New odorless method for the Corey-Kim and Swern oxidations utilizing dodecyl methyl sulfide (Dod-S-Me)

Development of the odorless dodecyl methyl sulfide (Dod-S-Me, 1) as an alternative for dimethyl sulfide (DMS) and new odorless methods for the Corey-Kim and Swern oxidations are described. These reactions have been developed with a view toward green chemistry, utilizing Dod-S-Me (1) and common solvents instead of dichloromethane.     

Meso-tetrakis[o-(N-methyl)pyridinium]porphyrin ensembles with axially coordinated cyclodextrin-penetrating phenethylimidazole: reversible dioxygen-binding in aqueous DMF solution

alpha-Cyclodextrin (alpha CD)-penetrating 2-methyl-1-phenethylimidazole coordinates to the zinc(II) and iron(II) complexes of meso-tetrakis[o-(N-methyl)pyridinium] porphyrinate, giving non-covalently linked alpha CD-porphyrin ensembles; the iron(II) complex can reversibly bind and release dioxygen in aqueous DMF solution.     

Use of odorless thiols: formal asymmetric Michael addition of hydrogen sulfide to alpha-substituted alpha,beta-unsaturated carbonyl compounds

[reaction: see text] The Michael addition to alpha-substituted alpha,beta-unsaturated esters and amides using complex A containing a chiral odorless thiol proceeded diastereoselectively. The Michael adducts were converted to beta-mercapto esters and amides via a Wagner-Meerwein rearrangement with boron trifluoride etherate and a thiol exchange reaction using odorless 1-dodecanethiol. This conversion constitutes a formal asymmetric Michael addition of hydrogen sulfide to alpha,beta-unsaturated carbonyl compounds using odorless thiols instead of the toxic hydrogen sulfide.     

High-Spin Polyphenoxyls Attached to Star-Shaped Poly(phenylenevinylene)s

Star-shaped poly(1,2-phenylenevinylene)s 4-substituted with multiple pendant phenoxyls (2 and 3) were synthesized by polymerizing 2-bromo-4-(acetoxyphenyl)styrene in the presence of 1,3,5-triiodobenzene or 1,3,5-tris(3',5'-diiodophenyl)benzene as the core via a simple one-pot Heck reaction and subsequent hydrolysis, phenolate formation, and heterogeneous oxidation. ESR spectra indicated a delocalized spin distribution into the core parts of the star-shaped molecules. The polyradicals, 2 and 3, were in a high-spin state at low temperature, and the ferromagnetic behavior was enhanced for the polyradical with a higher molecular weight. Although an average S of 3 remained at 3/2 to 4/2, the polyradical 2 even with a spin concentration of 0.8 spin/unit revealed an average S of 7/2 to 8/2. The 1,3,5-benzene core acted as an effective magnetic coupler to align the spins of the pendant phenoxyls through the star-shaped pi-conjugated backbone.     

Copper-catalyzed addition reaction of γ,γ-dialkoxyallylic zirconium species with imines

In the presence of CuCN, reaction of γ,γ-dialkoxyallylic zirconium species 1 with imines proceeded at the γ-position of 1 to give gem-dialkoxyhomoallylic amines 3 in high yield. In this reaction, γ,γ-dialkoxyallylic zirconium species 1 acts as an α,β-unsaturated acyl anion equivalent.     

Temperature programmed desorption analysis of sol-gel-derived titania films

Sol-gel-derived titania films were analyzed by temperature programmed desorption (TPD) and X-ray diffraction (XRD) techniques. The relationship between the TPD curves measured for two types of titania gel films and their crystal structures was investigated. On the basis of the analyses, a preparation process for a titania sol solution containing anatase nanocrystals was designed and developed. Using this process, a colloidal anatase titania sol solution was prepared by heating aqueous titanium hydroxide containing HCl at 60°C for 2 h. The nanocrystal structure of the titania films obtained by coating the sol on glass substrates was confirmed by TPD and XRD measurements.     

