scholarly journals Asymmetric Radical Reaction in the Coordination Sphere. IV. Ruthenium(II)-Catalyzed Asymmetric Addition of Sulfonyl Chloride to 1-Phenylpropene

1989 ◽  
Vol 62 (2) ◽  
pp. 648-650 ◽  
Author(s):  
Masayuki Kameyama ◽  
Nobumasa Kamigata
Keyword(s):  
Coordination Sphere ◽  
Radical Reaction ◽  
Sulfonyl Chloride ◽  
Asymmetric Addition

The Structure of Radiation Cross-Linked Poly (ethylene oxide) Gels

1971 ◽  
Vol 29 ◽  
pp. 76-77
Author(s):  
C. E. Cluthe ◽  
G. G. Cocks
Keyword(s):  
Molecular Weight ◽  
Ethylene Oxide ◽  
Parallel Plate ◽  
Average Molecular Weight ◽  
Radical Reaction ◽  
Free Radical Reaction ◽  
Nitrogen Gas ◽  
Poly Ethylene Oxide ◽  
Poly Ethylene ◽  
Initial Viscosity

Aqueous solutions of a 1 weight-per cent poly (ethylene oxide) (PEO) were degassed under vacuum, transferred to a parallel plate viscometer under a nitrogen gas blanket, and exposed to Co60 gamma radiation. The Co60 source was rated at 4000 curies, and the dose ratewas 3.8x105 rads/hr. The poly (ethylene oxide) employed in the irradiations had an initial viscosity average molecular weight of 2.1 x 106.The solutions were gelled by a free radical reaction with dosages ranging from 5x104 rads to 4.8x106 rads.

Large-cluster and combined fluorescent and gold immunoprobes

1996 ◽  
Vol 54 ◽  
pp. 892-893
Author(s):  
Richard D. Powell ◽  
James F. Hainfeld ◽  
Carol M. R. Halsey ◽  
David L. Spector ◽  
Shelley Kaurin ◽  
...  
Keyword(s):  
Metal Cluster ◽  
Sulfonyl Chloride ◽  
Gel Filtration ◽  
Cross Linking ◽  
Site Specific ◽  
Fab Fragments ◽  
Cluster Label ◽  
Covalently Linked ◽  
Texas Red ◽  
Fold Excess

Two new types of covalently linked, site-specific immunoprobes have been prepared using metal cluster labels, and used to stain components of cells. Combined fluorescein and 1.4 nm “Nanogold” labels were prepared by using the fluorescein-conjugated tris (aryl) phosphine ligand and the amino-substituted ligand in the synthesis of the Nanogold cluster. This cluster label was activated by reaction with a 60-fold excess of (sulfo-Succinimidyl-4-N-maleiniido-cyclohexane-l-carboxylate (sulfo-SMCC) at pH 7.5, separated from excess cross-linking reagent by gel filtration, and mixed in ten-fold excess with Goat Fab’ fragments against mouse IgG (obtained by reduction of F(ab’)2 fragments with 50 mM mercaptoethylamine hydrochloride). Labeled Fab’ fragments were isolated by gel filtration HPLC (Superose-12, Pharmacia). A combined Nanogold and Texas Red label was also prepared, using a Nanogold cluster derivatized with both and its protected analog: the cluster was reacted with an eight-fold excess of Texas Red sulfonyl chloride at pH 9.0, separated from excess Texas Red by gel filtration, then deprotected with HC1 in methanol to yield the amino-substituted label.

