.

Preparation and oxidative polymerization of 2-fluoro-6(3-methyl-2-butenyl)phenol

2-Fluoro-6-(3-methyl-2-butenyl)phenol(FMBP) is prepared by the reaction of 2-fluorophenol with 1-chloro-3-methyl-2-butene in the presence of metallic sodium. FMBP is oxidatively polymerized with a copper-pyridine catalyst to yield poly[oxy-2-fluoro-6-(3-methyl-2-butenyl)-1,4-phenylene]. FMBP is also copolymerized with 2, 6-dimethylphenol(DMP). The copolymerizability of FMBP is discussed.

Soluble cyclopentadienylated polymers

AbstractCopolymers from styrene and a mixture of p‐ and m‐chloromethylstyrene were reacted with sodium cyclopentadienide in THF and precipitated in methanol at temperatures lower than −20°C to obtain soluble cyclopentadienylated polymers. Due to extensive gelation, the content of cyclopentadienyl groups could not be increased to more than 4 mol‐% except with extremely low molecular weight polymers. An improved method, in which the copolymer was cyclopentadienylated in the presence of metallic sodium, gave soluble polymers with up to 29 mol‐% cyclopentadienyl groups. Pendant cyclopentadienyl groups undergo Diels‐Alder/retro‐Diels‐Alder addition to give thermoreversible cross‐linked polymers. The amount of gel fraction of a 4 mol‐% cyclopentadienylated polymer as a function of the heating time was examined in the temperature range of 40–80°C. The DSC curve of a 29 mol‐% cyclopentadienylated polymer showed an exothermic peak due to the Diels‐Alder reaction and an endothermic peak starting around 390°C, a temperature higher than that found for the degradation of polystyrene.

Investigation of the dimerization reaction of certain ?-substituted pyridine bases in the presence of metallic sodium and Raney Ni catalysts

1. The dimerization ofβ-substituted pyridine bases depends effectively on the steric factors of the substituents in the pyridine ring. 2. The formation of the corresponding dimers from pyridine bases passes through a charge transfer complex in the first stage of the reaction with subsequent formation of anion radicals and paramagnetica complexes. 3. On interacting cordiamin with metallic sodium and Raney Ni newβ-substituted derivatives of 4,4′- and 2,2′-dipyridyls were obtained, viz. 3,3′-di-(N,N-diethylcarbamido)-4,4′-dipyridyl and 5,5′-di-(N,N-diethylcarbamido)-2,2′-dipyridyl.

Formaldehyde polymers, 26. Syntheses and condensations of substituted triphenoxy and triphenyl derivatives of 1,3,5‐triazine

Abstract2,4,6‐Tris(4‐hydroxymethyl‐2,6‐dimethylphenoxy)‐1,3,5‐triazine (4a), 2,4,6‐tris(2,6‐dimethylphenoxy)‐1,3,5‐triazine (4b), and 2,4,6‐triphenoxy‐1,3,5‐triazine (4c) were synthesized by reactions of 2,4,6‐trichloro‐1,3,5‐triazine (3) with 4‐hydroxymethyl‐2,6‐dimethylphenol (2), 2,6‐dimethylphenol (1), and phenol, respectively, in the presence of metallic sodium or sodium hydroxide. 2,4,6‐Tris(4‐hydroxyphenyl)‐1,3,5‐triazine (4d) was prepared by trimerization of p‐cyanophenol. The condensation polymerization of 4a and cocondensations of 4a, with the other 1,3,5‐triazine derivatives or with novolak resin were carried out in the presence of p‐toluenesulfonic acid at 200°C. In the cocondensations of 4a with 4b, 4c, 4d, 2,4,6‐tris(2‐hydroxyphenyl)‐1,3,5‐triazine (4e) or with novolak resin, the reactivity of the comonomers was found to decrease in the order: novolak resin ≫4e≥4c&gt;4b&gt;4d. The disappearance of the absorption band belonging to the hydroxymethyl group as well as the appearance of the carbonyl absorptions could be observed in the IR spectrum of the condensation resins, however, only small intensities of carbonyl absorptions in the spectrum of the cocondensation product of 4a with novolak resin. The thermal decomposition of the resins was determined by thermogravimetry.

The Reaction of Phenolic Compounds with Isoprenoids. VIII. The o-Isoprenylation of Phenols in the Presence of Metallic Sodium

Abstract Phenols (phenol, hydroquinone, resorcinol, and o-cresol) reacted with prenyl halides (3-methyl-2-buteny chloride and geranyl chloride) in the presence of an alkali metal (Na) in ether. In these reactions, phenols with the corresponding prenyl group at the ortho position were obtained selectively.

Reactions expanding the aziridine ring

Azirine reacts with 2-vinylpyridine in the presence of metallic sodium with the formation of N-[fl -(pyridin-2-yl)e thyl]azirine. The reaction of the latter with HBr and H2S leads to N-bromoethyl)- and N-(/~ -mercaptoethyl)- N- [fl -(pyridin-2-yl)e thyl]amines. Carbon oxysulfide and carbon disulfide react at room temperature with N-~-(pyridin-2-y l)ethyl]azirine to form copolymers in a ratio of 1 : 1. Carbon dioxide forms only N-~ -(pyridin-2-yl)e thyl]oxazolinone under similar conditions. Azirine adds to styrene in the presence of metallic sodium [2,3]. We have observed the addition of azirine to 2-vinylpyridine under similar conditions with the formation of N-[fi-(pyridin-2 -yl)ethyl]azirin e (I). The three-membered ring of the azirine (I) is easily cleaved under the action of hydrobromic acid, giving the dihydrobromide of the amine (Ha}, which was also obtained by treating with hydrobromic acid the product of the ethoxylation of N-[fl-(pyridin-2 -yl)ethyl]amine. The reaction of the azirine (1) with hydrogen sulfide formed the aminoethyl mercaptan (IIb), which was also prepared by the alkaline treatment of the dihydrobromide of N-{fl -[fl -(pyridin-2-yl)e thylamino]ethyl} isothiouronium bromide. Under the action of catalytic amounts of hydrohalic acids, (I) polymerizes, giving a water-soluble low polymer. The reaction of the azirine (D with carbon dioxide, carbon oxysulfide, and carbon disulfide, unlike that of the N-arylazirines, takes place without a catalyst. Carbon oxysulfide and carbon disulfide react very vigorously at room temperature, giving the peculiar copolymers (III).

Synthesis of 3?,5-di(piperidin-2-yl)-2, 4?-bipyridyl from anabasine

The possibility of the formation of 3′,5-di(piperidin-2-yl)-2,4′-bipyridyl by the dehydrogenative condensation of anabasine in the presence of metallic sodium at 50–60‡C has been shown.

Dimerization of N-methylanabasine in the presence of metallic sodium

In a study of the dimerization of N-methylanabasine in the presence of metallic sodium under conditions for the dimerization of pyridine, it was found that the reaction does not take place at room temperature while at 50–70° C it leads to the formation ofβ,β′-di(1-methylpiperid-2-yl)-γ,γ′-bipyridyl. Oxidation of the latter yielded 4,4′-bipyridyl-5, 5′-dicarboxylic acid, the decarboxylation of which gaveγ,γ′-bipyridyl.