Depolymerization of poly(2,6-dimethyl-1,4-phenylene oxide) under oxidative conditions

Depolymerization of an engineering plastic, poly(2,6-dimethyl-1,4-phenylene oxide) (PPO), was accomplished by using 2,6-dimethylphenol (DMP) under oxidative conditions. The addition of an excess amount of DMP to a solution of PPO in the presence of a CuCl/pyridine catalyst yielded oligomeric products. When PPO (M(n)=1.0x10(4), M(w)/M(n)=1.2) was allowed to react with a sufficient amount of DMP, the molecular weight of the product decreased to M(n)=4.9x10(2) (M(w)/M(n)=1.5). By a prolonged reaction with the oxidant, the oligomeric product was repolymerized to produce PPO essentially identical to the starting material, making the oligomer useful as a reusable resource. During the depolymerization reaction, an intermediate phenoxyl radical was observed by ESR spectroscopy. Kinetic analysis showed that the rate of the oxidation of PPO was about 10 times higher than that of DMP. These results show that a monomeric phenoxyl radical attacks the polymeric phenoxyl to induce the redistribution via a quinone ketal intermediate, leading to the substantial decrease in the molecular weight of PPO, which is much faster than the chain growth.     

Computational examination of the electrophilic reaction on oxidative polymerization of phenyltrimethylsilane with sulfur chloride

Phenyltrimethylsilane possesses a higher HOMO energy (–9.34 eV) than nonsubstituted benzene (>0.41 eV). The π electron of the phenyltrimethylsilane localizes on the benzene ring at the ipso position rather than at the para position. Two center energies calculated by the MNDO-PM3 method indicate that the C? Si bond is facilitated to cleave in comparison with the C? H (para position) one of the benzene ring. Phenyltrimethylsilane and phenyl bis(trimethylsilane) were polymerized with sulfur chloride through the cationic oxidative polymerization. The product is isolated as oligo(p-phenylene sulfide), with a melting point of 150–190°C. An electrophile attacks the carbon atom linked to the Si atom in phenyltrimethylsilane. The new synthetic route of PPS can be established on the basis of the computational calculation.     

Radical copolymerization of proto-hemin dimethyl ester

Iron(III) proto-porphyrin IX dimethyl ester (HDME) can copolymerize with π-conjugated monomers binding at one end of the polymer chain. Apparent Q, e values of HDME were Q = 70 and e = ?0.17. The copolymerization of HDME with π-unconjugated monomer was feasible by using π-conjugated monomer as a third component. When unconjugated vinylimidazoles were used as monomers, the obtained ternary copolymers of HDME formed intramacromolecular complexes of iron(II) porphyrin with vinylimidazole residues, which gave stable carbon monoxide adducts.     

Oxygen-Binding Profile of the Iron Porphyrin Complex Embedded in Polymerized Liposome: Effect of the Polymerized Liposome on the Stability and the Oxygen-Binding Ability of the Iron Porphyrin Complex

5,10,15,20-Tetra(α,α,α,α, -o-(2′, 2′-dimethyl-20′-(2′ α-trimethylammonioethyl)phosphonatoxyeicosanamido)phenyl)porphinatoiron(II) (lipidheme) complex embedded in polymerized liposome was prepared by polymerizing l-(9-(p-vinylbenzoyl)nonanoyl)-2-O-octadecyl-rac-glycero-3-phosphocholine in the presence of lipid-heme under ultraviolet irradiation. The polymerization proceeded rapidly, and the reduction of the hemin to the heme occurred spontaneously during the polymerization. The lipid-heme complex embedded in the polymerized liposome bound molecular oxygen reversibly under physiological conditions (pH 7, 37°C) and was chemically, physically, and mechanically stable during storage for a long period and even in a high-speed flow system. The oxygen-binding affinity was not affected by the type of medium due to the effect of the rigid polymerized liposome.