One-pot Synthesis of Pyrazolone Sulfones by Iodine-catalyzed Sulfenylation of Pyrazolones with Aryl Sulfonyl Hydrazides Followed by Oxidation in Water

2018 ◽  
Vol 15 (3) ◽  
pp. 380-387
Author(s):  
Xia Zhao ◽  
Xiaoyu Lu ◽  
Lipeng Zhang ◽  
Tianjiao Li ◽  
Kui Lu
Keyword(s):  
Double Bond ◽  
Efficient Method ◽  
Room Temperature ◽  
Sulfonyl Chloride ◽  
Antibacterial Activities ◽  
Oxidation Reactions ◽  
Reaction Conditions ◽  
One Pot ◽  
X Ray ◽  
Amide Form

Aim and Objective: Pyrazolone sulfones have been reported to exhibit herbicidal and antibacterial activities. In spite of their good bioactivities, only a few methods have been developed to prepare pyrazolone sulfones. However, the substrate scope of these methods is limited. Moreover, the direct sulfonylation of pyrazolone by aryl sulfonyl chloride failed to give pyrazolone sulfones. Thus, developing a more efficient method to synthesize pyrazolone sulfones is very important. Materials and Method: Pyrazolone, aryl sulphonyl hydrazide, iodine, p-toluenesulphonic acid and water were mixed in a sealed tube, which was heated to 100°C for 12 hours. The mixture was cooled to 0°C and m-CPBA was added in batches. The mixture was allowed to stir for 30 min at room temperature. The crude product was purified by silica gel column chromatography to afford sulfuryl pyrazolone. Results: In all cases, the sulfenylation products were formed smoothly under the optimized reaction conditions, and were then oxidized to the corresponding sulfones in good yields by 3-chloroperoxybenzoic acid (m-CPBA) in water. Single crystal X-ray analysis of pyrazolone sulfone 4aa showed that the major tautomer of pyrazolone sulfones was the amide form instead of the enol form observed for pyrazolone thioethers. Moreover, the C=N double bond isomerized to form an α,β-unsaturated C=C double bond. Conclusion: An efficient method to synthesize pyrazolone thioethers by iodine-catalyzed sulfenylation of pyrazolones with aryl sulfonyl hydrazides in water was developed. Moreover, this method was employed to synthesize pyrazolone sulfones in one-pot by subsequent sulfenylation and oxidation reactions.

Coordination state of cobalt(II) ions in solution and on a sulphonated organic polymer

1979 ◽  
Vol 44 (8) ◽  
pp. 2330-2337 ◽  
Author(s):  
Jindřiška Maternová ◽  
Anastas A. Andreev ◽  
Dimitrii M. Shopov ◽  
Karel Setínek
Keyword(s):  
Acetic Acid ◽  
Coordination Sphere ◽  
Glacial Acetic Acid ◽  
Organic Polymer ◽  
Octahedral Complex ◽  
Coordination State ◽  
Tetrahedral Symmetry ◽  
Liquid Acid ◽  
Homogeneous Phase ◽  
Bromide Ion

It was found spectroscopically that cobalt(II) acetate dissolved in glacial acetic acid forms the octahedral complex [Co(OAc)2(HOAc)4] which in the presence of bromide ions gives the octahedral [Co(OAc)Br(HOAc)4] and tetrahedral bromo(acetate)cobalt(II) complexes with the higher number of Br- ions. When attached to an organic polymer cobalt(II) ions are bonded in the form of octahedral [Co(H2O)6]2+ cations which form with acetic acid similar complexes as in homogeneous phase and are able to coordinate one bromide ion. Drying the copolymer possessing octahedral hexaaquocobalt(II) cations leads to tetrahedral aquocomplexes which are solvated by gaseous acetic acid and converted into the acetate complexes with the liquid acid. The latter contain the acid in the inner coordination sphere and have tetrahedral symmetry.

Photooxidation effect of cupric complexes on aliphatic alcohols in nonaqueous solutions

1982 ◽  
Vol 47 (8) ◽  
pp. 2061-2068 ◽  
Author(s):  
Jan Sýkora ◽  
Mária Jakubcová ◽  
Zuzana Cvengrošová
Keyword(s):  
Coordination Sphere ◽  
Alcohol Oxidation ◽  
Aliphatic Alcohols ◽  
Oxidation Products ◽  
Molar Ratio ◽  
Quantum Yields ◽  
Nonaqueous Solutions ◽  
The Absolute ◽  
Absolute Quantum

In the photolysis of copper(II)-chloride-alcohol-acetonitrile systems (cCu = 1 mmol l-1, copper(II)-to-chloride molar ratio 1 : 2 to 1 : 8, 10% (v/v) alcohol), Cu(II) is reduced to Cu(I), and methanol, ethanol, 1-propanol, or 1-butanol is oxidized to the corresponding aldehyde, 2-propanol to acetone. In the case of 1-propanol and 1-butanol, chlorinated aldehydes are formed in addition too. The measured quantum yields of the photoreduction of Cu(II) to Cu(I) lay in the range of ΦCu(I) = 4.5 to 40 mmol einstein-1, the absolute quantum yields of the alcohol oxidation products were 2.3 to 47 mmol einstein-1. The photoactive components are chlorocupric complexes [CuClx](2-x)+ (x = 1-4). The presence of complexes with a higher number of chloroligands in the coordination sphere (x = 3, 4) brings about a decrease in the Cu(II) photoreduction rate. The decrease in the photoreduction rate observed in the presence of dioxygen is explained in terms of re-oxidation of copper(I) by the latter, resulting in an increase in the concentration of the photochemically active cupric complexes. The catalytic aspects of the systems in question are discussed with respect to this effect.

Complexes of copper(II) and nickel(II) with a Schiff base bonded to a polymeric support

1983 ◽  
Vol 48 (7) ◽  
pp. 2021-2027 ◽  
Author(s):  
Eliška Kálalová ◽  
Olga Populová ◽  
Štěpánka Štokrová ◽  
Pavel Stopka
Keyword(s):  
Magnetic Properties ◽  
Schiff Base ◽  
Coordination Sphere ◽  
Polymer Matrix ◽  
Glycidyl Methacrylate ◽  
Epr Spectra ◽  
Polymeric Support ◽  
Tetrahedral Configuration ◽  
Paramagnetic Complexes

Copper(II) and nickel(II) ions were bonded in complexes of salicylideneimine type on a glycidyl methacrylate-ethylenedimethacrylate copolymer. The geometry of the complexes on the polymer was studied by measuring their magnetic properties, EPR spectra, and ultraviolet-visible spectra.Only paramagnetic complexes possessing a pseudo-tetrahedral configuration were found. The effect of the polymer matrix and of the immobility of the bonded Schiff base on the distortion of the coordination sphere of the central ion is discussed.

Über den Mechanismus der Bildung von Polyanionen in wäßriger Lösung. Zum Bildungsmechanismus eines Polytetramolybdations [Mo4O144-]n / On the Mechanism of Formation of Polyanions in Aqueous Solution. Concerning the Mechanism of Formation of a Polytetramolybdate Ion [Mo4O144-]n

1976 ◽  
Vol 31 (6) ◽  
pp. 737-748 ◽  
Author(s):  
Karl-Heinz Tytko
Keyword(s):  
Aqueous Solution ◽  
Coordination Sphere ◽  
Analytical Formula ◽  
Reaction Pathways ◽  
Mechanism Of Formation ◽  
X Ray ◽  
Theoretical Considerations

Possible structures and the pertinent reaction pathways for the polymetalate ion present in a slightly soluble polymetalate having the analytical formula A2O · 2 MOs have been derived on the basis of theoretical considerations. Structure and kind of combination of the tetrameric units of one of the possibilities are in agreement with the results of X-ray structure analyses. First the previously proposed planar tetrametalate ion [M4O12(OH)4]4--is formed by stepwise aggregation according to an addition mechanism. This species undergoes a rearrangement of the coordination sphere of two of the M atoms and is then subject to a polycondensation resulting in a polytetrametalate chain, [M4O144-]n.

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